WO2025257308A1 - Biodegradable two-part composition for skin protection against uv radiation - Google Patents
Biodegradable two-part composition for skin protection against uv radiationInfo
- Publication number
- WO2025257308A1 WO2025257308A1 PCT/EP2025/066379 EP2025066379W WO2025257308A1 WO 2025257308 A1 WO2025257308 A1 WO 2025257308A1 EP 2025066379 W EP2025066379 W EP 2025066379W WO 2025257308 A1 WO2025257308 A1 WO 2025257308A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- anhydrous
- hydrous
- composition
- formula
- part composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/88—Two- or multipart kits
- A61K2800/882—Mixing prior to application
Definitions
- Biodegradable two-part composition for skin protection against UV radiation
- the present invention relates to a two-part composition
- a two-part composition comprising a) an anhydrous part comprising a base and at least one compound according to formula (I), and b) a hydrous part comprising at least water.
- the present invention relates to a process for the protection of keratin materials and the use of a two-part composition as defined herein for UV-protection of keratin materials.
- Mycosporine-Like Amino Acids such as Shinorine are natural protective agents against UV-induced skin damage (V. Geraldes et al. Mycosporine-Like Amino Acids (MAAs): Biology, Chemistry and Identification Features. Pharmaceuticals, 2021, 14(1), 63 and A.
- MAAs Mycosporine-Like Amino Acids
- Antioxidants 2021, 10(5), 683. They provide excellent UV protection for keratin materials.
- MAAs are biodegradable natural compounds, in contrast to e.g. state-of-the-art UV absorbers for skin protection.
- MAAs are sensitive to certain environmental parameters such as light, oxygen or water. The degradation of MAAs occurs when formulated in the presence of these parameters, which is often contrary to the desired results.
- MAAs show strong discoloration in contact with water and/or glycols after several days (see e.g. Example 1). Significant degradation of MAAs (e.g. Shinorine) occurs if MAAs are dissolved in cosmetic emulsions or in aqueous solutions after storage at 40-50° C for 4-6 weeks. This is an inacceptable change of initial properties of the cosmetic product. According to ISO/TR 18811:2018, the stability of a cosmetic product is its ability to resist change or variation of its initial properties over time under stated or reasonably foreseeable conditions of storage.
- the stability can be evaluated in real time by monitoring the state of a product under reasonably expected conditions of storage, or in accelerated study designed to speed up naturally occurring destabilization processes due to intrinsic or extrinsic factors and which predicts the behavior over the long term.
- the typical shelf-life of a sunscreen product is of two years (recommended time period that a cosmetic product can be kept after its production, during which the defined quality of the product remains acceptable under expected conditions of distribution, storage, display and usage).
- typical testing conditions are 3, 6, 12, 24 and 36 months at 25° C and 1, 3, 6, 12, 24 months at 40° C.
- typical testing conditions are 3, 6, 12, 24 and 36 months at 25° C and 1, 3, 6, 12, 24 months at 40° C.
- In some regions like Asia standard conditions are set to 50° C to cover exposition to high temperatures during transport or use in summer.
- compositions consisting of two separate parts (two-part compositions) have been proposed, wherein one part comprises the active agent and the other part comprises the carrier system.
- two-part compositions for caring for keratin materials, wherein one part contains ferulic acid, which is separated from the hydrous part. Before application, the two parts are mixed to form a solution.
- the solution obtained is difficult to apply to the skin, because due to the very low viscosity it runs down the skin easily and is difficult to handle.
- Freeze-drying of an aqueous solution containing neutralized MAAs or MAA salts leads to a powdered form of the UV filter.
- the freeze-dried product obtained is dissolved in water just before use.
- This solution has the disadvantages of being complex and quite expensive.
- the solution obtained is difficult to apply to the skin, because due to the very low viscosity it runs down the skin easily and is difficult to handle.
- JP 6719267 B2 describes a solution containing stabilized MAAs, wherein the MAA is mixed with one or more substances selected from the group consisting of a -glucosyl hesperidin, erythorbic acid, a -glucosylrutin, glutathione, sodium disulfite, albumin, gallic acid, EDTA, sodium metaphosphate, sodium citrate, aspartic acid, glutamic acid, arginine, cysteine, methionine, serine, glucose, trehalose, sorbitol, allose, ?
- JP 6719267 B2 does not fully overcome the aforementioned problems.
- composition based on MAAs wherein the MAAs can quickly dissolve into the carrier system for application on the skin without degradation of the active ingredient. It has been another object of the present invention to provide a composition based on MAAs, which has whitening/lightening, antifine lines and anti-inflammation properties. Furthermore, it has been an object of the present invention to provide a composition based on MAAs, which has a high UV protection, i.e. a high SPF (Sun Protection Factor) and/or UVA-PF (UVA Protection Factor) and at the same time is comfortable to apply for the user.
- SPF Sun Protection Factor
- UVA-PF UVA Protection Factor
- the two-part composition of the present invention provides a composition of MAAs of formula (I), wherein the MAA as active ingredient is quickly provided for application to keratin materials, in particular the skin, without degradation of the MAA as active ingredient or discoloration of the composition after a short period of time.
- the claimed two-part composition allows for high UV- protection and does not cause skin irritations.
- the two-part composition of the present invention provides an environmentally friendly composition for UV-protection.
- the two-part composition of the present invention can be easily prepared and is thus economically advantageous.
- the present invention relates to a two-part composition
- a two-part composition comprising a) an anhydrous part comprising a base and at least one compound according to formula (I) or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof, wherein
- X is NR N ;
- R 1 is C 1 -C 2 -alkyl
- R 2 is H
- R 4 is H or OR a ;
- R a is H; and optionally al) cosmetic oils; a2) UV filters; a3) surfactants and/or emulsifier; a4) sensory enhancers; a5) consistency agents; a6) film forming agents; a7) UV performance booster like scattering particles a8) preservatives; and/or a9) perfumes; and b) a hydrous part comprising at least water, and optionally bl) alcohols; b2) UV filters; b3) surfactants and/or emulsifier; b4) sensory enhancers; b5) thickeners; b6) film forming agents; b7) UV performance boosters; b8) preservatives; b9) humectants; and/or blO) perfumes and wherein the anhydrous part and the hydrous part are separate.
- said compound of formula (I) is a compound according to the following formula
- the anhydrous part comprises the compound of formula (I) in an amount of from 0.1 % to 20 % by weight, based on the total weight of the two-part composition.
- the anhydrous part comprises the compound of formula (I) in an amount of from 1 % to 8% by weight, based on the total weight of the two-part composition.
- the base of the anhydrous part a) is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline, preferably wherein the base is anhydrous.
- the base of the anhydrous part a) is selected from the group consisting of sodium bicarbonate and sodium carbonate, preferably anhydrous sodium bicarbonate and anhydrous sodium carbonate.
- the base of the anhydrous part a) in an amount of from 0.1 % to 3 % by weight, preferably in an amount of from 0.3 % to 2.5 % by weight, based on the total weight of the two-part composition.
- the hydrous part b) of the composition comprises water in an amount of from 3 % to 70 % by weight, based on the total weight of the two-part composition.
- the UV filter comprised in the hydrous part is selected from the group consisting of [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2- oxo- 1- (sulfo methyl) -3 -bicyclo [2.2.1] hepta ny lid ene] methyl] phenyl] methyl ide ne] -7,7- dimethyl-2-oxo-l-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphor sulfonic acid), 2-phenyl-lH-benzimidazole-5-sulfonic acid (INCI phenylbenzimidazole sulfonic acid), disodium phenyl dibenzimidazole tetrasulfonate, 2- ethylhexyl-(2E)-3-(4-methoxyphenyl)acryl
- the UV filter comprised in the anhydrous part is selected from the group consisting of 1 - (4- (1 ,1 -di methy lethy I) pheny I) - 3-(4-methoxyphenyl)propane-l, 3-dione (I NCI butyl methoxydibenzoylmethane), 2-(2H- benzotriazo I -2 -y I) -6- [(2 -ethyl hexyl oxy) methy I] -4- methy I phenol, 2 -(2 H- benzotriazo I -2-yl) -4- methy 1-6- [2 -methy 1-3- [1,3,3,3-tetra methy 1-1 -[(tri methy Isi ly l)oxy] -1 - disiloxanyl] propyl] phenol (INCI drometrizole trisiloxane), titanium dioxide,
- the anhydrous part a) contains the compound according to formula (I) and the base.
- the hydrous part b) contains only water and no other ingredients.
- the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of from 20 % to 60 %. In another preferred embodiment of said two-part composition, the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of larger or equal to 60 %.
- the present invention relates to a process for the UV-protection of keratin materials, comprising mixing the anhydrous part and the hydrous part of the two- part composition together to form a solution or emulsion before applying the solution or emulsion to the keratin materials.
- the present invention relates to the use of the two-part composition for UV-protection of keratin materials.
- the two-part composition has an UV-A protection, which is at least one third of the sun protection factor of the two-part composition and/or shows a critical wavelength of at least 370 nm.
- a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group, which preferably consists of these embodiments only.
- the terms “first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)” etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
- compound(s) according to the invention comprises the compound(s) as defined herein as well as a salt, hydrate, stereoisomer, tautomer or N-oxide thereof.
- the compounds according to the invention may have one or more centres of chirality.
- the invention provides both the single pure enantiomers or pure diastereomers of the compounds according to the invention, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds according to the invention or their mixtures.
- Suitable compounds according to the invention also include all possible geometrical stereoisomers (cis/trans isomers or E/Z isomers) and mixtures thereof. Cis/trans isomers may e.g. be present with respect to an amide group.
- stereoisomer(s) encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one centre of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
- the present invention relates to every possible stereoisomer of the compounds of formula (I), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
- the compounds of formula (I) may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities.
- the present invention relates to amorphous and crystalline compounds of formula (I), mixtures of different crystalline states of the respective compound of formula (I), as well as amorphous or crystalline salts thereof.
- Salts of the compounds of the formula (I) may be pharmaceutically acceptable salts, such as those containing counterions present in drug products listed in the US FDA Orange Book database. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality.
- Suitable anionic counterions are in particular chloride, bromide, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, trifluoroacetate, propionate and butyrate, furthermore lactate, gluconate, and the anions of poly acids such as succinate, oxalate, maleate, fumarate, malate, tartrate and citrate, furthermore sulfonate anions such as besylate (benzenesulfonate), tosylate (p-toluenesulfonate), napsylate (naphthalene-2-sulfonate), mesylate (methanesulfonate), esylate (ethanesulfon
- hydrate in connection with the compounds of formula (I) refers to a compound of formula (I), which incorporates water molecules in the crystalline structure but does not alter the chemical structure of formula (I).
- the compounds of formula (I), in particular shinorine are used as hydrate.
- Tautomers may be formed, if a substituent is present at the compound of formula (I), which allows for the formation of tautomers such as keto-enol tautomers or the like.
- the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
- the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
- alkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms.
- alkyl group examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,
- alkenyl denotes in each case an unsaturated hydrocarbon group having usually 2 to 6, preferably 2 to 4 carbon atoms comprising at least one carbon-carbon double bond in any position, e.g. vinyl (ethenyl), allyl (2-propen-l-yl), 1-propen-l-yl,
- heterocyclyl or “heterocyclic ring” as used herein includes, unless otherwise indicated, in general a 3- to 9-membered, preferably a 4- to 8-membered or 5- to 7- membered, more preferably 5- or 6-membered, in particular 5-membered monocyclic ring.
- the heterocycle is saturated, wherein saturated means that only single bonds are present.
- the heterocycle typically comprises one or more, e.g. 1, 2, 3, or 4, preferably 1, 2, or 3 heteroatoms selected from N, 0 and S as ring members, where S-atoms as ring members may be present as S, SO or SO 2 .
- the remaining ring members are carbon atoms.
- the saturated heterocycle as used herein comprises at least one nitrogen atom, namely the nitrogen atom to which R 2 and R 3 are attached.
- the saturated heterocycle comprises 0, 1, or 2, preferably 0 or 1, more preferably 0 heteroatoms selected from N, 0 and S as ring members, where S- atoms as ring members may be present as S, SO or SO 2 .
- S, SO or SO 2 is to be understood as follows:
- saturated heterocycles include pyrrolidine, pyrrolidinone, morpholine, thiomorpholine, piperidine or piperazine.
- keratin materials refers to any material comprising keratin, including natural and synthetic materials. Particular examples of keratin materials are the skin, hair, nails, feathers, horns, claws, and hooves. A preferred keratin material is human skin.
- anhydrous part refers to a part of the composition, wherein no water has been added such that the water present is only due to residual water or hydrates of the components in the anhydrous part.
- the anhydrous part does not contain any water other than in the form of hydrates of the components in the anhydrous part. More preferably, the anhydrous part does not contain any water other that in the form of the hydrate of the compound of formula (I).
- the water content is preferably less than 0.1 % by weight relative to the weight of the anhydrous part.
- hydrophilic part refers to a part of the composition, wherein water has been added.
- suitable bases of the anhydrous part include alkali metal salts, alkaline earth metal salts, or ammonium salts such as, e.g., carbonates, bicarbonates, or oxides.
- the bases that are part of the anhydrous part are preferably anhydrous bases.
- the hydrous part may comprise a base or an aqueous solution of a base.
- cosmetic oils also encompass emollients and can be chosen from all oils, preferably physiologically acceptable oils, in particular mineral, animal, vegetable, or synthetic oils; especially non-volatile hydrocarbon oils and/or non-volatile silicone oils, and their mixtures.
- Exemplary cosmetic oils include but are not limited to castor oil, avocado oil, olive oil, sweet almond oil, wheat germ oil, sesame oil, cottonseed oil, coconut oil, corn oil, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, apricot kernel oil, hazelnut oil, borago oil, peanut oil, sesame oil, jojoba oil, argan oil, rosehip oil, black seed oil, grape seed oil, walnut oil, palm oil, medium chain diglycerides, medium chain triglycerides (MCT), and mixtures thereof.
- castor oil avocado oil, olive oil, sweet almond oil, wheat germ oil, sesame oil, cottonseed oil, coconut oil, corn oil, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, apricot kernel oil, hazelnut oil, borago oil, peanut oil, sesame oil, jojoba oil, argan oil, rosehip oil, black seed oil, grape
- Medium chain di- or triglycerides are preferably based on C 6 -C 18 fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, cocoglycerides, wheat germ glycerides, etc.) or fatty acid esters of polyglycerol (polyglyceryl -n) such as polyglyceryl-4 caprate, polyglyceryl-2-isostearate, etc.
- polyglycerol polyglyceryl -n
- UV-filter refers to organic or inorganic compounds or mixtures thereof, which can absorb and optionally reflect UV radiation caused by sunlight. UV-filter can be classified based on their UV protection curve as UV-A, UV-B or broadband filters. In the context of the present application, broadband filters may be listed as UV-A filters, as they also provide UV-A protection. In other words, preferred UV-A filters also include broadband filters.
- broadband filters may be listed as UV-A filters, as they also provide UV-A protection. In other words, preferred UV-A filters also include broadband filters.
- the definition of “broadband” protection (also referred to as broadspectrum or broad protection) is based on the “critical wavelength”. For broadband coverage, UV-B and UV-A protection must be provided. According to the US requirements, a critical wavelength of at least 370 nm is required for achieving broad spectrum protection.
- Organic UV filters include triazine derivatives, triazole derivatives, benzotriazole derivatives, benzophenone derivatives, dibenzoylmethane derivatives, camphor derivatives, cinnamates, salicylates, benzimidazole sulfonic acid derivatives, polysilicone-15, para-amino benzoic acid (PABA) derivatives, and combinations thereof.
- PABA para-amino benzoic acid
- organic UV filters are ethylhexyl triazone (EHT), dimethyl para-aminobenzoate (ED PABA), PEG-25 PABA, ethylhexyl salicylate (EHS), ethylhexyl methoxy cinnamate (EHMC), iso-amyl methoxy cinnamate (IMC), octocrylene (OCR), phenyl benzimidazole sulfonic acid (PBSA), 4-methyl benzylidene camphor (4-MBC), butyl methoxy dibenzoylmethane (BMDBM), terephthalidine dicamphor sulfonic acid (TDSA), drometrizole trisiloxane (DTS), methylene bis- benzotriazolyl tetramethylbutylphenol (MBBT), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), benzophenone-3 (
- UV-protection refers to protection of keratin materials from UV radiation by absorbing or reflecting UV radiation. UV-protection as used herein refers to UV-A protection and/or UV-B protection.
- SPF sunscreen protection factor
- UV-A protection factor As regards the UV-A protection factor (UVA-PF), it is recommended by the European Commission that all sunscreen or cosmetic compositions should have an UVA protection factor, which is at least one third of the labelled sun protection factor (SPF), e.g. if the sunscreen composition has an SPF of 30 the UVA protection factor has to be at least 10. UVA-PF can be measured in vivo according to the ISO24442 or in vitro according to the ISO24443.
- critical wavelength is defined as the wavelength at which the area under the UV protection curve (% protection versus wavelength) represents 90 % of the total area under the curve in the UV region (290-400 nm).
- a critical wavelength of 370 nm indicates that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e. wavelengths from 290-320 nm, but extends to 370 nm in such a way that 90 % of the total area under the protective curve in the UV region are reached at 370 nm.
- body-care product or “cosmetic composition” refers to any product suitable to apply to the mammalian body, preferably to the human body, such as, e.g. sunscreen compositions, bath and shower products, preparations containing fragrances and odoriferous substances, hair-care products, dentifrices, decorative preparations, and cosmetic formulations containing active ingredients.
- sunscreen composition refers to any topical product, which absorbs certain parts of UV radiation and which may further reflect and scatter certain parts of UV radiation.
- sunscreen composition is to be understood as not only including sunscreen compositions, but also any cosmetic compositions that provide UV protection.
- topical product refers to a product that is applied to the surface of a material or the body, preferably to a keratin material, such as the skin, and can refer, e.g., to sprays, lotions, creams, oils, foams, powders, or gels.
- the sunscreen composition may comprise one or more active agents, e.g., organic UV filters, as well as other ingredients or additives, e.g., emulsifiers, emollients, viscosity regulators, stabilizers, preservatives, or fragrances.
- the term “daily care composition” refers to any topical product, which reflects or absorbs certain parts of UV radiation and is used as an everyday care product for the human body, e.g., for face, body or hair.
- the daily care composition may comprise one or more active agents, e.g., organic or inorganic UV filters, as well as other ingredients or additives, e.g., emulsifiers, emollients, viscosity regulators, stabilizers, preservatives, or fragrances.
- Suitable bath and shower additives are, e.g., shower gels, bath-salts, bubble baths and soaps.
- Suitable preparations containing fragrances and odoriferous substances are in particular scents, perfumes, toilet waters and shaving lotions (aftershave preparations).
- Suitable hair-care products are, e.g., shampoos for humans and animals, in particular dogs, hair conditioners, products for styling and treating hair, perming agents, hair sprays and lacquers, hair gels, hair fixatives and hair dyeing or bleaching agents.
- Suitable dentifrices are, e.g., tooth creams, toothpastes, mouth-washes, mouth rinses, antiplaque preparations and cleaning agents for dentures.
- Suitable decorative preparations are, e.g., lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions.
- Suitable cosmetic formulations containing active ingredients are, e.g., hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations.
- light stabilizers are compounds suitable for protecting a product, e.g., a body-care product, household cleaning and treating agents, agrar-formulations, food, polymers (such as plastics, coatings, printing, packaging, lacquers, textiles) against photolytic degradation.
- the light stabilizer is usually present in the body-care product in a concentration of 50 to 1000 ppm.
- household cleaning and treating agent refers to any product suitable to clean or treat household objects, e.g., liquid scouring agents, glass detergents, neutral cleaners (allpurpose cleaners), acid household cleaners (bath), WC cleaners, preferably in washing, rinsing and dishwashing agents, clear rinsing agents, dishwasher detergents, shoe polishes, polishing waxes, floor detergents and polishes, metal, glass and ceramic cleaners, textilecare products, agents for removing rust, color and stains (stain remover salt), furniture and multipurpose polishes and leather dressing agents (leather sprays).
