220082 Composition with improved SPF and UVA photoprotection Technical field [0001] The present invention relates to sunscreen products, cosmetic and pharmaceutical preparations or homecare products having UVA and/or UVB protection comprising an organic UV-filter and a certain mycosporine-like amino acid compound. The products and preparations provide improved SPF performance and UVA photoprotection. In addition, the products and preparations according to the present invention provide broad-spectrum photo-protection from UV radiation. Additionally, the present invention relates to the use of such mycosporine-like amino acid compound for boosting SPF and UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an organic UV-filter. Furthermore, the present invention relates to a method of enhancing the SPF and UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an organic UV-filter by the addition of a certain mycosporine-like amino acid compound. Finally, the present invention relates to a method of providing anti-aging benefits to skin, whitening or preventing darkening of skin, improving the appearance of skin, diminishing the visible signs of skin aging and improving skin’s radiance and firmness by topically applying the sunscreen product or cosmetic or pharmaceutical preparation according to the present invention to the skin. Background Art [0002] The negative effects of exposure of UV light are well-known. Prolonged exposure to sunlight causes damage such as sunburn to the skin and dries out hair making it brittle. When skin is exposed to UV light having a wavelength of from 290 nm to 400 nm, long term damage can lead to serious conditions such as skin cancer, the type of damage depending on the wavelength of the radiation. [0003] Sunlight includes two types of UV rays: long wave ultraviolet A (UVA: wavelength 320 to 400 nm) and shortwave ultraviolet B (UVB: wavelength 280 to 320 nm). UVA is
220082 further divided into two wavelength ranges namely UVA1 (340 to 400 nm) and UVA2 (320 to 340 nm). [0004] UVA rays account for the majority (95 %) of UV radiation. They have longer wavelength than UVB and UVC rays which means they have less energy (shorter wavelengths have more energy than longer wavelengths). Due to their longer wavelength, they can penetrate into the dermis which is predominantly made up of collagen. When UVA rays are absorbed by the skin they create free radicals which can damage cells and DNA and break down collagen. This is why UVA rays are highly associated with premature aging. The skin damage caused by UVA radiation accelerates the appearance of aging, for example, loss of skin elasticity and the appearance of wrinkles. This process is commonly referred to as photo-aging. As skin ages, the outer skin layer (epidermis) thins, even though the number of the cells remain largely unchanged. The number of pigment-containing cells (melanocytes), however, decreases. Therefore, the skin appears pale and translucent. Large pigment spots (age spots, liver spots or lentigos) may appear in the sun-exposed areas. Changes in the connective tissue reduce the skin’s strength and elasticity, which becomes more noticeable in sun-exposed areas (solar elastosis). Elastosis produces a leathery, weather-beaten appearance common to farmers and sailors, which spend a large amount of time outdoors. Moreover, UVA radiation can trigger phototoxic or photo allergic skin reactions. [0005] UVB rays account for less than 5 % of UV radiation and, due to their shorter wavelength, can only penetrate the epidermis. Here, they are directly absorbed by DNA and melamine and can cause gene mutations that, if not corrected by the cells’ natural defense can lead to the rapid multiplication of mutated cells and eventually result in skin cancer. The damage done by UVB rays can be seen almost immediately in the form of sunburn, an inflammatory response to the skin damage. [0006] UVC rays are by far the most damaging of the three types of UV rays. However, they are entirely absorbed by the atmosphere due to their short wavelength and, thus, are unable to reach our skin.
220082 [0007] To attenuate these negative effects of UV-radiation, i.e. for the purpose of protecting the skin and keratin materials against UV-radiation, anti-sun/sunscreen compositions comprising screening agents that are active in the UVA range and in the UVB range, i.e. within the full range of 280 nm to 400 nm, are generally used. [0008] UV-filters are compounds which have a pronounced absorption capacity for ultraviolet radiation. They are used especially in sunscreen products, cosmetic, dermatological or pharmacological preparations or homecare products, but also to improve the light fastness of industrial products, such as paints, varnishes, plastics, textiles, polymers such as, for example, polymers and copolymers of mono- and di- olefins, polystyrenes, polyurethanes, polyamides, polyesters, polyurea and polycarbonates, packaging materials and rubbers. [0009] The UV-filters are classified as UVA-filters and UVB filters depending on the location of their absorption maxima; if a UV-filter absorbs both UVA and UVB, it is referred to as a UVA/UVB broadband absorber or UVA/UVB broadband filter. [0010] In order to achieve the desired maximum protection from UV-radiation sunscreen products or cosmetic, especially dermatological, and pharmacological preparations are formulated to contain a mixture of UV-filters with varying concentrations and the choice of UV-filters used is determined by the legislation within the country or economic area. For example, UV-filters which can be used for the protection of skin are regulated in the USA by the America FDA via their OTC monograph system and are regulated in the European Union by the Cosmetic Regulation. Regulations covering the use of UV-filters exist in other countries and regions as well. These regulations not only stipulate the filters which can be used but also fix a maximum usage level for each UV-filter. [0011] In order to achieve a broad-spectrum of UV protection, sunscreen formulations typically comprise a combination of several organic UV-filters, which may be supplemented with inorganic UV-filters in order to increase the efficacy.
220082 [0012] However, the use of organic UV-filters is subject to continuously increasing concerns because they are suspected to be a possible cause of skin irritations and allergies in sensitive person and their potentially harmful effect on the environment. In addition, some organic UV-filters suffer from photo-instability. [0013] The number of known UVA-filters and especially approved UVA-filters is small and therefore products are limited in what UVA-filters can be used to provide broad- spectrum protection. [0014] Thus, there is still an ongoing need to provide further substances which improve SPF performance and UVA photoprotection of sunscreen products, cosmetic or pharmaceutical preparations or homecare products comprising an organic UV-filter. [0015] Accordingly, it is the object of the present invention to provide organic UV-filter comprising sunscreen products, cosmetic or pharmaceutical preparations or homecare products having UVA and/or UVB protection which exhibit an improved SPF performance as well as an improved UVA photoprotection. It would be desirable that the sunscreen products, cosmetic or pharmaceutical preparations or homecare products provides an improved UV-filter performance, in particular UVA photoprotection, and thus, may allow to reduce the amount of organic UV-filter agent without affecting the envisaged SPF. [0016] It is another object of the present invention to provide the use a substance, for boosting the SPF performance and UVA photoprotection in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an organic UV- filter. [0017] It is still another object of the present invention to provide a method of enhancing or boosting SPF performance and UVA photoprotection in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an organic UV-filter. [0018] It is a further object of the present invention to provide a method of providing anti- aging benefits to skin, whitening or preventing darkening of skin, improving the
220082 appearance of skin, diminishing the visible signs of skin aging and improving skin’s radiance and firmness by a sunscreen product of cosmetic or pharmaceutical preparation comprising an organic UV-filter. [0019] Surprisingly, it has been found that the SPF performance and the UVA photoprotection in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product having UVA and/or UVB protection can be significantly improved by the addition of a certain mycosporine-like amino acid compound. [0020] The problem is solved by the subject matter of the independent patent claims. Further aspects of the present invention are however also apparent from the wording of the dependent patent claims, the following detailed description in conjunction with the accompanying examples and figures. Summary of the invention [0021] In order to accomplish the above problem, the present invention provides in a first aspect a sunscreen product, a cosmetic or pharmaceutical preparation or a homecare product, comprising or consisting of (a) at least one primary organic UV-filter; (b) at least one mycosporine-like amino acid compound, represented either by the general formula (I)

formula (I), as defined herein, or a tautomer or a salt thereof; or
220082 represented by the general formula (II)

formula (II), as defined herein, or a tautomer or a salt thereof; or any mixture of the afore-mentioned compounds. [0022] In a second aspect, the present invention provides for the use of at least one mycosporine-like amino acid compound (b) as defined herein or a mixture thereof for boosting the SPF performance and the UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising at least one organic UV-filter. [0023] In a still further aspect, the present invention relates to a method of enhancing or boosting the SPF performance and the UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising at least one organic UV-filter, said method comprising the addition of an effective amount of a mycosporine-like amino acid compound (b) as defined herein or a mixture thereof to said sunscreen product, cosmetic or pharmaceutical preparation or homecare product. [0024] Finally, the present invention relates to a method of providing anti-aging benefits to skin, whitening or preventing darkening of skin, improving the appearance of skin, diminishing the visible signs of skin aging and improving skin’s radiance and firmness by topically applying the sunscreen product or cosmetic or pharmaceutical preparation according to the present invention to the skin or hair.
220082 Detailed description of the invention [0025] In the context of the present invention, the following general meanings apply: [0026] The terms “comprising”, “including”, and “containing” are to be understood as open-ended terms and mean that the named components following said term are essential but not “limited to”, and other components may be added and are still embraced by the present invention. [0027] The term “consisting of” as used according to the present invention means that the total amount of components (a) and (b) adds up to 100 % by weight, based on the total weight of the sunscreen product, cosmetic or pharmaceutical preparation or homecare product, and signifies that the subject matter is closed-ended and can only include the limitations that are expressly recited. [0028] Whenever reference is made to “comprising” it is intended to cover both meanings as alternatives, that is the meaning can be either “comprising” or “consisting of” unless the context dictates otherwise. [0029] The term “at least one …compound” means that the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention can comprise either one of said subsequently described individual compound or a mixture of two, three, four, five, six or even more different of said subsequently compounds. [0030] The term “optionally” means that the subsequently described compound may but need not to be present in the composition, and that the description includes variants, where the compound is included or variants, where the compound is absent. [0031] A “sunscreen product” in the context of the present invention, also known as sunblock, sun cream or suntan lotion, is a photoprotective topical product for the skin including UV-filter compounds that absorbs or reflects some of the sun's ultraviolet (UV) radiation and thus helps protect against sunburn and most
220082 importantly prevent skin cancer. Sunscreens come as lotions, sprays, gels, foams (such as an expanded foam lotion or whipped lotion), sticks, powders and other topical products. UV-absorbing compounds are used not only in sunscreen, but also in other personal care products, such as lipstick, shampoo, hair spray, body wash, toilet soap, and insect repellent. [0032] The term “cosmetic or pharmaceutical preparations” in the context of the present invention are compositions for cosmetic or pharmaceutical purposes which contain a UV- filter in order to protect skin or hair against UV-radiation. In addition to providing photo- protection, the cosmetic or pharmaceutical preparations according to the present invention are useful for providing anti-aging benefits to skin, whitening or preventing darkening of skin, improving appearance of skin, diminishing the visible signs of skin aging and improving skin’s radiance and firmness. [0033] The term “homecare products” in the context of the present invention are the essentials for daily care and cleaning purpose in households. They are used for maintaining hygiene and a good aura of the homes. The home care products generally include include laundry detergents (powder, liquid and tablet), fabric conditioners, dishwashing detergents (liquid and tablet), hard floor and surface cleaners, glass cleaners, carpet cleaners, oven cleaners, air fresheners, disinfectants, stain removers, car wash products. These products are usually manufactured in the form of a liquid, powder, spray, granules and others. Such formulations prevent premature photodamage and photobleaching to surfaces and the homecare product itself. [0034] The sunscreen products, cosmetic or pharmaceutical preparations or homecare products of the present invention provide an enhanced SPF performance and UVA photoprotection, as well as broad-spectrum photo-protection from UV radiation. [0035] Sun Protection Factor (SPF) indicates a sunscreen’s, cosmetic or pharmaceutical preparation’s or homecare product’s ability to protect against UVB rays but does not adequately designate to what extent (if any) a sunscreen composition protects against UVA radiation. SPF is a measure of how much solar energy (UV radiation) is required to produce sunburn on protected skin, i.e., in the presence of sunscreen, relative to the
220082 amount of solar energy required to produce sunburn on unprotected skin. As the SPF value increases, sunburn protection increases. An artificial UV source is used to irradiate skin until there is erythema (minimal erythema dose – MED) with and without sunscreen. SPF is then calculated by dividing the MED of the protected skin by the MED of the unprotected skin, i.e. how long it takes the skin to burn with and without sunscreen. In theory, this means that a sunscreen with an SPF of 50 means that one can be exposed to UV radiation for 50x longer before burning. [0036] UVA-photoprotection is expressed in UVA-protection factor (UVA-PF). UVA-PF is similar to SPF in that it is a measure of how well a sunscreen protects the skin from UVA radiation. It is performed in a similar manner by irradiating the skin with UVA. This can be done in vivo with human skin or in vitro, where it is performed by applying the sunscreen to an PMMA plate (Polymethymethacrylate plate) and measuring how much UVA passes through the slide with or without the sunscreen. To characterize protection from UVA radiation, the PPD (Persistent Pigment Darkening) method, which measures the color of the skin observed 2 to 4 hours after exposure of the skin to UVA radiation, is used. The PPD method appears to correlate well with the in vitro UVA-PF testing. [0037] The UVA-PF based on Persistent Pigment Darkening (PPD) is designated as “UVAPPDPF” and is expressed mathematically by the ratio of the dose of UVA radiation necessary to reach the pigmentation threshold with the UV screening agent (MPPDp) to the dose of UVA radiation necessary to reach the pigmentation threshold without UV screening agent (MPPDnp), as shown below: MPPDp UVAPPDPF = ------------ MPPDnp [0038] The UVAPPDPF of the sunscreen product, cosmetic or pharmaceutical preparation or homecare product is typically at least 4. Skin properly treated with a cosmetic composition having a UVAPPDPF of 4 means that it takes about 4 time longer for the skin to darken (i.e. to reach the threshold level of pigment darkening) compared to skin without
220082 treatment with the sunscreen product, cosmetic or pharmaceutical preparation or homecare product. [0039] The term “broad-spectrum photo-protection” means photo-protection from both UVA and UVB radiation. Broad-spectrum is based on the breadth of protection offered by a sunscreen in the UVA and UVB spectrums. In order for a sunscreen to be considered broad-spectrum, it must have achieved a critical wavelength of at least 370 nm, meaning that 10 % of the protection that the sunscreen offers has to be for wavelengths above 370 nm. A critical wavelength > 370 nm is a rigorous minimum that sunscreen products should achieve to be labelled as broad-spectrum”. [0040] In order to calculate the critical wavelength (ʎc), mathematical integration of the measured spectral absorbance from 190 nm to 400 nm is performed to calculate the area beneath the absorbance curve. The critical wavelength value is based upon the inherent shape and breadth of the absorbance cure, not its amplitude. The critical wavelength is the wavelength below which 90 % of the area under the absorbance curve sides. The critical wavelength for a UVB sunscreen is less than that for a sunscreen that protects against both UVB and UVA. A higher critical wavelength ensures more UV protection, especially from longer wavelength UVA rays. For example, a sunscreen with a critical wavelength of 370 nm provides more protection against UVA rays than a sunscreen with a critical wavelength of 350 nm. [0041] The combination of in vivo SPF rating and critical wavelength provides a complete description of a product’s photoprotective characteristics. [0042] According to the present invention, the primary object of the present invention is solved by a sunscreen product, cosmetic, especially dermatological, or pharmaceutical preparation or homecare product, comprising or consisting of (a) at least one primary organic UV-filter; and (b) at least one mycosporine-like amino acid compound, represented either by the general formula (I)
220082

formula (I), wherein - Z is selected from the group consisting of O-R2’ or amide’; - R’ is selected from the group consisting of ^ an unsubstituted or substituted alkyl, ^ an unsubstituted or substituted alkenyl, ^ an unsubstituted or substituted alkynyl, ^ an unsubstituted or substituted alkoxy, ^ an unsubstituted or substituted alkylthio, ^ an unsubstituted or substituted alkanoyl/acyl R-C(=O)-, ^ an unsubstituted or substituted cycloalkyl, ^ an unsubstituted or substituted aryl, ^ an unsubstituted or substituted heterocycloalkyl, and ^ an unsubstituted or substituted heteroaryl; - R1’ is selected from the group consisting of CH2, unsubstituted or substituted CH(alkyl), unsubstituted or substituted CH(cycloalkyl), unsubstituted or substituted CH(aryl), unsubstituted or substituted CH(heterocycloalkyl), unsubstituted or substituted CH(heteroaryl), CR7’R8’, C=O, halogen, O, S, SO, SO2, NH, unsubstituted or substituted N(alkyl), unsubstituted or substituted N(alkenyl), unsubstituted or substituted N(alkynyl), unsubstituted or substituted N(alkoxy), unsubstituted or substituted N(alkylthio), unsubstituted or substituted N(cycloalkyl), unsubstituted or substituted N(aryl), unsubstituted or substituted N(heterocycloalkyl), and unsubstituted or substituted N(heteroaryl), and unsubstituted or substituted C-spirocycles; - R2’ is selected from the group consisting of H, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio,
220082 unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, and unsubstituted or substituted heteroaryl; - amide’ is selected from the group consisting of NH2, unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9’R10’, unsubstituted or substituted -N(O- alkyl)(alkyl) (Weinreb amide), -N(OH)(H) (hydroxamate), and unsubstituted or substituted -N(OH)(alkyl) (alkylated hydroxamate); - R3’ is selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, -C- OH, -R-C-OH, -C(=O)-O-Y, -R-C(=O)-O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2, NH2, unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9’R10’, and unsubstituted or substituted C- spirocycles; - R7’ and R8’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, -C- OH, -R-C-OH, -C(=O)-O-Y, -R-C(=O)-O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2, NH2, unsubstituted or substituted NH(alkyl), unsubstituted or substituted
220082 NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), and unsubstituted or substituted NR9’R10’; - R9’ und R10’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, and unsubstituted or substituted heteroaryl; - Y is selected from the group consisting of H and unsubstituted or substituted alkyl; and - R is unsubstituted or substituted alkyl; or a tautomer or a salt thereof; or represented by the general formula (II)