- liquid scouring agents e.g., liquid scouring agents, glass detergents, neutral cleaners (allpurpose cleaners), acid household cleaners (bath), WC cleaners, preferably in washing, rinsing and dishwashing agents, clear rinsing agents, dishwasher detergents, shoe polishes, polishing waxes, floor detergents and polishes, metal, glass and ceramic cleaners, textilecare
- household cleaning agents are aqueous or alcoholic (e.g. ethanol or isopropyl alcohol) solutions of one or more of the following components: anionic, nonionic, amphoteric and/or cationic surfactants soaps, prepared by saponification of animal and vegetable greases organic acids, like hydrochloric acid, phosphoric acid, or sulfuric acid, for basic products inorganic (NaOH or KOH) or organic bases; abrasives for improved cleaning of surfaces, waxes and/or silicones for maintenance and protection of surfaces, polyphosphates, substances which eliminate hypochlorite or halogens; -peroxides comprising bleaching activators like TAED, for example sodium perborate or H 2 O 2 ; enzymes; in washing detergents discoloration inhibitors, soil-release compounds, grey scale inhibitors, foam inhibitors, fluorescent whitening agents; cleaning agents based on wax may comprise solvents selected from benzine, turpentine and/or paraffines and emulsifiers based
- photostability refers to the ability of a UV filter or any other molecule, which is exposed to sunlight, to stay stable upon irradiation. In particular, this means that the compound does not undergo a degradation process upon UV radiation.
- consistency agent refers to any ingredient, which builds viscosity to deliver optimal product consistency.
- consistency agents include particularly consistency regulators/thickeners.
- Film forming agents as used herein include film forming polymers, which may provide improved water resistance and rub-off resistance.
- Humectants refer to water-absorbing (hygroscopic) substances, which are used to keep things moist.
- Humectants are molecules comprising several hydrophilic groups, e.g. hydroxyl groups.
- Humectants are often used in cosmetics in order to increase and maintain moisture in the skin or hair. They attract water/moisture e.g. from the outer layer of the skin or from the atmosphere via absorption and draw the moisture against e.g. the epidermis.
- Humectants can include but are not limited to e.g. triethylene glycol, tripropylene glycol, propylene glycol, PPGs, glycerol, sorbitol, hexylene glycol, butylene glycol, urea or collagen.
- biodegradable or “biodegradability” in the context of the compounds of formula (I) or the organic components of the two-part composition refers to the capacity of said compounds or components to biodegrade.
- the compound(s) of formula (I) or the organic components are defined as biodegradable or having a certain biodegradability, this refers to each of the compounds of formula (I) and each of the individual organic components of the two-part composition being biodegradable and not the mixture thereof.
- Primary biodegradation refers to the alteration in the chemical structure of a substance brought about by biological action and resulting in the loss of a specific property of that substance.
- Ultimate biodegradation (aerobic) relates to the level of degradation achieved when the test substance is totally utilized by micro-organism resulting in the production of carbon dioxide, water, mineral salts and new microbial cellular constituents (biomass).
- Biodegradation can be further classified in two groups, substances which are “readily biodegradable” and substances which are “partially biodegradable”. “Readily biodegradable” is an arbitrary classification of chemicals which have passed certain specified screening tests for ultimate biodegradability. These tests are so stringent that it is assumed that such compounds will rapidly and completely biodegrade in aquatic environments under aerobic conditions.
- Partially biodegradable relates to a classification of chemicals for which there is unequivocal evidence of biodegradation (primary or ultimate) in any test of biodegradability.
- Partially biodegradable is a term for substances that can be biodegraded under specific conditions. The test for partial biodegradability is not as stringent as a ready biodegradation study.
- biodegradable includes partially biodegradable and readily biodegradable. As used herein, if a compound of formula (I) or an organic component of the two-part composition is partially biodegradable, this means having a biodegradability of more than 20% (>20%) but less than 60% ( ⁇ 60%).
- partially biodegradable as used herein is defined as > 20% but ⁇ 60% biodegradability as measured by OECD 301 F testing.
- a compound of formula (I) or an organic component of the two-part composition is readily biodegradable, this means having a biodegradability of larger or equal to 60% (>60%).
- readily biodegradable as used herein is defined as >60% biodegradability as measured by OECD 301 F testing.
- the biodegradability of an organic component can be assessed via different OECD 301 A-F measurements.
- the biodegradability has been assessed via a small-scale measurement of the OECD 301 F testing method. The procedure of the OECD 301 F is described as follows.
- OECD 301 F test For the principal of the OECD 301 F test it is referred to the OECD Guidelines for the Testing of Chemicals, Section 3, Environmental fate and behavior (doi.org/10.1787/2074577x).
- a measured volume of inoculated mineral medium containing a known concentration of test substance (100 mg test substance/l giving at least 50-100 mg ThOD/l) as the nominal sole source of organic carbon, is stirred in a closed flask at a constant temperature for up to 28 days.
- the consumption of oxygen is determined either by measuring the quantity of oxygen (produced electrolytically) required to maintain constant gas volume in the respirometer flask, or from the change in volume or pressure (or a combination of the two) in the apparatus.
- Evolved carbon dioxide is absorbed in a solution of potassium hydroxide or another suitable absorbent.
- the amount of oxygen taken up by the microbial population during biodegradation of the test substance is expressed as a percentage of ThOD or, less satisfactorily, COD.
- ThOD describes the theoretical oxygen demand and COD describes the common oxygen demand.
- the OECD 301 F test was performed as follows: Biodegradation in wastewater was tested in triplicate using the OECD 301 F manometric respirometry method.
- OECD 301 F is an aerobic test that measures biodegradation of a sample by measuring the consumption of oxygen.
- 100 mg/L test substance which is the nominal sole source of carbon was added along with the inoculum (aerated sludge taken from Mannheim waste water treatment plant). This was stirred in a closed flask at a constant temperature of 22 ° C for 28 days.
- the consumption of oxygen was determined by measuring the change in pressure in the apparatus using an OxiTopC. Evolved carbon dioxide was absorbed in a solution of sodium hydroxide.
- Nitrification inhibitors were added to the flask to prevent usage of oxygen due to nitrification.
- the amount of oxygen taken up by the microbial population during biodegradation of the test substance was expressed as a percentage of ThOD (theoretical oxygen demand, which was measured by the elemental analysis of the compound).
- ThOD theoretical oxygen demand, which was measured by the elemental analysis of the compound.
- a positive control Glucose/Glucosamine was run along with the test samples for each cabinet.
- Biodegradation can then be calculated according to the following formula according to the OECD Guideline for the Testing of Chemicals, Section 3:
- % degradation is calculated according to the following formula according to the OECD Guidelines for the Testing of Chemicals, Section 3: 100
- organic component denotes any organic compound, i.e., any compound comprising organic carbon.
- this refers to any carbon-containing compound except for the following carbon-containing compounds, which are considered inorganic compounds: carbides, carbonates (salts of carbonic acid characterized by the CO 3 2- anion, and thus not carbonate esters), bicarbonates (salts of carbonic acid characterized by the HCO 3 ’ anion), carbonic acid, CO, CO 2 , and inorganic cyanides (salts characterized by the ON’ anion).
- elemental forms of carbon such as graphite, diamond, fullerenes, or carbon nanotubes, are not considered organic carbon.
- fine lines refers to small, shallow creases that form on thin, delicate skin. Fine lines on the face are associated with repetitive movements (e.g., frowning, smiling, squinting, and laughing). Usually, fines lines first form around the eyes and mouth. In particular, fine lines are less than two millimeters deep and are associated with the earliest signs of aging. Over time, these fine lines can develop into deeper folds and wrinkles.
- Figure 1 shows the concentration of shinorine in Sample C of Example 2 relative to day 0 (100 %) determined by HPLC directly after preparation of Sample C (day 0, room temperature) and after storage at 40 ° C for different time periods.
- Figure 2 shows the concentration of shinorine in Sample D of Example 2 relative to day 0 (100 %) determined by HPLC directly after preparation of Sample D (day 0, room temperature) and after storage at 50 ° C for different time periods.
- Figure 3 shows the UV absorbance of the mixture of part I and part II of Table lb of Example lb after storage at 50 ° C at different time periods.
- the solid line shows the absorbance directly after mixing (TO), the dotted line shows the absorbance after 8 days storage of the mixture at 50° C and the dashed line shows the absorbance after 31 days storage of the mixture at 50 ° C.
- the present invention relates to a two-part composition
- a two-part composition comprising a) an anhydrous part comprising a base and at least one compound according to formula (I) or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof, wherein
- X is NR N ;
- R 1 is C 1 -C 2 -alkyl
- R 2 is H
- R 4 is H or OR a ;
- the anhydrous part a) comprising the compound of formula (I) and the hydrous part b
- degradation of the compound of formula (I) after a short period of time is prevented.
- the mixture of the compound of formula (I) and the base of the anhydrous part a) can quickly dissolve in the hydrous part b) comprising water, forming a homogeneous solution or emulsion for application as UV protection for keratin materials.
- the homogeneous solution or emulsion is formed after mixing of the anhydrous part and the hydrous part for less than 30 seconds, even within 10 seconds.
- X is NR N ;
- R N is C 1 -C 2 -alkyl-OR a , wherein each substitutable carbon atom in the aforementioned groups is independently unsubstituted or substituted with one substituent R x ;
- R 1 is Cj-alkyl
- R 2 is H
- R 4 is H
- R a is H.
- X is NR N ;
- R N is C 2 -a I ky I -0 R a , wherein the carbon atom in the aforementioned group next to the N- atom is substituted with one substituent R x ;
- R 1 is Cj-alkyl
- R 2 is H
- R 4 is H
- R a is H.
- the compound of formula (I) is a compound according to the following formula (la)
- the compound of formula (la) represents shinorine.
- the compound of formula (I) represents the MAA shinorine. Even more preferably the compound of formula (I) represents a shinorine hydrate.
- the compound of formula (I) is (E)-N-[(5S)-3-[(carboxymethyl)amino]-5-hydroxy-5-(hydroxymethyl)-2- methoxycyclohex-2-en-l-ylidene]-L-serine.
- the shinorine hydrate is suitable for the described two-part composition because it hardly absorbs moisture even under high humidity and has therefore a high storage stability.
- the compounds of formula (I), in particular the compound of formula (la), can be obtained according to the method disclosed in EP 3 144 392 Al.
- a MAA biosynthetic enzyme gene is introduced into a microorganism by genetic recombination and the microorganism is extrace 11 u I a r ly cultured producing the MAA.
- the microbial cell and the extracellular culture solution are separated, and the MAA is recovered from the extracellular culture solution.
- the shinorine hydrate or shinorine hydrous crystals can be obtained according to the method described in JP2018052883A.
- the UV filter preferably does not crystallize after application to the human skin and subsequent evaporation of water. It has surprisingly been found that specific MAA salts do not crystallize after evaporation of water (deliquescent behavior). In particular, it has surprisingly been found that by incorporating the MAA shinorine hydrate and a base into the anhydrous phase of the two-part composition, the shinorine hydrate remains stable for storage. Further, it has surprisingly been found that upon mixing of the anhydrous part comprising the shinorine hydrate and the base with the hydrous part comprising water, the shinorine hydrate forms the corresponding salt which does not crystallize after application to the human skin and subsequent evaporation of water.
- the compound of formula (I) is used in the form of a hydrate thereof.
- the compound of formula (I) is a compound of formula (la), which is used in the form of a hydrate thereof.
- a hydrate of a compound of formula (I) or a compound of formula (la) denotes a compound of formula (I) or a compound of formula (la) which formed crystals that incorporate water in the crystalline structure without chemical alteration of the compound of formula (I) or the compound of formula (la).
- the anhydrous part comprises a base and at least one compound according to formula (I) as defined above or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof.
- the anhydrous part comprises the compound of formula (I) in an amount of from 0.1 % to 20 % by weight, based on the total weight of the two-part composition. In a preferred embodiment of the present invention, the anhydrous part comprises the compound of formula (I) in an amount of from 1 % to 8% by weight, based on the total weight of the two-part composition.
- the anhydrous part comprises the compound of formula (I) in an amount of from 5 % to 80% by weight, based on the total weight of the anhydrous part of the two-part composition.
- the amounts of the compound of formula (I) given above refer to the amount of only one compound of formula (I) or to the amount of a mixture of more than one compound of formula (I).
- the amounts of the compound of formula (I) given above refer to the sum of the amounts of each compound of formula (I) present in the anhydrous part of the two-part composition.
- the anhydrous part a) further comprises a base.
- the base provides neutralization of the acidic compounds of formula (I) to provide, after mixing of the anhydrous part with the hydrous part of the two-part composition, a keratin friendly, in particular skin friendly, pH of the composition.
- the keratin friendly or skin friendly pH is in the range of from 4.5 to 8.
- the base of the anhydrous part a) is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline.
- the base of the anhydrous part a) is preferably anhydrous.
- the base of the anhydrous part a) is anhydrous.
- the base of the anhydrous part a) is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline, wherein each of the base is anhydrous.
- the base of the anhydrous part a) is a carbonate or a bicarbonate, preferably an anhydrous carbonate or anhydrous bicarbonate.
- the base of the anhydrous part a) is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, and magnesium bicarbonate, preferably anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous potassium carbonate, anhydrous potassium bicarbonate, anhydrous ammonium carbonate, anhydrous ammonium bicarbonate, anhydrous calcium carbonate, anhydrous calcium bicarbonate, anhydrous magnesium carbonate, and anhydrous magnesium bicarbonate.
- the base of the anhydrous part a) is selected from the group consisting of sodium bicarbonate and sodium carbonate, preferably anhydrous sodium bicarbonate and anhydrous sodium carbonate. In a more preferred embodiment, the base of the anhydrous part a) is sodium carbonate, preferably anhydrous sodium carbonate.
- the base of the anhydrous part provides neutralization of the acidic compounds of formula (I) to provide, after mixing of the anhydrous part and the hydrous part of the two-part composition, a keratin friendly, in particular skin friendly, pH of the composition (pH 4.5 to 8).
- the base of the anhydrous part is preferably present in an amount sufficient to neutralize the acidic compounds of formula (I) and to provide, after mixing of the anhydrous part and the hydrous part, a composition with a pH in the range of from 4.5 to 8.
- the two-part composition comprises the base of the anhydrous part a) in an amount of from 5 % to 90 % by weight, preferably in an amount of from 25 % to 65 % by weight, based on the weight of the compound of formula (I). In another embodiment of the present invention, the two-part composition comprises the base of the anhydrous part a) in an amount of from 0.1 % to 3 % by weight, preferably in an amount of from 0.3 % to 2.5 % by weight, based on the total weight of the two-part composition.
- the two-part composition comprises the base of the anhydrous part a) in an amount of from 25 % to 65 % by weight, based on the weight of the compound of formula (I) and in an amount of from 0.3 % to 2.5 % by weight, based on the total weight of the two-part composition.
- the amount of base may vary. The skilled person knows how to adjust the amount of the base depending on the base strengths, e.g., using lower amounts of stronger bases and higher amounts of weaker bases.
- the hydrous phase b) may comprise a base, in particular an aqueous solution of a base. The amount of the base in the anhydrous part a) may be lower if the hydrous phase b) comprises a base.
- the hydrous part b) comprises an aqueous solution of a base.
- the hydrous part comprises at least water.
- the hydrous part of the composition comprises water in an amount of from 3 % to 70 % by weight, based on the total weight of the two-part composition.
- the hydrous part of the composition comprises water in an amount of from 30 % to 60 % by weight, based on the total weight of the two-part composition.
- the anhydrous part a) and the hydrous part b) may comprise one or more additional ingredients.
- Preferred embodiments regarding the additional ingredients of the anhydrous part a) and the hydrous part b) of the two-part composition of the present invention are defined hereinafter and are relevant for all aspects of the invention. It is to be understood that the following preferred embodiments regarding the additional ingredients of the anhydrous part a) and the hydrous part b) of the two-part composition are preferred alone or in combination with the preferred embodiments regarding the anhydrous phase a), the compounds of formula (I), in particular the compounds of formula (la), and the hydrous phase b) defined above.
- the anhydrous part a) further comprises al) cosmetic oils; a2) UV filters; a3) surfactants and/or emulsifier; a4) sensory enhancers; a5) consistency agents; a6) film forming agents; a7) UV performance booster like scattering particles; a8) preservatives; and/or a9) perfumes.
- the hydrous part b) further comprises bl) alcohols; b2) UV filters; b3) surfactants and/or emulsifier; b4) sensory enhancers; b5) thickeners; b6) film forming agents; b7) UV performance boosters; b8) preservative; b9) humectants; and/or blO) perfumes.
- the two-part composition comprises at least one additional UV filter, other than the compound of formula (I).
- the two-part composition further comprises from 1 to 3 additional UV filters, other than the compound of formula (I).
- the two-part composition provides an even higher protection against UV radiation.
- the further UV filter and/or light stabilizer, other than the compound of formula (I) may be present in the hydrous part b) or the anhydrous part a). If the hydrous part b) does not only contain water, the further UV filter and/or light stabilizer, other than the compound of formula (I), is preferably in the hydrous part b).
- the anhydrous part a) comprises at least one UV filter other than the compound of formula (I). In another embodiment of the present invention, the anhydrous part a) comprises one UV filter other than the compound of formula (I).
- the hydrous part b) comprises at least one UV filter other than the compound of formula (I). In another embodiment, the hydrous part b) comprises from 1 to 3 UV filters other than the compound of formula (I). In another embodiment, the hydrous part b) comprises at least 2, preferably 2 to 3, UV filters other than the compound of formula (I).
- the hydrous part b) may comprise a UV filter other than the compound of formula (I).
- the UV filter comprised in the hydrous part is selected from the group consisting of 1 - (4- (1 ,1 -di methy lethy I) pheny I) -3-(4- methoxyphenyl)propane-l, 3-dione (I NCI butyl methoxydibenzoylmethane), 2-(2H- benzotriazo I -2 -y I) -6- [(2 -ethyl hexyl oxy) methy I] -4- methy I phenol, 2 -(2 H- benzotriazo I -2-yl) -4- methy 1-6- [2 -methy 1-3- [1,3,3,3-tetra methy 1-1 -[(tri methy Isi ly l)oxy] -1 - disiloxanyl] prop
- the UV filter comprised in the hydrous part is selected from the group consisting of [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-l- (su If om ethyl) -3 -bicyclo [2.2.1] hepta ny lid ene] methyl] phenyl] methyl ide ne]-7,7-di methyl -2- oxo-l-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphor sulfonic acid), 2-phenyl-lH-benzimidazole-5-sulfonic acid (INCI phenylbenzimidazole sulfonic acid), disodium phenyl dibenzimidazole tetrasulfonate, 2-ethylhexyl-(2E)-3-(4- meth
- the UV filter comprised in the hydrous part is selected from the group consisting of 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4- bis- ⁇ [4-(2-ethy I -hexyloxy) -2- hydroxy]-phenyl]-6-(4-methoxyphenyl)-l,3,5 triazine (INCI bis-ethylhexyloxyphenol meth oxy phenyl triazine), 4,4',4"- (1,3,5-triazi ne-2,4,6-triyltrii mi no) tris- benzoic acid -tris (2-
- the anhydrous part a) may comprise a UV filter other than the compound of formula (I).
- the UV filter comprised in the anhydrous part is selected from the group consisting of 1 - (4- (1, 1 -d i methylethyl) pheny I) -3- (4- methoxyphenyl)propane-l, 3-dione (I NCI butyl methoxydibenzoylmethane), 2-(2H- benzotriazo I -2 -y I) -6- [(2 -ethyl hexyl oxy) methyl] -4- methyl phenol, 2 -(2 H- benzotriazo I -2-yl) -4- methy I -6- [2-methy I -3- [1,3,3,3-tetramethy I -1 - [(tri methy I si ly I) oxy] -1 - disiloxanyl] propyl] phenol (I NCI drometrizole trisiloxane), ethylhexyl
- the UV filter comprised in the anhydrous part is selected from the group consisting of 1 - (4- (1, 1 -d i methylethyl) pheny I) -3- (4- methoxyphenyl)propane-l, 3-dione (I NCI butyl methoxydibenzoylmethane), 2-(2H- benzotriazo I -2 -y I) -6- [(2 -ethyl hexyl oxy) methy I] -4- methy I phenol, 2 -(2 H- benzotriazo I -2-y Dimethyl -6- [2-methy I -3- [1,3,3,3-tetramethy 1-1 -[(tri methy lsilyl)oxy]-l- disiloxanyl] propyl] phenol (INCI drometrizole trisiloxane), titanium dioxide, zinc oxide, and combinations thereof.
- the UV filter comprised in the anhydrous part is selected from the group consisting of titanium dioxide, zinc oxide, and combinations thereof.
- Preferred cosmetic oils include
- Vegetable oils esters of linear or branched fatty acids with linear or branched fatty alcohols include esters of aromatic carboxylic acids with linear or branched fatty alcohols; di- and tricarboxylic acid esters with linear or branched alcohols; esters of hydroxycarboxylic acids with linear or branched fatty alcohols; esters of linear or branched fatty acids with polyhydric alcohol; mono-, di-, tri-glycerides based on C6-C18 fatty acids; guerbet alcohols such as octyldodecanol; hydrocarbons; ethers such as dicaprylyl ether.
- cosmetic oils are C 12 -C 15 alkyl benzoate, caprylic/capric triglyceride, butylene glycol dicaprylate/dicaprate, propylene glycol dicaprylate/dicaprate, diisopropyl sebacate, octyldodecanol, isopropyl palmitate, isopropyl myristate, dicaprylyl carbonate, phenethyl benzoate, dibutyl adipate, diisopropyl adipate, triethyl citrate and tributyl citrate , octyldodecanol, hydrogenated polyisobutene, mineral oil, squalene, isohexadecane, coconut oil, sweet almond oil, wheat germ oil, sesame oil, cottonseed oil, coconut oil, avocado oil, corn oil, castor oil, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil,
- cosmetic oils encompass the group of emollients.
- emollients and cosmetic oils can be used interchangeably.
- Preferred surfactants i.e., surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, alpha-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, protein fatty acid condensation products, preferably based on wheat proteins.
- Preferred emulsifiers include glucose derivatives such as cetearyl glucoside, arachidyl glucoside, lauryl glucoside, polyglyceryl -3 methylglucose distearate, methyl glucose sesquistearate; sucrose derivative such as sucrose polystearate, sucrose palmitate; sorbitol derivatives such as polysorbate-n, PEG-10 sorbitan laurate; fatty alcohol polyglycolethers and fatty acid polyglycolethers such as ceteareth-20, beheneth-25, steareth-2, PEG-100 stearate; glycerides of fatty acids such as glyceryl stearate, glyceryl oleate; glumatic acid derivatives such as sodium stearoyl glutamate; sulfosuccinic acid derivatives such as disodium Cetearyl sulfosuccinate; phosphoric acid derivatives such as potassium cetyl phosphate;
- Preferred consistency agents for the anhydrous part include consistency regulators such as fatty alcohols such as guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, cetearyl alcohol, stearyl alcohol, oleyl alcohol, octyldodecanol, benzoate C12-C15 alcohols, acetylated lanolin alcohol, behenyl alcohol; fatty acids such as stearic acid; fatty acid esters such as myristyl stearate, lauryl lactate or glyceryl stearate; waxes including animal waxes, plant waxes, mineral or petroleum waxes such as beeswax, carnauba wax, microcrystalline wax, ceresin, ozocerite; silicium dioxide.
- consistency regulators such as fatty alcohols such as guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including
- Preferred thickeners for the hydrous part include: polysaccharides or derivatives such as xanthan gum, guar gum, agar gum, alginates, gel Ian gum, carraghenan glucomannan; polyacrylates or homopolymers of reticulated acrylic acids or polyacrylamides such as carbomers, acrylate copolymers, acrylate / C 10 -C 30 -a I ky I acrylate crosspolymer, acrylate / beheneth-25 methacrylate copolymer; silicate derivatives such as magnesium silicates or aluminum silicates; cellulose derivatives such as hydroxypropyl cellulose; pectines or modified cellulose such as hydroxycellulose or hydroxypropyl methylcellulose.
- polysaccharides or derivatives such as xanthan gum, guar gum, agar gum, alginates, gel Ian gum, carraghenan glucomannan
- Preferred sensory enhancers include polyamide derivatives such as nylon-12; polymethyl methacrylates; silica; mica; poly methyl si I sesquioxane; polyethylene; starch derivatives such as aluminum starch octenylsuccinate; dimethicone derivatives; boron nitride;
- Preferred humectants include
- UV performance booster like scattering particles include any particles or microparticles that can scatter light in order to enhance the protection of the skin from UV- light but do not absorb UV-light like UV filters.
- UV performance booster like scattering particles include microcrystalline cellulose (such as SunSpheresTM BIO SPF Booster), calcium carbonate, hydroxyapatite, styrene/acrylates copolymer (such as SunSpheresTM powder), (microspherical) silica (such as Sunsil 130 L, Sunsil 130 NP, SOLESPHERETM H-33 and SOLESPHERETM H-53), and silica (and) cetyl alcohol (Sunsil- Oleol30).
- microcrystalline cellulose such as SunSpheresTM BIO SPF Booster
- Ca carbonate such as SunSpheresTM BIO SPF Booster
- hydroxyapatite such as SunSpheresTM powder
- styrene/acrylates copolymer such as SunSpheresTM powder
- Preferred film forming agents include anionic, zwitterionic, amphoteric and non-ionic polymers such as vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols, acrylamidopropyl-trimethylammonium chloride/acrylate copolymers, octyl acrylamide/methyl methacrylate-tert-butylaminoethyl methacrylate/2- hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vi ny I py rro I ido n e/d i methy I
- Preferred alcohols are alcohols containing from 2 to 6 carbon atoms, preferably monoalcohols containing from 2 to 6 carbon atoms. Particularly preferred alcohols include ethanol, isopropanol, or mixtures thereof.
- preservatives can be present in the two-part composition in the anhydrous part and/or in the hydrous part.
- Preferred preservatives include phenoxyethanol; benzyl alcohol; methyl-, ethyl-, propyl-, butyl-, and isobutylparaben; zingerone.
- perfumes can be present in the two-part composition in the anhydrous part and/or the hydrous part.
- Preferred perfumes are selected from the group consisting of limonene, citral, linalool, alpha-isomethylionon, geraniol, citronellol, 2-isobutyl-4-hydroxy-4-methyltetrahydropyrane, 2 -tert.
- anhydrous part and/or the hydrous part of the two-part composition comprise two or more additional ingredients, combinations of the ingredients as defined above are also part of the invention.
- the skilled person is able to select and adjust the ingredients of the anhydrous part and the hydrous part depending on the desired application of the solution or emulsion resulting after mixing of the anhydrous part and the hydrous part.
- the anhydrous part a) contains only the compound according to formula (I) and the base.
- the anhydrous part a) of the two-part composition is solid.
- all additional ingredients of the two-part composition are in the hydrous part.
- the two-part composition comprises a) an anhydrous part containing a base and at least one compound according to formula (I); and b) a hydrous part comprising water and at least one ingredient selected from bl), b2) , b3), b4), b5), b6), b7), b8), b9) and blO).
- the two-part composition comprises a) an anhydrous part containing a base and at least one compound according to formula (la); and b) a hydrous part comprising water, and at least one emulsifier b3), and optionally further ingredients selected from bl), b2), b4) , b5), b6), b7), b8), b9) and blO).
- the two-part composition comprises a) an anhydrous part containing a base and at least one compound according to formula (I); and b) a hydrous part comprising water, and at least one water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter b2) other than the compound of formula (I), at least one emulsifier b3), and optionally further ingredients selected from bl), b4) , b5), b6), b7), b8, b9 and blO).
- the two-part composition comprises a) an anhydrous part containing sodium carbonate, preferably anhydrous sodium carbonate, and a compound according to formula (la); and b) a hydrous part comprising water, and at least one, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter b2) other than the compound of formula (I), at least one emulsifier b3), and optionally further ingredients selected from bl), b4), b5), b6), b7), b8), b9) and blO).
- the two-part composition comprises a) an anhydrous part containing sodium carbonate, preferably anhydrous sodium carbonate, and a compound according to formula (la); and b) a hydrous part comprising water, and at least 1, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter selected from the group consisting of 2-ethylhexyl-(2E)-3-(4- methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2 - [4- (d iethy I a m i no) -2 - hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4-bis- ⁇ [4- (2-ethyl-hexyloxy)-2-hydroxy]-phenyl ⁇ -6-(4-me
- the hydrous part b) contains only water and no other ingredients.
- all ingredients of the two- part composition are in the anhydrous part, such that only water has to be added to form the solution or emulsion for UV protection of keratin materials, in particular the skin.
- the anhydrous part is solid, waxy, or liquid.
- the two-part composition comprises a) an anhydrous part comprising a base and at least one compound according to formula (I) and at least one ingredient selected from al), a2), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part containing only water and no other ingredients.
- the two-part composition comprises a) an anhydrous part comprising a base and at least one compound according to formula (la), at least one additional oil soluble UV filter and/or liquid oil miscible UV filter and/or oil dispersible UV filter a2) other than the compound of formula (I), and at least one ingredient selected from al), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part containing only water and no other ingredients.
- la an anhydrous part comprising a base and at least one compound according to formula (la), at least one additional oil soluble UV filter and/or liquid oil miscible UV filter and/or oil dispersible UV filter a2) other than the compound of formula (I), and at least one ingredient selected from al), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part containing only water and no other ingredients.
- the two-part composition comprises a) an anhydrous part comprising sodium carbonate, preferably anhydrous sodium carbonate, and a compound according to formula (la), and at least one additional oil soluble UV filter and/or liquid oil miscible UV filter and/or oil dispersible UV filter a2) other than the compound of formula (I), and at least one ingredient selected from al), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part containing only water and no other ingredients.
- the two-part composition comprises a) an anhydrous part comprising sodium carbonate, preferably anhydrous sodium carbonate, and a compound according to formula (la), and an additional oil soluble UV filter and/or liquid oil miscible UV filter and/or oil dispersible UV filter selected from the group consisting of titanium dioxide, zinc oxide, and a combination thereof, at least one emulsifier a3), at least one film forming agent a6), and optionally further ingredients selected from al), a4), a5), a7), a8) and a9); and b) a hydrous part containing only water and no other ingredients.
- an anhydrous part comprising sodium carbonate, preferably anhydrous sodium carbonate, and a compound according to formula (la)
- an additional oil soluble UV filter and/or liquid oil miscible UV filter and/or oil dispersible UV filter selected from the group consisting of titanium dioxide, zinc oxide, and a combination thereof, at least one emulsifier a3), at least one film forming agent
- the two-part composition comprises a) an anhydrous part comprising a base and at least one compound according to formula (I) and at least one ingredient selected from al), a2), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part comprising water and at least one ingredient selected from bl), b2) , b3), b4), b5), b6), b7), b8), b9) and blO).
- the anhydrous part is solid, waxy, or liquid.
- the anhydrous part and/or the hydrous part comprises at least one additional UV filter other than the compound of formula (I).
- the additional UV filter other than the compound of formula (I) is preferably in the hydrous part b).
- the two-part composition comprises a) an anhydrous part comprising a base and at least one compound according to formula (la), and at least one ingredient selected from al), a2), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part comprising water, and at least one, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter b2) other than the compound of formula (I), and at least one ingredient selected from bl), b2), b3), b4), b5), b6), b7), b8), b9) and blO).
- the two-part composition comprises a) an anhydrous part comprising sodium carbonate, preferably anhydrous sodium carbonate, and at least one compound according to formula (la), at least one cosmetic oil al), at least one emulsifier a3), at least one consistency agent a5), and optionally further ingredients selected from a4), a6), and a7); and b) a hydrous part comprising water, and at least one, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter b2) selected from the group consisting of 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hex
- the two-part composition comprises a) an anhydrous part comprising sodium carbonate, preferably anhydrous sodium carbonate, and at least one compound according to formula (la), at least one cosmetic oil al), at least one emulsifier a3), at least one consistency agent a5), and optionally further ingredients selected from a4), a6), and a7); and b) a hydrous part comprising water, and at least one, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter b2) selected from the group consisting of 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl he
- MAA’s such as the compounds of formula (I) are biodegradable natural compounds.
- the compound of formula (la), shinorine is biodegradable.
- the two-part composition of the present invention allows for a composition for UV protection, wherein at least one UV filter is biodegradable.
- the two-part composition of the present invention allows for a composition for UV protection, wherein all organic components of the anhydrous part and the hydrous part are biodegradable.
- the organic components of the anhydrous part a) and the hydrous part b) are partially biodegradable. Partial biodegradability is defined as having a biodegradability of from 20 % to 60 % by OECD 301 F.
- the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of from 20 % to 60 % by OECD 301 F.
- the organic components of the anhydrous part a) and the hydrous part b) are readily biodegradable.
- Ready biodegradability is defined as having a biodegradability of larger or equal to 60 % by OECD 301 F.
- the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of larger or equal to 60 % by OECD 301 F.
- biodegradability, partial biodegradability, or ready biodegradability refers to the biodegradability, partial biodegradability, or ready biodegradability of each individual organic component of the anhydrous part a) and the hydrous part b) and not of a mixture of two or more individual organic components.
- the solution or emulsion to apply to the keratin materials for UV- protection can easily and quickly be prepared by mixing the anhydrous part and the hydrous part of the two-part composition before application to the keratin material.
- the homogeneous solution or emulsion is formed after mixing of the anhydrous part and the hydrous part for less than 30 seconds, even within 10 seconds.
- the present invention relates to a process for the UV-protection of keratin materials, comprising mixing the anhydrous part and the hydrous part of the two- part composition together to form a solution or emulsion before applying the solution or emulsion to the keratin materials.
- the present invention relates to a process for the UV-protection of keratin materials, comprising mixing the anhydrous part and water to form a solution or emulsion before applying the solution or emulsion to the keratin materials.
- the present invention relates to the use of the two-part composition for UV- protection of keratin materials, preferably the skin.
- the two-part composition for UV-protection of keratin materials the preferred embodiments defined above, in particular regarding the compound of formula (I), the base, the water content, the anhydrous part, the hydrous part and the optional additional ingredients, are also preferred.
- said two-part composition has an UV-A protection, which is at least one third of the sun protection factor as defined above. For example, if the sun protection factor of a two-part composition is 30, the UV-A protection of the given two-part composition has to be at least 10.
- the UV-A protection of said two-part composition as defined above has to show a critical wavelength of at least 370 nm.
- said two-part composition has an UV-A protection, which is at least one third of the sun protection factor as defined above, and shows a critical wavelength of at least 370 nm.
- the two-part composition of the present invention provides whitening/lightening, anti-aging, in particular anti-fine line, and anti-inflammation benefits for the skin.
- the two-part composition as defined herein in particular the solution or emulsion prepared by mixing the anhydrous part and the hydrous part of the two-part composition according to the invention is particularly suitable for protection of keratin materials, in particular the skin, from UV radiation.
- the present invention relates in one embodiment to the use of the two-part composition as defined herein (including all embodiments thereof as described herein) as a body-care product, preferably a sunscreen-composition.
- the present invention relates in one embodiment to the use of the solution or emulsion prepared by mixing the anhydrous part and the hydrous part of the two-part composition as defined herein (including all embodiments thereof as described herein) as a body-care product, preferably a sunscreen-composition.
- the two-part composition as defined herein is used for protection of the keratin material, in particular the skin, from UV radiation.
- the present invention relates to the use of the two-part composition as light stabilizer in cosmetic compositions, home-care compositions, cleaning compositions or agrochemical compositions.
- UV-light can also have negative effects on the integrity and the durability of other materials and products such as active raw materials in agrar formulations, food (such as fruit and vegetables), body-care products, household cleaning and treating agents, polymers, plastics, coatings, ink printing, packaging, paint, lacquer, and textiles.
- the two-part composition of the present invention can also be used for UV-protection of active raw materials in agrochemical formulations, food (such as fruit and vegetables), body-care products, household cleaning and treating agents, polymers, plastics, coatings, ink printing, packaging, paint, lacquer, and textiles.
- the compounds of formula (I), in particular the compound of formula (la), are suitable as light stabilizers.
- the two-part composition of the present invention provides a composition with improved photostability.
- the two-part composition of the present invention provides a body-care product or household cleaning and treating agent, preferably a sunscreen composition, with improved photostability.
- the two-part composition as defined herein is used for protecting the body-care product or the household cleaning and treating agents from UV degeneration.
- shinorine was used in the form of shinorine hydrate as described in detail above and in JP2018052883A. Further, it is to be understood with regard to the examples provided below that if not specifically indicated otherwise % refers to % by weight.
- Example 1 Stability tests of Shinorine solution in water at room temperature
- Shinorine was dissolved in water resulting in a composition of 20 % Shinorine and 80 % water.
- the solution was stored at room temperature in a closed 10 mL glass bottle for certain time periods (0 days, 1 day, 3 days, 7days, 10 days, 14 days, 21 days and 42 days).
- Sample A the solution was purged with nitrogen to displace oxygen.
- Sample B was kept with air contact. The color change of sample A and sample B was observed during the storage time at certain time periods. If the formulations are stored for more than 24 hours a color change from colorless/l ight brown into dark brown can be observed for all samples.
- Shinorine was dissolved in water. The initial acidic solution after dissolving of Shinorine was neutralized by addition of approximately 1 equivalent of NaOH. The concentration of Shinorine (in anionic form) is adjusted to 9-10 % by weight. The samples were stored in closed vials at different temperatures. The concentration of Shinorine was determined by HPLC at different times. The results of the measurement of the concentration of Shinorine at different times by HPLC is shown in Table 1 below and Figure 1 and 2.
- Sample C (40° C) and Sample D (50° C) further showed a discoloration at 7 days of storage, wherein at a time of 0 days the solution was a clear colorless solution and after 7 days turned into a dark brown solution.
- Sample C (40° C) and Sample D (50° C) further showed a discoloration at 7 days of storage, wherein at a time of 0 days the solution was a clear colorless solution and after 7 days turned into a dark brown solution.
- Example 3 Shinorine storage stability
- Shinorine in powdered form was stored for 67 days at room temperature and 50 ° C in a closed container. There was no significant discoloration observable.
- the mixtures formed a clear colorless solution and a pH value in the skin-friendly range of 4.5-8 could be achieved.
- Composition la Clear microemulsion (Hydrous part liquid / Anhydrous part solid)
- Second compartment (part I I) comprising Shinorine (anhydrous) was colorless (white) and remained white after 1-month storage at 50° C.
- First compartment (part I) comprising water and the remaining ingredients was colorless and remained colorless after 1-month storage at 50° C.
- composition lb
- part I as shown in Table l.b below were heated to 100° C under stirring until complete dissolution.
- the solution was cooled to room temperature under stirring and subsequently stored in a closed container.
- the ingredients of part II as shown in Table l.b below were incorporated at room temperature in a closed container, wherein humidity should be avoided.
- the anhydrous part (part II) and the hydrous part (part I) were stored in separate containers until used.
- part I and part I I were mixed immediately before use by incorporating part I I into part I and shaking of the container by hand until complete dissolution.
- the obtained solution has a pH of 7.5 without the requirement of further adjustment.
- the emulsion is applied to the skin as soon as it is homogeneous.
- Composition lb Clear microemulsion (Hydrous part liquid / Anhydrous part solid)
- Second compartment (part I I) comprising Shinorine (anhydrous) was colorless (white) and remained white after 1-month storage at 50° C.
- First compartment (part I) comprising water and the remaining ingredients was colorless and remained colorless after 1-month storage at 50° C.
- composition lb For comparative Composition lb the ingredients of part I and part II of Composition lb were mixed as a final formulation and stored at 50 ° C for 31 days. The results of the appearance of the final formulation during the storage time at 50° C are shown in Table 1.1. b below.
- a precise dosage dispenser with two distinct orifices was used to deposit 80% of first compartment (hydrous part) on skin and 20% of second compartment (anhydrous part). Both parts were mixed just before use by spreading the product on the skin. The pH value of the resulting formulation was 7.5 without the requirement of further adjustment.
- Composition 2a Boite de Pandore (Hydrous part liquid / anhydrous part liquid)
- the method of assessing the in vitro SPF is as described above for Composition lb.