formula (II), wherein - R” is selected from the group consisting of ^ an unsubstituted or substituted alkyl, ^ an unsubstituted or substituted alkenyl, ^ an unsubstituted or substituted alkynyl, ^ an unsubstituted or substituted alkoxy, ^ an unsubstituted or substituted alkylthio, ^ an unsubstituted or substituted alkanoyl/acyl R-C(=O)-, ^ an unsubstituted or substituted cycloalkyl,
220082 ^ an unsubstituted or substituted aryl, ^ an unsubstituted or substituted heterocycloalkyl, and ^ an unsubstituted or substituted heteroaryl; - R1” is selected from the group consisting of CH2, unsubstituted or substituted CH(alkyl), unsubstituted or substituted CH(cycloalkyl), unsubstituted or substituted CH(aryl), unsubstituted or substituted CH(heterocycloalkyl), unsubstituted or substituted CH(heteroaryl), -CR7”R8”, C=O, halogen, O, S, SO, SO2, NH, unsubstituted or substituted N(alkyl), unsubstituted or substituted N(alkenyl), unsubstituted or substituted N(alkynyl), unsubstituted or substituted N(alkoxy), unsubstituted or substituted N(alkylthio), unsubstituted or substituted N(cycloalkyl), unsubstituted or substituted N(aryl), unsubstituted or substituted N(heterocycloalkyl), unsubstituted or substituted N(heteroaryl), and unsubstituted or substituted C-spirocycles; - R2” is selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, -C- OH, -C(=O)-O-Y, -C(=O)-amide”, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2, NH2, unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9”R10”, and unsubstituted or substituted C- spirocycles; - X is selected from the group consisting of CH2, unsubstituted or substituted CH(alkyl), unsubstituted or substituted CH(alkenyl), unsubstituted or substituted CH(alkynyl), unsubstituted or substituted CH(alkoxy), unsubstituted or substituted CH(alkylthio), unsubstituted or substituted CH(cycloalkyl), unsubstituted or substituted CH(aryl), unsubstituted or substituted CH(heterocycloalkyl), unsubstituted or substituted CH(heteroaryl),
220082 -CR7”R8”, C=O, O, S, SO, SO2, NH, unsubstituted or substituted N(alkyl), unsubstituted or substituted N(alkenyl), unsubstituted or substituted N(alkynyl), unsubstituted or substituted N(alkoxy), unsubstituted or substituted N(alkylthio), unsubstituted or substituted N(cycloalkyl), unsubstituted or substituted N(aryl), unsubstituted or substituted N(heterocycloalkyl), unsubstituted or substituted N(heteroaryl), and unsubstituted or substituted C- spirocycles; - R7” and R8” which may be identical or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, -C- OH, -R-C-OH, -C(=O)-O-Y, -R-C(=O)-O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2, NH2, unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl) and unsubstituted or substituted NR9”R10”; - amide” is selected from the group consisting of NH2, unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9”R10”, unsubstituted or substituted -N(O- alkyl)(alkyl) (Weinreb amide), -N(OH)(H) (hydroxamate), and unsubstituted or substituted -N(OH)(alkyl) (alkylated hydroxamate); - R9” und R10” which may be identical or different, are independently from each other selected from the group consisting of H, OH, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl,
220082 unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, and unsubstituted or substituted heteroaryl; - Y is selected from the group consisting of H and unsubstituted or substituted alkyl; and - R is unsubstituted or substituted alkyl; or a tautomer or a salt thereof; or any mixture of the afore-mentioned compounds. [0043] The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the invention contains at least one primary organic UV-filter (a) that provide protection from UVA and/or UVB radiation. [0044] An organic UV-filter is a compound or a mixture of compounds that block or absorb ultraviolet (UV) light. UV classifications include UVA (320 to 400 nm), UVB (290 to 320 nm) and UVC (200 to 280 nm). UV absorbing compounds are used not only in sunscreen, but also in other personal care products, such as lipstick, shampoo, hair spray, body wash, toilet soap, and insect repellent. Chemical filters protect against UV- radiation by absorbing, reflecting, or scattering. By contrast, reflection and scattering are accomplished by inorganic physical UV-filters, such as titanium dioxide (TiO2) and zinc oxide (ZnO). Absorption, mainly of UVB, is done by organic UV-filters, which are known as chemical UV-filters. [0045] Non-limiting examples of organic UV-filters include: (i) sparingly soluble UV-filters (not appreciably soluble in either water or oil) such as Methylene Bis-Benzotriazolyl Tetramethylbutylphenol, Tris- Biphenyl Triazine, Methanone, 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl- ]phenyl]; (ii) oil soluble organic UV-filters (at least partially soluble in oil or organic solvent), such as Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Butyl Methoxydibenzoylmethane (BMBM), Oxybenzone, Sulisobenzone, Diethylhexyl
220082 Butamido Triazone (DBT), Drometrizole Trisiloxane, Ethylhexyl Methoxycinnamate (EHMC), Ethylhexyl Salicylate (EHS), Ethylhexyl Triazone (EHT), Homosalate, Isoamyl p-Methoxycinnamate, 4- Methylbenzylidene Camphor, Octocrylene (OCR), Polysilicone-15, and Diethylamino Hydroxy Benzoyl Hexyl Benzoate (DHHB); and (iii) water soluble UV-filters such as Phenylbenzimidazole Sulfonic Acid (PBSA), Sulisobenzone-sodium salt, Benzydilene Camphor Sulfonic Acid, Camphor Benzalkonium Methosulfate, Cinoxate, Disodium Phenyl Dibenzylmidazole Tetrasulfonate, Terephthalylidene Dicamphor Sulfonic Acid, PABA, and PEG-25 PAB; and any mixture thereof. [0046] According to the present invention, many different organic compounds can serve as UV-filters. They fall into several structural classes: (1) Benzophenones a. Benzophenone-3 (BP3) b. Benzophenone-4 (BP4) (2) Salicylates a. Homosalate (HMS) b. 2-ethylhexyl salicylate (EHS) (3) p-Aminobenzoic acid and derivatives a. Ethylhexyl dimethyl PABA (OD-PABA) b. 4-p-aminobenzoic acid (PABA) (4) Benzimidazole derivatives a. Phenylbenzimidazole sulfonic acid (PMDSA) b. Disodium phenyl dibenzimidazole tetrasulfonate (bisdisulizole disodium) (5) Triazines a. Ethylhexyltriazone (OT) b. Diethylhexyl butamido triazone (DBT) c. Bis-ethylhexyloxyphenol methoxyphenyl triazine (EMT) (6) Benzotriazoles a. Drometrizole trisiloxane (DRT) b. Methylene bis-benzotriazolyl tetramethylbutylphenol (MBP, biscotrizole) (7) Dibenzoylmethane derivatives a. 4-tert-Butyl-4’-methoxydibenzoylmethane (BM-DBM, avobenzone)
220082 (8) Cinnamates a. Ethylhexyl methoxycinnamate (OMC) b. Isoamyl p-methoxycinnamate (IMC, amiloxate) (9) Camphor derivatives a. Terephtalydene dicamphor sulfonic acid (PDSA) b. 3-benzylidene camphor (3BC) c. Benzylidene camphor sulfonic acid (BCSA) d. 4-methylbenzylidene camphor (4-MBC) e. Polyacrylamidomethyl benzylidene camphor (PBC) (10) Camphor benzalkonium methosulfate (CBM). [0047] The at least one primary organic UV-filter is selected from the group consisting of Camphor Benzalkonium Methosulfate, Homosalate, Benzophenone-3, Phenylbenzimidazole Sulfonic Acid, Terephthalylidene Dicamphor Sulfonic Acid, Butyl Methoxydibenzoylmethane, Benzylidene Camphor Sulfonic Acid, Octocrylene, Polyacrylamidomethyl Benzylidene Camphor, Ethylhexyl Methoxycinnamate, PEG-25 PABA, Isoamyl p-Methoxycinnamate, Ethylhexyl Triazone, Drometrizole Trisiloxane, Diethylhexyl Butamido Triazone, 4-Methylbenzylidene Camphor, Ethylhexyl Salicylate, Ethylhexyl Dimethyl PABA, Benzophenone-4, Benzophenone-5, Methylene Bis- Benzotriazolyl Tetramethylbutylphenol (nano), Disodium Phenyl Dibenzimidazole Tetrasulfonate, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Polysilicone-15, Diethylamino Hydroxy benzoyl Hexyl Benzoate, Tris-Biphenyl Triazine (nano), Phenylene Bis-Diphenyltriazine, Methoxypropylamino Cyclohexenylidene Ethoxyethylcyanoacetate, Bis-(Diethylaminohydroxybenzoyl Benzoyl) Piperazine, TEA-Salicylate, Benzophenone- 8, PABA, Ethylhexyl Dimethyl PABA, Menthyl Anthranilate, and any mixture thereof. [0048] More preferred, the at least one primary organic UV-filter is selected from the group consisting of Camphor Benzalkonium Methosulfate, Benzophenone-3, Terephthalylidene Dicamphor Sulfonic Acid, Benzylidene Camphor Sulfonic Acid, Polyacrylamidomethyl Benzylidene Camphor, PEG-25 PABA, Drometrizole Trisiloxane, Ethylhexyl Dimethyl PABA, Benzophenone-4, Benzophenone-5, Methylene Bis- Benzotriazolyl Tetramethylbutylphenol, Polysilicone-15, Titanium Dioxide (nano), Tris- biphenyl triazine (nano), Phenylene Bis-Diphenyltriazine, Methoxypropylamino
220082 Cyclohexenylidene Ethoxyethylcyanoacetate, Bis-(Diethylaminohydroxybenzoyl Benzoyl) Piperazine, Benzophenone-8, Ethylhexyl Dimethyl PABA, Homosalate, Phenylbenzimidazole Sulfonic Acid, Butyl Methoxydibenzoylmethane, Octocrylene, Ethylhexyl Methoxycinnamate, Isoamyl p-Methoxycinnamate, Ethylhexyl Triazone, Diethylhexyl Butamido Triazone, 4-Methylbenzylidene Camphor, Ethylhexyl Salicylate, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Diethylamino Hydroxy benzoyl Hexyl Benzoate, Menthyl Anthranilate, and any mixture thereof. [0049] Most preferred, the at least one primary organic UV-filter is selected from the group consisting of Homosalate, Phenylbenzimidazole Sulfonic Acid, Butyl Methoxydibenzoylmethane, Octocrylene, Ethylhexyl Methoxycinnamate, Isoamyl p- Methoxycinnamate, Ethylhexyl Triazone, Diethylhexyl Butamido Triazone, 4- Methylbenzylidene Camphor, Ethylhexyl Salicylate, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Diethylamino Hydroxy benzoyl Hexyl Benzoate, Menthyl Anthranilate, and any mixture thereof. [0050] The primary organic UV-filters cited before which can be used in the context of the present invention are preferred but naturally are not limiting. [0051] The aforesaid primary organic UV-filters are used in the sunscreen, cosmetic or pharmaceutical preparation or homecare product either as a single component or in a mixture with two, three, four or more further of said UV-filter(s) as specified above. [0052] In order to optimize the SPF, i.e. to obtain a high SPF in a range of 6 to 100, preferably in a range of 6 to 70, and to cover a broad UVA and UVB range, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention comprises at least two, more preferably at least three, most preferably at least four or even more different organic UV-filters. Advantageously, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention comprises at least one organic UVA-filter and at least one organic UVB filter. Such sunscreen products or cosmetic or pharmaceutical preparations according to
the present invention provide broad-spectrum photo protection, i.e. protection from both UVA and UVB. [0053] In a preferred variant the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention comprises a combination with one or more broadband filters which are selected from the group consisting of 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, tetrahydroxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n- octoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, sodium hydroxymethoxy benzophenone sulfonate, disodium-2,2'-dihydroxy-4,4'-dimethoxy-5,5'- disulfobenzophenone, phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(1,3,3,3- tetramethyl-1-(trimethylsilyl)oxy)disiloxyanyl) propyl), 2,2'-methylene-bis-(6-(2H- benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)phenol) (methylene-bis-benzotriazolyl tetramethylbutylphenol), 2,4-bis- ^4-(2-ethylhexyloxy)-2-hydroxyphenyl ^-1,3,5-triazine, 2,4-bis- ^ ^(4-(2-ethylhexyloxy)-2-hydroxy ^phenyl ^-6-(4-methoxyphenyl)-1,3,5-triazine (INCI: Aniso Triazin), 2,4-bis- ^ ^(4-(3-sulfonato)-2-hydroxypropyloxy)-2-hydroxy ^phenyl ^- 6-(4-methoxyphenyl)-1,3,5-triazine sodium salt, 2,4-bis- ^ ^(3-(2-propyloxy)-2- hydroxypropyloxy)-2-hydroxy ^phenyl ^-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis- ^ ^4-(2- ethylhexyloxy)-2-hydroxy ^phenyl ^-6- ^4-(2-methoxyethylcarbonyl) phenylamino ^-1,3,5- triazine, 2,4-bis- ^ ^4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy ^phenyl ^-6- ^4-(2- ethylcarboxyl) phenylamino ^-1,3,5-triazine, 2,4-bis- ^ ^4-(2-ethylhexyloxy)-2- hydroxy ^phenyl ^-6-(1-methylpyrrol-2-yl)-1,3,5-triazine, 2,4-bis- ^ ^4-tris- (trimethylsiloxysilylpropyloxy)-2-hydroxy ^phenyl ^-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis- ^ ^4-(2''-methylpropenyloxy)-2-hydroxy ^phenyl ^-6-(4-methoxyphenyl)-1,3,5- triazine, 2,4-bis- ^ ^4-(1',1',1',3',5',5',5'-heptamethylsiloxy-2''-methylpropyloxy)-2- hydroxy ^phenyl ^-6-(4-methoxyphenyl)-1,3,5-triazine, dioctylbutylamidotriazone (INCI: Dioctylbutamidotriazone), 2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]- 6-(2-ethylhexyl)-imino-1,3,5-triazine, 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)tris-benzoic acid-tris(2-ethyl-hexylester) (also: 2,4,6-tris[anilino(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5- triazine (INCI: Octyl Triazone), 2,4,6-tribiphenyl-4-yl-1,3,5-triazine, 2-ethylhexyl 4- methoxycinnamate (ethylhexyl methoxycinnamate), benzoic acid, 2-hydroxy-, 3,3,5-
trimethylcyclohexyl ester (Homosalate), 2-ethylhexyl salicylate (Ethylhexyl Salicylate), 2- ethylhexyl 4-(dimethylamino)benzoate (Ethylhexyl Dimethyl PABA), N,N,N-Trimethyl-4- (2-oxoborn-3-ylidenemethyl) anilinium methyl sulfate (Camphor Benzalkonium Methosulfate), dimethicodiethylbenzalmalonate (Polysilicone-15), and any mixtures thereof. [0054] The component (b) in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the first aspect of the present invention is at least one mycosporine-like amino acid compound represented either by the general formula (I)

formula (I), as defined herein; or represented by the general formula (II)

formula (II), as defined herein.
[0055] Mycosporine-like amino acids (MAAs) are small secondary metabolites produced by organisms that live in environments with high volumes of sunlight, usually marine environments. The MAAs are imine derivatives of mycosporines and contain an amino cyclohexene imine ring linked to an amino acid, amino alcohol or amino group. The compounds are capable of electron delocalization. In addition, said compounds demonstrate antioxidant qualities. [0056] Unless stated otherwise, in the context of the present invention, especially for the definition of the mycosporine-like amino acid compounds represented by any of the general formulae the following general meanings apply: [0057] The term "or" or "and/or" is used as a function word to indicate that two words or phrases are to be taken together or separately. [0058] The endpoints of all ranges directed to the same component or property are inclusive and independently combinable. [0059] The term "compound(s)" or "compound(s) of the present invention" refers to all compounds encompassed by the structural formula (I) and/or formula (lI) and/or formula (III) and/or formula (IV) disclosed herein and includes each subgenus and all specific compounds within the formula whose structure is disclosed herein. [0060] The compounds may be identified by either their chemical structure and/or chemical name. When the chemical structure and chemical name are in conflict, the chemical structure determines the identity of the compound. [0061] The term “halogen” residue/moiety or group alone or as part of another substituent according to the present invention refers to F, Cl, Br or I. [0062] The term "alkyl" alone or as part of another substituent according to the present invention refers to a saturated or mono- or polyunsaturated linear or branched monovalent hydrocarbon radical obtained by removing a hydrogen atom from a single carbon atom of a corresponding parent alkane.
[0063] In a preferred variation, the term "alkyl" also includes any alkyl moieties in radicals derived therefrom, such as alkoxy, alkylthio, alkylsulphonyl saturated linear or branched hydrocarbon radicals having 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. [0064] If the alkyl radical is further bonded to another atom, it becomes an alkylene radical or alkylene group. In other words, the term "alkylene" also refers to a divalent linear or branched alkyl. For example, -CH2CH3 is an ethyl, while -CH2CH2- is an ethylene. [0065] The term "alkylene" alone or as part of another substituent refers to a saturated linear or branched divalent hydrocarbon radical obtained by removing two hydrogen atoms from a single carbon atom or two different carbon atoms of a starting alkane. [0066] In preferred variants according to the present invention, the linear or branched alkyl group or alkylene group comprises 1 to 10 carbon atoms. In other still more preferred variants, the linear or branched alkyl group or alkylene group comprises 1 to 6 carbon atoms. [0067] More preferred according to the invention are saturated linear or branched C1 to C6 alkyl groups or saturated linear or branched C1 to C6 alkylene groups. [0068] Most preferred the linear or branched alkyl groups or alkylene groups with 1 to 4 carbon atoms. [0069] Preferred alkyl radicals/moieties or alkyl groups include, but are not limited to: C1 to C6 alkyl comprising methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1- methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2- dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1- methylpropyl and 1-ethyl-2-methylpropyl.
220082 [0070] The alkyl group or alkylene group as defined above may further be substituted. [0071] The term "alkyl" or "alkylene" further includes radicals or groups having any degree of saturation, i.e., groups having only single carbon-carbon bonds ("alkyl" or "alkylene"), groups having one or more double carbon-carbon bonds ("alkenyl"), radicals having one or more triple carbon-carbon bonds ("alkynyl"), and groups having a mixture of single, double and/or triple carbon-carbon bonds. [0072] The term "alkenyl" alone or as part of another substituent according to the present invention refers to an unsaturated linear or branched monovalent hydrocarbon radical having at least one carbon-carbon double bond (C=C double bond). The radical may be in either the cis or trans conformation around the double bond(s). So that the term "alkenyl" also includes the corresponding cis/trans isomers. [0073] In preferred variants according to the present invention, the linear or branched alkenyl group comprises 2 to 10 carbon atoms. In other preferred variants, the linear or branched alkenyl group comprises 2 to 6 carbon atoms. [0074] In still further preferred variants, the linear or branched alkenyl group comprises 2 to 4 carbon atoms. [0075] Preferred according to the invention are mono- or di-unsaturated linear or branched C1 to C6 alkenyl groups. [0076] Typical alkenyl radicals or alkenyl groups include, but are not limited to, ethenyl; propenyls such as prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl (allyl), prop-2-en-2-yl, cycloprop-1-en-1-yl, cycloprop-2-en-1-yl; butenyls such as but-1-en-1-yl, but-1-en-2-yl, 2- methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-2-yl, buta-1,3-dien-1-yl, buta-1,3-dien-2-yl and the like. [0077] The alkenyl group as defined above may further be substituted.
220082 [0078] The term "alkynyl" alone or as part of another substituent according to the present invention refers to an unsaturated linear or branched monovalent hydrocarbon radical having at least one carbon-carbon triple bond (C≡C triple bond). [0079] In preferred variants according to the present invention, the linear or branched alkynyl group comprises 2 to 10 carbon atoms. In other preferred variants, the alkynyl group comprises 2 to 6 carbon atoms. In still further preferred variants, the alkynyl group comprises 2 to 4 carbon atoms. [0080] Most preferred according to the invention are mono- or di-unsaturated linear or branched C1 to C6 alkynyl groups. [0081] Typical alkynyl radicals/moieties or alkynyl groups include, but are not limited to, ethynyl; propynyls such as prop-1-yn-1-yl, prop-2-in-1-yl, etc.; butynyls such as but-1-in- 1-yl, but-1-in-3-yl, but-3-in-1-yl, and the like. [0082] The alkynyl group as defined above may further be substituted. The alkyl group or alkylene group as defined above may further be substituted. [0083] The term "alkoxy" alone or as part of another substituent according to the present invention refers to a linear or branched radical of the formula -O-R, where R is alkyl or substituted alkyl, as defined herein. [0084] In preferred variants according to the present invention, the linear or branched alkoxy group comprises 2 to 10 carbon atoms. In other preferred variants, the linear or branched alkoxy group comprises 2 to 6 carbon atoms. In still further preferred variants, the linear or branched alkoxy group comprises 2 to 4 carbon atoms. [0085] Most preferred according to the invention are linear or branched C1 to C6 alkoxy groups. [0086] Typical alkoxy radicals/moieties or alkoxy groups include C1 to C6 alkoxy comprising C1 to C4 alkoxy such as. methoxy, ethoxy, n-propoxy, 1-methylethoxy,
220082 butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy; as well as pentoxy, 1- methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2- dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2- methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2- dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3- dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2- trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy. [0087] In a preferred variant, the alkoxy radical or alkoxy group is 2-allyloxyethoxy. [0088] The alkoxy group or alkylene group as defined above may further be substituted. [0089] The term "alkylthio" or "thioalkoxy" alone or as part of another substituent according to the present invention refers to a radical of the formula -S-R, wherein R is alkyl or substituted alkyl, as defined herein. [0090] According to the invention, the term "alkyl" or "alkylene" also includes heteroalkyl radicals or heteroalkyl groups. The term "heteroalkyl" by itself or as part of other substituents refers to alkyl groups in which one or more of the carbon atom(s) is/are independently replaced by the same or another heteroatom or by the same or another heteroatomic group(s). Typical heteroatoms or heteroatomic groups that may replace the carbon atoms include, but are not limited to, -O-, -S-, -N-, -Si-, -NH-, -S(O)- , -S(O)2-, -S(O)NH-, -S(O)2NH-, and the like, and combinations thereof. The heteroatoms or heteroatomic groups may be located at any internal position of the alkyl group. [0091] Typical heteroatomic groups that may be included in these groups include, but are not limited to, -O-, -S-, -O-O-, -S-S-, -O-S-, -NRR-, =NN=, -N=N-, -N=N-NRR, -PR-, - P(O)2-, -POR-, -O-P(O)2-, -SO-, -SO2-, -SR2OR-, and the like, wherein R is independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, substituted arylalkyl, cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted cycloheteroalkyl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, heteroarylalkyl or substituted heteroarylalkyl as defined herein.
220082 [0092] The alkyl group or alkylene group as defined above may further be substituted. [0093] The term "acyl" or “alkanoyl” alone or as part of another substituent according to the present invention refers to a radical R(C=O)-, wherein R is hydrogen, unsubstituted or substituted alkyl, unsubstituted substituted cycloalkyl, unsubstituted or substituted aryl, arylalkyl, unsubstituted or substituted arylalkyl, unsubstituted or substituted heteroalkyl, unsubstituted or substituted heteroarylalkyl, as defined herein. [0094] Representative examples include, but are not limited to, formyl, acetyl, propionyl, butyryl, valeryl, benzoyl, cyclohexylcarbonyl, cyclohexylmethylcarbonyl, benzylcarbonyl, and the like. [0095] The term "cycloalkyl" alone or as part of another substituent according to the present invention refers to a saturated or mono- or polyunsaturated, non-aromatic, cyclic monovalent hydrocarbon radical in which the carbon atoms are ring-linked and which has no heteroatom. [0096] The carbon ring can occur as a monocyclic compound, which has only a single ring, or as a polycyclic compound, which has two or more rings. [0097] In one preferred variation, the term "cycloalkyl" includes a three- to ten- membered monocyclic cycloalkyl radical or cycloalkyl group or a nine- to twelve- membered polycyclic cycloalkyl radical or cycloalkyl group. In other still more preferred variants, the cycloalkyl moiety comprises a five-, six- or seven-membered monocyclic cycloalkyl moiety or a nine- to twelve-membered bicyclic cycloalkyl moiety. [0098] In a preferred embodiment according to the present invention, a cycloalkyl radical or group comprises 3 to 20 carbon atoms. In an even more preferred embodiment, a cycloalkyl radical comprises 6 to 15 carbon atoms. In a most preferred embodiment, a cycloalkyl radical comprises 6 to 10 carbon atoms. Most preferred are monocyclic C3 to C7 cycloalkyl groups.
220082 [0099] Typical cycloalkyl radicals or cycloalkyl groups include, but are not limited to, saturated carbocyclic radicals having 3 to 20 carbon atoms, such as C3 to C12 carbocyclyl, comprising cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl; cyclopentyl, cyclohexyl, cycloheptyl, as well as cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl- methyl, cyclobutyl-ethyl, cyclopentyl-methyl, cyclopentyl-ethyl, cyclohexyl-methyl, or C3- to C7-carbocyclyl comprising cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl-methyl, cyclopentyl-ethyl, cyclohexyl- methyl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, ,3-dien-1-yl and the like. [0100] Polycyclic cycloalkyl radicals or cycloalkyl groups preferred according to the invention include but are not limited to naphthyl, indenyl groups and the like. [0101] According to the invention, the term "cycloalkyl" also includes cycloalkenyls, i.e. unsaturated cyclic hydrocarbon radicals containing C=C double bonds between two carbon atoms of the ring molecule. In a broader sense, cycloalkenyls are compounds with one, two or more double bond(s), where the number of possible, mostly conjugated double bonds in the molecule depends on the ring size. [0102] Typical cycloalkenyls include, but are not limited to, cyclopropenyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, and the like. [0103] According to the invention, the term "cycloalkyl" further includes cycloalkynyls, i.e. unsaturated, -C≡C-triple bonds, containing cyclic hydrocarbon radicals between two carbon atoms of the ring molecule, the triple bond depending on the ring size for reasons of ring tension. [0104] Typical cycloalkynyles include cyclooctin. [0105] The cycloalkyl, cycloalkenyl or cycloalkynyl moieties or groups, as defined above, may further be substituted.
220082 [0106] The term "aryl" alone or as part of another substituent according to the present invention refers to a monovalent aromatic hydrocarbon radical derived by removing a hydrogen atom from a single carbon atom of an aromatic ring SY-stem. [0107] In one preferred variation, the term "aryl" includes a three- to ten-membered monocyclic aryl radical or aryl group or a nine- to twelve-membered polycyclic aryl radical or aryl group. In other still more preferred variants, the carboaryl radical comprises a five- , six- or seven-membered monocyclic carboaryl radical or a nine- to twelve-membered bicyclic carboaryl radical. [0108] In a preferred embodiment according to the present invention, the aryl radical comprises 3 to 20 carbon atoms. In a preferred variation, the aryl moiety comprises 6 to 15 ring atoms. In an even more preferred embodiment, an aryl radical comprises 6 to 10 carbon atoms. [0109] Most preferred according to the invention are monocyclic C3 to C10 aryl groups. Most preferred are monocyclic C3 to C7 aryl groups. [0110] Typical aryl radicals include, without being limited thereto, benzene, phenyl, biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyl, fluorenyl, indenyl, and phenanthrenyl. Typical carboaryl moieties further include, but are not limited to, groups derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, corone, fluoranthene, fluorene, hexacene, hexaphene, hexalene, as- indacene, S-indacene, indane, indene, naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene and the like. [0111] Aromatic polycyclic aryl radicals or aryl groups preferred according to the invention include, but are not limited to, naphthalene, biphenyl and the like. [0112] The aryl moiety or group, as defined above, may further be substituted.
220082 [0113] The term "arylalkyl" alone or as part of another substituent according to the present invention refers to an acyclic alkyl group in which one of the hydrogen atoms attached to a carbon atom, typically a terminal or sp carbon atom, is replaced by an aryl group as defined herein. In other words, arylalkyl may also be considered as alkyl substituted by aryl. Typical arylalkyl groups include, but are not limited to, benzyl, 2- phenylethan-1-yl, 2-phenylethen-1-yl, naphthylmethyl, 2-naphthylethan-1-yl, 2- naphthylethen-1-yl, naphthobenzyl, 2-naphthophenylethan-1-yl, and the like. [0114] The term "heteroarylalkyl" alone or as part of another substituent refers to a cyclic alkyl group in which one of the hydrogen atoms attached to a carbon atom is replaced by a heteroaryl group. In a preferred embodiment according to the present invention, the heteroarylalkyl group is a 6- to 20-membered heteroarylalkyl, e.g., the alkyl, alkenyl, or alkynyl group of the heteroarylalkyl is a C1- to C6-alkyl and the heteroaryl group is a 5- to 15-membered heteroaryl group. In other embodiments, the heteroarylalkyl is a 6- to 13-membered heteroarylalkyl, e.g., the alkyl, alkenyl, or alkynyl group is a C1- to C3-alkyl and the heteroaryl group is a 5 to 10-membered heteroaryl. [0115] The term "heterocycloalkyl" alone or as part of another substituent according to the present invention refers to a saturated or mono- or polyunsaturated, non-aromatic, cyclic monovalent hydrocarbon radical in which one or more carbon atom(s) is/are independently replaced by the same or a different heteroatom. Typical heteroatoms to replace the carbon atom(s) include, but are not limited to, N, P, O, S, Si, etc. Typical heterocycloalkyl groups include, without being limited thereto, groups derived from epoxides, azirines, thiiranes, imidazolidine, morpholine, piperazine, piperidine, pyrazolidine, pyrrolidone, quinuclidine and the like. [0116] In a preferred embodiment according to the present invention, the "heterocycloalkyl" moiety or group comprises 3 to 20 ring atoms. In a preferred variation, the heterocycloalkyl moiety comprises 6 to 15 ring atoms. In an even more preferred embodiment, the heterocycloalkyl moiety comprises 6 to 10 carbon atoms.
220082 [0117] The heterocycloalkyl moiety can occur as a monocyclic compound, which has only a single ring, or as a polycyclic compound, which has two or more rings, such as bicyclic, tricyclic or spirocyclic. [0118] Preferably, the term "heterocycloalkyl" includes three- to seven-membered, saturated or mono- or polyunsaturated heterocycloalkyl moieties comprising one, two, three or four heteroatoms selected from the group consisting of O, N and S. The heteroatom or heteroatoms may occupy any position in the heterocycloalkyl ring. [0119] In one preferred variation, the term "heterocycloalkyl" includes a three- to ten- membered monocyclic heterocycloalkyl radical or a nine- to twelve-membered polycyclic heterocycloalkyl radical. In other still more preferred variants, the heterocycloalkyl moiety comprises a five-, six- or seven-membered monocyclic heterocycloalkyl moiety or a nine- to twelve-membered bicyclic heterocycloalkyl moiety. [0120] In a preferred embodiment according to the present invention, the "heterocycloalkyl" moiety or group comprises 3 to 20 ring atoms. In a preferred variation, the heterocycloalkyl moiety comprises 6 to 15 ring atoms. In an even more preferred embodiment, the heterocycloalkyl moiety comprises 6 to 10 carbon atoms. [0121] Most preferred according to the invention are monocyclic heterocycloalkyl radicals comprising 3 to 12 carbon atoms. Most preferred are monocyclic heterocycloalkyl radicals having 5 to 7 ring atoms. [0122] Typical heterocycloalkyl moieties include, but are not limited to: Five- or six- membered, saturated or monounsaturated heterocycloalkyl containing one or two nitrogen atoms and/or one oxygen or sulphur atom or one or two oxygen and/or sulphur atoms as ring members comprising 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2- tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3- lsoxazolidinyl, 4-lsoxazolidinyl, 5-lsoxazolidinyl, 3-lsothiazolidinyl, 4-lsothiazolidinyl, 5- lsothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4- oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-lmidazolidinyl, 4-lmidazolidinyl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 1-
220082 piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4- hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5- hexahydropyrimidinyl, 2-piperazinyl and the like. [0123] The heterocycloalkyl moiety or group, as defined above, may further be substituted. [0124] The term "heteroaryl" by itself or as part of another substituent according to the present invention refers to a monovalent heteroaromatic radical obtained by removing a hydrogen atom from a single atom of a heteroaromatic ring SY-stem. Typical heteroaryl radicals, or. Heteroaryl groups include, but are not limited to, those derived from acridine, β-carboline, chroman, chromium, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromium, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, thiazole, thiophene, triazole, xanthene and the like are derived. [0125] The heteroaryl moiety can occur as a monocyclic compound having only a single ring or as a polycyclic compound having two or more rings. [0126] In one preferred variation, the term "heteroaryl" includes a three- to ten- membered monocyclic heteroaryl radical or a nine- to twelve-membered polycyclic heteroaryl radical. In other still more preferred variants, the heteroaryl moiety comprises a five-, six- or seven-membered monocyclic heteroaryl moiety or a nine- to twelve- membered bicyclic heteroaryl moiety. [0127] Preferably, the term "heteroaryl" includes three- to seven-membered monocyclic heteroaryl radicals comprising one, two, three or four heteroatoms selected from the group consisting of O, N and S. The heteroatom or heteroatoms may occupy any position in the heteroaryl ring.
220082 [0128] In a preferred embodiment according to the present invention, the heteroaryl moiety or group comprises 3 to 20 ring atoms. In an even more preferred variant, the heteroaryl moiety comprises 6 to 15 ring atoms. In a most preferred embodiment, the heteroaryl group comprises 6 to 10 ring atoms. Most preferred according to the invention are monocyclic C3 to C7 heteroaryl groups. [0129] Particularly preferred heteroaryl moieties or heteroaryl groups include, but are not limited to, those derived from furan, thiophene, pyrrole, benzothiophene, benzofuran, benzimidazole, indole, pyridine, pyrazole, quinoline, imidazole, oxazole, isoxazole, and pyrazine. [0130] Five-membered aromatic heteroaryl radicals containing, in addition to carbon atoms, one, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring atoms include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3- pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2- thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-lmidazolyl, 4-lmidazolyl, and 1,3,4-triazol-2-yl. [0131] Five-membered aromatic heteroaryl radicals containing one, two, three or four nitrogen atoms as ring atoms include 1-, 2- or 3-pyrrolyl, 1-, 3- or 4-pyrazolyl, 1-, 2- or 4- lmidazolyl, 1,2,3-[1H]-triazol-1-yl, 1,2,3-[2H]-triazol-2-yl, 1,2,3-[1H]-triazol-4-yl, 1,2,3- [1H]-triazol-5-yl, 1,2,3-[2H]-triazol-4-yl, 1,2,4-[1H]-triazol-1-yl, 1,2,4-[1H]-triazol-3-yl, 1,2,4-[1H]-triazol-5-yl, 1,2,4-[4H]-triazol-4-yl, 1,2,4-[4H]-triazol-3-yl, [1H]-tetrazol-1-yl, [1H]-tetrazol-5-yl, [2H]-tetrazol-2-yl, [2H]-tetrazol-5-yl and the like. [0132] Five-membered aromatic heteroaryl radicals containing a heteroatom selected from oxygen or sulphur and optionally one, two or three nitrogen atoms as ring atoms include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 3- or 4-lsoxazolyl, 3- or 4-isothiazolyl, 2-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4- thiadiazol-2-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and 1,3,4-oxadiazol-2-yl. [0133] Six-membered heteroaryl radicals containing, in addition to carbon atoms, one or two or one, two or three nitrogen atoms as ring atoms, and comprising, for example.2- pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl,
220082 5-pyrimidinyl, 2-pyrazinyl, 1,2,4-triazin-3-yl; 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl and 1,3,5- triazin-2-yl. [0134] The heteroaryl moiety or group, as defined above, may further be substituted. [0135] The term “C-spirocycles” in the context of the present application means compounds that have at least two molecular rings with only one common atom. The simplest spiro compounds are bicyclic (having just two rings) or have a bicyclic portion as part of the larger ring system, in either case with the two rings connected through the defining single common atom. The one common atom connecting the participating rings distinguishes spiro compounds from other bicycles: from isolated ring compounds like biphenyl that have no connecting atoms, from fused ring compounds like decalin having two rings linked by two adjacent atoms, and from bridged ring compounds like norbornane with two rings linked by two non-adjacent atoms. Spiro compounds may be fully carbocyclic (all carbon) or heterocyclic (having one or more non- carbon atom, such as N, O and S). The common atom that connects the two (or sometimes three) rings is called the spiro atom. Preferably, the spiro atom is a carbon atom. More preferably, the C-spirocycles compound means compounds that are fully carbocyclic (all carbon). [0136] The term "substituted" in the context of the present invention means that one or more hydrogen atoms of the indicated radical or group is/are independently replaced by the same or a different substituent(s). Additionally, the term "substituted" specifically provides for one or more, i.e., two, three, four, five, six or more, substitutions commonly used in the art. However, it is generally known that the substituents should be selected so that they do not adversely affect the useful properties of the compound or its function. [0137] Suitable substituents in the context of the present invention preferably include halogen groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy groups or heteroaryloxy groups, arylalkyl or heteroarylalkyl groups, arylalkoxy or heteroarylalkoxy groups, amino groups, alkyl and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, carboxyl groups,
220082 alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, cycloalkyl groups, cyano groups, C1 to C6 alkylthio groups, arylthio groups, nitro groups, keto groups, acyl groups, boronate or boronyl groups, phosphate or phosphonyl groups, sulfamyl groups, sulfonyl groups, sulfinyl groups, and combinations thereof. [0138] Substituents or substituent groups useful for substituting saturated carbon atoms in the indicated group or radical more preferably include, but are not limited to, halogen, hydroxyl, alkyl, alkenyl, alkynyl, alkoxyl, -NH2, amino (primary, secondary, or tertiary), nitro, thiol, thioether, imine, cyano, amido, phosphonato, phosphine, carboxyl, thiocarbonyl, sulfonyl, sulfonamide, ketone, aldehyde, ester, acetyl, acetoxy, carbamoyl, oxygen (O); haloalkyl (e.g., trifluoromethyl); aminoacyl and aminoalkyl, carbocyclic cycloalkyl, which may be monocyclic or fused or non-fused polycyclic (e.g., cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl), or a heterocycloalkyl, which may be monocyclic or fused or non-fused polycyclic (e.g. pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, or thiazinyl), carbocyclic or heterocyclic, monocyclic or fused or non-fused polycyclic aryl (e.g., phenyl, naphthyl, pyrrolyl, indolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, quinolinyl, isoquinolinyl, acridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, benzimidazolyl, benzothiophenyl, or benzofuranyl), -CO2CH3, -CONH2, -OCH2CONH2; -SO2NH2, -OCHF2, -CF3, -OCF3. [0139] According to the invention, the substituents used to replace a particular radical or radical may in turn be further substituted, typically with one or more of the same or different radicals selected from the various groups indicated above and as defined in detail above. In the case of substituted combinations such as substituted arylalkyl, either the aryl or the alkyl group may be substituted, or both the aryl and the alkyl group may be substituted with one or more substituents. [0140] In a preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) of general formula (I) is either an acid compound or an ester compound represented by the general formula (III)
220082