- Composition 2a has an in vitro SPF of 51.
- Composition 2b has an in vitro SPF of 51.
- a precise dosage dispenser with two distinct orifices was used to deposit 80% of first compartment (hydrous part) on skin and 20% of second compartment (anhydrous part). Both parts were mixed just before use by spreading the product on the skin.
- the pH value of the resulting formulation was 7.15.
- Second compartment (anhydrous part) comprising Shinorine was white.
- First compartment (hydrous part) comprising O/W emulsion was yellow.
- Finished formulation (comprising anhydrous and hydrous part) was yellow.
- First compartment (hydrous part) and second compartment (anhydrous part) were stored separately at 50° C for 30 days and did not show a significant color change.
- Part II Process of manufacture of two-part composition Part II was prepared by milling Shinorine as shown in Table 3 below, for example in a mortar, until a fine powder was obtained. The obtained powder was mixed with the other ingredients of part II as shown in Table 3 below until a homogeneous mixture was obtained. Subsequently part II was mixed with the ingredients of part III as shown in Table 3 below and the resulting waxy mixture was stored in a closed container, wherein humidity should be avoided (second compartment: Anhydrous part).
- Composition 3 comprises only biodegradable and mineral UV filters.
- Composition 3 Ecofriendly dry formulation ready to go (Hydrous part liquid (only water) / Anhydrous part solid)
- Second compartment (part II and part III) comprising Shinorine (anhydrous) was colorless (white) and remained white after 1-month storage at 50° C.
- First compartment (part I) comprising water was colorless and remained colorless after 1-month storage at 50° C.
- the ingredients of part I and part II as shown in Table 4 below were heated to 75° C under stirring and part II was added into part I slowly under stirring and was further homogenized.
- the solution was cooled to room temperature under stirring and subsequently stored in a closed container (first compartment, hydrous part).
- the powdered ingredients of part IV as shown in Table 4 below were dispersed in oil (preferably by oil milling).
- the ingredients of part III as shown Table 4 below were mixed and heated to 75° C until completely dissolved. Part III was cooled down to 45-50° C and phase IV was added under stirring until the mixture becomes liquid.
- the resulting oil suspension was stored in a closed container, wherein humidity should be avoided (second compartment, anhydrous part).
- First compartment (hydrous part) and second compartment (anhydrous part) were stored in separate containers until usage.
- the anhydrous part and the hydrous part were mixed immediately before use.
- First compartment (hydrous part) and second compartment (anhydrous part) were stored in separate containers until usage.
- the anhydrous part and the hydrous part were mixed immediately before use.
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Abstract
The present invention relates to a two-part composition comprising a) an anhydrous part comprising a base and at least one compound according to formula (I), and b) a hydrous part comprising at least water.
Description
Biodegradable two-part composition for skin protection against UV radiation
Description
The present invention relates to a two-part composition comprising a) an anhydrous part comprising a base and at least one compound according to formula (I), and b) a hydrous part comprising at least water. Furthermore, the present invention relates to a process for the protection of keratin materials and the use of a two-part composition as defined herein for UV-protection of keratin materials.
Mycosporine-Like Amino Acids (MAAs) such as Shinorine are natural protective agents against UV-induced skin damage (V. Geraldes et al. Mycosporine-Like Amino Acids (MAAs): Biology, Chemistry and Identification Features. Pharmaceuticals, 2021, 14(1), 63 and A.
Singh et al. Exploring Mycosporine-Like Amino Acids (MAAs) as Safe and Natural Protective Agents against UV-lnduced Skin Damage. Antioxidants, 2021, 10(5), 683). They provide excellent UV protection for keratin materials. MAAs are biodegradable natural compounds, in contrast to e.g. state-of-the-art UV absorbers for skin protection.
L-Serine, N -[3- [(carboxy methyl) ami no] -5 -hydroxy-5- (hydroxy methyl) -2- m ethoxy-2 - cyclohexen-l-ylidene]; Shinorine
These properties make it an excellent candidate as a cosmetic or dermatological UV filter for sun protection of skin and for combating and/or preventing skin ageing. Unfortunately, because of their chemical structure, MAAs are sensitive to certain environmental parameters such as light, oxygen or water. The degradation of MAAs occurs when formulated in the presence of these parameters, which is often contrary to the desired results.
MAAs show strong discoloration in contact with water and/or glycols after several days (see e.g. Example 1). Significant degradation of MAAs (e.g. Shinorine) occurs if MAAs are dissolved in cosmetic emulsions or in aqueous solutions after storage at 40-50° C for 4-6 weeks. This is an inacceptable change of initial properties of the cosmetic product.
According to ISO/TR 18811:2018, the stability of a cosmetic product is its ability to resist change or variation of its initial properties over time under stated or reasonably foreseeable conditions of storage. The stability can be evaluated in real time by monitoring the state of a product under reasonably expected conditions of storage, or in accelerated study designed to speed up naturally occurring destabilization processes due to intrinsic or extrinsic factors and which predicts the behavior over the long term. The typical shelf-life of a sunscreen product is of two years (recommended time period that a cosmetic product can be kept after its production, during which the defined quality of the product remains acceptable under expected conditions of distribution, storage, display and usage).
Therefore, typical testing conditions are 3, 6, 12, 24 and 36 months at 25° C and 1, 3, 6, 12, 24 months at 40° C. In some regions like Asia standard conditions are set to 50° C to cover exposition to high temperatures during transport or use in summer.
If the active agent is not suitable for presenting in the carrier system for a long time, compositions consisting of two separate parts (two-part compositions) have been proposed, wherein one part comprises the active agent and the other part comprises the carrier system. For example, WO 2021/056412 discloses a two-part composition for caring for keratin materials, wherein one part contains ferulic acid, which is separated from the hydrous part. Before application, the two parts are mixed to form a solution.
Using MAAs in powdered form and dissolving it in water just before use leads to aqueous solutions. Because of the high acidity of the solution obtained, it is aggressive and risks causing substantial irritation of the skin. In order to achieve sufficient UV protection, high concentrations of shinorine in the water phase of cosmetic emulsions are expected (>10 %). Freshly prepared aqueous solutions containing 2-10 % shinorine however have a pH of approximately 2. The pH of cosmetic products designed for everyday application must be compatible with the physiological skin pH, which is between 4.5-5.5.
In addition, the solution obtained is difficult to apply to the skin, because due to the very low viscosity it runs down the skin easily and is difficult to handle.
Freeze-drying of an aqueous solution containing neutralized MAAs or MAA salts leads to a powdered form of the UV filter. The freeze-dried product obtained is dissolved in water just before use. This solution has the disadvantages of being complex and quite expensive. In addition, the solution obtained is difficult to apply to the skin, because due to the very low viscosity it runs down the skin easily and is difficult to handle.
JP 6719267 B2 describes a solution containing stabilized MAAs, wherein the MAA is mixed with one or more substances selected from the group consisting of a -glucosyl hesperidin, erythorbic acid, a -glucosylrutin, glutathione, sodium disulfite, albumin, gallic acid, EDTA, sodium metaphosphate, sodium citrate, aspartic acid, glutamic acid, arginine, cysteine,
methionine, serine, glucose, trehalose, sorbitol, allose, ? -cyclodextrin, potassium sorbate, sodium benzoate, parahydroxy sodium benzoate, lysine hydrochloride, glucosamine hydrochloride, mannitol, sodium hyaluronate, ergothioneine and tocopherol acetate, and solvent to produce solution. However, the approach disclosed in JP 6719267 B2 does not fully overcome the aforementioned problems.
Therefore, there is a need for a cosmetic product containing at least one MAA (salt, hydrate, tautomer, crystalline, amorphous, solvate), which can achieve a high dissolution rate of the MAA as active ingredient, prevents degradation of the MAA as active ingredient for remaining the effect, causes no skin irritations and can be cost economically prepared.
Therefore, it has been an object of the present invention to provide a composition based on MAAs, wherein the MAAs can quickly dissolve into the carrier system for application on the skin without degradation of the active ingredient. It has been another object of the present invention to provide a composition based on MAAs, which has whitening/lightening, antifine lines and anti-inflammation properties. Furthermore, it has been an object of the present invention to provide a composition based on MAAs, which has a high UV protection, i.e. a high SPF (Sun Protection Factor) and/or UVA-PF (UVA Protection Factor) and at the same time is comfortable to apply for the user.
It has surprisingly been found that at least some of the above objects can be achieved by the subject matter of the present invention as described hereinafter and in the claims. In particular, it has been found by the inventors that the two-part composition of the present invention provides a composition of MAAs of formula (I), wherein the MAA as active ingredient is quickly provided for application to keratin materials, in particular the skin, without degradation of the MAA as active ingredient or discoloration of the composition after a short period of time. Further, the claimed two-part composition allows for high UV- protection and does not cause skin irritations. Considering that MAAs are biodegradable natural compounds, the two-part composition of the present invention provides an environmentally friendly composition for UV-protection. In addition, the two-part composition of the present invention can be easily prepared and is thus economically advantageous.
Thus, according to one embodiment, the present invention relates to a two-part composition comprising a) an anhydrous part comprising a base and at least one compound according to formula (I)
or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof, wherein
X is NRN;
RN is C1-C4-alkyl-ORa, or C1-C4-alkyl-(C=O)ORa, wherein each substitutable carbon atom in the aforementioned groups is independently unsubstituted or substituted with one or more, same or different substituents Rx;
R1 is C1-C2-alkyl;
R2 is H;
R3 is C1-C3-alkyl-(C=O)ORa;
R4 is H or ORa;
Rx is C(=O)ORa, or C1-C2-alkyl; and
Ra is H; and optionally al) cosmetic oils; a2) UV filters; a3) surfactants and/or emulsifier; a4) sensory enhancers; a5) consistency agents; a6) film forming agents; a7) UV performance booster like scattering particles a8) preservatives; and/or a9) perfumes; and b) a hydrous part comprising at least water, and optionally bl) alcohols; b2) UV filters; b3) surfactants and/or emulsifier; b4) sensory enhancers; b5) thickeners; b6) film forming agents; b7) UV performance boosters; b8) preservatives; b9) humectants; and/or blO) perfumes and wherein the anhydrous part and the hydrous part are separate.
In a more preferred embodiment of said two-part composition, said compound of formula (I) is a compound according to the following formula
In another preferred embodiment of said two-part composition, the anhydrous part comprises the compound of formula (I) in an amount of from 0.1 % to 20 % by weight, based on the total weight of the two-part composition.
In a more preferred embodiment of said two-part composition, the anhydrous part comprises the compound of formula (I) in an amount of from 1 % to 8% by weight, based on the total weight of the two-part composition.
In another preferred embodiment of said two-part composition, the base of the anhydrous part a) is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline, preferably wherein the base is anhydrous.
In a more preferred embodiment of said two-part composition, the base of the anhydrous part a) is selected from the group consisting of sodium bicarbonate and sodium carbonate, preferably anhydrous sodium bicarbonate and anhydrous sodium carbonate.
In another preferred embodiment of said two-part composition, the base of the anhydrous part a) in an amount of from 0.1 % to 3 % by weight, preferably in an amount of from 0.3 % to 2.5 % by weight, based on the total weight of the two-part composition.
In another preferred embodiment of said two-part composition, the hydrous part b) of the composition comprises water in an amount of from 3 % to 70 % by weight, based on the total weight of the two-part composition.
In another preferred embodiment of said two-part composition, the UV filter comprised in the hydrous part is selected from the group consisting of [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2- oxo- 1- (sulfo methyl) -3 -bicyclo [2.2.1] hepta ny lid ene] methyl] phenyl] methyl ide ne] -7,7- dimethyl-2-oxo-l-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphor sulfonic acid), 2-phenyl-lH-benzimidazole-5-sulfonic acid (INCI phenylbenzimidazole sulfonic acid), disodium phenyl dibenzimidazole tetrasulfonate, 2- ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2- [4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4- bis-{[4-(2-ethy I -hexyl oxy) -2 -hydroxy] -phenyl] -6- (4- meth oxy phenyl) -1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine), 4,4',4"-(l,3,5-triazine-2,4,6-
triyl tri i m i n o) tris- benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), (RS)-2- ethylhexyl-2-hydroxybenzoate (INCI ethylhexyl salicylate), titanium dioxide, zinc oxide and combinations thereof.
In another preferred embodiment of said two-part composition, the UV filter comprised in the anhydrous part is selected from the group consisting of 1 - (4- (1 ,1 -di methy lethy I) pheny I) - 3-(4-methoxyphenyl)propane-l, 3-dione (I NCI butyl methoxydibenzoylmethane), 2-(2H- benzotriazo I -2 -y I) -6- [(2 -ethyl hexyl oxy) methy I] -4- methy I phenol, 2 -(2 H- benzotriazo I -2-yl) -4- methy 1-6- [2 -methy 1-3- [1,3,3,3-tetra methy 1-1 -[(tri methy Isi ly l)oxy] -1 - disiloxanyl] propyl] phenol (INCI drometrizole trisiloxane), titanium dioxide, zinc oxide, and combinations thereof.
In another preferred embodiment of said two-part composition, the anhydrous part a) contains the compound according to formula (I) and the base.
In another preferred embodiment of said two-part composition, the hydrous part b) contains only water and no other ingredients.
In another preferred embodiment of said two-part composition, the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of from 20 % to 60 %. In another preferred embodiment of said two-part composition, the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of larger or equal to 60 %.
In another aspect, the present invention relates to a process for the UV-protection of keratin materials, comprising mixing the anhydrous part and the hydrous part of the two- part composition together to form a solution or emulsion before applying the solution or emulsion to the keratin materials.
In another aspect, the present invention relates to the use of the two-part composition for UV-protection of keratin materials.
In another embodiment of said use, the two-part composition has an UV-A protection, which is at least one third of the sun protection factor of the two-part composition and/or shows a critical wavelength of at least 370 nm.
Preferred embodiments of the present invention can be found in the claims, the description and the examples. It is to be understood that the features mentioned above and those still to be illustrated below of the subject matter of the invention are preferred not only in the respective given combination but also in other combinations without leaving the scope of the invention.
Definitions
Before describing preferred embodiments of the present invention in detail, definitions important for understanding the present invention are given.
As used in this specification and in the appended claims, the singular forms of "a" and "an" also include the respective plurals unless the context clearly dictates otherwise. In the context of the present invention, the terms "about" and "approximately" denote an interval of accuracy that a person skilled in the art will understand to still ensure the technical effect of the feature in question. The term typically indicates a deviation from the indicated numerical value of ± 20 %, preferably ± 15 %, more preferably ± 10 %, and even more preferably ± 5 %. It is to be understood that the term "comprising" is not limiting. For the purposes of the present invention, the term "consisting of" is considered to be a preferred embodiment of the term "comprising of". If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group, which preferably consists of these embodiments only. Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
The term "compound(s) according to the invention", or "compounds of formula (I)" comprises the compound(s) as defined herein as well as a salt, hydrate, stereoisomer, tautomer or N-oxide thereof.
Depending on the substitution pattern, the compounds according to the invention may have one or more centres of chirality. The invention provides both the single pure enantiomers or pure diastereomers of the compounds according to the invention, and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds according to the invention or their mixtures. Suitable compounds according to the invention also include all possible geometrical stereoisomers (cis/trans isomers or E/Z isomers) and mixtures thereof. Cis/trans isomers may e.g. be present with respect to an amide group. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one centre of chirality in the molecule, as well as geometrical isomers (cis/trans isomers). The present invention relates to every possible stereoisomer of the compounds of formula (I), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
The compounds of formula (I) may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention relates to amorphous and crystalline compounds of formula (I), mixtures of different
crystalline states of the respective compound of formula (I), as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula (I) may be pharmaceutically acceptable salts, such as those containing counterions present in drug products listed in the US FDA Orange Book database. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality. Suitable anionic counterions are in particular chloride, bromide, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, trifluoroacetate, propionate and butyrate, furthermore lactate, gluconate, and the anions of poly acids such as succinate, oxalate, maleate, fumarate, malate, tartrate and citrate, furthermore sulfonate anions such as besylate (benzenesulfonate), tosylate (p-toluenesulfonate), napsylate (naphthalene-2-sulfonate), mesylate (methanesulfonate), esylate (ethanesulfonate), and ethanedisulfonate. They can be formed by reacting compounds according to the invention that have a basic functionality with an acid of the corresponding anion.
The term “hydrate” in connection with the compounds of formula (I) refers to a compound of formula (I), which incorporates water molecules in the crystalline structure but does not alter the chemical structure of formula (I). Preferably, the compounds of formula (I), in particular shinorine, are used as hydrate.
Tautomers may be formed, if a substituent is present at the compound of formula (I), which allows for the formation of tautomers such as keto-enol tautomers or the like.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
The term "alkyl" as used herein denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,
1-ethylpropyl, 1, 1 -di methyl propyl, and 1,2-dimethylpropyl. Methyl, ethyl, n-propyl, isopropyl, and iso-butyl, are particularly preferred.
The term “alkenyl” as used herein denotes in each case an unsaturated hydrocarbon group having usually 2 to 6, preferably 2 to 4 carbon atoms comprising at least one carbon-carbon double bond in any position, e.g. vinyl (ethenyl), allyl (2-propen-l-yl), 1-propen-l-yl,
2-propen-2-yl, methallyl (2-methylprop-2-en-l-yl), 2-buten-l-yl, 3-buten-l-yl, 2-penten-l- yl, 3-penten-l-yl, 4-penten-l-yl, l-methylbut-2-en-l-yl, 2-ethylprop-2-en-l-yl and the like. If geometric isomers are possible with regard to the double bond, the present invention relates to both, the E- and Z-isomers. The bonding of vinyl is exemplified below:
The term “heterocyclyl” or “heterocyclic ring” as used herein includes, unless otherwise indicated, in general a 3- to 9-membered, preferably a 4- to 8-membered or 5- to 7- membered, more preferably 5- or 6-membered, in particular 5-membered monocyclic ring. The heterocycle is saturated, wherein saturated means that only single bonds are present. The heterocycle typically comprises one or more, e.g. 1, 2, 3, or 4, preferably 1, 2, or 3 heteroatoms selected from N, 0 and S as ring members, where S-atoms as ring members may be present as S, SO or SO2. The remaining ring members are carbon atoms. The saturated heterocycle as used herein comprises at least one nitrogen atom, namely the nitrogen atom to which R2 and R3 are attached. Preferably, in addition to said nitrogen atom to which R2 and R3 are attached, the saturated heterocycle comprises 0, 1, or 2, preferably 0 or 1, more preferably 0 heteroatoms selected from N, 0 and S as ring members, where S- atoms as ring members may be present as S, SO or SO2. The skilled person is aware that S, SO or SO2 is to be understood as follows:
Further, a skilled person is aware that resonance structures of the oxidized forms may be possible. Examples of saturated heterocycles include pyrrolidine, pyrrolidinone, morpholine, thiomorpholine, piperidine or piperazine.
As used herein, the term “keratin materials” refers to any material comprising keratin, including natural and synthetic materials. Particular examples of keratin materials are the skin, hair, nails, feathers, horns, claws, and hooves. A preferred keratin material is human skin.
As used herein, the term “anhydrous part” refers to a part of the composition, wherein no water has been added such that the water present is only due to residual water or hydrates of the components in the anhydrous part. Preferably, the anhydrous part does not contain any water other than in the form of hydrates of the components in the anhydrous part. More preferably, the anhydrous part does not contain any water other that in the form of the hydrate of the compound of formula (I). The water content is preferably less than 0.1 % by weight relative to the weight of the anhydrous part.
As used herein, “hydrous part” refers to a part of the composition, wherein water has been added.
As used herein, suitable bases of the anhydrous part include alkali metal salts, alkaline earth metal salts, or ammonium salts such as, e.g., carbonates, bicarbonates, or oxides. The bases that are part of the anhydrous part are preferably anhydrous bases. In addition, also the hydrous part may comprise a base or an aqueous solution of a base.
As used herein, “cosmetic oils” also encompass emollients and can be chosen from all oils, preferably physiologically acceptable oils, in particular mineral, animal, vegetable, or synthetic oils; especially non-volatile hydrocarbon oils and/or non-volatile silicone oils, and their mixtures. Exemplary cosmetic oils include but are not limited to castor oil, avocado oil, olive oil, sweet almond oil, wheat germ oil, sesame oil, cottonseed oil, coconut oil, corn oil, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, apricot kernel oil, hazelnut oil, borago oil, peanut oil, sesame oil, jojoba oil, argan oil, rosehip oil, black seed oil, grape seed oil, walnut oil, palm oil, medium chain diglycerides, medium chain triglycerides (MCT), and mixtures thereof. Medium chain di- or triglycerides are preferably based on C6-C18 fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, cocoglycerides, wheat germ glycerides, etc.) or fatty acid esters of polyglycerol (polyglyceryl -n) such as polyglyceryl-4 caprate, polyglyceryl-2-isostearate, etc. A detailed list of cosmetic oils can be found in the description below.
The term “UV-filter” as used herein refers to organic or inorganic compounds or mixtures thereof, which can absorb and optionally reflect UV radiation caused by sunlight. UV-filter can be classified based on their UV protection curve as UV-A, UV-B or broadband filters. In the context of the present application, broadband filters may be listed as UV-A filters, as they also provide UV-A protection. In other words, preferred UV-A filters also include broadband filters. The definition of “broadband” protection (also referred to as broadspectrum or broad protection) is based on the “critical wavelength”. For broadband coverage, UV-B and UV-A protection must be provided. According to the US requirements, a critical wavelength of at least 370 nm is required for achieving broad spectrum protection.
Organic UV filters include triazine derivatives, triazole derivatives, benzotriazole derivatives, benzophenone derivatives, dibenzoylmethane derivatives, camphor derivatives, cinnamates, salicylates, benzimidazole sulfonic acid derivatives, polysilicone-15, para-amino benzoic acid (PABA) derivatives, and combinations thereof. Examples of organic UV filters are ethylhexyl triazone (EHT), dimethyl para-aminobenzoate (ED PABA), PEG-25 PABA, ethylhexyl salicylate (EHS), ethylhexyl methoxy cinnamate (EHMC), iso-amyl methoxy cinnamate (IMC), octocrylene (OCR), phenyl benzimidazole sulfonic acid (PBSA), 4-methyl benzylidene camphor (4-MBC), butyl methoxy dibenzoylmethane (BMDBM), terephthalidine dicamphor sulfonic acid (TDSA), drometrizole trisiloxane (DTS), methylene bis- benzotriazolyl tetramethylbutylphenol (MBBT), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), benzophenone-3 (B3), benzophenone-4 (B4), menthyl anthranilate (MA), diethylhexyl butamido triazone (DBT), benzylidene malonate polysiloxane (BMP), disodium phenyl dibenzimidazole tetrasulfonate (DPDT), homomentyl salicylate (HMS), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), tris biphenyl triazine (TBT), 3,3’-(l,4- phenylene)bis(5,6-diphenyl-l,2,4-triazine) (T riasorb), methoxypropylamino
cyclohexenylidene ethoxyethylcyanoacetate, bis-(diethylaminohydroxybenzoyl benzoyl) piperazine (HAA299), or mixtures thereof. Inorganic UV filters include titanium dioxide, zinc oxide, iron oxide, cerium oxide and mixtures thereof.
The term “UV-protection” as used herein refers to protection of keratin materials from UV radiation by absorbing or reflecting UV radiation. UV-protection as used herein refers to UV-A protection and/or UV-B protection.
The term “sun protection factor (SPF)" as used herein indicates how well the skin is protected by a sunscreen composition mainly from UV-B radiation. In particular, the factor indicates how much longer the protected skin may be exposed to the sun without getting a sunburn in comparison to untreated skin. For example, if a sunscreen composition with an SPF of 15 is evenly applied to the skin of a person usually getting a sunburn after 10 minutes in the sun, the sunscreen allows the skilled person to stay in the sun 15 times longer. In other words, SPF 15 means that 1/15 of the burning UV radiation will reach the skin, assuming sunscreen is applied evenly at a thick dosage of 2 milligrams per square centimeter (mg/cm2). As regards the UV-A protection factor (UVA-PF), it is recommended by the European Commission that all sunscreen or cosmetic compositions should have an UVA protection factor, which is at least one third of the labelled sun protection factor (SPF), e.g. if the sunscreen composition has an SPF of 30 the UVA protection factor has to be at least 10. UVA-PF can be measured in vivo according to the ISO24442 or in vitro according to the ISO24443.
The term “critical wavelength” is defined as the wavelength at which the area under the UV protection curve (% protection versus wavelength) represents 90 % of the total area under the curve in the UV region (290-400 nm). For example, a critical wavelength of 370 nm indicates that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e. wavelengths from 290-320 nm, but extends to 370 nm in such a way that 90 % of the total area under the protective curve in the UV region are reached at 370 nm. The term “body-care product” or “cosmetic composition” refers to any product suitable to apply to the mammalian body, preferably to the human body, such as, e.g. sunscreen compositions, bath and shower products, preparations containing fragrances and odoriferous substances, hair-care products, dentifrices, decorative preparations, and cosmetic formulations containing active ingredients.
The term “sunscreen composition” or “sunscreen” refers to any topical product, which absorbs certain parts of UV radiation and which may further reflect and scatter certain parts of UV radiation. Thus, the term “sunscreen composition” is to be understood as not only including sunscreen compositions, but also any cosmetic compositions that provide UV protection.
The term “topical product” refers to a product that is applied to the surface of a material or the body, preferably to a keratin material, such as the skin, and can refer, e.g., to sprays,
lotions, creams, oils, foams, powders, or gels. According to the present invention the sunscreen composition may comprise one or more active agents, e.g., organic UV filters, as well as other ingredients or additives, e.g., emulsifiers, emollients, viscosity regulators, stabilizers, preservatives, or fragrances.
The term “daily care composition” refers to any topical product, which reflects or absorbs certain parts of UV radiation and is used as an everyday care product for the human body, e.g., for face, body or hair. The daily care composition may comprise one or more active agents, e.g., organic or inorganic UV filters, as well as other ingredients or additives, e.g., emulsifiers, emollients, viscosity regulators, stabilizers, preservatives, or fragrances. Suitable bath and shower additives are, e.g., shower gels, bath-salts, bubble baths and soaps.
Suitable preparations containing fragrances and odoriferous substances are in particular scents, perfumes, toilet waters and shaving lotions (aftershave preparations).
Suitable hair-care products are, e.g., shampoos for humans and animals, in particular dogs, hair conditioners, products for styling and treating hair, perming agents, hair sprays and lacquers, hair gels, hair fixatives and hair dyeing or bleaching agents.
Suitable dentifrices are, e.g., tooth creams, toothpastes, mouth-washes, mouth rinses, antiplaque preparations and cleaning agents for dentures.
Suitable decorative preparations are, e.g., lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions.
Suitable cosmetic formulations containing active ingredients are, e.g., hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations.
The term “light stabilizers” as used herein are compounds suitable for protecting a product, e.g., a body-care product, household cleaning and treating agents, agrar-formulations, food, polymers (such as plastics, coatings, printing, packaging, lacquers, textiles) against photolytic degradation. The light stabilizer is usually present in the body-care product in a concentration of 50 to 1000 ppm.
The term “household cleaning and treating agent” refers to any product suitable to clean or treat household objects, e.g., liquid scouring agents, glass detergents, neutral cleaners (allpurpose cleaners), acid household cleaners (bath), WC cleaners, preferably in washing, rinsing and dishwashing agents, clear rinsing agents, dishwasher detergents, shoe polishes, polishing waxes, floor detergents and polishes, metal, glass and ceramic cleaners, textilecare products, agents for removing rust, color and stains (stain remover salt), furniture and multipurpose polishes and leather dressing agents (leather sprays).
Preferably, household cleaning agents are aqueous or alcoholic (e.g. ethanol or isopropyl alcohol) solutions of one or more of the following components: anionic, nonionic, amphoteric and/or cationic surfactants soaps, prepared by saponification of animal and vegetable greases organic acids, like hydrochloric acid, phosphoric acid, or sulfuric acid, for
basic products inorganic (NaOH or KOH) or organic bases; abrasives for improved cleaning of surfaces, waxes and/or silicones for maintenance and protection of surfaces, polyphosphates, substances which eliminate hypochlorite or halogens; -peroxides comprising bleaching activators like TAED, for example sodium perborate or H2O2; enzymes; in washing detergents discoloration inhibitors, soil-release compounds, grey scale inhibitors, foam inhibitors, fluorescent whitening agents; cleaning agents based on wax may comprise solvents selected from benzine, turpentine and/or paraffines and emulsifiers based on wax; filling agents like silicates, polyphosphates, Zeolithes for powdery cleaning agents; pigments, lakes or soluble dyes; perfumes; and light stabilizers, antioxidants and chelating agents.
The term “photostability” refers to the ability of a UV filter or any other molecule, which is exposed to sunlight, to stay stable upon irradiation. In particular, this means that the compound does not undergo a degradation process upon UV radiation.
The term “consistency agent” as used herein refers to any ingredient, which builds viscosity to deliver optimal product consistency. Thus, consistency agents include particularly consistency regulators/thickeners.
“Film forming agents” as used herein include film forming polymers, which may provide improved water resistance and rub-off resistance.
As used herein, “humectants” refer to water-absorbing (hygroscopic) substances, which are used to keep things moist. Humectants are molecules comprising several hydrophilic groups, e.g. hydroxyl groups. Humectants are often used in cosmetics in order to increase and maintain moisture in the skin or hair. They attract water/moisture e.g. from the outer layer of the skin or from the atmosphere via absorption and draw the moisture against e.g. the epidermis. Humectants can include but are not limited to e.g. triethylene glycol, tripropylene glycol, propylene glycol, PPGs, glycerol, sorbitol, hexylene glycol, butylene glycol, urea or collagen.
As used herein, “biodegradable” or “biodegradability” in the context of the compounds of formula (I) or the organic components of the two-part composition refers to the capacity of said compounds or components to biodegrade. In particular, if the compound(s) of formula (I) or the organic components are defined as biodegradable or having a certain biodegradability, this refers to each of the compounds of formula (I) and each of the individual organic components of the two-part composition being biodegradable and not the mixture thereof. Primary biodegradation refers to the alteration in the chemical structure of a substance brought about by biological action and resulting in the loss of a specific property of that substance. Ultimate biodegradation (aerobic) relates to the level of degradation achieved when the test substance is totally utilized by micro-organism resulting in the production of carbon dioxide, water, mineral salts and new microbial cellular constituents (biomass). Biodegradation can be further classified in two groups, substances
which are “readily biodegradable” and substances which are “partially biodegradable”. “Readily biodegradable” is an arbitrary classification of chemicals which have passed certain specified screening tests for ultimate biodegradability. These tests are so stringent that it is assumed that such compounds will rapidly and completely biodegrade in aquatic environments under aerobic conditions. “Partially biodegradable” relates to a classification of chemicals for which there is unequivocal evidence of biodegradation (primary or ultimate) in any test of biodegradability. Partially biodegradable is a term for substances that can be biodegraded under specific conditions. The test for partial biodegradability is not as stringent as a ready biodegradation study. As used herein, biodegradable includes partially biodegradable and readily biodegradable. As used herein, if a compound of formula (I) or an organic component of the two-part composition is partially biodegradable, this means having a biodegradability of more than 20% (>20%) but less than 60% (< 60%). In particular, partially biodegradable as used herein is defined as > 20% but < 60% biodegradability as measured by OECD 301 F testing. As used herein, if a compound of formula (I) or an organic component of the two-part composition is readily biodegradable, this means having a biodegradability of larger or equal to 60% (>60%). In particular, readily biodegradable as used herein is defined as >60% biodegradability as measured by OECD 301 F testing. In general, the biodegradability of an organic component can be assessed via different OECD 301 A-F measurements. With regard to the present invention it is to be understood that the biodegradability has been assessed via a small-scale measurement of the OECD 301 F testing method. The procedure of the OECD 301 F is described as follows.
For the principal of the OECD 301 F test it is referred to the OECD Guidelines for the Testing of Chemicals, Section 3, Environmental fate and behavior (doi.org/10.1787/2074577x). A measured volume of inoculated mineral medium, containing a known concentration of test substance (100 mg test substance/l giving at least 50-100 mg ThOD/l) as the nominal sole source of organic carbon, is stirred in a closed flask at a constant temperature for up to 28 days. The consumption of oxygen is determined either by measuring the quantity of oxygen (produced electrolytically) required to maintain constant gas volume in the respirometer flask, or from the change in volume or pressure (or a combination of the two) in the apparatus. Evolved carbon dioxide is absorbed in a solution of potassium hydroxide or another suitable absorbent. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by blank inoculum, run in parallel) is expressed as a percentage of ThOD or, less satisfactorily, COD. ThOD describes the theoretical oxygen demand and COD describes the common oxygen demand.
In particular, in the present case, the OECD 301 F test was performed as follows: Biodegradation in wastewater was tested in triplicate using the OECD 301 F manometric respirometry method. OECD 301 F is an aerobic test that measures biodegradation of a sample by measuring the consumption of oxygen. To a measured volume of medium, 100
mg/L test substance, which is the nominal sole source of carbon was added along with the inoculum (aerated sludge taken from Mannheim waste water treatment plant). This was stirred in a closed flask at a constant temperature of 22 ° C for 28 days. The consumption of oxygen was determined by measuring the change in pressure in the apparatus using an OxiTopC. Evolved carbon dioxide was absorbed in a solution of sodium hydroxide. Nitrification inhibitors were added to the flask to prevent usage of oxygen due to nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by blank inoculum, run in parallel) was expressed as a percentage of ThOD (theoretical oxygen demand, which was measured by the elemental analysis of the compound). A positive control Glucose/Glucosamine was run along with the test samples for each cabinet.
Biodegradation can then be calculated according to the following formula according to the OECD Guideline for the Testing of Chemicals, Section 3:
% degradation is calculated according to the following formula according to the OECD Guidelines for the Testing of Chemicals, Section 3: 100
The term “organic component” as used herein denotes any organic compound, i.e., any compound comprising organic carbon. In the context of the present invention, this refers to any carbon-containing compound except for the following carbon-containing compounds, which are considered inorganic compounds: carbides, carbonates (salts of carbonic acid characterized by the CO3 2- anion, and thus not carbonate esters), bicarbonates (salts of carbonic acid characterized by the HCO3’ anion), carbonic acid, CO, CO2, and inorganic cyanides (salts characterized by the ON’ anion). Further, elemental forms of carbon, such as graphite, diamond, fullerenes, or carbon nanotubes, are not considered organic carbon. The term “fine lines” as used herein refers to small, shallow creases that form on thin, delicate skin. Fine lines on the face are associated with repetitive movements (e.g., frowning, smiling, squinting, and laughing). Usually, fines lines first form around the eyes and mouth. In particular, fine lines are less than two millimeters deep and are associated with the earliest signs of aging. Over time, these fine lines can develop into deeper folds and wrinkles.
Brief description of the Figures
Figure 1 shows the concentration of shinorine in Sample C of Example 2 relative to day 0 (100 %) determined by HPLC directly after preparation of Sample C (day 0, room temperature) and after storage at 40 ° C for different time periods.
Figure 2 shows the concentration of shinorine in Sample D of Example 2 relative to day 0 (100 %) determined by HPLC directly after preparation of Sample D (day 0, room temperature) and after storage at 50 ° C for different time periods.
Figure 3 shows the UV absorbance of the mixture of part I and part II of Table lb of Example lb after storage at 50 ° C at different time periods. The solid line shows the absorbance directly after mixing (TO), the dotted line shows the absorbance after 8 days storage of the mixture at 50° C and the dashed line shows the absorbance after 31 days storage of the mixture at 50 ° C.
Detailed description
Preferred embodiments regarding the two-part composition of the present invention as well as the use thereof are described hereinafter. It is to be understood that the preferred embodiments of the invention are preferred alone or in combination with each other.
As indicated above, the present invention relates to a two-part composition comprising a) an anhydrous part comprising a base and at least one compound according to formula (I)
or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof, wherein
X is NRN;
RN is C1-C4-alkyl-ORa, or C1-C4-alkyl-(C=O)ORa, wherein each substitutable carbon atom in the aforementioned groups is independently unsubstituted or substituted with one or more, same or different substituents Rx;
R1 is C1-C2-alkyl;
R2 is H;
R3 is C1-C3-alkyl-(C=O)ORa;
R4 is H or ORa;
Rx is C(=O)ORa, or C1-C2-alkyl; and
Ra is H; and b) a hydrous part comprising at least water; and wherein the anhydrous part and the hydrous part are separate.
By separating the anhydrous part a) comprising the compound of formula (I) and the hydrous part b), degradation of the compound of formula (I) after a short period of time is prevented. Further, the inventors have found that the mixture of the compound of formula (I) and the base of the anhydrous part a) can quickly dissolve in the hydrous part b) comprising water, forming a homogeneous solution or emulsion for application as UV protection for keratin materials. In particular, the homogeneous solution or emulsion is formed after mixing of the anhydrous part and the hydrous part for less than 30 seconds, even within 10 seconds.
Preferred embodiments regarding the compounds of formula (I) or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof, which are relevant for all aspects of the invention, are defined hereinafter.
In a preferred embodiment of the present invention, in the compound of formula (I), X is NRN;
RN is C1-C2-alkyl-ORa, wherein each substitutable carbon atom in the aforementioned groups is independently unsubstituted or substituted with one substituent Rx;
R1 is Cj-alkyl;
R2 is H;
R3 is C1-C2-alkyl-(C=O)ORa;
R4 is H;
Rx is C(=O)ORa; and
Ra is H.
In a more preferred embodiment of the present invention, in the compound of formula (I), X is NRN;
RN is C2-a I ky I -0 Ra, wherein the carbon atom in the aforementioned group next to the N- atom is substituted with one substituent Rx;
R1 is Cj-alkyl;
R2 is H;
R3 is C1-alkyl-(C=O)ORa;
R4 is H;
Rx is C(=O)ORa; and
Ra is H.
In a particularly preferred embodiment of the present invention, the compound of formula (I) is a compound according to the following formula (la)
The compound of formula (la) represents shinorine.
Preferably, the compound of formula (I) represents the MAA shinorine. Even more preferably the compound of formula (I) represents a shinorine hydrate.
Thus, in another particularly preferred embodiment of the present invention, the compound of formula (I) is (E)-N-[(5S)-3-[(carboxymethyl)amino]-5-hydroxy-5-(hydroxymethyl)-2- methoxycyclohex-2-en-l-ylidene]-L-serine.
It has surprisingly been found by the inventors of the present invention that in particular the shinorine hydrate is suitable for the described two-part composition because it hardly absorbs moisture even under high humidity and has therefore a high storage stability.
The compounds of formula (I), in particular the compound of formula (la), can be obtained according to the method disclosed in EP 3 144 392 Al. In short, a MAA biosynthetic enzyme gene is introduced into a microorganism by genetic recombination and the microorganism is extrace 11 u I a r ly cultured producing the MAA. Subsequently, the microbial cell and the extracellular culture solution are separated, and the MAA is recovered from the extracellular culture solution. The shinorine hydrate or shinorine hydrous crystals can be obtained according to the method described in JP2018052883A.
For sufficient UV protection, the UV filter preferably does not crystallize after application to the human skin and subsequent evaporation of water. It has surprisingly been found that specific MAA salts do not crystallize after evaporation of water (deliquescent behavior). In particular, it has surprisingly been found that by incorporating the MAA shinorine hydrate and a base into the anhydrous phase of the two-part composition, the shinorine hydrate remains stable for storage. Further, it has surprisingly been found that upon mixing of the anhydrous part comprising the shinorine hydrate and the base with the hydrous part comprising water, the shinorine hydrate forms the corresponding salt which does not crystallize after application to the human skin and subsequent evaporation of water. Thus, in one embodiment of the present invention, the compound of formula (I) is used in the form of a hydrate thereof. In particular, in a preferred embodiment, the compound of formula (I) is a compound of formula (la), which is used in the form of a hydrate thereof. In this connection, a hydrate of a compound of formula (I) or a compound of formula (la) denotes a
compound of formula (I) or a compound of formula (la) which formed crystals that incorporate water in the crystalline structure without chemical alteration of the compound of formula (I) or the compound of formula (la).