formula (III), wherein R’, R1’, R2’ and R3’ have the same meaning as defined above for general formula (I); or is an amide compound represented by the general formula (IV)
formula (IV), wherein R’, R1’, amide’ and R3’ have the same meaning as defined above for general formula (I). [0141] In a preferred variant according to the first aspect of the present invention, in the formula (IV), the amide’ is NH2. [0142] In a more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an acid compound represented by the general formula (III-acid), wherein R’, R1’ and R3’ have the same meaning as defined above for general formula (I)

220082 formula (III-acid). [0143] Such mycosporine-like amino acid compounds are particularly photo-stable and temperature-stable compounds and show stability in pH solution or in different emulsion types and do not degrade. [0144] In a preferred variant according to the first aspect of the present invention, in the general formula (I), formula (III) or formula (IV) R’ or in the general formula (II) R” is selected from the group consisting of unsubstituted or substituted alkenyl, unsubstituted
or substituted alkynyl, unsubstituted or substituted , unsubstituted or substituted
, unsubstituted or substituted
, unsubstituted or
substituted , and unsubstituted or substituted , wherein the dotted line designates the binding site to the cyclohexene-imine ring. [0145] In a more preferred variant, in the general formula (I) R’ or in the general formula (II) R” is an unsubstituted or substituted alkenyl. [0146] In a more preferred variant, in the general formula (I) R’ or in the general formula (II) R” is an unsubstituted or substituted alkynyl.
220082 [0147] Such mycosporine-like amino acid derivatives exhibit a pronounced SPF and UVA photoprotection improving effect against organic UV-filters due to their olefinic/aromatic structure in the R’ or R” radical. [0148] In a more preferred variant, in the general formula (I), formula (III) or formula (IV)
R’ or in the general formula (II) R” is an unsubstituted or substituted . [0149] In a further preferred variant, in the general formula (I), formula (III) or formula (IV) R’ or in the general formula (II) R” is an
unsubstituted or substituted . [0150] In a further preferred variant, in the general formula (I), formula (III) or formula (IV) R’ or in the general formula (II) R” is an
unsubstituted or substituted . [0151] In a further preferred variant, in the general formula (I), formula (III) or formula (IV) R’ or in the general formula (II) R” is an
unsubstituted or substituted . [0152] In a further preferred variant, in the general formula (I), formula (III) or formula (IV) R’ or in the general formula (II) R” is an
unsubstituted or substituted .
220082 [0153] In a further preferred variant, in the general formula (I), formula (III) or formula (IV) R’ or in the general formula (II) R” is an
unsubstituted or substituted . [0154] In a further preferred variant, in the general formula (I), formula (III) or formula (IV) R’ or in the general formula (II) R” is an
and unsubstituted or substituted . [0155] Most preferred are mycosporine-like amino acid compound according to general formula (I), formula (III) or formula (IV) wherein R’ is an unsubstituted or substituted
. [0156] Such mycosporine-like amino acid derivatives exhibit a particular pronounced SPF and UVA photoprotection improving effect against organic UV-filters due to their aromatic structure in the R’ or R” radical. [0157] In a still more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is represented either by the general formula (V)
220082

formula (V), wherein - R1’, Z and R3’ have the same meaning as defined above for general formula (I); - R4’, R5’ and R6’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, -C-OH, -R-C-OH, -C(=O)-O-Y, -R-C(=O)-O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2, NH2, unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), and unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9’R10’, and unsubstituted or substituted C- spirocycles; - R9’ und R10’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, and unsubstituted or substituted heteroaryl;
220082 - Y is selected from the group consisting of H and unsubstituted or substituted alkyl; and - R is unsubstituted or substituted alkyl; or a tautomer or a salt thereof; or by the general formula (VI)

formula (VI), wherein - R1”, R2” and X have the same meaning as defined above for general formula (II); - R4”, R5” and R6” which may be identical or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, -C-OH, -R-C-OH, -C(=O)-O-Y, -R-C(=O)-O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2, NH2, unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), and unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9”R10”, and unsubstituted or substituted C- spirocycles;
220082 - R9” und R10” which may be identical or different, are independently from each other selected from the group consisting of H, OH, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, and unsubstituted or substituted heteroaryl; - Y is selected from the group consisting of H and unsubstituted or substituted alkyl; and - R is unsubstituted or substituted alkyl; or a tautomer or a salt thereof; or any mixture of the afore-mentioned compounds. [0158] In a further preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound is a compound according to general formula (I), formula (III) or formula (IV), wherein - R’ is unsubstituted or substituted phenyl; and/or - Z is -O-R2’ or amide’; and/or - R1’ is selected from the group consisting of CH2, C(methyl)2, O, S, SO, SO2, NH and N(alkyl); and/or - R2’ is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl,

isobutyl, tert-butyl, , , , (2-ethyl- hexyl) and phenyl; and/or - amide’ is selected from the group consisting of NH2, NHalkyl, N(alkyl)2, -N(O- alkyl)(alkyl) (Weinreb amide) and -N(OH)(H) (hydroxamate); and/or - R3’ is selected from the group consisting of H, methyl, ethyl, -O-methyl, -C(=O)-OH, -C(=O)-CH3, -C(=O)-C3H7 and -C(=O)-O-methyl; and/or - alkyl is selected from the group consisting of methyl, ethyl, propyl and butyl.
220082 [0159] In a more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound is a compound according to general formula (I), formula (III) or formula (IV), wherein - R’ is unsubstituted or substituted phenyl; and/or - Z is -O-R2’ or amide’; and/or - R1’ is either CH2 or C(methyl)2; and/or - R2’ is either H or ethyl or isopropyl or 2-ethylhexyl or phenyl; and/or - amide’ is either NH2 or N(methyl)2 or N(ethyl)2 or -N(O-alkyl)(alkyl) (Weinreb amide) or -N(OH)(H) (hydroxamate); and/or - R3’ is either H or -O-methyl or -C(=O)-OH or -C(=O)-CH3 or -C(=O)-O-methyl; and/or - alkyl is either methyl or ethyl or propyl or butyl. [0160] In another preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound is a compound according to general formula (II) or general formula (VI), wherein - R” is unsubstituted or substituted phenyl; and/or - R1” is selected from the group consisting of CH2, C(methyl)2, O, S, SO, SO2, NH and N(alkyl); and/or - R2” is selected from the group consisting of -C-OH, -C(=O)-O-Y, and -C(=O)- amide”; and/or - X is selected from the group consisting of C, C=O, O, S, SO, SO2, NH, and N(alkyl); and/or - Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl,

isobutyl, tert-butyl, , , , (2-ethyl- hexyl) and phenyl; and/or - amide” is selected from the group consisting of NH2, NHalkyl, N(alkyl)2, -N(O- alkyl)(alkyl) (Weinreb amide) and -N(OH)(H) (hydroxamate); and/or - alkyl is selected from the group consisting of methyl, ethyl, propyl and butyl.
220082 [0161] In a more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound is a compound according to general formula (II) or formula (VI), wherein - R” is unsubstituted or substituted phenyl; and/or - R1” is either CH2 or C(methyl)2; and/or - R2” is either -C(=O)-O-Y, or -C(=O)-amide”; and/or - X is S; and/or - Y is either H or ethyl or isopropyl or 2-ethylhexyl or phenyl; and/or - amide” is either NH2 or N(methyl)2 or N(ethyl)2 or -N(O-alkyl)(alkyl) (Weinreb amide) or -N(OH)(H) (hydroxamate); and/or - alkyl is either methyl or ethyl or propyl or butyl. [0162] In a still more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid is a compound according to general formula (I), formula (III) or formula (IV), wherein R4’, R5’ and R6’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, methyl, ethyl, iso-propyl, tert.-butyl, and O-methyl. [0163] Alternatively, the mycosporine-like amino acid compound is a compound according to general formula (II) or formula (VI), wherein R4”, R5” and R6” which may be identical or different, are independently from each other selected from the group consisting of H, OH, methyl, ethyl, iso-propyl, tert.-butyl and O-methyl. [0164] In a most preferred variant according to the first aspect of the present invention, in the general formula (I), formula (III) or formula (IV) R’ or in the general formula (II) R” is selected from the group consisting of
220082 ,

wherein the dotted line at the radical designates the binding site to the cyclohexene imine ring. [0165] Alternatively, in the general formula (V), formula (VI), formula (VII), formula (VIII), formula (IX) or formula (X) the substituted phenyl bonded to the imino functionality is selected from the group consisting of ,

wherein the dotted line designates the binding site to the cyclohexene imine ring. [0166] In a still further preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound is a compound according to general formula (II), formula (VI), formula (IX) or formula (X) wherein X is S. [0167] Such mycosporine-like amino acid compounds alter the UV absorption profile of the sunscreen product, cosmetic or pharmaceutical preparation or homecare product and broaden the UV absorption spectrum of the formulation across the UV radiation spectrum.
220082 [0168] In a still further preferred variant according to the present invention, in the general formulae (I) to (X) n is 1. [0169] In a preferred alternatively variant the mycosporine-like amino acid compound (b) is represented by the general formula (A)

formula (A), wherein R1’, R3’, R4’, R5’ and R6’ have the same meaning as defined above for general formula (V). [0170] In a preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) of general formula (I) is either an acid compound or an ester compound represented by the general formula (VII):
formula (VII), wherein R1’, R2’, R3’, R4’, R5’ and R6’ have the same meaning as defined above for general formula (V).
220082 [0171] In a preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an acid compound represented by the general formula (VII-acid)
formula (VII-acid), wherein R1’, R3’, R4’, R5’ and R6’ have the same meaning as defined above for general formula (V). [0172] Such mycosporine-like amino acid compounds are particularly photo-stable and temperature-stable compounds and show stability in pH solution or in different emulsion types and do not degrade. [0173] In a preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an ester compound represented by the general formula (VII-ester)

formula (VII-ester), wherein R1’, R3’, R4’, R5’ and R6’ have the same meaning as defined above for general formula (V).
220082 [0174] Preferably, the alkyl residue in the formula (VII-ester) is methyl or ethyl or propyl or butyl. Most preferred the alkyl residue in the formula (VII-ester) is methyl. Such ester compounds are particularly stable. [0175] In an alternative preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an amide compound represented by the general formula (VIII) '
formula (VIII), wherein R1’, amide’, R3’, R4’, R5’ and R6’ have the same meaning as defined above for general formula (V). [0176] In a more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an amide compound represented by the general formula (VIII-amide)
formula (VIII-amide), wherein R1’, R3’, R4’, R5’ and R6’ have the same meaning as defined above for general formula (V) and R11’ and R12’ are independently from each other selected from the group consisting of H, OH and alkyl.
220082 [0177] In a further preferred variant, the R11’ alkyl and R12’ alkyl in the formula (VIII- amide) are independently from each other selected from methyl, ethyl, propyl or butyl. [0178] Preferably, R11’ and R12’ in the formula (VIII-amide) are each H or each methyl. [0179] In a still more preferred variant, the mycosporine-like amino acid compound (b) is a Weinreb amide compound represented by the general formula (VIII-Weinreb amide)

formula (VIII-Weinreb amide), wherein R1’, R3’, R4’, R5’ and R6’ have the same meaning as defined above for general formula (V). [0180] In a preferred variant, the alkyl residue in the formula (VIII-Weinreb amide) is selected from the group consisting of methyl, ethyl, propyl and butyl, more preferred the alkyl residue is methyl. [0181] Alternatively, in a still more preferred variant, the mycosporine-like amino acid compound (b) is a hydroxamate compound represented by the general formula (VIII- hydroxamate derivative)
formula (VIII-hydroxamate derivative),
220082 wherein R1’, R3’, R4’, R5’ and R6’ have the same meaning as defined above for general formula (V). [0182] Alternatively, in a still further preferred variant, the amide compound (VIII-amide) the mycosporine-like amino acid compound (b) is an alkylated hydroxamate derivative represented by the general formula (VIII-alkylated hydroxamate derivative)
formula (VIII-alkylated hydroxamate derivative), wherein R1’, R3’, R4’, R5’ and R6’ have the same meaning as defined above for general formula (V). [0183] In a preferred variant, the alkyl residue in the formula (VIII-alkylated hydroxamate derivative) is selected from the group consisting of methyl, ethyl, propyl and butyl, more preferred the alkyl is methyl. [0184] In a more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an alcohol compound represented by the general formula (IX-alcohol)
formula (IX-alcohol), wherein R1”, X, R4”, R5” and R6” have the same meaning as defined above for general formula (VI).
220082 [0185] Alternatively, in a more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an acid compound represented by the general formula (IX-acid)
formula (IX-acid), wherein R1”, X, R4”, R5” and R6” have the same meaning as defined above for general formula (VI). [0186] Alternatively, in a more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an ester compound represented by the general formula (VII-ester)
formula (IX-ester), wherein R1”, X, R4”, R5” and R6” have the same meaning as defined above for general formula (VI). [0187] Preferably, the alkyl residue in the formula (VII-ester) is methyl or ethyl or propyl or butyl, more preferred the alkyl residue is methyl.
220082 [0188] In an alternative more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an amide compound represented by the general formula (X) ``
formula (X), wherein R1”, amide”, X, R4”, R5” and R6” have the same meaning as defined above for general formula (VI). [0189] In a more preferred alternatively variant according to the first aspect of the present invention, the mycosporine-like amino acid compound (b) is an amide compound represented by the general formula (X-amide)
R6 ´´ formula (X-amide), wherein R1”, X, R4”, R5” and R6” have the same meaning as defined above for general formula (VI) and R11” and R12” are independently from each other selected from the group consisting of H, OH and alkyl. [0190] Preferably, the R11” alkyl and R12” alkyl in the formula (X-amide) is methyl or ethyl or propyl or butyl. [0191] Preferably, R11’ and R12’ in the formula (X-amide) are each H or each ethyl.
220082 [0192] In a still more preferred variant, the mycosporine-like amino acid compound (b) is a Weinreb amide compound represented by the general formula (X-Weinreb amide)

R6 ´´ formula (X-Weinreb amide), wherein R1”, X, R4”, R5” and R6” have the same meaning as defined above for general formula (VI). [0193] In a preferred variant, the alkyl residue in the formula (X-Weinreb amide) is selected from the group consisting of methyl, ethyl, propyl and butyl, more preferred the alkyl residue is methyl. [0194] Alternatively, in a still more preferred variant, the mycosporine-like amino acid compound (b) is a hydroxamate derivative represented by the general formula (X- hydroxamate acid derivative)
R6 ´´ formula (X-hydroxamate derivative), wherein R1”, X, R4”, R5” and R6” have the same meaning as defined above for general formula (VI)
220082 [0195] Alternatively, in a still further preferred variant, the amide compound (VIII-amide) the mycosporine-like amino acid compound (b) is an alkylated hydroxamate derivative represented by the general formula (VIII-alkylated hydroxamate derivative)