It is to be understood that the following embodiments of the two-part compositions comprising the compound of formula (I) apply to two-part compositions comprising the compound of formula (I) as defined above, including two-part compositions comprising the compound of formula (la).
Preferred embodiments regarding the anhydrous part a) of the two-part composition of the present invention, which are relevant for all aspects of the invention, are defined hereinafter.
In one embodiment of the present invention, the anhydrous part comprises a base and at least one compound according to formula (I) as defined above or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof.
In another embodiment of the present invention, the anhydrous part comprises the compound of formula (I) in an amount of from 0.1 % to 20 % by weight, based on the total weight of the two-part composition. In a preferred embodiment of the present invention, the anhydrous part comprises the compound of formula (I) in an amount of from 1 % to 8% by weight, based on the total weight of the two-part composition.
In another preferred embodiment of the present invention, the anhydrous part comprises the compound of formula (I) in an amount of from 5 % to 80% by weight, based on the total weight of the anhydrous part of the two-part composition.
It is to be understood that the amounts of the compound of formula (I) given above refer to the amount of only one compound of formula (I) or to the amount of a mixture of more than one compound of formula (I). Thus, in the latter case, the amounts of the compound of formula (I) given above refer to the sum of the amounts of each compound of formula (I) present in the anhydrous part of the two-part composition.
As indicated above, the anhydrous part a) further comprises a base. The base provides neutralization of the acidic compounds of formula (I) to provide, after mixing of the anhydrous part with the hydrous part of the two-part composition, a keratin friendly, in particular skin friendly, pH of the composition. The keratin friendly or skin friendly pH is in the range of from 4.5 to 8.
In one embodiment of the present invention, the base of the anhydrous part a) is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium
carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline.
To exclude or minimize the water present in the anhydrous part of the two-part composition, the base of the anhydrous part a) is preferably anhydrous. Thus, in one embodiment of the present invention, the base of the anhydrous part a) is anhydrous. In another embodiment of the present invention, the base of the anhydrous part a) is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline, wherein each of the base is anhydrous.
Further, if carbonates or bicarbonates are used as base of the anhydrous part a), CO2 is formed upon addition of the anhydrous part a) with the hydrous part b), which supports the mixing of the anhydrous part and the hydrous part. Thus, in one embodiment of the present invention, the base of the anhydrous part a) is a carbonate or a bicarbonate, preferably an anhydrous carbonate or anhydrous bicarbonate. In another embodiment, the base of the anhydrous part a) is selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, and magnesium bicarbonate, preferably anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous potassium carbonate, anhydrous potassium bicarbonate, anhydrous ammonium carbonate, anhydrous ammonium bicarbonate, anhydrous calcium carbonate, anhydrous calcium bicarbonate, anhydrous magnesium carbonate, and anhydrous magnesium bicarbonate. In a preferred embodiment, the base of the anhydrous part a) is selected from the group consisting of sodium bicarbonate and sodium carbonate, preferably anhydrous sodium bicarbonate and anhydrous sodium carbonate. In a more preferred embodiment, the base of the anhydrous part a) is sodium carbonate, preferably anhydrous sodium carbonate.
As indicated above, the base of the anhydrous part provides neutralization of the acidic compounds of formula (I) to provide, after mixing of the anhydrous part and the hydrous part of the two-part composition, a keratin friendly, in particular skin friendly, pH of the composition (pH 4.5 to 8). Thus, the base of the anhydrous part is preferably present in an amount sufficient to neutralize the acidic compounds of formula (I) and to provide, after mixing of the anhydrous part and the hydrous part, a composition with a pH in the range of from 4.5 to 8.
In one embodiment of the present invention, the two-part composition comprises the base of the anhydrous part a) in an amount of from 5 % to 90 % by weight, preferably in an amount of from 25 % to 65 % by weight, based on the weight of the compound of formula (I). In another embodiment of the present invention, the two-part composition comprises
the base of the anhydrous part a) in an amount of from 0.1 % to 3 % by weight, preferably in an amount of from 0.3 % to 2.5 % by weight, based on the total weight of the two-part composition. In one embodiment, the two-part composition comprises the base of the anhydrous part a) in an amount of from 25 % to 65 % by weight, based on the weight of the compound of formula (I) and in an amount of from 0.3 % to 2.5 % by weight, based on the total weight of the two-part composition. Depending on the base strength of the base used, the amount of base may vary. The skilled person knows how to adjust the amount of the base depending on the base strengths, e.g., using lower amounts of stronger bases and higher amounts of weaker bases. Further, also the hydrous phase b) may comprise a base, in particular an aqueous solution of a base. The amount of the base in the anhydrous part a) may be lower if the hydrous phase b) comprises a base. Thus, in one embodiment of the present invention, the hydrous part b) comprises an aqueous solution of a base.
Preferred embodiments regarding the hydrous part b) of the two-part composition of the present invention, in particular in connection with the embodiments of the anhydrous part defined above, are defined hereinafter and are relevant for all aspects of the invention. In one embodiment of the present invention, the hydrous part comprises at least water. In another embodiment of the present invention, the hydrous part of the composition comprises water in an amount of from 3 % to 70 % by weight, based on the total weight of the two-part composition. In a more preferred embodiment, the hydrous part of the composition comprises water in an amount of from 30 % to 60 % by weight, based on the total weight of the two-part composition.
As indicated above, the anhydrous part a) and the hydrous part b) may comprise one or more additional ingredients. Preferred embodiments regarding the additional ingredients of the anhydrous part a) and the hydrous part b) of the two-part composition of the present invention are defined hereinafter and are relevant for all aspects of the invention. It is to be understood that the following preferred embodiments regarding the additional ingredients of the anhydrous part a) and the hydrous part b) of the two-part composition are preferred alone or in combination with the preferred embodiments regarding the anhydrous phase a), the compounds of formula (I), in particular the compounds of formula (la), and the hydrous phase b) defined above.
In one embodiment of the present invention, the anhydrous part a) further comprises al) cosmetic oils; a2) UV filters; a3) surfactants and/or emulsifier; a4) sensory enhancers; a5) consistency agents;
a6) film forming agents; a7) UV performance booster like scattering particles; a8) preservatives; and/or a9) perfumes.
In another embodiment of the present invention, the hydrous part b) further comprises bl) alcohols; b2) UV filters; b3) surfactants and/or emulsifier; b4) sensory enhancers; b5) thickeners; b6) film forming agents; b7) UV performance boosters; b8) preservative; b9) humectants; and/or blO) perfumes.
In one embodiment of the present invention, the two-part composition comprises at least one additional UV filter, other than the compound of formula (I). Preferably, the two-part composition further comprises from 1 to 3 additional UV filters, other than the compound of formula (I).
In connection with this embodiment, the two-part composition provides an even higher protection against UV radiation. The further UV filter and/or light stabilizer, other than the compound of formula (I), may be present in the hydrous part b) or the anhydrous part a). If the hydrous part b) does not only contain water, the further UV filter and/or light stabilizer, other than the compound of formula (I), is preferably in the hydrous part b).
Thus, in one embodiment of the present invention, the anhydrous part a) comprises at least one UV filter other than the compound of formula (I). In another embodiment of the present invention, the anhydrous part a) comprises one UV filter other than the compound of formula (I).
In another embodiment of the present invention, the hydrous part b) comprises at least one UV filter other than the compound of formula (I). In another embodiment, the hydrous part b) comprises from 1 to 3 UV filters other than the compound of formula (I). In another embodiment, the hydrous part b) comprises at least 2, preferably 2 to 3, UV filters other than the compound of formula (I).
As indicated above, the hydrous part b) may comprise a UV filter other than the compound of formula (I).
In one embodiment of the two-part composition, the UV filter comprised in the hydrous part is selected from the group consisting of 1 - (4- (1 ,1 -di methy lethy I) pheny I) -3-(4- methoxyphenyl)propane-l, 3-dione (I NCI butyl methoxydibenzoylmethane), 2-(2H- benzotriazo I -2 -y I) -6- [(2 -ethyl hexyl oxy) methy I] -4- methy I phenol, 2 -(2 H- benzotriazo I -2-yl) -4- methy 1-6- [2 -methy 1-3- [1,3,3,3-tetra methy 1-1 -[(tri methy Isi ly l)oxy] -1 - disiloxanyl] propyl] phenol (I NCI drometrizole trisiloxane), ethylhexyl triazone (EHT), dimethyl para-aminobenzoate (ED PABA), PEG-25 PABA, ethylhexyl salicylate (EHS), ethylhexyl methoxy cinnamate (EH MC), iso-amyl methoxy cinnamate (I MC), octocrylene (OCR), 4- methyl benzylidene camphor (4-MBC), drometrizole trisiloxane (DTS), methylene bis- benzotriazolyl tetramethylbutylphenol (M BBT), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), benzophenone-3 (B3), benzophenone-4 (B4), menthyl anthranilate (MA), diethylhexyl butamido triazone (DBT), benzylidene malonate polysiloxane (BMP), disodium phenyl dibenzimidazole tetrasulfonate (DPDT), homomentyl salicylate (HMS), diethylamino hydroxybenzoyl hexyl benzoate (DHH B), tris bipenyl triazine (TBT), 3,3’-(l,4- phenylene) bis(5,6-diphenyl-l,2,4-triazine) (T riasorb), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate, bis-(diethylaminohydroxybenzoyl benzoyl) piperazine (HAA299), (2-{4- [2- (4- Diethyla mi no-2- hydroxy- benzoyl) -benzoyl] -pi perazine-1- carbony I}- pheny I) -(4-d iethyla mi no-2 -hydroxy- pheny I) -methanone, [(3Z)-3-[[4-[(Z)-[7,7- d i methy I -2 -oxo-1 - (sulfomethyl) -3 -bicyclo [2.2.1] hepta ny I ide ne] methy I] pheny I] methy I ide ne]- 7,7-dimethyl-2-oxo-l-bicyclo[2.2.1] heptanyl] methanesulfonic acid (I NCI terephthalylidene dicamphor sulfonic acid), 2-phenyl-lH-benzimidazole-5-sulfonic acid (INCI phenylbenzimidazole sulfonic acid), disodium phenyl dibenzimidazole tetrasulfonate, 2- ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2- [4-(diethylamino)-2-hydroxybenzoyl] benzoate (I NCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4- bis-{[4-(2-ethyl -hexyl oxy) -2 -hydroxy] -pheny I] -6- (4- meth oxy pheny I) -1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine), 4,4',4"-(l,3,5-triazine-2,4,6- triy I tri i m i n o) tris- benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), (RS)-2- ethylhexyl-2-hydroxybenzoate (INCI ethylhexyl salicylate), 3,4,5-trimethoxycinnamic acid (CAS 90-50-6), acetovanillone (CAS 498-02-2), apigenin (CAS 520-36-5), bis(cyano butylacetate) anthracenediylidene (CAS 2128716-83-4), caffeic acid (CAS 501-16-6, 331- 39-5), caffeic acid phenethyl ester (CAS 104594-70-9), caprylyloxyphenylamino dimethyltetrahydro benzothiazine carboxylic acid (CAS 1629023-01-3), chlorogenic acid (CAS 327-97-9), croconic acid (CAS 488-86-8), croconic acid derivative (CAS 2755724-99-1, 2755725-01-8), daidzein (CAS 486-66-8), ellagic acid (CAS 476-66-4, 133039-73-3), ethyl (3R)-3,4,5,6,7,8-hexahydro-8- [(4- meth oxy pheny I) imino] -6,6-di methyl -2 H-l, 4- benzothiazine-3-carboxylate (CAS 2699128-33-9), ethyl ferulate (CAS 28028-62-8, 4046-02- 0), ethyl protocatechuate (CAS 3943-89-3), ethylhexyl methoxycrylene (CAS 947753-66-4), Feriu liShield™ Hemp (feruloyl hemp glycerides), ferulic acid (CAS 1135-24-6), FeruliShield ™ (feruloyl glycerides, feruloyl soybean glyceride FSG-33, feruloyl coconut glyceride FCG-
33, feruloyl hemp glyceride FHG-33), folic acid (CAS 59-30-3), genistein (CAS 446-72-0), Guanidine, compd. with 4, 5-dihydroxy-4-cyclopentene-l, 2, 3-trione (2:1) (CAS 2755725-00- 7), Helioguard™ 365 (Mibelle Biochemistry), hispolon (CAS 173933-40-9), Kaempferia Galanga Root Extract (CAS 92347-13-2), Kaempferol (CAS 520-18-3), lignin, lignosulfonate, Kraft lignin, soda lignin, organosolv lignin, ligno sulfonate, Liposhield® HEV Melanin, EINECS #: 232-473-6 (CAS 8049-97-6), luteolin (CAS 491-70-3), melanin (CAS 8049-97-6), methoxyphenylimino dimethylcyclohexenyl ethyl glycinate (2640340-86-7), methoxyphenylimino dimethylhexahydro benzothiazine carboxylic acid (CAS 1629023-04-6), methyl salicylate (CAS 119-36-8), methyl vanil late (CAS 3943-74-6), N-[(3E)-3-[(4- Methoxyphenyl)imino]-5,5-dimethyl-l-cyclohexen-l-yl]glycine (CAS 1509902-01-5), p- coumaric acid (CAS 7400-08-0), pongamol (CAS 484-33-3), protocatechuic acid (CAS 99- 50-3), quercetin (CAS 117-39-5), resveratrol trimethyl ether (CAS 22255-22-7), rutin (CAS 153-18-4, 207671-50-9 (Hydrat), 250249-75-3 (Tri hyd rat)) , sinapic acid (CAS 530-59-6), trolamine salicylate (CAS 2174-16-5), troxerutin (CAS 7085-55-4), vanillic acid (CAS 121- 34-6), isoamyl p-methoxycinnamate (amiloxate) (CAS 71617-10-2), menthyl anthranilate (meradimate) (CAS 134-09-8), homomentyl salicylate (homosalate) (CAS 118-56-9), pongamol (CAS 484-33-3), coffee bean extract (e.g. obtained by supercritical CO2 extraction of recycled coffee grounds), padimate O (CAS 21245-02-3), titanium dioxide, zinc oxide, iron oxide, cerium oxide, and combinations thereof.
In another embodiment of the two-part composition, the UV filter comprised in the hydrous part is selected from the group consisting of [(3Z)-3-[[4-[(Z)-[7,7-dimethyl-2-oxo-l- (su If om ethyl) -3 -bicyclo [2.2.1] hepta ny lid ene] methyl] phenyl] methyl ide ne]-7,7-di methyl -2- oxo-l-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphor sulfonic acid), 2-phenyl-lH-benzimidazole-5-sulfonic acid (INCI phenylbenzimidazole sulfonic acid), disodium phenyl dibenzimidazole tetrasulfonate, 2-ethylhexyl-(2E)-3-(4- methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2 - [4- (d iethy I a m i no) -2 - hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4-bis-{[4- (2-ethyl-hexyloxy)-2-hydroxy]-phenyl]-6-(4-methoxyphenyl)-l,3,5 triazine (INCI bisethyl hexyl oxy pheno I methoxy phenyl triazine), 4,4',4"-(l,3,5-triazine-2,4,6-triyltriimino)tris- benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), (RS)-2-ethylhexyl-2- hydroxybenzoate (INCI ethylhexyl salicylate), titanium dioxide, zinc oxide and combinations thereof.
In another embodiment of the two-part composition, the UV filter comprised in the hydrous part is selected from the group consisting of 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4- bis-{[4-(2-ethy I -hexyloxy) -2- hydroxy]-phenyl]-6-(4-methoxyphenyl)-l,3,5 triazine (INCI bis-ethylhexyloxyphenol
meth oxy phenyl triazine), 4,4',4"- (1,3,5-triazi ne-2,4,6-triyltrii mi no) tris- benzoic acid -tris (2- ethylhexyl)ester (INCI ethylhexyl triazone), (RS)-2-ethylhexyl-2-hydroxybenzoate (INCI ethylhexyl salicylate), titanium dioxide, zinc oxide and combinations thereof.
As indicated above, the anhydrous part a) may comprise a UV filter other than the compound of formula (I).
In one embodiment of the two-part composition, the UV filter comprised in the anhydrous part is selected from the group consisting of 1 - (4- (1, 1 -d i methylethyl) pheny I) -3- (4- methoxyphenyl)propane-l, 3-dione (I NCI butyl methoxydibenzoylmethane), 2-(2H- benzotriazo I -2 -y I) -6- [(2 -ethyl hexyl oxy) methyl] -4- methyl phenol, 2 -(2 H- benzotriazo I -2-yl) -4- methy I -6- [2-methy I -3- [1,3,3,3-tetramethy I -1 - [(tri methy I si ly I) oxy] -1 - disiloxanyl] propyl] phenol (I NCI drometrizole trisiloxane), ethylhexyl triazone (EHT), dimethyl para-aminobenzoate (ED PABA), PEG-25 PABA, ethylhexyl salicylate (EHS), ethylhexyl methoxy cinnamate (EHMC), iso-amyl methoxy cinnamate (IMC), octocrylene (OCR), phenyl benzimidazole sulfonic acid (PBSA), 4-methyl benzylidene camphor (4-MBC), terephthalidine dicamphor sulfonic acid (TDSA), drometrizole trisiloxane (DTS), methylene bis-benzotriazolyl tetramethylbutylphenol (M BBT), bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT), benzophenone-3 (B3), benzophenone-4 (B4), menthyl anthranilate (MA), diethylhexyl butamido triazone (DBT), benzylidene malonate polysiloxane (BMP), disodium phenyl dibenzimidazole tetrasulfonate (DPDT), homomentyl salicylate (H MS), diethylamino hydroxybenzoyl hexyl benzoate (DH HB), tris biphenyl triazine (TBT), 3,3’-(l,4- phenylene) bis(5,6-diphenyl-l,2,4-triazine) (T riasorb), methoxypropylamino cyclohexenylidene ethoxyethylcyanoacetate, bis-(diethylaminohydroxybenzoyl benzoyl) piperazine (HAA299), (2 -{4- [2- (4- Diethyl a mi no-2- hydroxy- benzoyl) -benzoyl] -pi perazine-1- carbonyl]-phenyl)-(4-diethylamino-2-hydroxy-phenyl)-methanone, titanium dioxide, zinc oxide, iron oxide, cerium oxide, and combinations thereof.
In one embodiment of the two-part composition, the UV filter comprised in the anhydrous part is selected from the group consisting of 1 - (4- (1, 1 -d i methylethyl) pheny I) -3- (4- methoxyphenyl)propane-l, 3-dione (I NCI butyl methoxydibenzoylmethane), 2-(2H- benzotriazo I -2 -y I) -6- [(2 -ethyl hexyl oxy) methy I] -4- methy I phenol, 2 -(2 H- benzotriazo I -2-y Dimethyl -6- [2-methy I -3- [1,3,3,3-tetramethy 1-1 -[(tri methy lsilyl)oxy]-l- disiloxanyl] propyl] phenol (INCI drometrizole trisiloxane), titanium dioxide, zinc oxide, and combinations thereof.
In another embodiment of the two-part composition, the UV filter comprised in the anhydrous part is selected from the group consisting of titanium dioxide, zinc oxide, and combinations thereof.
Preferred cosmetic oils include
Vegetable oils esters of linear or branched fatty acids with linear or branched fatty alcohols; esters of aromatic carboxylic acids with linear or branched fatty alcohols; di- and tricarboxylic acid esters with linear or branched alcohols; esters of hydroxycarboxylic acids with linear or branched fatty alcohols; esters of linear or branched fatty acids with polyhydric alcohol; mono-, di-, tri-glycerides based on C6-C18 fatty acids; guerbet alcohols such as octyldodecanol; hydrocarbons; ethers such as dicaprylyl ether.
Examples of cosmetic oils are C12-C15 alkyl benzoate, caprylic/capric triglyceride, butylene glycol dicaprylate/dicaprate, propylene glycol dicaprylate/dicaprate, diisopropyl sebacate, octyldodecanol, isopropyl palmitate, isopropyl myristate, dicaprylyl carbonate, phenethyl benzoate, dibutyl adipate, diisopropyl adipate, triethyl citrate and tributyl citrate , octyldodecanol, hydrogenated polyisobutene, mineral oil, squalene, isohexadecane, coconut oil, sweet almond oil, wheat germ oil, sesame oil, cottonseed oil, coconut oil, avocado oil, corn oil, castor oil, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, apricot kernel oil, hazelnut oil, borago oil, peanut oil, sesame oil, jojoba oil, argan oil, rosehip oil, black seed oil, grape seed oil, walnut oil, palm oil, particularly preferably coconut oil.