R6 ´´ formula (X-alkylated hydroxamate derivative), wherein R1”, X, R4”, R5” and R6” have the same meaning as defined above for general formula (VI). [0196] In a preferred variant, the alkyl residue in formula (X-alkylated hydroxamate derivative) is selected from the group consisting of methyl, ethyl, propyl and butyl, more preferred the alkyl residue is methyl. [0197] In a still more preferred variant according to the present invention, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprises at least one mycosporine-like amino acid compound selected from the group consisting of the following compounds I-1 to I-128 according to the general formula (I) and II-1 to II-192 according to the general formula (II): Table 1:
220082
220082
220082
220082
220082
220082
220082
220082
220082
or a tautomer or a salt thereof, or any mixture of the afore-said compounds. [0198] In in the above specified mycosporine-like amino acid compounds according to formula (I) or formula (II) phenyl may be unsubstituted or substituted as defined above, and R2’, amide’, Y, amide“ and alkyl have the same meaning as defined above. [0199] Preferably, in the above specified mycosporine-like amino acid compounds according to formula (I) or formula (II) R2’ is selected from the group consisting of H,
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, , ,
220082
, (2-ethylhexyl) and phenyl; amide’ is selected from the group consisting of NH2, NHalkyl, N(alkyl)2, -N(O-alkyl)(alkyl) (Weinreb amide) and -N(OH)(H) (hydroxamate); Y is selected from the group consisting of H, methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, tert-butyl, , , , (2-ethylhexyl) and phenyl; amide” is selected from the group consisting of NH2, NHalkyl, N(alkyl)2, -N(O-alkyl)(alkyl) (Weinreb amide) and -N(OH)(H) (hydroxamate); and alkyl is selected from the group consisting of methyl, ethyl, propyl and butyl. [0200] Most preferred according to the first aspect of the present invention, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprises at least one mycosporine-like amino acid compound selected from the group consisting of: Table 2:
220082
220082
or a tautomer or a salt thereof, or any mixture of the afore-said compounds. [0201] Among the above specified mycosporine-like amino acid compounds the compounds MAA-2 salt and MAA-9 acid are particularly preferred, since they have a
220082 pronounced SPF and UVA photoprotection boosting effect. Most preferred is MAA-9. Said compound having an acid functionality is photo-stable and temperature-stable and show stability in pH solution or in oil-in-water emulsions and does not degrade. [0202] Most preferred according to the first aspect of the present invention, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprises at least one mycosporine-like amino acid compound selected from the group consisting of: MAA-12: ,
, MAA-14:
, or a tautomer or a salt thereof, or any mixture of the afore-said compounds, wherein alkyl is preferably either methyl or ethyl or propyl or butyl, most preferred methyl.
220082 [0203] Said most preferred mycosporine-like amino acid compounds are used either as single substance or in a mixture with one, two or more different mycosporine-like amino acid compounds as defined herein. [0204] The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the first aspect of the present invention is further characterized in that it does not contain one or more of the following mycosporine-like amino acid compounds: SY-14:
(R,E)-8-((4-methoxyphenylimino)-6,6-dimethyl- 3,4,4,6,7- hexahydro-2H-benzo[b][1,4] thiazine-3-carboxylic acid (CAS1629023-04-06); IUPAC: 8-(4-methoxyanilino)-6,6- dimethyl-2,3,5,7-tetrahydro-1,4-benzothiazine-3-carboxylic acid; SY-17:
I-(3-((4methoxyphenyl)imino)- 5,5 deimethylcyclohex-1-en-1-yl) glycine (CAS 1509902- 01-5); IUPAC: 2-[[(3E)-3-(4-methoxyphenyl)imino-5,5-dimethyl-cyclohexen-1- yl]amino]acetic acid as well as the ester derivative thereof: SY-17-3:
220082
IUPAC: Ethyl 2-[[(3E)-3-(4-methoxyphenyl)imino-5,5-dimethyl-cyclohexen-1- yl]amino]acetate SY-20:

6,6-dimethyl-8((4-(octyloxy)phenyl)imino)- 3,4,5,6,7,8-hexahydro-2H-benzo [b][1,4] thiazin-3-carboxylic acid (CAS 1629023-01-3); IUPAC: 6,6-dimethyl-8-(4-octoxyanilino)- 2,3,5,7-tetrahydro-1,4-benzothiazine-3-carboxylic acid. [0205] Various mycosporine-like amino acid compounds (b) as described herein contain one or more chiral centers, and, thus, can exist as racemic mixtures of enantiomers, mixtures of diastereomers or enantiomerically or optically pure compounds. It should also be noted the compounds of the invention include E and Z isomers, or a mixture thereof, and cis and trans isomers or a mixture thereof. [0206] Accordingly, the chemical structures of general formulae (I) to (X) and mycosporine-like amino acid compounds explicitly disclosed herein include all possible enantiomers and diastereomers or stereoisomers. [0207] In certain embodiments, the mycosporine-like amino acid compounds (b) of the invention are isolated as either the E or Z isomer. In other embodiments, the compounds of the invention are a mixture of the E and Z isomers.
220082 [0208] Alternatively, stereomerically pure compounds are used in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention. As used herein and unless otherwise indicated, the term “stereomerically pure” means that one stereoisomer of a compound is substantially free of other stereoisomers of that compound or one geometric isomer (e.g., about a double bond) is substantially free of the other geometric isomer. For example, a stereomerically pure compound of the invention having one chiral centre, will be substantially free of the opposite enantiomer of the compound. A stereomerically pure compound of the invention having two chiral centres, or a composition thereof, will be substantially free of other diastereomers of the compound. A stereomerically pure compound of the invention having a double bond capable of E/Z isomerism, or a composition thereof, will be substantially free of one of the E/Z isomers. [0209] A typical stereomerically pure compound comprises greater than about 80 % by weight of one stereoisomer or E/Z isomer of the compound and less than about 20 % by weight of other stereoisomers or E/Z isomer of the compound, more preferably greater than about 90 % by weight of one stereoisomer or E/Z isomer of the compound and less than about 10 % by weight of the other stereoisomers or E/Z isomer of the compound, even more preferably greater than about 95 % by weight of one stereoisomer or E/Z isomer of the compound and less than about 5 % by weight of the other stereoisomers or E/Z isomer of the compound, and most preferably greater than about 97 % by weight of one stereoisomer or E/Z isomer of the compound and less than about 3 % by weight of the other stereoisomers or E/Z isomer of the compound. [0210] As used herein and unless otherwise indicated, the term “stereomerically enriched” means a compound of the invention, or a composition thereof, that comprises greater than about 60 % by weight of one stereoisomer or E/Z isomer of a compound of the invention, preferably greater than about 70 % by weight, more preferably greater than about 80 % by weight of one stereoisomer or E/Z isomer of a compound of the invention. [0211] Thus, it should be noted that unless stated otherwise, the term mycosporine-like amino acid compound according to formulae (I) to (X) as well as individual mycosporine- like amino acid compounds specified herein, are to be interpreted as encompassing
220082 racemic mixtures of enantiomers, mixtures of diastereomers or enantiomerically or optically pure compounds. [0212] Due to their amino-cyclohexene-imine structure and their capability of electron delocalization, the compounds according to general formulae (I) to (X) are in equilibrium with their tautomer structures, in which the hydrogen of the amino group changes its places with the double bond of the cyclohexene ring. [0213] Tautomerism is defined as each of two or more isomers of a compound which exist together in equilibrium and are readily interchanged by migration of an atom or group within the molecule. Tautomeric pure or enriched systems will readily interchange into the equilibrium state over time. [0214] The tautomers of general formula (I) are represented by general formulae (I-tau):

↔ formula (I) formula (I-tau). [0215] The tautomers of general formula (II) are represented by general formula (II-tau):

↔ formula (II) formula (II-tau).
220082 [0216] The above principles of tautomerism and redeposition explained on the basis of the mycosporine-like amino acid compounds according to the general formula (I) and (II) are likewise applicable with respect to any of the mycosporine-like amino acid compounds defined by the general formula (III) to (X) or with respect to any individual mycosporine- like amino acid compounds specified herein. [0217] Thus, in the following and throughout the description, the reference to a mycosporine-like amino acid compound represented by any general formulae (I) to (X) or to an individual mycosporine-like amino acid compound specified herein encompasses likewise its tautomer isomer(s). [0218] The mycosporine-like amino acid compounds according to formulae (I) to (VIII) as well as individual mycosporine-like amino acid compounds specified herein are used according to the first aspect of the present invention either in neutral, i.e. uncharged form, or in the form of their salts, such as an acid addition salt, with inorganic or organic acids. [0219] The term “salt” in the context of the present invention refers to a salt of a compound that possesses the desired effect or pharmacological activity of the parent compound. Such salts include: (1) acid addition salts formed with inorganic acids, or formed with organic acids, preferably monovalent or polyvalent carboxylic acids; or (2) salts formed when an acidic proton present in the starting compound is replaced by a metal ion, e.g., an alkali metal ion, an alkaline earth ion, or an aluminium ion; or coordinated with an organic base. [0220] Among the salts, acid addition salts are again particularly preferred, since the mycosporine-like amino acid compounds according to the general formulae (I) to (X) or the mycosporine-like amino acid compounds specified herein comprise a protonable N atom. [0221] The inorganic acids that form acid addition salts with the mycosporine-line amino acid compound used according to the present invention are preferably selected from the group consisting of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid,
220082 phosphoric acid and the like. Among the salts most preferred are the hydrochlorides or sulfates. Particularly preferred is the hydrochloride salt or the sulfate salt or the phosphate salt. [0222] Even more preferred are acid addition salts with organic mono- or polycarboxylic acids. Further preferred are acid addition salts with organic mono- or polycarboxylic acids, wherein the carboxylic acid is selected from saturated or mono- or polyunsaturated C1 to C30 monocarboxylic acids, saturated or mono- or polyunsaturated C3 to 10 di- or tricarboxylic acids. The carboxylic acid may be mono- or poly-substituted with hydroxy groups, preferably α-hydroxycarboxylic acids in which the hydroxy group is located on the carbon atom adjacent to the carboxy group. Many representatives occur naturally as so- called fruit acids. Preferred α-hydroxycarboxylic acids are: malic acid, citric acid, 2- hydroxy-4-methylmercaptobutyric acid, glycolic acid, isocitric acid, mandelic acid, lactic acid, tartronic acid, or tartaric acid. [0223] The organic acids that form acid addition salts with the mycosporine-like amino acid compounds used according to the present invention are preferably selected from the group consisting of amino acids, acetic acid, trifluoroacetic acid, propionic acid, hexanoic acid, cyclopentane propionic acid, glycolic acid, pyruvic acid, lactic acid, malonic acid, oxalic acid, succinic acid, malic acid, maleic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, 3-(4-hydroxybenzoyl)benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, 1,2-ethanedisulfonic acid, 2- hydroxyethanesulfonic acid, benzenesulfonic acid, 4-chlorobenzenesulfonic acid, 2- naphthalenesulfonic acid, 4-toluenesulfonic acid, camphorsulfonic acid, 4- methylbicyclo[2. 2.2]-oct-2-ene-1-carboxylic acid, glucoheptonic acid, 3-phenylpropionic acid, trimethylacetic acid, tert. butylacetic acid, laurylsulfuric acid, gluconic acid, glutamic acid, hydroxynaphthoic acid, salicylic acid, stearic acid, muconic acid, 4-hydroxybutanoic acid, and the like. [0224] Among the organic acids that form acid addition salts with the mycosporine-like amino acid compounds used according to the present invention, acetic acid, lactic acid, malonic acid, succinic acid, malic acid, citric acid, or tartaric acid are most preferred.
220082 [0225] The metal ions for salt formation that replace an acidic proton present in the starting compound are selected from the group consisting of alkali metal ions, preferably Na+ or K+, alkaline earth metal ions, preferably Ca++, Mg++, and Al+++. [0226] The coordinating organic base for salt formation is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N-methylglucamine, and the like. [0227] In the following description and claims, and unless stated otherwise, the term mycosporine-like amino acid compound includes both the neutral, uncharged form of the compound/molecule and equally the salt form of the compound. [0228] The salt form of the mycosporine-like amino acid compounds leads to a lower logPOW and, thus, making the compounds more hydrophilic, which results in a better water solubility. In particular, the cationic salts of the mycosporine-like amino acid compounds support emulsification processes in emulsions, due to their surface active, i.e. co- emulsifying, properties. In addition, the cationic salt form of the mycosporine-like compounds shows excellent substantivity behaviour on skin and hair: most conditioning actives are cationic; the conditioning effect leads to a softer skin feel, which makes the end products more accepted by the consumer. In addition, the mycosporine-like amino acid compounds in the cationic salt form exhibit antimicrobial activity. [0229] In a particular advantageously variant, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the first aspect of the present invention comprises one of the following combinations of components (a) and (b): ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl
220082 Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with at least one compound according to formula (I) as defined herein; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate combined with at least one compound according to formula (II) as defined herein; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with at least one compound according to formula (V) as defined herein; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with at least one compound according to formula (VI) as defined herein; or
220082 [0230] Such combinations of an organic UV-filter and a mycosporine-like amino acid compound show a synergistic SPF performance and UVA photoprotection improving effect of the sunscreen products, cosmetic or pharmaceutical preparation or homecare product. [0231] More preferred combinations of component (a) and (b) in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the first aspect of the present invention are: ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-1; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-2; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl
220082 Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-3; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-4; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-5; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-6; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or
220082 Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-7; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-8; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-9; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-10; or
220082 ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-11. [0232] In particular, the combinations with the mycosporine-like amino acid compounds MAA-1, MAA-2, MAA-3, MAA-4, MAA-5, MAA-6, MAA-7, MAA-8, MAA-9, MAA-10 or MAA-11 and an organic UV-filter show a synergistic SPF performance and UVA photoprotection improving effect. This SPF performance and UVA photoprotection improving effect can especially be observed when the mycosporine-like amino acid is in its salt form, i.e. in its cationic form. The synergistic SPF performance and UVA photoprotection improving effect is especially pronounced for the mycosporine-like amino acid compounds MAA-2 salt or MAA-9 acid, when combined with any of the inorganic UV- filter. [0233] Most preferred combinations of component (a) and (b) in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the first aspect of the present invention are: ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-12; or
220082 ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-13; or ▪ at least one organic UV-filter: Homosalate and/or Phenylbenzimidazole and/or Sulfonic Acid and/or Butyl Methoxydibenzoylmethane and/or Octocrylene and/or Ethylhexyl Methoxycinnamate and/or Isoamyl p-Methoxycinnamate and/or Ethylhexyl Triazone and/or Diethylhexyl Butamido Triazone and/or 4- Methylbenzylidene Camphor and/or Ethylhexyl Salicylate and/or Disodium Phenyl Dibenzimidazole Tetrasulfonate and/or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine and/or Diethylamino Hydroxy benzoyl Hexyl Benzoate and/or Menthyl Anthranilate, combined with MAA-14. [0234] A synergistic SPF performance and UVA photoprotection improving effect can especially be demonstrated for the mycosporine-like amino acid compounds MAA-12, MAA-13 or MAA-14, when combined with any of the organic UV-filters as specified above. [0235] In the preparation of the sunscreen products, cosmetic or pharmaceutical preparations or homecare products according to the present invention, the compounds defined herein may be used in combination with other UV-absorbing agent(s), which is/are different from the at least one primary organic UV-filter (a), in order to further optimize the SPF, i.e. to obtain a high SPF in a range of 6 to 100, preferably in a range of 6 to 70, and to cover a broad UVA and UVB range. [0236] Therefore, the at least organic UV-filter (a) in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product as defined herein, is advantageously combined with at least one primary inorganic UV-filter and/or with at least on secondary sun protection ingredient or secondary sun protection UV-filter.
220082 [0237] The primary inorganic UV-filter is selected from the group of pigments consisting of titanium dioxide (TiO2) (amorphous or crystallized in rutile and/or anatase form), zinc oxide (ZnO), iron oxide (Fe2O3), zirconium oxide (ZrO2), silicon (SiO2), manganese (e.g. MnO), aluminium (Al2O3), cerium oxide (Ce2O3), barium carbonate (BaCO3), calcium carbonate (CaCO3), and mixtures thereof. [0238] Preferably, the inorganic UV-filter is titanium dioxide, zinc oxide, and mixtures thereof, more preferably the inorganic UV-filter is titanium oxide and/or zinc oxide, and most preferably, the inorganic UV-filter is zinc oxide. ZnO has a broad UVA/UVB absorption curve, while TiO2 provides better UVB protection. [0239] According to another variant, the inorganic UV-filter is in form of particles having a weight medium particle size d50 from 1 nm to 1000 nm, preferably from 3 nm to 800 nm, more preferably from 5 nm to 600 nm, and most preferably from 10 nm to 400 nm. [0240] The inorganic UV-filters also encompass nano pigments (mean size of the primary particles: generally from 1 nm to 100 nm, preferably from 3 nm to 90 nm, more preferred from 5 nm to 80 nm and most preferred from 10 to 70 nm) of untreated or treated metal oxides such as, for example, nano pigments of titanium dioxide (TiO2) (amorphous or crystallized in rutile and/or anatase form), zinc oxide (ZnO), iron oxide (Fe2O3), zirconium oxide (ZrO2), silicon (SiO2), manganese (e.g. MnO), aluminium (Al2O3), cerium oxide (Ce2O3), barium carbonate (BaCO3), calcium carbonate (CaCO3), or mixtures thereof. [0241] The treated nano pigments and non-nano pigments are pigments that have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds, such as amino acids, beeswax, fatty acids, fatty acid esters, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal (titanium or aluminium) alkoxides, polyethylene, silicones, proteins (collagen or elastin), alkanolamines, silicon oxides, metal
oxides, sodium hexametaphosphate, alumina or glycerol, hydrated silica, stearic acid, jojoba esters, or glutamic acid derivates. [0242] The treated nano pigments and non-nano pigments may more particularly be titanium oxides treated with silica and alumina, alumina and aluminium stearate, alumina and aluminium laurate, iron oxides and iron stearate, silica, alumina and silicone, sodium hexametaphosphate, octyltrimethoxysilane, alumina and stearic acid, alumina and glycerol, or alumina and silicone or polyhydroxy stearic acid, hydrated silica, jojoba esters, glutamic acid and derivates. Other titanium oxide nano pigments treated with a silicone are preferably TiO2 treated with octyltrimethylsilane, preferably for which the mean size of the elementary particles is from 25 to 40 nm; TiO2 treated with a polydimethylsiloxane, preferably for which the mean size of the elementary particles is 21 nm; or TiO2 treated with a polydimethylhydrogenosiloxane, preferably for which the mean size of the elementary particles is 25 nm. [0243] The coated zinc oxide nano pigments and zinc oxide non-nano pigments are for example ZnO coated with polymethylhydrogenosiloxane; ZnO dispersions in cyclopolymethylsiloxane/ oxyethylenated polydimethylsiloxane, containing 30 % or 80 % of nano or non-nano zinc oxides coated with silica and polymethylhydrogenosiloxane; ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl as a dispersion in cyclopentasiloxane; ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane; ZnO coated with triethoxycaprylylsilane; ZnO coated with polyhydroxystearic acid; alumina-treated ZnO dispersed in an ethylhexyl methoxycinnamate/PVP- hexadecene/methicone copolymer mixture; ZnO coated with silica and polymethylsilsesquioxane; ZnO dispersed in hydroxystearic acid polycondensate; or ZnO coated with a mixture of steaoryl glutamic acid, jojoba esters, polyhydroxystearic acid, isopropyl titanium triisostearate, hydrogenated olive oil stearyl esters, cetearyl nonanoate, cera alba, and sodium stearoyl lactylate. [0244] Also preferred are particulate UV-filters or inorganic pigments, which can optionally be hydrophobed, such as the oxides of iron (Fe2O3), zirconium (ZrO2), silicon
(SiO2), manganese (e.g. MnO), aluminium (Al2O3), cerium (e.g. Ce2O3), barium carbonate (BaCO3), calcium carbonate (CaCO3), or mixtures thereof. [0245] The afore specified inorganic UV-filters are used in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product either as a single component or in a mixture with two, three, four or more of said inorganic UV-filters. [0246] The combination of effective sun protection UV-filters of different categories such as UVA-filter, UVB-filter, broadband filter, and/or inorganic pigments provides reliable protection against the different UV rays in the wavelength range of 290 to 400 nm. [0247] In a further preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the invention contains the primary UV- filters, i.e. in particular organic UV-filters and/or inorganic pigments (UV-filtering pigments), in a total amount so that the product or preparation according to the invention has a sun protection factor SPF of 6 to 100, preferably 6 to 70. Such compositions according to the invention are particularly suitable for protecting the skin, hair and nails. [0248] Besides the group of primary organic and/or inorganic UV-filters (a) mentioned above, secondary sun protection ingredients of the antioxidant type may also be advantageously used in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention in order to further optimize UV protection. [0249] Secondary sun protection ingredients of the antioxidant type interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin. [0250] Typical examples of secondary sun protection ingredients are amino acids (for example arginine, lysine, glycine, histidine, tyrosine, tryptophane) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as D,L- carnosine, D-carnosine, L-carnosine and derivatives thereof (for example anserine), carotenoids, carotenes (for example alpha-carotene, beta-carotene, lycopene) and
220082 derivatives thereof, chlorogenic acid and derivatives thereof, liponic acid and derivatives thereof (for example dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (for example thioredoxine, glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, alpha-linoleyl, cholesteryl and glyceryl esters thereof) and their salts, dilaurylthiodipropionate, distearyl- thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (for example butionine sulfoximines, homocysteine sulfoximine, butionine sulfones, penta-, hexa- and hepta-thionine sulfoximine) in very small compatible dosages, also (metal) chelators (for example alpha-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrine), alpha-hydroxy acids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (for example linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives thereof (for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, sinapic acid, sinapoyl malate, sinapate ester derivatives, selenium and derivatives thereof (for example selenium methionine), stilbenes and derivatives thereof (for example stilbene oxide, trans-stilbene oxide) and derivatives of these active substances suitable for the purposes of the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids). [0251] The group of secondary sun protection ingredients also encompasses plant- based extract(s). Said plant-based extracts have antioxidative and in general photoprotective properties and interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin, thus, are effective in preventing skin aging. The plant extracts with UV protection properties are selected from the group consisting of Lignin/Cellulose, Lignin, Lignin Hydrolyzed, Propolis and green propolis, Galanga Extract, macro and micro algae (Porphyra, red algae (Porphyra Umbilicalis), Palmaria
220082 palmata, Saccharina latissimaCorallina pilulifera, Eckloina cava, Sargassum sagamianum, Porphyra rosengurttii, Sargassum siliquastrum, Thalassiosira weissflogii, Green Microalgae (e.g. Interfilum and Klebsormidium), Seaweed (e.g. Padina australis, Euchema, cottonii), Pongamia Glabra Seed Oil, Karanja oil (Millettia pinnata), Rhatania Extrakt (Krameria lappacea), Lichens, Soybean, Caper (Capparis spinosa), Bamboo, Green Coffee oil, Buriti Oil (Mauritia flexuosa), Black Sea Cucumber (Holothuria atra), Cyanobacteria, Fernblock (Polypodium leucotomos), Green Tee, Black Tea (Camellia sinensis), Aloe vera, Walnut, Borage oil, Evening primrose oil, Avocado oil, Tea tree oil, Red Clover (Trifolium pratense L.), Soybean (Glycine max L.), Caper (Capparis spinosa), Almonds, Flame of the forest (Spathodea campanulata), Milk thistle (Silybum marianum L.), Cashew nut shell, Grape, Red Orange, Pomegranate (Punica granatu), Bilberry (Vaccinium myrtillus L.), Bog blueberry (Vaccinium uliginosum L.), Strawberry (Fragaria ananassa), Foti (Polygonum multiflorum Thunb), Turmeric (Curcuma longa L.), Ginseng (Panax ginseng), English ivy (Hedera helix), Broccoli (Brassica oleracea var italica), Tamarind (Tamarindus indica), Opuntia ficus-indica, Coffee, Basil (Ocimum basilicum, Linn.), pomegranate seed oil(Punica granatum), wheat germ oil (Triticum vulgare), blackcurrant seed oil (Ribes nigrum), sesameoil (Sesamum indicum), carrot root (Daucuscarota sativa), raspberry seed oil (Rubus idaeus), traditional medicinal plants from Sri Lanka (Aporosa lindleyana (Euphorbiaceae), Atalantia ceylanica (Rutaceae), Hibiscus furcatus (Malvaceae), Olaxzeylanica (Olacaceae), Ophiorrhiza mungos (Rubiaceae), Argyreia populifolia (Convolvulaceae), Ipomoea mauritiana (Convolvulaceae), Lasia spinosa (Araceae), Leucas zeylanica (Lamiaceae), Plectranthus zeylanicus (Lamiaceae) and Brazil (D. gardneriana seeds, L. microphylla leafs, Amburana cearensis, Aspidosperma cuspa, Aspidosperma pyrifolium, Croton sonderianus, Curatella americana, Dimophandra gardneriana, Lippia microphylla, Luehea paniculata, Sida galheirensis and any mixture thereof. [0252] Preferably, the plant extracts with UV protection properties are selected from the group consisting of Lignin/Cellulose, Lignin, Lignin Hydrolyzed, Galanga Extract, Porphyra, red algae (Porphyra Umbilicalis), Green Microalgae (e.g. Interfilum and Klebsormidium), Seaweed (e.g. Padina australis, Euchema, cottonii), Pongamia Glabra Seed Oil, Karanja oil (Millettia pinnata), Rhatania Extrakt (Krameria lappacea), Soybean, Bamboo, Buriti Oil (Mauritia flexuosa), Cyanobacteria, Fernblock (Polypodium
220082 leucotomos), Green Tee, Black Tea (Camellia sinensis), Evening primrose oil, Cashew nut shell, Pomegranate (Punica granatu), and any mixture thereof. [0253] Advantageous the amount of secondary sun protection substances in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention is advantageously from 0.005 to 5.0 % by weight, preferably 0.01 to 4.0 % by weight, more preferred 0.05 to 3.0 % by weight, based on the total weight of the ready-to-use formulation. [0254] The UV-filters are incorporated either in the aqueous or in the lipophilic part of the sunscreen product, cosmetic or pharmaceutical preparation or homecare product, depending on whether they are water or oil (fat) soluble/miscible UV-filters or may even be added to the final product by standard methods known to a person skilled in the art. [0255] The primary organic UV-filter (a) according to the first aspect of the present invention is present in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.01 to 55.0 % by weight, based on the total weight of the final formulation. In a preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or cosmetic product comprises the organic UV-filter (a) in an amount of 0.1 to 50.0 % by weight, based on the total weight of the final formulation. In a more preferred variant, the organic UV-filter (a) is advantageously used in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product in an amount of at 0.5 to 45.0 % by weight, based on the total weight of the final formulation. In a most preferred variant, the organic e UV-filter is advantageously used in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product in an amount of 1.0 to 40.0 % by weight, based on the total weight of the final formulation. [0256] For a mixture of organic UV-filters, the above amounts relate to the total content of the organic UV-filters in the mixture, i.e. the amount is the sum of the content of all organic UV-filters in the mixture.
220082 [0257] The primary organic UV-filter (a) and further UV-filter components such as primary inorganic UV-filters and/or secondary UV-filters, as defined herein, i.e. the total amount of UV-filters, are present in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention, in an amount of 0.1 to 85.0 % by weight, based on the total weight of the final formulation. In a preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprises the organic UV-filter (a) and further UV-filter components as defined herein in an amount of 0.3 to 80.0 % by weight, based on the total weight of the final formulation. In a more preferred variant, the organic UV-filter (a) and further UV-filter components as defined herein are advantageously used in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.5 to 75.0 % by weight, based on the total weight of the final formulation. Thus, the above amounts relate to the sum of the content of all primary organic and inorganic UV-filters present in the sunscreen, cosmetic or pharmaceutical preparation or homecare product. [0258] The at least one mycosporine-like amino acid compound (b) according to the first aspect of the present invention is present in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.001 to 15.0 % by weight, based on the total weight of the final formulation. In a preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprises the at least one mycosporine-like amino acid compound (b) in an amount of 0.01 to 10.0 % by weight, based on the total weight of the final formulation. In a more preferred variant, the at least one mycosporine-like amino acid compound (b) is advantageously used in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product in an amount of at 0.05 to 7.5 % by weight, based on the total weight of the final formulation. In a most preferred variant, the at least one mycosporine-like amino acid compound is advantageously used in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product in an amount of at 0.1 to 5.0 % by weight, based on the total weight of the final formulation. [0259] For a mixture of mycosporine-like amino acid compounds (b), the above amounts relate to the total content of the mycosporine-like amino acid compounds in the mixture,
220082 i.e. the amount is the sum of the content of all mycosporine-like amino acid compounds (b) in the mixture. [0260] Advantageously, the sunscreen product according to the first aspect of the present invention comprises (i) 0.01 to 55.0 % by weight of at least one primary organic UV-filter; and (ii) 0.001 to 15 % by weight of at least one mycosporine-like amino acid compound as defined herein; based on the based on the total weight of the final formulation. [0261] In a preferred variant, the cosmetic or pharmaceutical preparation according to the first aspect of the present invention comprises (iii) 1.0 to 40.0 % by weight of at least one primary organic UV-filter; and (iv) 0.1 to 5.0 % by weight of at least one mycosporine-like amino acid compound as defined herein; based on the based on the total weight of the final formulation. [0262] The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention provides broad spectrum photo-protection und therefore provide protection from both UVA and UVB radiation. Typically, the compositions of the present invention have an SPF (UVB) of at least 6. The SPF, however, can vary as needed. Preferably, the SPF (UVB) of the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention is at least 6, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or even more. [0263] Furthermore, the SPF (UVA) or UVA-PF of the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention is 1 to 50, preferably at least 10 and most preferred more than 2. [0264] As the sunscreen product, cosmetic or pharmaceutical, in particular dermatological, preparation or homecare product according to the present invention are intended for topical application, such as in the form of ointments, pastes, creams and
220082 gels, they are preferably based on a cosmetically or pharmaceutically acceptable carrier. Most common acceptable carrier is water. Acceptable carries other than water include glycerin, C1-4 alcohols, organic solvents, fatty alcohols, fatty ethers, fatty esters, polyols, glycols, vegetable oils, mineral oils, liposomes, laminar lipid materials, water, or a mixture thereof. Non-limiting examples of organic solvents include mono alcohols and polyols such as ethyl alcohol, isopropyl alcohol, propyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or ethers thereof such as, for example, monomethyl ether of propylene glycol, butylene glycol, hexylene glycol, dipropylene glycol as well as alkyl ethers of diethylene glycol, for example monoethyl ether or monobutyl ether of diethylene glycol. Other suitable examples of organic solvents are ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, propane diol, and glycerin. The organic solvents can be volatile or non-volatile compounds. The total amount of carrier in the compositions can vary but is typically 40 to 90 wt.%, based on the total weight of the composition. [0265] The compositions of the present invention may include at least one water-soluble or organic solvent. Non-limiting examples of organic solvents include monoalcohols and polyols such as ethyl alcohol, isopropyl alcohol, propyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or ethers thereof such as, for example, monomethyl ether of propylene glycol, butylene glycol, hexylene glycol, dipropylene glycol as well as alkyl ethers of diethylene glycol, for example monoethyl ether or monobutyl ether of diethylene glycol. Other suitable examples of organic solvents are ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, propane diol, and glycerin. The organic solvents can be volatile or non-volatile compounds. [0266] Further non-limiting examples of water-soluble solvents include alkanols (polyhydric alcohols such as glycols and polyols) such as glycerin, 1 ,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, hexylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 1 ,3-butanediol, 2,3-butanediol, 1 ,4-butanediol, 3-methyl-1 ,3- butanediol, 1 ,5-