With regard to the above-described preferred cosmetic oils it is to be understood that cosmetic oils encompass the group of emollients. In other words, the term emollients and cosmetic oils can be used interchangeably.
Preferred surfactants, i.e., surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, alpha-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides,
alkylamidobetaines, protein fatty acid condensation products, preferably based on wheat proteins.
Preferred emulsifiers include glucose derivatives such as cetearyl glucoside, arachidyl glucoside, lauryl glucoside, polyglyceryl -3 methylglucose distearate, methyl glucose sesquistearate; sucrose derivative such as sucrose polystearate, sucrose palmitate; sorbitol derivatives such as polysorbate-n, PEG-10 sorbitan laurate; fatty alcohol polyglycolethers and fatty acid polyglycolethers such as ceteareth-20, beheneth-25, steareth-2, PEG-100 stearate; glycerides of fatty acids such as glyceryl stearate, glyceryl oleate; glumatic acid derivatives such as sodium stearoyl glutamate; sulfosuccinic acid derivatives such as disodium Cetearyl sulfosuccinate; phosphoric acid derivatives such as potassium cetyl phosphate; fatty acid esters of polyglyceryl such as polyglyceryl-3-diisostearate, polyglyceryl-2- dipolyhydroxystearate; oxyalkenylated organomodified silicone / polysiloxane / polyalkyl / polyether copolymers and derivatives.
Preferred consistency agents for the anhydrous part include consistency regulators such as fatty alcohols such as guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, cetearyl alcohol, stearyl alcohol, oleyl alcohol, octyldodecanol, benzoate C12-C15 alcohols, acetylated lanolin alcohol, behenyl alcohol; fatty acids such as stearic acid; fatty acid esters such as myristyl stearate, lauryl lactate or glyceryl stearate; waxes including animal waxes, plant waxes, mineral or petroleum waxes such as beeswax, carnauba wax, microcrystalline wax, ceresin, ozocerite; silicium dioxide.
Preferred thickeners for the hydrous part include: polysaccharides or derivatives such as xanthan gum, guar gum, agar gum, alginates, gel Ian gum, carraghenan glucomannan; polyacrylates or homopolymers of reticulated acrylic acids or polyacrylamides such as carbomers, acrylate copolymers, acrylate / C10-C30-a I ky I acrylate crosspolymer, acrylate / beheneth-25 methacrylate copolymer; silicate derivatives such as magnesium silicates or aluminum silicates; cellulose derivatives such as hydroxypropyl cellulose;
pectines or modified cellulose such as hydroxycellulose or hydroxypropyl methylcellulose.
Preferred sensory enhancers include polyamide derivatives such as nylon-12; polymethyl methacrylates; silica; mica; poly methyl si I sesquioxane; polyethylene; starch derivatives such as aluminum starch octenylsuccinate; dimethicone derivatives; boron nitride;
HDI / trimethylol hexyllactone crosspolymer; perlite.
Preferred humectants include
- 1,2 pentadiol;
- 1,2 hexandiol;
- 1,2 octandiol;
- 1,2 decandiol;
2-methyl-l,3-propandiol.
Preferred UV performance booster like scattering particles include any particles or microparticles that can scatter light in order to enhance the protection of the skin from UV- light but do not absorb UV-light like UV filters. Examples of UV performance booster like scattering particles include microcrystalline cellulose (such as SunSpheres™ BIO SPF Booster), calcium carbonate, hydroxyapatite, styrene/acrylates copolymer (such as SunSpheres™ powder), (microspherical) silica (such as Sunsil 130 L, Sunsil 130 NP, SOLESPHERE™ H-33 and SOLESPHERE™ H-53), and silica (and) cetyl alcohol (Sunsil- Oleol30).
Preferred film forming agents include anionic, zwitterionic, amphoteric and non-ionic polymers such as vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols,
acrylamidopropyl-trimethylammonium chloride/acrylate copolymers, octyl acrylamide/methyl methacrylate-tert-butylaminoethyl methacrylate/2- hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vi ny I py rro I ido n e/d i methy I a m i n oethy I methacrylate/vinyl caprolactam terpolymers, derivatized cellulose ethers and silicones.
Preferred alcohols are alcohols containing from 2 to 6 carbon atoms, preferably monoalcohols containing from 2 to 6 carbon atoms. Particularly preferred alcohols include ethanol, isopropanol, or mixtures thereof.
With regard to the present invention it is to be understood that preservatives can be present in the two-part composition in the anhydrous part and/or in the hydrous part.
Preferred preservatives include phenoxyethanol; benzyl alcohol; methyl-, ethyl-, propyl-, butyl-, and isobutylparaben; zingerone.
Further, with regard to the present invention it is to be understood that also perfumes can be present in the two-part composition in the anhydrous part and/or the hydrous part. Preferred perfumes are selected from the group consisting of limonene, citral, linalool, alpha-isomethylionon, geraniol, citronellol, 2-isobutyl-4-hydroxy-4-methyltetrahydropyrane, 2 -tert. -pentyl cyclo hexyl acetate, 3-methyl-5-phenyl-l-pentanol, 7 -acetyl -1,1, 3, 4, 4, 6- hexamethyltetraline, adipine acid diester, alpha-amylcinnamaldehyde, alpha-methylionon, amyl C butylphenylmethylpropionalcinnamal, amylsalicylate, amylcinnamylalcohol, anisalcohol, benzoin, benzylalcohol, benzylbenzoate, benzylcinnamate, benzylsalicylate, bergamot oil, bitter orange oil, butylphenylmethylpropioal, cardamom oil, cedrol, cinnamal, cinnamylalcohol, citronnellylmethylcrotonate, lemon oil, coumarin, diethylsuccinate, ethyllinalool, eugenol, evernia furfuracea extracte, evernia prunastri extracte, farensol, guajak wood oil, hexylcinnamal, hexylsalicylate, hydroxycitronellal, lavender oil, lemon oil, linaylacetate, mandarine oil, menthyl PCA, methylheptenone, nutmeg oil, rosemary oil, sweet orange oil, terpineol, tonka bean oil, triethylcitrate, vanillin and combinations thereof Perfumes
In connection with the above preferred embodiments, it is to be understood that if the anhydrous part and/or the hydrous part of the two-part composition comprise two or more
additional ingredients, combinations of the ingredients as defined above are also part of the invention.
The skilled person is able to select and adjust the ingredients of the anhydrous part and the hydrous part depending on the desired application of the solution or emulsion resulting after mixing of the anhydrous part and the hydrous part.
In one embodiment of the present invention, the anhydrous part a) contains only the compound according to formula (I) and the base. In connection with this embodiment, the anhydrous part a) of the two-part composition is solid. Further, in connection with this embodiment, all additional ingredients of the two-part composition are in the hydrous part. Thus, in one embodiment of the present invention, the two-part composition comprises a) an anhydrous part containing a base and at least one compound according to formula (I); and b) a hydrous part comprising water and at least one ingredient selected from bl), b2) , b3), b4), b5), b6), b7), b8), b9) and blO).
In another embodiment, the two-part composition comprises a) an anhydrous part containing a base and at least one compound according to formula (la); and b) a hydrous part comprising water, and at least one emulsifier b3), and optionally further ingredients selected from bl), b2), b4) , b5), b6), b7), b8), b9) and blO).
In another embodiment, the two-part composition comprises a) an anhydrous part containing a base and at least one compound according to formula (I); and b) a hydrous part comprising water, and at least one water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter b2) other than the compound of formula (I), at least one emulsifier b3), and optionally further ingredients selected from bl), b4) , b5), b6), b7), b8, b9 and blO).
In a preferred embodiment, the two-part composition comprises a) an anhydrous part containing sodium carbonate, preferably anhydrous sodium carbonate, and a compound according to formula (la); and b) a hydrous part comprising water, and at least one, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter b2) other than the compound of formula (I), at least one emulsifier b3), and optionally further ingredients selected from bl), b4), b5), b6), b7), b8), b9) and blO).
In a more preferred embodiment, the two-part composition comprises a) an anhydrous part containing sodium carbonate, preferably anhydrous sodium carbonate, and a compound according to formula (la); and b) a hydrous part comprising water, and at least 1, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter selected from the group consisting of 2-ethylhexyl-(2E)-3-(4- methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2 - [4- (d iethy I a m i no) -2 - hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4-bis-{[4- (2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-l,3,5 triazine (INCI bis-
ethyl hexyl oxy pheno I methoxy phenyl triazine), 4,4',4"- (1,3,5-triazi ne-2,4,6-triyltrii mi no)tris- benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), (RS)-2-ethylhexyl-2- hydroxybenzoate (INCI ethylhexyl salicylate), at least one emulsifier b3), and optionally further ingredients selected from bl), b4), b5), b6), b7), b8), b9) and blO).
In another embodiment of the present invention, the hydrous part b) contains only water and no other ingredients. In connection with this embodiment, all ingredients of the two- part composition are in the anhydrous part, such that only water has to be added to form the solution or emulsion for UV protection of keratin materials, in particular the skin. Depending on the additional ingredients al), a2), a3), a4), a5), a6), a7), a8) and/or a9) in the anhydrous part, the anhydrous part is solid, waxy, or liquid.
In one embodiment of the present invention, the two-part composition comprises a) an anhydrous part comprising a base and at least one compound according to formula (I) and at least one ingredient selected from al), a2), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part containing only water and no other ingredients.
In another embodiment, the two-part composition comprises a) an anhydrous part comprising a base and at least one compound according to formula (la), at least one additional oil soluble UV filter and/or liquid oil miscible UV filter and/or oil dispersible UV filter a2) other than the compound of formula (I), and at least one ingredient selected from al), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part containing only water and no other ingredients.
In a preferred embodiment, the two-part composition comprises a) an anhydrous part comprising sodium carbonate, preferably anhydrous sodium carbonate, and a compound according to formula (la), and at least one additional oil soluble UV filter and/or liquid oil miscible UV filter and/or oil dispersible UV filter a2) other than the compound of formula (I), and at least one ingredient selected from al), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part containing only water and no other ingredients.
In a more preferred embodiment, the two-part composition comprises a) an anhydrous part comprising sodium carbonate, preferably anhydrous sodium carbonate, and a compound according to formula (la), and an additional oil soluble UV filter and/or liquid oil miscible UV filter and/or oil dispersible UV filter selected from the group consisting of titanium dioxide, zinc oxide, and a combination thereof, at least one emulsifier a3), at least one film forming agent a6), and optionally further ingredients selected from al), a4), a5), a7), a8) and a9); and b) a hydrous part containing only water and no other ingredients.
In another embodiment of the present invention, the two-part composition comprises a) an anhydrous part comprising a base and at least one compound according to formula (I) and at least one ingredient selected from al), a2), a3), a4), a5), a6), a7), a8) and a9); and
b) a hydrous part comprising water and at least one ingredient selected from bl), b2) , b3), b4), b5), b6), b7), b8), b9) and blO). Depending on the additional ingredients al), a2), a3), a4), a5), a6), a7), a8) and/or a9) in the anhydrous part, the anhydrous part is solid, waxy, or liquid.
To provide an even higher protection against UV radiation, the anhydrous part and/or the hydrous part comprises at least one additional UV filter other than the compound of formula (I). In this connection, the additional UV filter other than the compound of formula (I) is preferably in the hydrous part b).
In one embodiment of the present invention, the two-part composition comprises a) an anhydrous part comprising a base and at least one compound according to formula (la), and at least one ingredient selected from al), a2), a3), a4), a5), a6), a7), a8) and a9); and b) a hydrous part comprising water, and at least one, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter b2) other than the compound of formula (I), and at least one ingredient selected from bl), b2), b3), b4), b5), b6), b7), b8), b9) and blO).
In a preferred embodiment of the present invention, the two-part composition comprises a) an anhydrous part comprising sodium carbonate, preferably anhydrous sodium carbonate, and at least one compound according to formula (la), at least one cosmetic oil al), at least one emulsifier a3), at least one consistency agent a5), and optionally further ingredients selected from a4), a6), and a7); and b) a hydrous part comprising water, and at least one, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter b2) selected from the group consisting of 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4- bis-{[4-(2-ethy I -hexyloxy) -2- hydroxy]-phenyl}-6-(4-methoxyphenyl)-l,3,5 triazine (INCI bis-ethylhexyloxyphenol meth oxy phenyl triazine), 4,4',4"-(l,3,5-triazine-2,4,6-triyltrii mi no) tris- benzoic acid -tris (2- ethylhexyl)ester (INCI ethylhexyl triazone), (RS)-2-ethylhexyl-2-hydroxybenzoate (INCI ethylhexyl salicylate), titanium dioxide, zinc oxide, at least one emulsifier b3), and optionally further ingredients selected from bl), b4), b5), b6), b7), b8), b9) and blO).
In a more preferred embodiment of the present invention, the two-part composition comprises a) an anhydrous part comprising sodium carbonate, preferably anhydrous sodium carbonate, and at least one compound according to formula (la), at least one cosmetic oil al), at least one emulsifier a3), at least one consistency agent a5), and optionally further ingredients selected from a4), a6), and a7); and b) a hydrous part comprising water, and at least one, preferably 1 to 3, more preferably 2 to 3, water soluble UV filter and/or water miscible UV filter and/or water dispersible UV filter
b2) selected from the group consisting of 2-ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4- bis-{[4-(2-ethy I -hexyloxy) -2- hydroxy]-phenyl}-6-(4-methoxyphenyl)-l,3,5 triazine (INCI bis-ethylhexyloxyphenol meth oxy phenyl triazine), 4,4',4"-(l,3,5-triazine-2,4,6-triyltrii mi no) tris- benzoic acid -tris (2- ethylhexyl)ester (INCI ethylhexyl triazone), (RS)-2-ethylhexyl-2-hydroxybenzoate (INCI ethylhexyl salicylate), titanium dioxide, zinc oxide, at least one emulsifier b3), at least one thickener b5), at least one film forming agent b6), at least one preservative b8), and optionally further ingredients selected from bl), b4), b7), b9) and blO).
As described above, MAA’s such as the compounds of formula (I) are biodegradable natural compounds. In particular, the compound of formula (la), shinorine, is biodegradable.
Therefore, the two-part composition of the present invention allows for a composition for UV protection, wherein at least one UV filter is biodegradable. In particular, the two-part composition of the present invention allows for a composition for UV protection, wherein all organic components of the anhydrous part and the hydrous part are biodegradable.
In one embodiment of the two-part composition of the present invention, the organic components of the anhydrous part a) and the hydrous part b) are partially biodegradable. Partial biodegradability is defined as having a biodegradability of from 20 % to 60 % by OECD 301 F.
Thus, in one embodiment of the two-part composition of the present invention, the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of from 20 % to 60 % by OECD 301 F.
In another embodiment of the two-part composition of the present invention, the organic components of the anhydrous part a) and the hydrous part b) are readily biodegradable. Ready biodegradability is defined as having a biodegradability of larger or equal to 60 % by OECD 301 F.
Thus, in another preferred embodiment of said two-part composition, the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of larger or equal to 60 % by OECD 301 F.
It is to be understood that the property of biodegradability, partial biodegradability, or ready biodegradability in the above embodiments refers to the biodegradability, partial biodegradability, or ready biodegradability of each individual organic component of the anhydrous part a) and the hydrous part b) and not of a mixture of two or more individual organic components.
As indicated above, the solution or emulsion to apply to the keratin materials for UV- protection can easily and quickly be prepared by mixing the anhydrous part and the hydrous part of the two-part composition before application to the keratin material. In particular, the
homogeneous solution or emulsion is formed after mixing of the anhydrous part and the hydrous part for less than 30 seconds, even within 10 seconds.
Thus, in one aspect, the present invention relates to a process for the UV-protection of keratin materials, comprising mixing the anhydrous part and the hydrous part of the two- part composition together to form a solution or emulsion before applying the solution or emulsion to the keratin materials.
If all ingredients of the two-part composition, except for water, are in the anhydrous part, only water has to be added to form the solution or emulsion for UV protection of the keratin materials.
Thus, in one embodiment, the present invention relates to a process for the UV-protection of keratin materials, comprising mixing the anhydrous part and water to form a solution or emulsion before applying the solution or emulsion to the keratin materials.
For the processes for the UV-protection of keratin materials, the preferred embodiments defined above, in particular regarding the compound of formula (I), the base, the water content, the anhydrous part, the hydrous part and the optional additional ingredients, are also preferred.
In one aspect, the present invention relates to the use of the two-part composition for UV- protection of keratin materials, preferably the skin. For the use of the two-part composition for UV-protection of keratin materials, the preferred embodiments defined above, in particular regarding the compound of formula (I), the base, the water content, the anhydrous part, the hydrous part and the optional additional ingredients, are also preferred. In a preferred embodiment of the use of the two-part composition, said two-part composition has an UV-A protection, which is at least one third of the sun protection factor as defined above. For example, if the sun protection factor of a two-part composition is 30, the UV-A protection of the given two-part composition has to be at least 10. In another preferred embodiment of the use of the two-part composition, the UV-A protection of said two-part composition as defined above has to show a critical wavelength of at least 370 nm. In another preferred embodiment of the use of the two-part composition as defined above, said two-part composition has an UV-A protection, which is at least one third of the sun protection factor as defined above, and shows a critical wavelength of at least 370 nm.
In addition to UV protection, the two-part composition of the present invention provides whitening/lightening, anti-aging, in particular anti-fine line, and anti-inflammation benefits for the skin.
In connection with the above embodiments, it is to be understood that the two-part composition as defined herein, in particular the solution or emulsion prepared by mixing the anhydrous part and the hydrous part of the two-part composition according to the invention
is particularly suitable for protection of keratin materials, in particular the skin, from UV radiation.
Thus, the present invention relates in one embodiment to the use of the two-part composition as defined herein (including all embodiments thereof as described herein) as a body-care product, preferably a sunscreen-composition. In particular, the present invention relates in one embodiment to the use of the solution or emulsion prepared by mixing the anhydrous part and the hydrous part of the two-part composition as defined herein (including all embodiments thereof as described herein) as a body-care product, preferably a sunscreen-composition. In connection with this embodiment, the two-part composition as defined herein is used for protection of the keratin material, in particular the skin, from UV radiation.
In another aspect, the present invention relates to the use of the two-part composition as light stabilizer in cosmetic compositions, home-care compositions, cleaning compositions or agrochemical compositions.
UV-light can also have negative effects on the integrity and the durability of other materials and products such as active raw materials in agrar formulations, food (such as fruit and vegetables), body-care products, household cleaning and treating agents, polymers, plastics, coatings, ink printing, packaging, paint, lacquer, and textiles. Thus, the two-part composition of the present invention can also be used for UV-protection of active raw materials in agrochemical formulations, food (such as fruit and vegetables), body-care products, household cleaning and treating agents, polymers, plastics, coatings, ink printing, packaging, paint, lacquer, and textiles.
In particular, it is to be understood that the compounds of formula (I), in particular the compound of formula (la), are suitable as light stabilizers. Thus, the two-part composition of the present invention provides a composition with improved photostability. In one embodiment, the two-part composition of the present invention provides a body-care product or household cleaning and treating agent, preferably a sunscreen composition, with improved photostability. In connection with this embodiment, the two-part composition as defined herein is used for protecting the body-care product or the household cleaning and treating agents from UV degeneration.
The present invention is further illustrated by the following examples.
Examples
With regard to the examples provided below it is to be understood that shinorine was used in the form of shinorine hydrate as described in detail above and in JP2018052883A. Further, it is to be understood with regard to the examples provided below that if not specifically indicated otherwise % refers to % by weight.