220082 pentanediol, tetraethylene glycol, 1 ,6-hexanediol, 2-methyl-2,4- pentanediol, polyethylene glycol, 1 ,2,4-butanetriol, 1 ,2,6-hexanetriol, 2-butene-1 ,4- diol, 2-ethyl-1 ,3- hexanediol, 2-methyl-2,4-pentanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-decanediol, and 4-methyl-1,2-pentanediol; alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t- butyl ether, diethylene glycol mono-t-butyl ether, 1 -methyl-1 -methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-iso-propyl ether; 2-pyrrolidone, N-methyl-2- pyrrolidone, 1 ,3-dimethyl-2- imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetine, diacetine, triacetine, sulfolane, and any mixture thereof. The total amount water-soluble or organic solvent(s) in the composition according to the present invention may vary but is typically 0.1 to 50 wt.%, based on the total weight of the composition. [0267] The compositions of the present invention may include at least one solubilizing agent. Solubilizing agents are compounds that help solubilize the UV-filter(s) and/or other components in the compositions. A particularly useful but non limiting example of a solubilizing agent is a hydrotrope. Hydrotropes (or hydrotropic agents) are a diverse class of typically water-soluble compounds that may be characterized by an amphiphilic molecular structure and an ability to dramatically increase the solubility of poorly soluble organic molecules in water. Non-limiting examples of hydrotopes include sodium 1 ,3- benzenedisulfonate, sodium benzoate, sodium 4-pyridinecarboxylate, sodium salicylate, sodium benzene sulfonate, caffeine, sodium p-toluene sulfonate, sodium butyl monoglycolsulfate, 4- aminobenzoic acid HCI, sodium cumene sulfonate, N,N- diethylnicotinamide, N-picolylnicotinamide, N-allylnicotinamide, 2-methacryloyloxyethyl phosphorylcholine, resorcinol, butylurea, pyrogallol, N-picolylacetamide 3.5, procaine
220082 HCI, proline HCI, nicotinamide, pyridine, 3-picolylamine, sodium ibuprofen, sodium xylenesulfonate, ethyl carbamate, pyridoxal hydrochloride, sodium benzoate, 2- pyrrolidone, ethylurea, N,N-dimethylacetamide, N-methylacetamide, and isoniazid and any mixture thereof. In some cases, particularly useful hydrotropes include nicotinamide (niacinamide), caffeine, sodium PCA, sodium salicylate, urea, and dhydroxyethyl urea, in particular nicotinamide (niacinamide) and/or caffeine. A combination of two or more, three or more, or four or more hydrotopes may also be used in the compositions according to the present invention. The total amount of solubilizing agent(s) in the compositions of the present invention may vary but are typically in an amount of 0.01 to 20 wt.%, based on the total weight of the composition. [0268] The sunscreen product, cosmetic or pharmaceutical preparation or homecare product may include at least one oil phase or at least one oil component, waxes, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, talc and zinc oxide or any mixture thereof. Powders include carriers such as lactose, talc, silica, aluminium hydroxide, calcium silicate and polyamide powder or any mixture thereof. Solutions and emulsions include carriers such as solvents such as water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, propylene glycol, etc. or any mixture thereof. However, preparations solely based on water are also possible. Oils, oil- in-water and water-in-oil emulsions, etc. are preferred. [0269] The oil phase or the oil component in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention which may be suitable are for example plant oils, hydrocarbons, fatty alcohols, fatty acid esters, or mixtures of two or more of the aforesaid oil components. [0270] The oil phase or oil component in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product is preferably a plant oil and even more preferably a liquid plant oil. It can also advantageously be a mixture of two or more plant oils components, especially liquid plant oil mixtures.
220082 [0271] Plant oils or vegetable oils are oils extracted from seeds, or less often, from other parts of fruits. Like animal fats, plant oils are mixtures of triglycerides. Soybean oil, rapeseed oil and cocoa butter are examples of plant oils from seeds. Olive oil, palm oil and rice bran oil are examples of oils from other parts of fruits. In common usage, plant oil or vegetable oil may refer exclusively to vegetable fats which are liquid at room temperature or at 35 to 37 °C skin temperature. Vegetable oils are usually edible. [0272] The term “plant oils” also includes unsaturated plant oils. Unsaturated oils or vegetable oils can be transformed through partial or complete “hydrogenation” into oils of higher melting point. The hydrogenation process involves “sparging” the oil at high temperature and pressure with hydrogen in the presence of a catalyst, typically a powdered nickel compound. As each carbon-carbon double-bond is chemically reduced to a single bond, two hydrogen atoms each form single bonds with the two carbon atoms. The elimination of double bonds by adding hydrogen atoms is called saturation; as the degree of saturation increases, the oil progresses toward being fully hydrogenated. An oil may be hydrogenated to increase resistance to rancidity (oxidation) or to change its physical characteristics. As the degree of saturation increases, the oil's viscosity and melting point increase. [0273] In a preferred variant, the plant oil is selected from the group consisting of Persea Gratissima (Avocado Oil), Abies Alba Seed Oil, Acacia Victoriae Seed Oil, Actinidia Chinensis (Kiwi) Seed Oil, Amaranthus Hypochondriacus Seed Oil, Arachis Hypogaea (Peanut) Oil, Astrocaryum Murumuru Seed Butter, Astrocaryum Tucuma Seed Butter, Astrocaryum Tucuma Seed Oil, Astrocaryum Vulgare Fruit Oil, Astrocaryum Vulgare Kernel Oil, Avena Sativa (Oat) Kernel Oil, Brassica Alba Seed Oil, Brassica Campestris (Rapeseed) Seed Oil, Butyrospermum Parkii (Shea) Butter, Butyrospermum Parkii (Shea) Oil, Calendula Officinalis Seed Oil, Calophyllum Inophyllum Seed Oil, Calophyllum Tacamahaca Seed Oil, Camellia Oleifera Seed Oil, Camellia Reticulata Seed Oil, Camellia Sinensis Seed Oil, Cannabis Sativa Seed Oil, Cannabis Sativa Seed/Stem Oil, Canola Oil, Carthamus Tinctorius (Safflower) Seed Oil, Chlorella Vulgaris Oil, Citrullus Lanatus (Watermelon) Seed Oil, Citrus Aurantifolia (Lime) Seed Oil, Citrus Aurantium Dulcis (Orange) Seed Oil, Citrus Grandis (Grapefruit) Seed Oil, Cocos Nucifera (Coconut) Oil, Cocos Nucifera (Coconut) Seed Butter, Coffea Arabica (Coffee)
220082 Seed Oil, Chlorella Oil (biotech), Corylus Americana (Hazelnut) Seed Oil, Corylus Avellana (Hazelnut) Seed Oil, Cucumis Melo (Melon) Seed Oil, Cucumis Sativus (Cucumber) Seed Oil, Cucurbita Pepo (Pumpkin) Seed Oil, Elaeis Guineensis (Palm) Oil, Elaeis (Palm) Fruit Oil, Glycine Soja (Soybean) Oil, GosSY-pium Herbaceum (Cotton) Seed Oil, GosSY-pium Hirsutum (Cotton) Seed Oil, Helianthus Annuus (Sunflower) Seed Oil, Macadamia Integrifolia Seed Oil, Macadamia Ternifolia Seed Oil, Mangifera Indica (Mango) Seed Butter, Mangifera Indica (Mango) Seed Oil, Melissa Officinalis Seed Oil, Microalgae Oil, Moringa Oleifera Seed Oil, Moringa Peregrina Seed Oil, Oenothera Biennis (Evening Primrose) Oil, Olea Europaea (Olive) Fruit Oil, Olus Oil, Orbignya Oleifera Seed Oil, Orbignya Speciosa Kernel Oil, Oryza Sativa (Rice) Bran/Germ Oil, Oryza Sativa (Rice) Bran Oil, Oryza Sativa (Rice) Germ Oil, Oryza Sativa (Rice) Lipids, Oryza Sativa (Rice) Seed Oil, Papaver Somniferum Seed Oil, Passiflora Edulis Seed Oil, Persea Gratissima (Avocado) Butter, Persea Gratissima (Avocado) Oil, Prunus Amygdalus Dulcis (Sweet Almond) Oil, Prunus Armeniaca (Apricot) Kernel Oil, Prunus Persica (Peach) Kernel Oil, Punica Granatum Seed Oil, Pyrus Malus (Apple) Seed Oil, Ricinoleic/Caproic/Caprylic/Capric Triglyceride(s), Ricinus Communis (Castor) Seed Oil, Rosa Canina Fruit Oil, Rosa Moschata Seed Oil, Rubus Idaeus (Raspberry) Seed Oil, Sesamum Indicum (Sesame) Seed Butter, Soybean Glycerides, Theobroma Cacao (Cocoa) Seed Butter, Theobroma Grandiflorum Seed Butter, Triticum Vulgare (Wheat) Bran Lipids, Triticum Vulgare (Wheat) Germ Oil, Vitis Vinifera (Grape) Seed Oil, Zea Mays (Corn) Germ Oil, and Zea Mays (Corn) Oil. [0274] The above specified plant oils are the most common natural lipid components used as basic substances for the manufacture of cosmetics or pharmaceutical formulations. [0275] Hydrocarbons (mineral oils) are in general organic compounds consisting entirely of hydrogen and carbon. As defined by IUPAC nomenclature or organic chemistry, the classifications for hydrocarbons are: 1. Saturated hydrocarbons are the simplest of the hydrocarbon species. They are composed entirely of single bonds and are saturated with hydrogen. The formula for acyclic saturated hydrocarbons (i.e., alkanes) is C
nH2
n+2.The most general form of saturated hydrocarbons is CnH2n+2(1-r), where r is the number of rings. Those with
220082 exactly one ring are the cycloalkanes. Saturated hydrocarbons are the basis of petroleum fuels and are found as either linear or branched species. 2. Unsaturated hydrocarbons have one or more double or triple bonds between carbon atoms. Those with double bond are called alkenes. Those with one double bond have the formula C
nH2
n (assuming non-cyclic structures). Those containing triple bonds are called alkynes. Those with one triple bond have the formula CnH2n−2. 3. Aromatic hydrocarbons, also known as arenes, are hydrocarbons that have at least one aromatic ring. [0276] Hydrocarbons can be inter alia liquids (e.g. hexane and benzene), waxes or low melting solids (e.g. paraffin wax and naphthalene). The term 'aliphatic' refers to non- aromatic hydrocarbons. Saturated aliphatic hydrocarbons are sometimes referred to as “paraffins”. Mineral oils and waxes are mixtures of predominantly saturated hydrocarbons consisting of straight‐chain, branched and ring structures with carbon chain lengths greater than C14. Mineral oils and waxes are chemical substances prepared from naturally occurring crude petroleum oil. They mainly consist of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). Hydrocarbons have been used for many decades in skin and lip care cosmetic products due to their excellent skin tolerance as well as their high protecting and cleansing performance and broad viscosity options. In contrast to vegetable oils, mineral oils are non‐allergenic since they are highly stable and not susceptible to oxidation or rancidity. [0277] A fatty alcohol (or long-chain alcohol) is usually a high-molecular-weight, straight- chain primary alcohol, but can also range from as few as 4 to 6 carbons to as many as 22 to 26, derived from natural fats and oils. The precise chain length varies with the source. Some commercially important fatty alcohols are lauryl, stearyl and oleyl alcohols. They are colourless oily liquids (for smaller carbon numbers) or waxy solids, although impure samples may appear yellow. Fatty alcohols usually have an even number of carbon atoms and a single alcohol group (–OH) attached to the terminal carbon. Some are unsaturated and some are branched. Most fatty alcohols in nature are found as waxes which are esters with fatty acids and fatty alcohols. The traditional sources of fatty alcohols have largely been various vegetable oils and these remain a large-scale feedstock. The alcohols are obtained from the triglycerides (fatty acid triesters), which
220082 form the bulk of the oil. The process involves the transesterification of the triglycerides to give methyl esters which are then hydrogenated to give the fatty alcohols. Fatty alcohols are also prepared from petrochemical sources. In the Ziegler process, ethylene is oligomerized using triethylaluminium followed by air oxidation. Alternatively, ethylene can be oligomerized to give mixtures of alkenes, which are subjected to hydroformylation, this process affording odd-numbered aldehyde, which is subsequently hydrogenated. Fatty alcohols are mainly used in the production of detergents and surfactants. They are components also of cosmetic solvents. They find use as co-emulsifiers, emollients and thickeners in cosmetics. [0278] In a preferred variant, the fatty alcohol is selected from the group consisting of phenyl propanol, dimethyl phenylbutanol, hexyldecanol, octyldodecanol, octyldecanol, tridecylalcohol, isostearyl alcohol, phenylisohexanol, phenylpropanol, trimethylbenzenepropanol, isoamylalcohol, isostearyl alcohol, and isotridecyl alcohol. In a more preferred variant, the fatty alcohol is selected from the group consisting of hexyldecanol, octyldodecanol, phenylpropanol, isoamylalcohol, and mixtures of two or more of the aforesaid fatty alcohols. The fatty alcohol can be used either as a single component or in a mixture with one or more further different fatty alcohol(s) as specified above. [0279] A fatty acid ester is a type of ester that results from the combination of a fatty acid with an alcohol. When the alcohol component is glycerol, the fatty acid esters produced can be monoglycerides, diglycerides or triglycerides. Fatty acid esters have a conditioning effect of softening the skin to create a smoothing sensation. They are also added to cosmetics to dissolve high-polarity active ingredients and UV absorbers. Esters of straight-chain fatty acids and lower alcohols are effective for dissolving slightly soluble ingredients for oils with a light touch during application. Isostearic acids and other liquid oils with branched fatty acids and unsaturated fatty acids are commonly used as emollients. Higher fatty acid esters and esters of higher alcohols with relatively high melting points are added to skin creams to adjust the application touch. [0280] In addition to the oil phase or oil component as defined above, the cosmetic or pharmaceutical preparation according to the present invention preferably includes one or
220082 more oil bodies. Suitable oil bodies, which form constituents of the O/W emulsions, are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C5 – C22 fatty acids with linear or branched C5 - C22 fatty alcohols or esters of branched C1 – C13 carboxylic acids with linear or branched C6 – C22 fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C6 – C22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C18 – C38 alkylhydroxy carboxylic acids with linear or branched C6 – C22 fatty alcohols, in particular Dioctyl Malate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C6 – C10 fatty acids, liquid mono-/di-/triglyceride mixtures based on C6 – C18 fatty acids, esters of C6 – C22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2 – C12 dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched CC – C22 fatty alcohol carbonates, such as, for example, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and/or branched C6-C22-alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.) and/or aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes.
220082 [0281] The sunscreen product, cosmetic or pharmaceutical, in particular dermatological, preparation or homecare product according to the present invention may advantageously combined with further standard excipients and/or active substances and/or additives and/or auxiliaries, such as are customarily used in such compositions, such as for example abrasives, anti-acne agents, agents against ageing of the skin, anti-cellulitis agents, anti-dandruff agents, anti-inflammatory agents, anti-microbial agents, irritation- preventing agents, irritation-inhibiting agents, antioxidants, astringents, odor absorbers, perspiration-inhibiting agents, antiseptic agents, anti-statics, binders, buffers, carrier materials, chelating agents, cell stimulants, cleansing agents, depilatory agents, surface- active substances, deodorizing agents, antiperspirants, softeners, emulsifiers, enzymes, enzyme inhibitors, essential oils, fibers, film-forming agents, fixatives, foam-forming agents, foam stabilizers, substances for preventing foaming, foam boosters, gelling agents, gel-forming agents, hair care agents, hair-setting agents, hair-straightening agents, moisture-donating agents, moisturizing substances, moisture-retaining substances, bleaching agents, strengthening agents, stain-removing agents, optically brightening agents, impregnating agents, dirt-repellent agents, dyes, friction-reducing agents, lubricants, moisturizing creams, ointments, opacifying agents, plasticizing agents, covering agents, polish, preservatives, gloss agents, green and synthetic polymers, powders, proteins, re-oiling agents, abrading agents, silicones, skin-soothing agents, skin-cleansing agents, skin care agents, skin-healing agents, skin-lightening agents, skin- protecting agents, skin-softening agents, hair promotion agents, cooling agents, skin- cooling agents, warming agents, skin-warming agents, stabilizers, surfactants, detergents, fabric conditioning agents, suspending agents, skin-tanning agents, actives modulating skin or hair pigmentation, matrix-metalloproteinase inhibitors, skin moisturizing agents, glycosaminoglycan stimulators, TRPV1 antagonists, desquamating agents, anti-cellulite agents or fat enhancing agents, hair growth activators or inhibitors, thickeners, rheology additives, vitamins, oils, waxes, pearlizing waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, α-hydroxy acids, polyhydroxyfatty acids, liquefiers, dyestuffs, colour-protecting agents, pigments, anti-corrosives, fragrances or perfume oils, aromas, flavouring substances, odoriferous substances, polyols, electrolytes, organic solvents, and mixtures of two or more of the aforesaid substances, as further described below.
220082 [0282] Of the above excipients and/or active substances and/or additives and/or auxiliaries emollients, rheology additives, agents to improve water resistance, film formers, silicones, dry-feel modifiers, skin moisturizing and/or moisture-retaining substances, lenitive substances, physiological cooling agents, antioxidants, emulsifiers, anti-microbial agents, preservatives, fragrances or perfume oils, and any mixture of two or more of the afore-mentioned substances are particularly preferred in the preparation of sunscreen products, cosmetic and pharmaceutical preparations and homecare products. [0283] Oil bodies and emollients: The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention advantageously includes one or more oil bodies or emollients. An emollient is an oleaginous or oily substance which helps to smooth and soften the skin, and may also reduce its roughness, cracking or irritation. Especially, in sunscreen products emollients counteract the known stickiness of some UV-filters and keep the crystalline and oil-soluble organic and inorganic UV-filters solubilized and prevent them from recrystallisation. In addition, emollients function as wetting agents for inorganic UV-filters for a homogeneous dispersion in the formulations. Suitable oil bodies are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6- C 13-carboxylic acids with linear or branched C6-C 22-fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C6-C22-fatty acids with branched alcohols, in particular 2-
220082 ethylhexanol, esters of C18-C38- alkylhydroxy carboxylic acids with linear or branched C6- C 22-fatty alcohols, in particular Dioctyl Malate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C6 -C10-fatty acids, liquid mono-/di- /triglyceride mixtures based on C6-C18-fatty acids, esters of C6- C22-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2- C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alcohol carbonates, such as, for example, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and/or branched C6-C22-alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or a symmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.) and/or aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes and any mixture thereof. [0284] Rheology modifiers: The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention advantageously includes one or more thickening agents and/or rheology modifier. The rheology modifier is present in an amount that prevents significant dripping or pooling of the composition after application to the skin. Preferably, the rheology modifier is a carbomer. In some embodiments, the rheology modifier is selected from stearic acid, palmitic acid, stearyl alcohol, cetyl alcohol, behenyl alcohol, stearic acid, palmitic acid, the polyethylene glycol ether of stearyl alcohol having an average of about 1 to about 21 ethylene oxide units, the polyethylene glycol ether of cetyl alcohol having an average of about 1 to about 5 ethylene oxide units, and mixtures thereof. [0285] Additional example of rheology modifiers include thickener or gelling agents, including substances which can increase the viscosity of a composition. Thickening agents include those that can increase the viscosity of a composition without substantially modifying the efficacy of the active ingredient within the formulation. Thickening agents
220082 can also increase the stability of the formulations of the present application. In certain aspects of the present application, thickening agents include hydrogenated polyisobutene or trihydroxy stearin, or a mixture of both. Additional non-limiting examples of additional thickening agents that can be used in the context of the present application include carboxylic acid polymers, crosslinked polyacrylate polymers, polyacrylamide polymers, polysaccharides, and gums. Examples of carboxylic acid polymers include crosslinked compounds containing one or more monomers derived from acrylic acid, substituted acrylic acids, and salts and esters of these acrylic acids and the substituted acrylic acids, wherein the crosslinking agent contains two or more carbon-carbon double bonds and is derived from a polyhydric alcohol (see CTFA International Cosmetic Ingredient Dictionary, Fourth Edition, 1991, pp. 12 and 80). Examples of commercially available carboxylic acid polymers include carbomers, which are homopolymers of acrylic acid crosslinked with allyl ethers of sucrose or pentaerythritol (e.g., Carbopol™ 900 series from B. F. Goodrich). Non-limiting examples of crosslinked polyacrylate polymers include cationic and nonionic polymers. [0286] Non-limiting examples of polyacrylamide polymers (including nonionic polyacrylamide polymers including substituted branched or unbranched polymers) include polyacrylamide, isoparaffin and Laureth-7, multi-block copolymers of acrylamides and substituted acrylamides with acrylic acids and substituted acrylic acids. [0287] Non-limiting examples of polysaccharides include cellulose, carboxymethyl hydroxyethylcellulose, cellulose acetate propionate carboxylate, hydroxyethylcellulose, hydroxyethyl ethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, methyl hydroxyethylcellulose, microcrystalline cellulose, sodium cellulose sulfate, and mixtures thereof. Another example is an alkyl substituted cellulose where the hydroxy groups of the cellulose polymer are hydroxyalkylated (preferably hydroxy ethylated or hydroxypropylated) to form a hydroxyalkylated cellulose which is then further modified with a C10-C30 straight chain or branched chain alkyl group through an ether linkage. Typically, these polymers are ethers of C10-C30 straight or branched chain alcohols with hydroxyalkylcelluloses. Other useful polysaccharides include scleroglucans comprising a linear chain of (1-3) linked glucose units with a (1-6) linked glucose every three unit.
220082 [0288] Non-limiting examples of gums that can be used with the present compositions include acacia, agar, algin, alginic acid, ammonium alginate, amylopectin, calcium alginate, calcium carrageenan, carnitine, carrageenan, dextrin, gelatin, gellan gum, guar gum, guar hydroxypropyltrimonium chloride, hectorite, hyaluroinic acid, hydrated silica, hydroxypropyl chitosan, hydroxypropyl guar, karaya gum, kelp, locust bean gum, natto gum, potassium alginate, potassium carrageenan, propylene glycol alginate, sclerotium gum, sodium carboxymethyl dextran, sodium carrageenan, tragacanth gum, xanthan gum, and mixtures thereof. In one embodiment, the thickening agent is Chondrus crispus (carrageenan) extract. [0289] Water resistance improving agents: The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention may advantageously include one or more agents for improving water resistance. An agent for improving water resistance is a hydrophobic material that imparts film forming and water resistance characteristics to an emulsion. Typical suitable water resistance improving agents include copolymers derived from polymerization of octadecene-1 and maleic anhydride. A preferred water resistance improving agent is a polyanhydride resin. Another preferred water resistance improving agent is a copolymer of vinyl pyrrolidone and eicosene monomers. The water resistance improving agent(s) is/are used in amounts effective to allow the final formulation to remain on the skin or surface after exposure to circulating water for at least 40 minutes, preferably 80 minutes. One or more water resistance improving agents can optionally be included in the final formulation in an amount ranging from 0.01 to 10.0 % by weight, preferably 0.05 to 8.0 % by weight, based on the total weight of the final formulation. [0290] Film formers: The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention may advantageously include one or more film formers or film forming agent. A film forming agent is a hydrophobic material that imparts water resistance and film forming characteristics to the sunscreen products, cosmetic or pharmaceutical preparations or homecare products. Standard film formers are preferably chitosan, microcrystalline chitosan, quaternized chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid and salts thereof and
220082 similar compounds. Preferred film formers for improving water resistance of the composition are selected from the group consisting of Polyamide-8 (such as Oleocraft LP 20 PA (MV)), Polyamide-3 (such as Oleocraft MP 32 PA (MV)), Trimethylpentanediol/Adipic Acid/Glycerin Crosspolymer (such as WetFilm), Octyldodecyl Citrate Crosspolymer (such as CosmoSurf CE 100), Polyglyceryl-3 Methyl Glucose Distearate (such as TegoCare 450), C28-52 Olefin/Undecylenic Acid Copolymer (such as Performa V6112), Hydrolyzed Jojoba esters, Jojoba Esters, Aqua (such as Floraester Jojoba K100), Cyclopentasiloxane Acrylates/Dimethicone copolymer (such as KP545), Acrylates/Beheneth-25 Methacylate Copolymer (such as Volarest), Styrene/Acrylates Copolymer (such as Dermacryl E Polymer), Polyurethane (such as Baycusan C1001), Polyurethane-2 and Polymethyl Methacrylate (such as Hybridur 875 Polymer), Acrylates/Octylacrylamide Copolymer (such as Dermacryl 2.0 Polymer), Beeswax (Cera Alba) (and) Sodium Stearoyl Lactylate (such as SymEffekt Sun), Pullulan, Xanthan Gum, Microcrystalline cellulose (and) Sphingomonas ferment extract (and) Cellulose gum (such as PemuPur™ START Polymer), Acacia Senegal Gum and Xanthan Gum (such as SOLAGUM™ AX), Microcrystalline Cellulose (and) Cellulose Gum (such as Natpure Cellgum Plus), Sodium Stearoyl Glutamate (such as AMISOFT® HS-11P), Hydrogenated Polycyclopentadiene (and) Caprylic/Capric Triglyceride (such as Koboguard® 5400 CCT), Glyceryl Hydrogenated Rosinate (and) Caprylic/Capric Triglyceride (and) Tocopherol (such as KOBOGUARD® NATURAL 2063-CCT), Galactoarabinan (such as LaraCare® A 200), C26-28 Alkyl Dimethicone (such as Wacker BELSIL® CDM 3526 VP), Caprylyl Methicone (such as Silsoft 034), Stearyl Dimethicone (and) Octadecene (such as Dowsil 2503 Cosmetic Wax), VP/Hexadecene Copolymer (such as Antaron™ V 216), Triacontanyl PVP (such as Antaron™ WP-660), Capryloyl Glycerin/Sebacic Acid Copolymer (such as LexFilm™ Sun Natural MB), Poly C10-30 Alkyl Acrylate (such as Tego SP 13 Sun Up), Microcrystalline Cellulose (such as Sunspheres™ BIO SPF Booster), and any mixture thereof. The aforesaid film forming agents are used in the sunscreen, cosmetic or pharmaceutical preparation or homecare product either as a single component or preferably in a mixture with two or more further of said film forming agents as specified above. The film forming agents are used in amounts effective to allow the final formulation to remain on the skin or surface after exposure to circulating water for at least 40 minutes, preferably 80 minutes. The film forming agents are present in the sunscreen product, cosmetic or pharmaceutical