Example 1: Stability tests of Shinorine solution in water at room temperature
Shinorine was dissolved in water resulting in a composition of 20 % Shinorine and 80 % water. The solution was stored at room temperature in a closed 10 mL glass bottle for certain time periods (0 days, 1 day, 3 days, 7days, 10 days, 14 days, 21 days and 42 days). For Sample A the solution was purged with nitrogen to displace oxygen. Sample B was kept with air contact. The color change of sample A and sample B was observed during the storage time at certain time periods. If the formulations are stored for more than 24 hours a color change from colorless/l ight brown into dark brown can be observed for all samples.
Example 2: Degradation of Shinorine in water
Shinorine was dissolved in water. The initial acidic solution after dissolving of Shinorine was neutralized by addition of approximately 1 equivalent of NaOH. The concentration of Shinorine (in anionic form) is adjusted to 9-10 % by weight. The samples were stored in closed vials at different temperatures. The concentration of Shinorine was determined by HPLC at different times. The results of the measurement of the concentration of Shinorine at different times by HPLC is shown in Table 1 below and Figure 1 and 2.
Table 1:
d=days; RT = room temperature
Sample C (40° C) and Sample D (50° C) further showed a discoloration at 7 days of storage, wherein at a time of 0 days the solution was a clear colorless solution and after 7 days turned into a dark brown solution.
Sample C (40° C) and Sample D (50° C) further showed a discoloration at 7 days of storage, wherein at a time of 0 days the solution was a clear colorless solution and after 7 days turned into a dark brown solution.
Example 3: Shinorine storage stability
Discoloration of the respective solutions was assessed by visual inspection. Shinorine hydrate is a white to slightly yellow powder.
Shinorine in powdered form was stored for 67 days at room temperature and 50 ° C in a closed container. There was no significant discoloration observable.
The mixtures of Shinorine and anhydrous Na2CO3, NaHCO3, CaCO3, MgCO3, or CaO as a base as shown in Table 2.1 - 2.5 below were stored for 55 - 67 days at room temperature and 50° C in a closed container. There was no significant discoloration observable.
In the presence of water, the mixtures formed a clear colorless solution and a pH value in the skin-friendly range of 4.5-8 could be achieved.
A suspension of Shinorine and the corresponding base as described above in the solvent dibutyl adipate (Cetiol® B) as shown in Table 2.1 - 2.5 below was stored for 55 - 67 days at room temperature and 50 ° C in a closed container. There was no significant discoloration observable.
Table 2.1:
7T = room temperature
Table 2.2:
7T = room temperature
Table 2.3:
Table 2.4:
Table 2.5:
7T = room temperature
Two-part compositions
Composition la
Process of manufacture of two-part composition
The ingredients of part I as shown in Table l.a below were heated to 100° C under stirring until complete dissolution. The solution was cooled to room temperature under stirring and subsequently stored in a closed container. The ingredients of part II as shown in Table l.a below were incorporated at room temperature in a closed container, wherein humidity should be avoided. The anhydrous part (part II) and the hydrous part (part I) were stored in separate containers until used. For usage, part I and part II were mixed immediately before
use by incorporating part I I into part I and shaking of the container by hand until complete dissolution. The obtained solution has a pH of 7.5 without the requirement of further adjustment. The emulsion is applied to the skin as soon as it is homogeneous. Table l.a
Composition la: Clear microemulsion (Hydrous part liquid / Anhydrous part solid)
Second compartment (part I I) comprising Shinorine (anhydrous) was colorless (white) and remained white after 1-month storage at 50° C. First compartment (part I) comprising water and the remaining ingredients was colorless and remained colorless after 1-month storage at 50° C.
Final formulation before usage obtained by mixing part I and part II was white.
Comparative Composition la:
For comparative Composition la the ingredients of part I and part I I of Composition la were mixed as a final formulation and stored at 50 ° C for 8 days. The results of the appearance of the final formulation during the storage time at different temperatures are shown in Table 1.1. a below.
Table 1.1. a
7T = room temperature; d = days
Composition lb:
Process of manufacture of two-part composition
The ingredients of part I as shown in Table l.b below were heated to 100° C under stirring until complete dissolution. The solution was cooled to room temperature under stirring and subsequently stored in a closed container. The ingredients of part II as shown in Table l.b below were incorporated at room temperature in a closed container, wherein humidity should be avoided. The anhydrous part (part II) and the hydrous part (part I) were stored in separate containers until used. For usage, part I and part I I were mixed immediately before use by incorporating part I I into part I and shaking of the container by hand until complete dissolution. The obtained solution has a pH of 7.5 without the requirement of further adjustment. The emulsion is applied to the skin as soon as it is homogeneous.
Table l.b:
Composition lb: Clear microemulsion (Hydrous part liquid / Anhydrous part solid)
Second compartment (part I I) comprising Shinorine (anhydrous) was colorless (white) and remained white after 1-month storage at 50° C. First compartment (part I) comprising
water and the remaining ingredients was colorless and remained colorless after 1-month storage at 50° C.
Final formulation before usage obtained by mixing part I and part II was white.
Comparative Composition lb:
For comparative Composition lb the ingredients of part I and part II of Composition lb were mixed as a final formulation and stored at 50 ° C for 31 days. The results of the appearance of the final formulation during the storage time at 50° C are shown in Table 1.1. b below.
Table 1.1. b:
d = days
UV performance of Composition lb
UV performance of Composition lb was assessed by applying the finished formulation (obtained by mixing part I and part II) on PMMA (polymethyl acrylate) plates and in vitro SPF was measured according to the following method.
Method to assess in vitro Sun Protection Factor (SPF)
End-product application rate 1.3 mg/cm2 on sandblasted PMMA plates (Helioscience ®). UV transmittance analysis with Labsphere UV-1000S Transmittance Analyser. The SPF value was calculated according to the following calculation
wherein E% = erythema action spectrum; S% = solar spectral irradiance and T% = spectral transmittance of the sample.
The UV performance of Composition lb was measured directly after mixing part I of the first compartment and part II of the second compartment (T=0) and after storage of the finished formulation at 50° C for 8 days and 31 days. The finished formulation after storage showed a significant loss of sun protection performance over time due to the degradation of Shinorine in formulations comprising water. The results of the SPF measurement are shown in Table 1.2. b below and Figure 3.
Table 1.2.b:
d = days
Composition 2a
Process of manufacture of two-part composition
The ingredients of part I and part II as shown in Table 2. a below were heated to 100° C under stirring and part I was added into part II and homogenized. The solution was cooled to room temperature under stirring and subsequently stored in a closed container (first compartment, hydrous part). The powdered ingredients of part IV as shown in Table 2. a below were dispersed in oil (preferably by oil milling). The ingredients of part III as shown Table 2. a below were mixed and heated to 75° C until completely dissolved. Part III was cooled down to 45-50° C and part IV was added under stirring until the mixture becomes liquid. The resulting oil suspension was stored in a closed container, wherein humidity should be avoided (second compartment, anhydrous part).
First compartment (hydrous part) and second compartment (anhydrous part) were stored in separate containers until usage.
A precise dosage dispenser with two distinct orifices was used to deposit 80% of first compartment (hydrous part) on skin and 20% of second compartment (anhydrous part). Both parts were mixed just before use by spreading the product on the skin. The pH value of the resulting formulation was 7.5 without the requirement of further adjustment.
Table 2. a:
Composition 2a: Boite de Pandore (Hydrous part liquid / anhydrous part liquid)
Method to assess in vitro Sun Protection Factor (SPF)
The method of assessing the in vitro SPF is as described above for Composition lb.
The UV performance of Composition 2a was measured by depositing on PMMA plates 80% of first compartment (hydrous part) and 20% of second compartment (anhydrous part). Both parts were mixed just before use by spreading the product on the PMMA plates and in vitro SPF was measured according to the method described for Composition lb.
Composition 2a has an in vitro SPF of 51.
Composition 2b
The ingredients of part I and part II as shown in Table 2.b below were heated to 100° C under stirring and part I was added into part II and homogenized. The emulsion was cooled to room temperature under stirring and subsequently stored in a closed container (first compartment, hydrous part). The powdered ingredients of part IV as shown in Table 2.b below were dispersed in oil (preferably by oil milling). The ingredients of part III as shown Table 2.b below were mixed and heated to 75° C until completely dissolved. Part III was cooled down to 45-50° C and part IV was added under stirring until the mixture becomes liquid. The resulting oil suspension was stored in a closed container, wherein humidity should be avoided (second compartment, anhydrous part).
First compartment (hydrous part) and second compartment (anhydrous part) were stored in separate containers until usage.
A precise dosage dispenser with two distinct orifices was used to deposit 80% of first compartment (hydrous part) on skin and 20% of second compartment (anhydrous part). Both parts were mixed just before use by spreading the product on the skin. The pH value of the resulting formulation was 7.15.
Table 2.b:
Composition 2b : Biodegradable Bofte de Pandore (Hydrous part liquid / anhydrous part liquid)
Second compartment (anhydrous part) comprising Shinorine was white. First compartment (hydrous part) comprising O/W emulsion was yellow. Finished formulation (comprising anhydrous and hydrous part) was yellow. First compartment (hydrous part) and second compartment (anhydrous part) were stored separately at 50° C for 30 days and did not show a significant color change. The final formulation obtained by mixing the two compartments before use (T=0) did also not show a significant color change.
Final formulation obtained by mixing the two compartments (Shinorine in contact with water) not directly applied but stored at 50 ° C for 30 days turned brown and lead to discoloration of Shinorine in water containing formulations. The results of the evaluation of the appearance are shown in Table 2.1.b below.
Table 2.1.b:
d = days
All organic ingredients, in particular the organic UV filters, used for Composition 2b are biodegradable as shown in Table 2.2. b below.
Table 2.2. b:
Composition 3
Process of manufacture of two-part composition Part II was prepared by milling Shinorine as shown in Table 3 below, for example in a mortar, until a fine powder was obtained. The obtained powder was mixed with the other ingredients of part II as shown in Table 3 below until a homogeneous mixture was obtained. Subsequently part II was mixed with the ingredients of part III as shown in Table 3 below and the resulting waxy mixture was stored in a closed container, wherein humidity should be avoided (second compartment: Anhydrous part).
Water of part I as shown in Table 3 below (first compartment: Hydrous part) was added just before use and subsequently shaken by hand until a homogeneous emulsion at pH 7.5 was obtained. The resulting emulsion was obtained quickly after combining the anhydrous part and the hydrous part.
Composition 3 comprises only biodegradable and mineral UV filters.
Table 3:
Composition 3: Ecofriendly dry formulation ready to go (Hydrous part liquid (only water) / Anhydrous part solid)
Second compartment (part II and part III) comprising Shinorine (anhydrous) was colorless (white) and remained white after 1-month storage at 50° C. First compartment (part I) comprising water was colorless and remained colorless after 1-month storage at 50° C.
Final formulation before usage obtained by mixing first and second compartment was white.
All organic ingredients, in particular the organic UV filters, used for Composition 3 are biodegradable as shown in Table 3.1 below.
Table 3.1:
Comparative Composition 3: For comparative Composition 3 the ingredients of the first and second compartment of Composition 3 were mixed as a final formulation and stored at 50 ° C for 30 days. The results of the measurement of the pH value and the appearance of the final formulation during the storage time at 50° C (0 days and 30 days) are shown in Table 3.1. below.
Table 3.1.:
d = days
Composition 4
Process of manufacture of two-part composition
The ingredients of part I and part II as shown in Table 4 below were heated to 75° C under stirring and part II was added into part I slowly under stirring and was further homogenized. The solution was cooled to room temperature under stirring and subsequently stored in a closed container (first compartment, hydrous part). The powdered ingredients of part IV as shown in Table 4 below were dispersed in oil (preferably by oil milling). The ingredients of part III as shown Table 4 below were mixed and heated to 75° C until completely dissolved. Part III was cooled down to 45-50° C and phase IV was added under stirring until the mixture becomes liquid. The resulting oil suspension was stored in a closed container, wherein humidity should be avoided (second compartment, anhydrous part).
First compartment (hydrous part) and second compartment (anhydrous part) were stored in separate containers until usage. For usage, the anhydrous part and the hydrous part were mixed immediately before use.
Table 4:
Hydrous part liquid / anhydrous part liquid
Composition 5
Process of manufacture of two-part composition The ingredients of part I and part II as shown in Table 5 below were heated to 80° C under stirring and part I was added into part II under stirring and was further homogenized. The solution was cooled to room temperature under stirring and subsequently stored in a closed container (first compartment, hydrous part). The powdered ingredients of part IV as shown in Table 5 below were dispersed in oil (preferably by oil milling). The ingredients of part III as shown Table 5 below were mixed and heated to 75° C until completely dissolved. Part III was cooled down to 45-50° C and phase IV was added under stirring until the mixture becomes liquid and cooled down to room temperature. The resulting oil suspension was
stored in a closed container, wherein humidity should be avoided (second compartment, anhydrous part).
First compartment (hydrous part) and second compartment (anhydrous part) were stored in separate containers until usage. For usage, the anhydrous part and the hydrous part were mixed immediately before use.
Table 5: Hydrous part liquid / anhydrous part liquid
Claims
1. A two-part composition comprising a) an anhydrous part comprising a base and at least one compound according to formula (I)
or a salt, hydrate, stereoisomer, tautomer or N-oxide thereof, wherein
X is NRN;
RN is C1-C4-alkyl-ORa, or C1-C4-alkyl-(C=O)ORa, wherein each substitutable carbon atom in the aforementioned groups is independently unsubstituted or substituted with one or more, same or different substituents Rx;
R1 is C1-C2-alkyl;
R2 is H;
R3 is C1-C3-alkyl-(C=O)ORa;
R4 is H or ORa;
Rx is C(=O)ORa, or C1-C2-alkyl; and
Ra is H; and optionally al) cosmetic oils; a2) UV filters; a3) surfactants and/or emulsifier; a4) sensory enhancers; a5) consistency agents; a6) film forming agents; a7) UV performance booster like scattering particles; a8) preservatives; and/or a9) perfumes and b) a hydrous part comprising at least water, and optionally bl) alcohols; b2) UV filters; b3) surfactants and/or emulsifier; b4) sensory enhancers; b5) thickeners; b6) film forming agents; b7) UV performance boosters; b8) preservatives; b9) humectants; and/or blO) perfumes; and wherein the anhydrous part and the hydrous part are separate.
2. The two-part composition according to claim, wherein said compound of formula (I) is a compound according to the following formula
3. The two-part composition according to one of claims 1 or 2, wherein the anhydrous part comprises the compound of formula (I) in an amount of from 0.1 % to 20 % by weight, based on the total weight of the two-part composition, in particular wherein the anhydrous part comprises the compound of formula (I) in an amount of from 1 % to 8% by weight, based on the total weight of the two-part composition.
4. The two-part composition according to any one of claims 1 to 3, wherein the base of the anhydrous part a) is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, alanine, ammonium carbonate, ammonium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, calcium oxide and choline, preferably wherein the base is anhydrous.
5. The two-part composition according to any one of claims 1 to 4, wherein the base of the anhydrous part a) is selected from the group consisting of sodium bicarbonate and sodium carbonate, preferably anhydrous sodium bicarbonate and anhydrous sodium carbonate.
6. The two-part composition according to any one of claims 1 to 5, wherein the composition comprises the base of the anhydrous part a) in an amount of from 0.1 % to 3 % by weight, preferably in an amount of from 0.3 % to 2.5 % by weight, based on the total weight of the two-part composition and/or wherein the hydrous part of the composition comprises water in an amount of from 3 % to 70 % by weight, based on the total weight of the two-part composition.
7. The two-part composition according to any one of claims 1 to 6, wherein the UV filter comprised in the hydrous part is selected from the group consisting of [(3Z)-3-[[4-[(Z)-[7,7- di methyl -2-oxo-l- (sulfomethyl) -3- bicyclo [2.2.1] hepta nylidene] methyl] phenyl] methyl idene]- 7,7-dimethyl-2-oxo-l-bicyclo[2.2.1]heptanyl]methanesulfonic acid (INCI terephthalylidene dicamphor sulfonic acid), 2-phenyl-lH-benzimidazole-5-sulfonic acid (INCI phenylbenzimidazole sulfonic acid), disodium phenyl dibenzimidazole tetrasulfonate, 2- ethylhexyl-(2E)-3-(4-methoxyphenyl)acrylate (INCI ethylhexyl methoxy cinnamate), hexyl 2- [4-(diethylamino)-2-hydroxybenzoyl]benzoate (INCI diethylamino hydroxybenzoyl hexyl benzoate), 2,4- bis-{[4-(2-ethy I -hexyl oxy) -2 -hydroxy] -phenyl] -6- (4- meth oxy phenyl) -1,3,5 triazine (INCI bis-ethylhexyloxyphenol methoxyphenyl triazine), 4,4',4"-(l,3,5-triazine-2,4,6- triy I tri i m i n o) tris- benzoic acid-tris(2-ethylhexyl)ester (INCI ethylhexyl triazone), (RS)-2- ethylhexyl-2-hydroxybenzoate (INCI ethylhexyl salicylate), titanium dioxide, zinc oxide and combinations thereof.
8. The two-part composition according to any one of claims 1 to 7, wherein the UV filter comprised in the anhydrous part is selected from the group consisting of l-(4-(l,l- di methylethyl) phenyl) -3- (4- methoxyphenyl) propane-1, 3-dione (INCI butyl meth oxydi benzoyl methane), 2-(2H-benzotriazol-2-yl)-6-[(2-ethylhexyloxy)methyl]-4- m ethyl ph eno I, 2-(2H -benzotriazol -2-yl) -4- methyl -6- [2- methyl -3- [1,3,3,3-tetramethy 1-1- [(t ri m ethy I s i ly I) oxy] - 1 -d isi I oxa ny I] pro py I] ph e no I (INCI drometrizole trisiloxane), titanium dioxide, zinc oxide, and combinations thereof.
9. The two-part composition according to any one of claims 1 to 8, wherein the hydrous part b) contains only water and no other ingredients.
10. The two-part composition according to any one of claims 1 to 9, wherein the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of from 20 % to 60 %, as measured by OECD 301 F testing.
11. The two-part composition according to any one of claims 1 to 10, wherein the organic components of the anhydrous part a) and the hydrous part b) have a biodegradability of larger or equal to 60 %, as measured by OECD 301 F testing.
12. A process for preparing a ready-to-use cosmetic composition comprising the steps of mixing the anhydrous part and the hydrous part of the two-part composition as defined in any one of claims 1 to 12 together to form a solution or emulsion.
13. A two-part composition as defined in any one of claims 1 to 12 for use in UV- protection of keratin materials.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP24182263.4 | 2024-06-14 | ||
| EP24182263 | 2024-06-14 |
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| WO2025257308A1 true WO2025257308A1 (en) | 2025-12-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2025/066379 Pending WO2025257308A1 (en) | 2024-06-14 | 2025-06-12 | Biodegradable two-part composition for skin protection against uv radiation |
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| WO (1) | WO2025257308A1 (en) |
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| EP3144392A1 (en) | 2014-05-13 | 2017-03-22 | The Kitasato Institute | Method for producing mycosporine-like amino acid using microbes |
| JP2018052883A (en) | 2016-09-29 | 2018-04-05 | 株式会社林原 | Shinorine hydrated crystal, and composition, production method and application of the same |
| JP6719267B2 (en) | 2016-04-27 | 2020-07-08 | 長瀬産業株式会社 | Solution containing stabilized mycosporine-like amino acid and method for producing the same |
| WO2021056412A1 (en) | 2019-09-27 | 2021-04-01 | L'oreal | Two-part composition for caring for keratin materials |
| WO2024027926A1 (en) * | 2022-08-05 | 2024-02-08 | Symrise Ag | Composition comprising a uv-filter stabilizer |
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2025
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| EP3144392A1 (en) | 2014-05-13 | 2017-03-22 | The Kitasato Institute | Method for producing mycosporine-like amino acid using microbes |
| JP6719267B2 (en) | 2016-04-27 | 2020-07-08 | 長瀬産業株式会社 | Solution containing stabilized mycosporine-like amino acid and method for producing the same |
| JP2018052883A (en) | 2016-09-29 | 2018-04-05 | 株式会社林原 | Shinorine hydrated crystal, and composition, production method and application of the same |
| WO2021056412A1 (en) | 2019-09-27 | 2021-04-01 | L'oreal | Two-part composition for caring for keratin materials |
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