220082 preparation or homecare product in an amount of 0.01 to 10.0 % by weight, preferably 0.05 to 8.0 % by weight, based on the total weight of the final formulation. [0291] Silicones: In order to impart a silky, spreadable, and luxurious texture and to make skin look and feel smoother, and additionally to improve processability (antifoaming) the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention preferably includes one or more silicones or silicone deratives. Suitable silicones can be chosen from the group consisting of Acefylline Methylsilanol Mannuronate, Acetylmethionyl Methylsilanol Elastinate Acrylates/Behenyl, Acrylate/Dimethicone Methacrylate Copolymer, Acrylates/Behenyl Methacrylate/Dimethicone Methacrylate Copolymer, Acrylates/Bis-Hydroxypropyl Dimethicone Crosspolymer, Acrylates/Dimethicone Copolymer, Acrylates/Dimethicone Methacrylate/Ethylhexyl Acrylate Copolymer, Acrylates/Dimethiconol Acrylate Copolymer, Acrylates/Ethylhexyl Acrylate/Dimethicone Methacrylate Copolymer, Acrylates/Octylacrylamide/Diphenyl Amodimethicone Copolymer, Acrylates/Polytri- methylsiloxymethacrylate Copolymer, Acrylates/Propyl Trimethicone Methacrylate Copolymer, Acrylates/Stearyl Acrylate/Dimethicone Methacrylate Copolymer, Acrylates/Tridecyl Acrylate/Triethoxysilylpropyl Methacrylate/Dimethicone Methacrylate Copolymer, Acrylates/Trifluoropropylmethacrylate/Polytrimethyl Siloxymethacrylate Copolymer, Amino Bispropyl Dimethicone, Aminoethylaminopropyl Dimethicone, Aminopropyl Dimethicone, Aminopropyl Phenyl Trimethicone, Aminopropyl Triethoxysilane, Ammonium Dimethicone PEG-7 Sulfate, Amodimethicone, Amodimethicone Hydroxystearate, Amodimethicone/Silsesquioxane Copolymer, Ascorbyl Carboxydecyl Trisiloxane, Ascorbyl Methylsilanol Pectinate, Behenoxy Dimethicone, Behentrimonium Dimethicone PEG-8 Phthalate, Behenyl Dimethicone, Bisamino PEG/PPG-41/3 Aminoethyl PG-Propyl Dimethicone, Bis-Aminopropyl/Ethoxy Aminopropyl Dimethicone, Bis(Butylbenzoate) Diaminotriazine Aminopropyltrisiloxane, Bis-Butyldimethicone Polyglyceryl-3, Bis-Butyloxyamodimethicone/PEG-60 Copolymer, Bis(C13-15 Alkoxy) Hydroxybutamidoamodimethicone, Bis(C13-15 Alkoxy) PG- Amodimethicone, Bis-(C1-8 Alkyl Lauroyl Lysine Decylcarboxamide) Dimethicone, Bis- Cetyl Cetyl Dimethicone, Bis-Cetyl/PEG-8 Cetyl PEG-8 Dimethicone, Bis-Diphenylethyl Disiloxane, Bis-Ethyl Ethyl Methicone, Bis-Gluconamidoethylaminopropyl Dimethicone, Bis-Hydrogen Dimethicone, Bis- Hydroxyethoxypropyl Dimethicone Bis-Hydroxylauryl,
220082 Dimethicone/IPDI Copolymer, Bis- Hydroxy/Methoxy Amodimethicone, Bis- Hydroxypropyl Dimethicone Behenate, Bis-Hydroxypropyl Dimethicone/SMDI Copolymer, Bis-lsobutyl PEG-14/Amodimethicone Copolymer, Bis-lsobutyl PEG- 15/Amodimethicone Copolymer, Bis-lsobutyl PEG/PPG-20/35/Amodimethicone Copolymer, Bis- lsobutyl PEG/PPG-10/7/Dimethicone Copolymer, Bis-lsobutyl PEG- 24/PPG-7/Dimethicone Copolymer, Bis-PEG-1 Dimethicone, Bis-PEG-4 Dimethicone, Bis-PEG-8 Dimethicone, Bis-PEG-12 Dimethicone,Bis-PEG-20 Dimethicone, Bis-PEG- 12 Dimethicone Beeswax, Bis-PEG-12 Dimethicone Candelillate, Bis-PEG-15 Dimethicone/IPDI Copolymer, Bis-PEG-15 Methyl Ether Dimethicone, Bis- PEG-18 Methyl Ether Dimethyl Silane, Bis-PEG/PPG-14/14 Dimethicone, Bis-PEG/PPG-15/5 Dimethicone, Bis-PEG/PPG-18/6 Dimethicone, Bis-PEG/PPG-20/20 Dimethicone, Bis- PEG/PPG- 16/16 PEG/PPG-16/16 Dimethicone, Bis-PEG/PPG-20/5 PEG/PPG-20/5 Dimethicone, Bisphenylhexamethicone, Bis-Phenylpropyl Dimethicone, Bispolyethylene Dimethicone, Bis- (Polyglyceryl-3 Oxyphenylpropyl) Dimethicone, Bis-(Polyglyceryl-7 Oxyphenylpropyl) Dimethicone, Bis-PPG-15 Dimethicone/IPDI Copolymer, Bis(PPG-7 Undeceneth-21) Dimethicone, Bis-Stearyl Dimethicone, Bis-Trimethoxysilylethyl Tetramethyldisiloxyethyl Dimethicone, Bis-Vinyldimethicone, Bis-Vinyl Dimethicone/Dimethicone Copolymer, Borage Seed Oil PEG-7 Dimethicone Esters, Butyl Acrylate/C6-14 Perfluoroalkylethyl Acrylate/Mercaptopropyl Dimethicone Copolymer, Butyl Acrylate/Hydroxypropyl Dimethicone Acrylate Copolymer, Butyl Dimethicone Acrylate/Cyclohexylmethacrylate/Ethylhexyl Acrylate Copolymer, Butyldimethicone Methacrylate/Methyl Methacrylate Crosspolymer, t-Butyl Dimethyl SiIyI Grape Seed Extract, Butyl Polydimethylsiloxyl Ethylene/Propylene/Vinylnorbornene Copolymer, C6-8 Alkyl C3-6 Alkyl Glucoside Dimethicone, C20-24 Alkyl Dimethicone,C24-28 Alkyl Dimethicone, C26-28 Alkyl Dimethicone, C30-45 Alkyl Dimethicone, C30-60 Alkyl Dimethicone, C32 Alkyl Dimethicone, C30-45 Alkyl Dimethicone/Polycyclohexene Oxide Crosspolymer, C26-28 Alkyldimethylsilyl Polypropylsilsesquioxane, C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane, C20-24 Alkyl Methicone, C24-28 Alkyl Methicone, C26-28 Alkyl Methicone, C30-45 Alkyl Methicone, C20-28 Alkyl Perfluorodecylethoxy Dimethicone, C26-54 Alkyl Tetradecyl Dimethicone, Capryl Dimethicone, Caprylyl Dimethicone Ethoxy Glucoside, Caprylyl Methicone, Caprylyl Trimethicone, Carboxydecyl Trisiloxane, Castor Oil Bis-Hydroxypropyl Dimethicone Esters Cerotyl Dimethicone, Cetearyl Dimethicone Crosspolymer, Cetearyl
220082 Dimethicone/Vinyl Dimethicone Crosspolymer, Cetearyl Methicone, Cetrimonium Carboxydecyl PEG-8 Dimethicone, Cetrimonium Dimethicone PEG-7 Phthalate, Cetyl Behenyl Dimethicone, Cetyl Dimethicone, Cetyl Dimethicone/Bis-Vinyldimethicone Crosspolymer, Cetyl HexacoSY-l Dimethicone, Cetyloxy Dimethicone, Cetyl PEG-8 Dimethicone, Cetyl PEG/PPG-15/15 Butyl Ether Dimethicone, Cetyl PEG/PPG-7/3 Dimethicone, Cetyl PEG/PPG-10/1 Dimethicone, Cetyl Triethylmonium Dimethicone PEG-8 Phthalate, Cetyl Triethylmonium Dimethicone PEG-8 Succinate, Copper Acetyl Tyrosinate Methylsilanol, Copper PCA Methylsilanol, C4-14 Perfluoroalkylethoxy Dimethicone, Cycloethoxymethicone, Cycloheptasiloxane, Cyclohexasiloxane, Cyclomethicone, Cyclopentasiloxane, Cyclophenylmethicone, Cyclotetrasiloxane,mCyclovinylmethicone, Cystine Bis-PG-Propyl Silanetriol, DEA PG- Propyl PEG/PPG-18/21 Dimethicone, Diisostearoyl Trimethylolpropane Siloxy Silicate, Dilauroyl Trimethylolpropane Siloxy Silicate, Dilinoleamidopropyl Dimethylamine Dimethicone PEG-7 Phosphate, Dimethicone, Dimethicone Crosspolymer, Dimethicone Crosspolymer-3, Dimethicone/Divinyldimethicone/Silsesquioxane Crosspolymer, Dimethicone Ethoxy Glucoside, Dimethicone Hydroxypropyl Trimonium Chloride, Dimethicone/Mercaptopropyl Methicone Copolymer, Dimethicone PEG-15 Acetate Dimethicone PEG-8 Adipate, Dimethicone PEG-7 Avocadoate, Dimethicone PEG-8 Avocadoate, Dimethicone PEG-8 Beeswax, Dimethicone PEG-8 Benzoate, Dimethicone PEG-8 Borageate, Dimethicone PEG-7 Cocoate, Dimethicone/PEG-10 Crosspolymer, Dimethicone/PEG-10/15 Crosspolymer, Dimethicone/PEG-15 Crosspolymer, Dimethicone PEG-7 Isostearate, Dimethicone PEG-8 Isostearate, Dimethicone PEG-7 Lactate, Dimethicone PEG-8 Lanolate, Dimethicone PEG-8 Laurate, Dimethicone PEG- 8 Meadowfoamate, Dimethicone PEG-7 Octyldodecyl Citrate, Dimethicone PEG-7 Olivate, Dimethicone PEG-8 Olivate, Dimethicone PEG-7 Phosphate, Dimethicone PEG- 8 Phosphate, Dimethicone PEG-10 Phosphate, Dimethicone PEG-7 Phthalate, Dimethicone PEG-8 Phthalate, Dimethicone PEG-8 Polyacrylate, Dimethicone PEG/PPG- 20/23 Benzoate, Dimethicone PEG/PPG-7/4 Phosphate, Dimethicone PEG/PPG-12/4 Phosphate, Dimethicone PEG-7 Succinate, Dimethicone PEG-8 Succinate, Dimethicone PEG-7 Sulfate, Dimethicone PEG-7 Undecylenate, Dimethicone PG-Diethylmonium Chloride, Dimethicone/Phenyl Vinyl Dimethicone Crosspolymer, Dimethicone/Polyglycerin-3 Crosspolymer, Dimethicone/PPG-20 Crosspolymer, Dimethicone Propylethylenediamine Behenate, Dimethicone Propyl PG-Betaine,
220082 Dimethicone/Silsesquioxane Copolymer, Dimethicone Silylate, Dimethicone/Vinyl Dimethicone Crosspolymer, Dimethicone/Vinyltrimethylsiloxysilicate Crosspolymer, Dimethiconol, Dimethiconol Arginine, Dimethiconol Beeswax, Dimethiconol Behenate, Dimethiconol Borageate, Dimethiconol Candelillate, Dimethiconol Carnaubate, Dimethiconol Cysteine, Dimethiconol Dhupa Butterate, Dimethiconol Fluoroalcohol Dilinoleic Acid, Dimethiconol Hydroxystearate, Dimethiconol lllipe Butterate, Dimethiconol/IPDI Copolymer, Dimethiconol Isostearate, Dimethiconol Kokum Butterate, Dimethiconol Lactate, Dimethiconol Meadowfoamate, Dimethiconol Methionine, Dimethiconol/Methylsilanol/Silicate Crosspolymer, Dimethiconol Mohwa Butterate, Dimethiconol Panthenol, Dimethiconol Sal Butterate, Dimethiconol/Silica Crosspolymer, Dimethiconol/Silsesquioxane Copolymer, Dimethiconol Stearate, Dimethiconol/Stearyl, Methicone/Phenyl Trimethicone Copolymer, Dimethoxysilyl Ethylenediaminopropyl Dimethicone, Dimethylaminopropylamido PCA Dimethicone, Dimethyl Oxobenzo Dioxasilane, Dimethylsilanol Hyaluronate, Dioleyl Tocopheryl Methylsilanol, Diphenyl Amodimethicone, Diphenyl Dimethicone, Diphenyl Dimethicone Crosspolymer Diphenyl Dimethicone?/inyl Diphenyl Dimethicone/Silsesquioxane Crosspolymer, Diphenylethyl Benzyloxy Dilsiloxane, Diphenylisopropyl Dimethicone, Diphenylsiloxy Phenyl/Propyl Trimethicone, Diphenylsiloxy Phenyl Trimethicone Disiloxane, Disodium Amodimethicone Disuccinamide, Disodium PEG-12 Dimethicone Sulfosuccinate, Disodium PEG-8 Lauryl Dimethicone Sulfosuccinate, Divinyldimethicone/Dimethicone Copolymer, Divinyldimethicone/Dimethicone Crosspolymer, Drometrizole Trisiloxane, Ethylhexyl Acrylate/VP/Dimethicone Methacrylate Copolymer, Ethyl Methicone, Ethyl Trisiloxane, Fluoro C2-8 Alkyldimethicone, Gluconamidopropyl Aminopropyl Dimethicone, 4-(2-Beta-Glucopyranosiloxy) Propoxy-2-Hydroxybenzophenone, Glyceryl Undecyl Dimethicone, Glycidoxy Dimethicone, Hexadecyl Methicone, Hexyl Dimethicone, Hexyl Methicone, Hexyltrimethoxysilane, Hydrogen Dimethicone, Hydrogen Dimethicone/Octyl Silsesquioxane Copolymer, Hydrolyzed Collagen PG-Propyl Dimethiconol, Hydrolyzed Collagen PG-Propyl Methylsilanediol, Hydrolyzed Collagen PG-Propyl Silanetriol, Hydrolyzed Keratin PG-Propyl Methylsilanediol, Hydrolyzed Sesame Protein PG-Propyl Methylsilanediol, Hydrolyzed Silk PG-Propyl Methylsilanediol, Hydrolyzed Silk PG-Propyl Methylsilanediol Crosspolymer, Hydrolyzed Soy Protein/Dimethicone PEG-7 Acetate, Hydrolyzed Soy Protein PG-Propyl Methylsilanediol, Hydrolyzed Vegetable Protein PG-Propyl Silanetriol, Hydrolyzed Wheat
220082 Protein/Cystine Bis-PG-Propyl Silanetriol Copolymer, Hydrolyzed Wheat Protein/Dimethicone PEG-7 Acetate, Hydrolyzed Wheat Protein/Dimethicone PEG-7 Phosphate Copolymer, Hydrolyzed Wheat Protein PG-Propyl Methylsilanediol, Hydrolyzed Wheat Protein PG-Propyl Silanetriol, Hydroxyethyl Acetomonium PG- Dimethicone, Hydroxypropyldimethicone, Hydroxypropyl Dimethicone Behenate, Hydroxypropyl Dimethicone Isostearate, Hydroxypropyl Dimethicone Stearate, Isobutylmethacrylate/Bis-Hydroxypropyl Dimethicone Acrylate Copolymer, Isobutylmethacrylate/Trifluoroethylmethacrylate/Bis-Hydroxypropyl Dimethicone Acrylate Copolymer, lsopentyl Trimethoxycinnamate Trisiloxane, lsopolyglyceryl-3 Dimethicone, lsopolyglyceryl-3 Dimethiconol, lsopropyl Titanium Triisostearate/Triethoxysilylethyl, Polydimethylsiloxyethyl Dimethicone Crosspolymer, lsostearyl Carboxydecyl PEG-8 Dimethicone, Lactoyl Methylsilanol Elastinate, Lauryl Dimethicone, Lauryl Dimethicone PEG-15 Crosspolymer, Lauryl Dimethicone PEG- 10 Phosphate, Lauryl Dimethicone/Polyglycerin-3 Crosspolymer, Lauryl Methicone, Lauryl PEG-8 Dimethicone, Lauryl PEG-10 Methyl Ether Dimethicone, Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone, Lauryl PEG/PPG-18/18 Methicone, Lauryl Phenylisopropyl Methicone, Lauryl Phenylpropyl Methicone, Lauryl Polydimethylsiloxyethyl Dimethicone/Bis-Vinyldimethicone Crosspolymer, Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone, Lauryl Trimethicone, Linoleamidopropyl PG-Dimonium Chloride Phosphate Dimethicone, Methacryloyl Propyltrimethoxysilane, Methicone, Methoxy Amodimethicone/Silsesquioxane Copolymer, Methoxycinnamidopropyl Polysilsesquioxane, Methoxycinnamoylpropyl Silsesquioxane Silicate, Methoxy PEG-13 Ethyl Polysilsesquioxane, Methoxy PEG/PPG- 7/3 Aminopropyl Dimethicone, Methoxy PEG/PPG-25/4 Dimethicone, Methoxy PEG-10 Propyltrimethoxysilane, Methyleugenyl PEG- 8 Dimethicone, Methylpolysiloxane Emulsion, Methylsilanol Acetylmethionate, Methylsilanol Acetyltyrosine, Methylsilanol Ascorbate, Methylsilanol Carboxymethyl Theophylline, Methylsilanol Carboxymethyl Theophylline Alginate, Methylsilanol Elastinate, Methylsilanol Glycyrrhizinate, Methylsilanol Hydroxyproline, Methylsilanol Hydroxyproline Aspartate, Methylsilanol Mannuronate, Methylsilanol PCA, Methylsilanol PEG-7 Glyceryl Cocoate, Methylsilanol/Silicate Crosspolymer, Methylsilanol Spirulinate, Methylsilanol Tri-PEG-8 Glyceryl Cocoate, Methyl Trimethicone, Methyltrimethoxysilane, Myristylamidopropyl Dimethylamine Dimethicone PEG-7 Phosphate, Myristyl Methicone, Myristyl Trisiloxane,
220082 Nylon-611/Dimethicone Copolymer, PCA Dimethicone, PEG-7 Amodimethicone, PEG-8 Amodimethicone, PEG-8 Cetyl Dimethicone, PEG-3 Dimethicone, PEG-6 Dimethicone, PEG-7 Dimethicone, PEG-8 Dimethicone, PEG-9 Dimethicone, PEG-10 Dimethicone, PEG-12 Dimethicone, PEG-14 Dimethicone, PEG-17 Dimethicone, PEG-10 Dimethicone Crosspolymer, PEG-12 Dimethicone Crosspolymer, PEG-8 Dimethicone Dimer Dilinoleate, PEG-8 Dimethicone/Dimer Dilinoleic Acid Copolymer, PEG-10 Dimethicone/Vinyl Dimethicone Crosspolymer, PEG-8 Distearmonium Chloride PG- Dimethicone, PEG-10/Lauryl Dimethicone Crosspolymer, PEG- 15/Lauryl Dimethicone Crosspolymer, PEG-15/Lauryl Polydimethylsiloxyethyl Dimethicone Crosspolymer, PEG- 8 Methicone, PEG-6 Methicone Acetate, PEG-6 Methyl Ether Dimethicone, PEG- 7 Methyl Ether Dimethicone, PEG-8 Methyl Ether Dimethicone, PEG-9 Methyl Ether Dimethicone, PEG-10 Methyl Ether Dimethicone, PEG-11 Methyl Ether Dimethicone, PEG-32 Methyl Ether Dimethicone, PEG-8 Methyl Ether Triethoxysilane, PEG-10 Nonafluorohexyl Dimethicone Copolymer, PEG-4 PEG-12 Dimethicone, PEG-8 PG- Coco-Glucoside Dimethicone, PEG-9 Polydimethylsiloxyethyl Dimethicone, PEG/PPG- 20/22 Butyl Ether Dimethicone, PEG/PPG-22/22 Butyl Ether Dimethicone, PEG/PPG- 23/23 Butyl Ether Dimethicone, PEG/PPG-24/18 Butyl Ether Dimethicone, PEG/PPG- 27/9 Butyl Ether Dimethicone, PEG/PPG-3/10 Dimethicone, PEG/PPG-4/12 Dimethicone, PEG/PPG-6/4 Dimethicone, PEG/PPG-6/11 Dimethicone, PEG/PPG-8/14 Dimethicone, PEG/PPG-8/26 Dimethicone, PEG/PPG-10/2 Dimethicone, PEG/PPG- 12/16 Dimethicone, PEG/PPG- 12/18 Dimethicone, PEG/PPG-14/4 Dimethicone, PEG/PPG-15/5 Dimethicone, PEG/PPG-15/15 Dimethicone, PEG/PPG-16/2 Dimethicone, PEG/PPG-16/8 Dimethicone, PEG/PPG-17/18 Dimethicone, PEG/PPG- 18/6 Dimethicone, PEG/PPG-18/12 Dimethicone, PEG/PPG-18/18 Dimethicone, PEG/PPG-19/19 Dimethicone, PEG/PPG-20/6 Dimethicone, PEG/PPG-20/15 Dimethicone, PEG/PPG-20/20 Dimethicone, PEG/PPG-20/23 Dimethicone, PEG/PPG- 20/29 Dimethicone, PEG/PPG-22/23 Dimethicone, PEG/PPG-22/24 Dimethicone, PEG/PPG-23/6 Dimethicone, PEG/PPG-25/25 Dimethicone, PEG/PPG-27/27 Dimethicone, PEG/PPG-30/10 Dimethicone, PEG/PPG-25/25 Dimethicone/Acrylates Copolymer, PEG/PPG-20/22 Methyl Ether Dimethicone, PEG/PPG-24/24 Methyl Ether Glycidoxy Dimethicone, PEG/PPG-10/3 Oleyl Ether Dimethicone, PEG/PPG-5/3 Trisiloxane, PEG-4 Trifluoropropyl Dimethicone Copolymer, PEG-8 Trifluoropropyl Dimethicone Copolymer, PEG-10 Trifluoropropyl Dimethicone Copolymer, PEG-8
220082 Trisiloxane, Perfluorocaprylyl riethoxysilylethyl Methicone, Perfluorononyl Dimethicone, Perfluorononyl Dimethicone/Methicone/Amodimethicone Crosspolymer, Perfluorononylethyl Carboxydecyl Behenyl Dimethicone, Perfluorononylethyl Carboxydecyl HexacoSY-l Dimethicone, Perfluorononylethyl Carboxydecyl Lauryl/Behenyl Dimethicone, Perfluorononylethyl Carboxydecyl Lauryl Dimethicone, Perfluorononylethyl Carboxydecyl PEG-8 Dimethicone, Perfluorononylethyl Carboxydecyl PEG-10 Dimethicone, Perfluorononylethyl Dimethicone/Methicone Copolymer, Perfluorononylethyl PEG-8 Dimethicone, Perfluorononylethyl Stearyl Dimethicone, Perfluorooctylethyl/Diphenyl Dimethicone Copolymer, Perfluorooctylethyl Triethoxysilane, Perfluorooctylethyl Trimethoxysilane, Perfluorooctylethyl Trisiloxane, Perfluorooctyl Triethoxysilane, PG-Amodimethicone, Phenethyl Dimethicone, Phenethyl Disiloxane, Phenyl Dimethicone, Phenylisopropyl Dimethicone, Phenyl Methicone, Phenyl Methiconol, Phenylpropyldimethylsiloxysilicate, Phenylpropyl Ethyl Methicone, Phenyl Propyl Trimethicone, Phenyl Propyl Trimethicone/Diphenylmethicone, Phenyl Trimethicone, Platinum Divinyldisiloxane, Polyacrylate-6, Polydiethylsiloxane, Polydimethylsiloxyethyl Dimethicone/Bis-Vinyldimethicone Crosspolymer, Polydimethylsiloxyethyl Dimethicone/Methicone Copolymer, Polydimethylsiloxy PEG/PPG-24/19 Butyl Ether Silsesquioxane, Polydimethylsiloxy PPG- 13 Butyl Ether Silsesquioxane, Polyglyceryl-3 Disiloxane Dimethicone, Polyglyceryl-3/Lauryl Polydimethylsiloxyethyl Dimethicone Crosspolymer, Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone, Poly(Glycol Adipate)/Bis-Hydroxyethoxypropyl Dimethicone Copolymer, Polymethylsilsesquioxane, Polymethylsilsesquioxane/Trimethylsiloxysilicate, Polyphenylsilsesquioxane, Polypropylsilsesquioxane, Polysilicone-1, Polysilicone-2, Polysilicone-3, Polysilicone-4, Polysilicone-5, Polysilicone-6, Polysilicone-7, Polysilicone-8, Polysilicone-9, Polysilicone- 10, Polysilicone-11, Polysilicone-12, Polysilicone-13, Polysilicone-14, Polysilicone-15, Polysilicone-16, Polysilicone-17, Polysilicone-18, Polysilicone-19, Polysilicone-20, Polysilicone-21, Polysilicone-18 Cetyl Phosphate, Polysilicone-1 Crosspolymer, Polysilicone-18 Stearate, Polyurethane-10, Potassium Dimethicone PEG-7 Panthenyl Phosphate, Potassium Dimethicone PEG- 7 Phosphate, PPG-12 Butyl Ether Dimethicone, PPG-2 Dimethicone, PPG-12 Dimethicone, PPG-27 Dimethicone, PPG-4 Oleth-10 Dimethicone, Propoxytetramethyl Piperidinyl Dimethicone, Propyl Trimethicone, Quaternium-80, Retinoxytrimethylsilane, Silanediol Salicylate, Silanetriol, Silanetriol
220082 Arginate, Silanetriol Glutamate, Silanetriol Lysinate, Silanetriol Melaninate, Silanetriol Trehalose Ether, Silica, Silica Dimethicone Silylate, Silica Dimethyl Silylate, Silica Silylate, Silicon Carbide, Silicone Quaternium-1, Silicone Quaternium-2, Silicone Quaternium-2 Panthenol Succinate, Silicone Quaternium-3, Silicone Quaternium-4, Silicone Quaternium-5, Silicone Quaternium-6, Silicone Quaternium-7, Silicone Quaternium-8, Silicone Quaternium-9, Silicone Quaternium-10, Silicone Quaternium-11, Silicone Quaternium-12, Silicone Quaternium-15, SiliconeQuaternium-16, Silicone Quaternium- 16/Glycidoxy Dimethicone Crosspolymer, Silicone Quaternium-17, Silicone Quaternium- 18, Silicone Quaternium-19, Silicone Quaternium-20, Silicone Quaternium-21, Silicone Quaternium- 22, Silicone Quaternium-24, Silicone Quaternium-25, Siloxanetriol Alginate, Siloxanetriol Phytate, Simethicone, Sodium Carboxydecyl PEG-8 Dimethicone, Sodium Dimethicone PEG-7 Acetyl Methyltaurate, Sodium Hyaluronate Dimethylsilanol, Sodium Lactate Methylsilanol, Sodium Mannuronate Methylsilanol, Sodium PCA Methylsilanol, Sodium PG-Propyldimethicone Thiosulfate Copolymer, Sodium PG-Propyl Thiosulfate Dimethicone, Sodium Propoxyhydroxypropyl Thiosulfate Silica, Sorbityl Silanediol, Soy Triethoxysilylpropyldimonium Chloride, Stearalkonium Dimethicone PEG-8 Phthalate, Stearamidopropyl Dimethicone, Steardimonium Hydroxypropyl Panthenyl PEG-7 Dimethicone Phosphate Chloride, Steardimonium Hydroxypropyl PEG-7 Dimethicone Phosphate Chloride, Stearoxy Dimethicone, Stearoxymethicone/Dimethicone Copolymer, Stearoxytrimethylsilane, Stearyl Aminopropyl Methicone, Stearyl Dimethicone, Stearyl/Lauryl Methacrylate Crosspolymer, Stearyl Methicone, Stearyl Triethoxysilanek, Stearyl Trimethicone, Styrene/Acrylates/Dimethicone Acrylate Crosspolymer, Styrene/Acrylates/Dimethicone Copolymer, TEA-Dimethicone PEG-7 Phosphate, Tetrabutoxypropyl Trisiloxane, Tetramethyl Hexaphenyl Tetrasiloxane, Tetramethyl Tetraphenyl Trisiloxane, Tocopheryloxypropyl Trisiloxane, Trideceth-9 PG- Amodimethicone, Triethoxycaprylylsilane, Triethoxysilylethyl Dimethicone/Methicone Copolymer, Triethoxysilylethyl Polydimethylsiloxyethyl Dimethicone, Triethoxysilylethyl Polydimethylsiloxyethyl Hexyl Dimethicone, Triethoxysilylpropylcarbamoyl Ethoxypropyl Butyl Dimethicone, Trifluoromethyl C1-4 Alkyl Dimethicone, Trifluoropropyl Cyclopentasiloxane, Trifluoropropyl Cyclotetrasiloxane, Trifluoropropyl Dimethicone, Trifluoropropyl Dimethicone/PEG-10 Crosspolymer, Trifluoropropyl Dimethicone/Trifluoropropyl Divinyldimethicone Crosspolymer, Trifluoropropyl Dimethicone/Vinyl Trifluoropropyl, Dimethicone/Silsesquioxane Crosspolymer,
220082 Trifluoropropyl Dimethiconol, Trifluoropropyldimethyl/trimethylsiloxysilicate, Trifluoropropyl Methicone, Trimethoxycaprylylsilane, Trimethoxysilyl Dimethicone, Trimethyl Pentaphenyl Trisiloxane, Trimethylsiloxyamodimethicone, Trimethylsiloxyphenyl Dimethicone, Trimethylsiloxysilicate, Trimethylsiloxysilicate/Dimethicone Crosspolymer, Trimethylsiloxysilicate/Dimethiconol Crosspolymer, Trimethylsiloxysilylcarbamoyl Pullulan, Trimethylsilyl Hydrolyzed Conchiolin Protein PG-Propyl Methylsilanediol Crosspolymer, Trimethylsilyl Hydrolyzed Silk PG-Propyl Methylsilanediol Crosspolymer, Trimethylsilyl Hydrolyzed Wheat Protein PG-Propyl Methylsilanediol Crosspolymer, Trimethylsilyl Pullulan, Trimethylsilyl Trimethylsiloxy Glycolate, Trimethylsilyl Trimethylsiloxy Lactate, Trimethylsilyl Trimethylsiloxy Salicylate, Triphenyl Trimethicone, Trisiloxane, Tris- Tributoxysiloxymethylsilane, Undecylcrylene Dimethicone, Vinyl Dimethicone, Vinyl Dimethicone/Lauryl Dimethicone Crosspolymer, Vinyl Dimethicone/Methicone Silsesquioxane Crosspolymer, Vinyldimethyl/Trimethylsiloxysilicate Stearyl Dimethicone Crosspolymer, VP/Dimethiconylacrylate/Polycarbamyl/Polyglycol Ester, Zinc Carboxydecyl Trisiloxane, Zinc Dimethicone PEG-8 Succinate, and mixtures thereof. More preferably, the silicones to be contained in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the invention are Dimethicone, Cyclomethicone, Cyclopentasiloxane, Cyclotetrasiloxane, Phenyl Trimethicone, and Cyclohexasiloxane. The total amount of silicone compound(s) in the compositions according to the present invention can vary but is typically 0.1 to 35.0 % by weight, based on the total weight of the composition. [0292] Dry-feel modifiers: The sunscreen product or cosmetic or pharmaceutical preparation according to the present invention is preferably combined with dry-feel modifiers. A dry-feel modifier is an agent which, when incorporated in an emulsion, imparts a "dry feel" to the skin when the emulsion dries. Dry-feel modifiers may also reduce sunscreen migration on the skin. Dry-feel modifiers can include starches, talc, kaolin, chalk, zinc oxide, silicone fluids, inorganic salts such as barium sulfate and sodium chloride, C6 to C12 alcohols such as octanol; sulfonated oils; surface treated silica, precipitated silica, fumed silica such as Aerosil® available from the Degussa Inc. of New York, N.Y. U.S.A. or mixtures thereof; dimethicone, a mixture of mixture of methylated linear siloxane polymers, available as DC200 fluid, tradename of Dow Corning, Midland,
220082 Mich. U.S.A. One or more dry-feel modifiers can optionally be included in the final formulations in amounts ranging from 0.01 to 20 % by weight, more preferably from 0.1 to 10.0 % by weight. [0293] Skin moisturizing and/or moisture-retaining substances: The sunscreen product or cosmetic or pharmaceutical preparation according to the present invention comprises advantageously one or more skin-moisturizing and/or moisture-retaining substances. Preferred skin moisturizing and/or moisture-retaining substances are selected from the group consisting of alkane diols or alkane triols comprising 3 to 12 carbon atoms, preferably C3-C10-alkane diols and C3-C10-alkane triols. More preferably the skin moisturizing agents are selected from the group consisting of glycerol, 1,2- propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,2-pentanediol, 1,2- hexanediol, 1,2-octanediol and 1,2-decanediol. Further skin moisturizing and/or moisture- retaining substances include sodium lactate, urea, urea derivatives, alcohols, glycerol, diols such as propylene glycol, hexylene glycol, collagen, elastin or hyaluronic acid, diacyl adipates, petrolatum, urocanic acid, lecithin, panthenol, phytantriol, lycopene, (pseudo- )ceramides, glycosphingolipids, cholesterol, phytosterols, chitosan, chondroitin sulfate, lanolin, lanolin esters, amino acids, alpha-hydroxy acids (such as citric acid, lactic acid, malic acid) and their derivatives, mono-, di- and oligosaccharides such as glucose, galactose, fructose, mannose, fructose and lactose, polysugars such as R-glucans, in particular 1,3-1,4-β-glucan from oats, alpha-hydroxy fatty acids, triterpene acids such as betulinic acid or ursolic acid, and algae extracts. [0294] Lenitive substances: The sunscreen product or cosmetic or pharmaceutical preparation according to the present invention can also contain advantageously one or more lenitive substances, wherein any lenitive substances can be used which are suitable or customary in cosmetic or pharmaceutical applications such as alpha-bisabolol, azulene, guaiazulene, 18-beta-glycyrrhetinic acid, allantoin, Aloe vera juice or gel, extracts of Hamamelis virginiana (witch hazel), Echinacea species, Centella asiatica, chamomile, Arnica montana, Glycyrrhiza species, algae, seaweed and Calendula officinalis, and vegetable oils such as sweet almond oil, baobab oil, olive oil and panthenol, Laureth-9, Trideceth-9 and 4-t-butylcyclohexanol.
220082 [0295] Physiological cooling agents: The sunscreen product or cosmetic or pharmaceutical preparation according to the present invention can be particularly advantageously combined with one or more physiological cooling agent(s). The use of cooling agents can alleviate itching. Preferred individual cooling agents for use within the framework of the present invention are listed below. The person skilled in the art can add many other cooling agents to this list; the cooling agents listed can also be used in combination with one another: which are preferably selected here from the following list: menthol and menthol derivatives (for example L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol) menthylethers (for example (I-menthoxy)-1,2- propanediol, (l-menthoxy)-2-methyl-1,2-propanediol, l-menthyl-methylether), menthone glyceryl acetal, menthone glyceryl ketal or mixtures of both, menthylesters (for example menthylformiate, menthylacetate, menthylisobutyrate, menthyhydroxyisobutyrat, menthyllactates, L-menthyl-L-lactate, L-menthyl-D-lactate, menthyl-(2-methoxy)acetate, menthyl-(2-methoxyethoxy)acetate, menthylpyroglutamate), menthylcarbonates (for example menthylpropyleneglycolcarbonate, menthylethyleneglycolcarbonate, menthylglycerolcarbonate or mixtures thereof), the semi-esters of menthols with a dicarboxylic acid or derivatives thereof (for example mono-menthylsuccinate, mono- menthylglutarate, mono-menthylmalonate, O-menthyl succinic acid ester-N,N- (dimethyl)amide, O-menthyl succinic acid ester amide), menthanecarboxylic acid amides (in this case preferably menthanecarboxylic acid-N-ethylamide [WS3] or N
α- (menthanecarbonyl)glycinethylester [WS5], menthanecarboxylic acid-N-(4- cyanophenyl)amide or menthanecarboxylic acid-N-(4-cyanomethylphenyl)amide, menthanecarboxylic acid-N-(alkoxyalkyl)amides), menthone and menthone derivatives (for example L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butyric acid derivatives (for example 2,3-dimethyl-2-(2-propyl)-butyric acid-N-methylamide [WS23]), isopulegol or its esters (I-(-)-isopulegol, I-(-)-isopulegolacetate), menthane derivatives (for example p-menthane-3,8-diol), cubebol or synthetic or natural mixtures, containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (for example 3-methyl-2(1- pyrrolidinyl)-2-cyclopentene-1-one) or tetrahydropyrimidine-2-one (for example icilin or related compounds), further carboxamides (for example N-(2-(pyridin-2-yl)ethyl)-3-p- menthanecarboxamide or related compounds), (1R,2S,5R)-N-(4-Methoxyphenyl)-5- methyl-2-(1-isopropyl)cyclohexane-carboxamide [WS12], oxamates and [(1R,2S,5R)-2- isopropyl-5-methyl-cyclohexyl] 2-(ethylamino)-2-oxo-acetate (X Cool). Cooling agents
220082 which are preferred due to their particular synergistic effect are l-menthol, d-menthol, racemic menthol, menthone glycerol acetal (trade name: Frescolat
® MGA), menthyl lactate (preferably l-menthyl lactate, in particular l-menthyl l-lactate (trade name: Frescolat
® ML)), substituted menthyl-3-carboxamides (such as menthyl-3-carboxylic acid N-ethyl amide), 2-isopropyl-N-2,3-trimethyl butanamide, substituted cyclohexane carboxamides, 3-menthoxypropane-1,2-diol, 2-hydroxyethyl menthyl carbonate, 2- hydroxypropyl menthyl carbonate and isopulegol. Particularly preferred cooling agents are l-menthol, racemic menthol, menthone glycerol acetal (trade name: Frescolat
® MGA), menthyl lactate (preferably l-menthyl lactate, in particular l-menthyl l-lactate (trade name: Frescolat
® ML)), 3-menthoxypropane-1,2-diol, 2-hydroxyethyl menthyl carbonate and 2- hydroxypropyl menthyl carbonate. Very particularly preferred cooling agents are l- menthol, menthone glycerol acetal (trade name: Frescolat
® MGA) and menthyl lactate (preferably l-menthyl lactate, in particular l-menthyl l-lactate (trade name: Frescolat
® ML). [0296] Antioxidants: The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention comprises advantageously one or more antioxidants. Suitable antioxidants encompass amino acids (preferably glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (preferably urocanic acid) and derivatives thereof, peptides, preferably D,L-carnosine, D-carnosine, L- carnosine and derivatives thereof (preferably anserine), carnitine, creatine, matrikine peptides (preferably lysyl-threonyl-threonyl-lysyl-serine) and palmitoylated pentapeptides, carotenoids, carotenes (preferably alpha-carotene, beta-carotene, lycopene) and derivatives thereof, lipoic acid and derivatives thereof (preferably dihydrolipoic acid), aurothioglucose, propyl thiouracil and other thiols (preferably thioredoxine, glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, gamma-linoleyl, cholesteryl, glyceryl and oligoglyceryl esters thereof) and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (preferably esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (preferably buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very small tolerated doses (e.g. pmol to μmol/kg), also (metal) chelators (preferably alpha-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin, alpha-hydroxy acids (preferably citric acid, lactic acid, malic acid), humic
220082 acid, bile acid, bile extracts, tannins, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof), unsaturated fatty acids and derivatives thereof (preferably gamma-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and derivatives thereof, ubiquinol and derivatives thereof, vitamin C and derivatives (preferably ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate, ascorbyl glucoside), tocopherols and derivatives (preferably vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoic resin, rutinic acid and derivatives thereof, flavonoids and glycosylated precursors thereof, in particular quercetin and derivatives thereof, preferably alpha-glucosyl rutin, rosmarinic acid, carnosol, carnosolic acid, resveratrol, caffeic acid and derivatives thereof, sinapic acid and derivatives thereof, ferulic acid and derivatives thereof, curcuminoids, chlorogenic acid and derivatives thereof, retinoids, preferably retinyl palmitate, retinol or tretinoin, ursolic acid, levulinic acid, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiac acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof (preferably ZnO, ZnSO4), selenium and derivatives thereof (preferably selenium methionine), superoxide dismutase, stilbenes and derivatives thereof (preferably stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these cited active ingredients which are suitable according to the invention or extracts or fractions of plants having an antioxidant effect, preferably green tea, rooibos, honeybush, grape, rosemary, sage, melissa, thyme, lavender, olive, oats, cocoa, ginkgo, ginseng, liquorice, honeysuckle, sophora, pueraria, pinus, citrus, Phyllanthus emblica or St. John's wort, grape seeds, wheat germ, Phyllanthus emblica, coenzymes, preferably coenzyme Q10, plastoquinone and menaquinone. Preferred antioxidants are selected from the group consisting of vitamin A and derivatives, vitamin C and derivatives, tocopherol and derivatives, preferably tocopheryl acetate, and ubiquinone. [0297] Emulsifiers: In addition, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention can also advantageously contain one or more emulsifiers in order to keep the sunscreen product, cosmetic or pharmaceutical preparation or homecare product stable. Emulsifiers include amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The
220082 emulsifiers are chosen in an appropriate manner according to the emulsion to be obtained. Preferred examples include: - products of the addition of 2 to 30 mol ethylene oxide and/or 0 to 5 mol propylene oxide onto linear C8-22 fatty alcohols, onto C12-22 fatty acids and onto alkyl phenols containing 8 to 15 carbon atoms in the alkyl group; - C12/18 fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol; - glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and ethylene oxide addition products thereof; - addition products of 15 to 60 mol ethylene oxide onto castor oil and/or hydrogenated castor oil; - polyol esters and in particular, polyglycerol esters such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate isostearate. Mixtures of compounds from several of these classes are also suitable; - addition products of 2 to 15 mol ethylene oxide onto castor oil and/or hydrogenated castor oil; - partial esters based on linear, branched, unsaturated or saturated C6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose); - mono-, di and trialkyl phosphates and mono-, di- and/or tri-PEG-alkyl phosphates and salts thereof; - wool wax alcohols; - polysiloxane/polyalkyl polyether copolymers and corresponding derivatives; - mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and/or mixed esters of C6-22 fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol, - polyalkylene glycols and - glycerol carbonate.
220082 [0298] The addition products of ethylene oxide and/or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or onto castor oil are known commercially available products. They are homologue mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C12/18 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as lipid layer enhancers for cosmetic formulations. The preferred emulsifiers are described in more detail as follows: [0299] Partial glycerides: Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quantities of triglyceride from the production process. Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto the partial glycerides mentioned are also suitable. [0300] Sorbitan esters: Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto the sorbitan esters mentioned are also suitable.
220082 [0301] Polyglycerol esters: Typical examples of suitable polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls
® PGPH), Polyglycerin-3-Diisostearate (Lameform
® TGI), Polyglyceryl-4 Isostearate (Isolan
® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care
® 450), Polyglyceryl-3 Beeswax (Cera Bellina
®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane
® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul
® WOL 1403), Polyglyceryl Dimerate Isostearate and mixtures thereof. Examples of other suitable polyolesters are the mono-, di- and triesters of trimethylol propane or pentaerythritol with lauric acid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like optionally reacted with 1 to 30 mol ethylene oxide. [0302] Anionic emulsifiers: Typical anionic emulsifiers are aliphatic C12 to C 22 fatty acids, such as palmitic acid, stearic acid or behenic acid for example, and C12 to C22 dicarboxylic acids, such as azelaic acid or sebacic acid for example. [0303] Amphoteric emulsifiers: Other suitable emulsifiers are amphoteric or zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3- carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a C8/18 alkyl or acyl group, contain at least one free amino group and at least one ^COOH- or -SO3H- group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N- alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl
220082 taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C12/18 acyl sarcosine. [0304] Antimicrobial agents: The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention can advantageously combined with an anti-microbial agent which act primarily against microorganisms, in particular bacteria, yeast and/or fungi and includes one or more anti-microbial agents such as Caprylhydroxamic Acid, o-Cymen-5-ol, Isopropylparaben, Capryloyl Glycine, Phenylpropanol, Tropolone, PCA Ethyl Cocoyl Arginate, 2-Methyl 5-Cyclohexylpentanol, Phenoxyethanol, Disodium EDTA, Methylparaben and its salts, Sodium Benzoate, Benzyl Alcohol, Potassium Sorbate, Benzyl Salicylate, Propylparaben, Sodium Methylparaben, Methylchloroisothiazolinone, Methylisothiazolinone, Ethylhexylglycerin, Butylparaben, Ethylparaben, Sodium Propylparaben, DMDM Hydantoin, Dehydroacetic Acid, Salicylic Acid, Chlorphenesin, Isobutylparaben, Sodium Ethylparaben, Diazolidinyl Urea, Diazolidinyl Urea, Farnesol, Bisabolol, Glyceryl Caprylate, Sodium Phytate or Phytic Acid, Sodium Levulinate or Levulinic Acid and esters and/or ketals thereof, Chlorhexidine, Glyceryl Laurate, Anisic Acid and its salts, Chlorhexidine Digluconate, TEA-salicylate, Phenethyl Alcohol, Glyceryl Caprate, Sorbitan Caprylate, Tetrasodium Glutamate Diacetate, Trisodium Ethylenediamine Disuccinate, Hydroxyethoxyphenyl Butanone, Hydroxyethoxyphenyl Butanol, Itaconic Acid, Octopirox, Propanediol Caprylate, Climbazole, Undecylenoyl Glycine, Thymol, 4-Hydroxyacetophenone, Lactic Acid, Sodium Lactate, Trisodium Dicarboxymethyl Alaninate, Frambinon, Xylityl caprylate, Benzoic acid 3-hyroxypropylester, Anisic acid 3-hydroxypropylester, 3-Hydroxypropyl 2- hydroxybenzoate,1,3-propanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2- octanediol, 1,2-nonanediol, 1,2-decanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3- heptanediol, 2,3-octanediol, 2,3-nonanediol, and any mixture thereof. [0305] In order to further enhance antimicrobial efficacy, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product as defined herein, is advantageously combined with at least one further antimicrobial agent which is different from the anti-microbial agents specified above. The combination with a further
220082 antimicrobial agent provides reliable protection against microbial degradation and deterioration of the preparation, in particular during storage. Additionally, the further different antimicrobial agent provides reliable protection against other microorganisms as described above, for example Corynebacterium, Anaerococcus, Finegoldia, Moraxella, Porphyromonas, Fusobacterium, Malassezia, Peptoniphilus, Streptococcus, Lactobacillus, Gardnerella, Fannyhessea, Epidermophyton, Trichophyton, Cutibacterium. Hence, the combination with a further different antimicrobial agent allows antimicrobial protection against different groups of microorganisms, and, thus, a broader spectrum of microorganism. The further different antimicrobial agent in the context of the present invention is preferably selected from the group consisting of 2-benzylheptanol, alkyl (C 12-22) trimethyl ammonium bromide and chloride, ascorbic acid and salts thereof, benzalkonium bromide, benzalkonium chloride, benzalkonium saccharinate, benzethonium chloride, Benzoic Acid, camphor, cetylpyridinium chloride, chlorhexidine diacetate, chlorhexidine dihydrochloride, chlorocresol, chloroxylenol, Cyclohexylglycerin, Dimethyl phenylbutanol, Dimethyl phenylpropanol, ethanol, ethyl lauroyl arginate HCl, Ethyl Lauroyl Arginate Laurate, eucalyptol, gluconic acid and salts thereof, glycerin, hexamidine, hexamidine diisethionate, Hexylglycerin, Iodopropynyl Butylcarbamate, jasmol, lauryl alcohol, Levulinic Acid and esters and/or ketals thereof, mannitol, menthol, methyl salicylate, Octenidine HCl, polyarginine, Polyglyceryl-10 Laurate, polyglyceryl-2 caprate, Polyglyceryl-3 caprylate, polylysine, Salvia Officinalis (Sage) Oil, silver chloride, silver citrate, sodium caproyl lactylate, Sodium Caproyl/Lauroyl Lactylate, sodium lauroyl lactylate, Sorbic Acid, sorbitol, Tetraselmis extract, triclocarban, triclosan, Triethyl citrate, Xylityl Sesquicaprylate, zinc citrate, zinc pyrithione, Zinc ricinoleate, and any mixture thereof. [0306] The aforesaid antimicrobial agents are used in the sunscreen, cosmetic or pharmaceutical preparation or homecare product either as a single component or preferably in a mixture with two or more further of said antimicrobial agents as specified above. The antimicrobial agent is present in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.01 to 25.0 % by weight, preferably 0.02 to 15.0 % by weight, most preferred in an amount of 0.05 to 6.0 % by weight, based on the total weight of the final formulation.
220082 [0307] Preservatives: For preservative purposes, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention preferably includes one or more preservatives which are suitable or customary in sunscreen products, cosmetic or pharmaceutical preparations or homecare products. Suitable and advantageously preservatives are, for example, benzoic acid, sodium benzoate, ammonium benzoate, butyl benzoate, calcium benzoate, ethyl benzoate, isobutyl benzoate, isopropyl benzoate, magnesium benzoate, mea-benzoate, methyl benzoate, phenyl benzoate, potassium benzoate, propyl benzoate, propionic acid, ammonium propionate, calcium propionate, magnesium propionate, potassium propionate, sodium propionate, salicylic acid, calcium salicylate, magnesium salicylate, measalicylate, sodium salicylate, potassium salicylate, teasalicylate, sorbic acid, calcium sorbate, sodium sorbate, potassium sorbate, o-phenylphenol, sodium sulfite, ammonium bisulfite, ammonium sulfite, potassium sulfite, potassium hydrogen sulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, chlorobutanol, 4-hydroxybenzoic acid, methylparaben, potassium ethylparaben, potassium paraben. sodium methylparaben, sodium ethylparaben, ethylparaben, sodium paraben, potassium methylparaben, calcium paraben, butylparaben, propylparaben, sodium propoylparaben, sodium butylparaben, potassium butylparaben, potassium propylparaben, dehydroacetic acid, sodium dehydroacetate, formic acid, sodium formate, dibromohexamidine isethionate, thimerosal, phenyl mercuric acetate, phenyl mercuric benzoate, undecylenic acid, potassium undecylenate, sodium undecylenate, calcium undecylenate, mea- undecylenate, tea-undecylenate, hexetidine, 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2- nitropropane-1,3-diol, dichlorobenzyl alcohol, triclocarban, p-chloro-m-cresol, triclosan, chloroxylenol, imidazolidinyl urea, polyaminopropyl; biguanide, phenoxyethanol, methenamine, climbazole, DMDM hydantoin, benzyl alcohol, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl)-2 pyridon, piroctone olamine, bromochlorophene, o-cymen-5-ol, methylchloroisothiazolinone and methylisothiazolinone, chlorhexidine, chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidine dihydrochloride, phenoxyisopropanol, behentrimonium chloride(1), cetrimonium bromide, cetrimonium chloride(2), laurtrimoniumbromide, laurtrimonium chloride, steartrimonium bromide, steartrimonium chloride (2), dimethyl oxazolidine, diazolidinyl urea, hexamidine, hexamidine diisethionate, hexamidine diparaben, hexamidine paraben, glutaral, 7- ethylbicyclooxazolidine, chlorphenesin, sodium hydroxymethylglycinate, silver chloride,
220082 benzethonium chloride, benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate, benzylhemiformal, iodopropynyl butylcarbamate, methylisothiazolinone, citric acid, silver citrate, hydroxyethoxy-phenyl butanone (HEPB) and any mixture thereof. [0308] Drugs: The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention are preferably combined with one or more drugs. In certain such embodiments, the pharmaceutically active agent is selected from anti-acne agents, agents used to treat rosacea, analgesics, anesthetics, anorectals, antihistamines, anti-inflammatory agents including non-steroidal anti- inflammatory drugs, antibiotics, antifungals, antivirals, antimicrobials, anti-cancer actives, scabicides, pediculicides, antineoplastics, antiperspirants, antipruritics, antipsoriatic agents, antiseborrheic agents, biologically active proteins and peptides, burn treatment agents, cauterizing agents, depigmenting agents, depilatories, diaper rash treatment agents, enzymes, hair growth stimulants, hair growth retardants including eflornithine and its salts and analogs, hemostatics, kerotolytics, canker sore treatment agents, cold sore treatment agents, dental and periodontal treatment agents, photosensitizing actives, skin protectant/barrier agents, steroids including hormones and corticosteroids, sunburn treatment agents, sunscreens, transdermal actives, nasal actives, vaginal actives, wart treatment agents, wound treatment agents, wound healing agents, etc. [0309] Especially useful are natural or naturally occurring anti-inflammatory mixtures of substances, in particular extracts or fractions from camomile, Aloe vera, Commiphora species, Rubia species, willow, willow-herb, oats, calendula, arnica, St John’s wort, honeysuckle, rosemary, Passiflora incarnata, witch hazel, ginger or Echinacea; preferably selected from the group consisting of extracts or fractions from camomile, Aloe vera, oats, calendula, arnica, honeysuckle, rosemary, witch hazel, ginger or Echinacea, and/or pure substances, preferably alpha-bisabolol, apigenin, apigenin-7-glucoside, gingerols, shogaols, gingerdiols, dehydrogingerdiones, paradols, natural or naturally occuring avenanthramides, preferably tranilast, avenanthramide A, avenanthramide B, avenanthramide C, non-natural or non-naturally occuring avenanthramides, preferably dihydroavenanthramide D, dihydroavenanthramide E, avenanthramide D, avenan- thramide E, avenanthramide F, boswellic acid, phytosterols, glycyrrhizin, glabridin and licochalcone A; preferably selected from the group consisting of alpha-bisabolol, natural
220082 avenanthramides, non-natural avenanthramides, preferably dihydroavenanthramide D, boswellic acid, phytosterols, glycyrrhizin, and licochalcone A, and/or allantoin, panthenol, lanolin, (pseudo-)ceramides, preferably Ceramide 2, hydroxypropyl bispalmitamide MEA, cetyloxypropyl glyceryl methoxypropyl myristamide, N-(1-hexadecanoyl)-4-hydroxy-L- proline (1-hexadecyl) ester, hydroxyethyl palmityl oxyhydroxypropyl palmitamide], glycosphingolipids, phytosterols, chitosan, mannose, lactose and ß-glucans, in particular 1,3->1,4-ß-glucan from oats. [0310] In addition to the above-described substances, further ingredients commonly used in sunscreen products, cosmetic or pharmaceutical preparations or homecare products, which are suitable or customary in the compositions of the present invention, can be used. [0311] The sunscreen product or cosmetic or pharmaceutical, in particular dermatological, preparation according to the first aspect of the present invention is intended for topical applications. The term “topical” is understood to mean external applications on a mammal’s skin or mucosa, which are in particular for the protection, treatment, care and cleansing of the skin, scalp, eyelashes, eyebrows, nails, mucous membranes and hair. The mammal is preferably a human. [0312] For topical application, the cosmetic or pharmaceutical preparation is either a rinse off or a leave on preparation. [0313] The sunscreen products cosmetic or pharmaceutical preparations or homecare products according to the present invention may be in the form of an aqueous solution, dispersions, a hydro alcoholic vehicle, a stick, an ointment, a gel, an aerosol (foams, sprays, propellant pump) and the like. [0314] The sunscreen product, cosmetic or pharmaceutical, in particular dermatological, preparation or homecare product according to the first aspect of the present invention can be present in different forms, e.g. in the form of a dispersion, in the form of a water free formulation, or in the form of an aqueous, aqueous/alcoholic, in particular
220082 aqueous/ethanolic, aqueous/glycolic or alcoholic/glycolic, in particular ethanolic/glycolic, based solution. [0315] In a preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the first aspect of the invention is a dispersion. The term “dispersion” in the context of the present invention means, that the sunscreen product, cosmetic or pharmaceutical preparation or homecare product is a disperse two-phase system consisting of colloidal particles (disperse phase) and a medium in which they are suspended (disperse medium). Both phases are not miscible with each other, only with an emulsifier. Such dispersions, for example emulsions, comprise the at least one oil component (without UV-filters) preferably in an amount of ≥ 1 % by weight, more preferably in an amount of ≥ 3 % by weight. [0316] Preferably, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the first aspect of the present invention takes various forms such as an emulsion, in particular a O/W emulsion, a W/O emulsion, a multiple emulsion, a hydrodispersion gel, a balm, a multiple emulsion of the water-in-oil type (W/O/WO) or of the oil-in-water type (O/W/O), PIT emulsion, Pickering emulsion, a micro- emulsion, a liquid, a lotion, a suspension, a milk, an ointment, a paste, a gel, a cream based, an oil based or a liposome-based formulation or a an aerosol such as foams and sprays, including all types of silicon based emulsions. [0317] In a most preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention is in the form of an emulsion as defined herein, advantageously in the form of an oil-in-water (O/W) emulsion comprising an oily phase dispersed in an aqueous phase in the presence of an O/W or polymeric emulsifier. [0318] If the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention is a dispersion, preferably an emulsion, the oil component (without UV-filters) is present in the cosmetic or pharmaceutical preparation in an amount of 0.01 to 50.0 % by weight, based on the total weight of the composition.
220082 In a preferred variant, the cosmetic or pharmaceutical preparation comprises the oil component in an amount of 0.1 to 45.0 % by weight, based on the total weight of the composition. In a particular preferred variant, the oil component is advantageously used in the cosmetic or pharmaceutical preparation in an amount of at 1.0 to 40 % by weight, based on the total weight of the composition. [0319] In a further variant, the sunscreen product, cosmetic or pharmaceutical, preferably dermatological, preparation or homecare product according to the first of the invention is a water free formulation, i.e. an oil formulation. [0320] If the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention is a water free formulation, i.e. an oil formulation, the oil component is present in the cosmetic or pharmaceutical preparation in an amount of ≥ 60 % by weight, preferably in an amount of ≥ 75 % by weight, more preferably in an amount of ≥ 90 % by weight, based on the total weight of the composition. [0321] Such water free formulations include e.g. oils, skin butters, powders, lip stick, antiperspirant/deo sticks, and decorative cosmetics. [0322] In addition, further water free formulations are likewise formulations on the basis of ethanol/diols/triols/glycols such as sprays or gels. [0323] Alternatively, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product as disclosed herein is an aqueous or an aqueous/alcoholic, preferably aqueous/ethanolic, or an aqueous/glycolic, or an alcoholic/glycolic, preferably ethanolic/glycolic, based solution. Typically, this could be glycerin in water or alcohol compositions. Said solutions are homogeneous one phase system of water/alcohol/glycol and additional components. The aqueous/alcoholic or aqueous/glycolic or alcoholic/glycolic based solution comprises an aliphatic alcohol or a glycol in an amount of 0.1 to 70.0 % by weight, preferably in an amount of 0.5 to 60.0 % by weight, more preferably in an amount of 1.0 to 50.0 % by weight, based on the total weight of the solution. The aliphatic alcohol is preferably selected from the group consisting of ethanol, isopropanol, n-propanol. The glycol is preferably selected from the group consisting of
220082 glycerin, propylene glycol, 1,3-Propanediol, 1,2-Propanediol, 1,2–C5 to C10-alkanediols, butylene glycol or dipropylene glycol. [0324] Preferably, the overall water content in the final aqueous based solutions can be ≥ 30 % by weight, more preferably ≥ 40 % by weight, most preferably ≥ 50 % by weight. [0325] Such aqueous or aqueous/alcoholic or aqueous/glycolic or alcoholic/glycolic based solutions include for example deo/antiperspirant preparations, after shave, cleansing preparations, or anti-acne preparations. [0326] In a preferred variant, the inventive composition is an impregnation solution in the form of an emulsion spray or ethanol/oil spray for wet wipes. [0327] The above formulations or compositions are prepared according to usual and known methods. [0328] The cosmetic preparation is a preparation for cosmetic and/or non-therapeutic use for personal care, skin protection, skin care, scalp protection, scalp care, hair care, nail care, in particular for the prevention and treatment of skin conditions, intolerant or sensitive skin, skin irritation, skin reddening, wheals, pruritis (itching), skin aging, wrinkle formation, loss of skin volume, loss of skin elasticity, piment spots, pigment abnormalities, skin dryness, flaking, greasiness, hypopigmentation and/or hyperpigmentation of the skin; or a preparation for animal care. [0329] Examples of personal care are preferably anti-ageing preparations, skin care emulsions, body oils, body lotions, cleansing lotions, face or body balms, after shave balms, after sun balms, deo emulsions, cationic emulsions, body gels, treatment creams, skin protection ointments, moisturizing gels, face and/or body moisturizers, light protective preparations (sunscreens), micellar water, hair sprays, color protection hair care products, skin lightning products, anti-dark-spot reparation, etc.
220082 [0330] The cosmetic preparations include also make-ups, eye-care preparation, eye shadows, mascara, eyeliner, lip care preparation such as lip stick, lip gloss, mail care preparations, such as nail varnish, nail varnish removers, [0331] Alternatively, the preparation according to the present invention is a preparation of medical use. [0332] The pharmaceutical, in particular dermatological, composition according to the present invention is preferably a preparation for the prevention and treatment of a condition of the skin or mucosa. [0333] Preferably, the pharmaceutical preparation according to the first aspect of the present invention is used in the prevention and/or treatment of dysfunctions of human hair, skin and/or nails, in particular dermatological or keratological diseases, wherein the dermatological or keratological diseases are selected from the group consisting of atopic dermatitis (neurodermitis), psoriasis, acneiform exanthema, sebostasis, xerosis, eczema, hyper seborrhea and hypo seborrhea, dermatitis, rosacea, erythema, wheals, pruritus (itching), inflammation, irritation, fibrosis, lichen planus, pityriasis rosea, pityriasis versicolor, autoimmune bullous diseases, urticaria, angioedema, allergic skin reactions, wound healing, tissue regeneration and in the treatment of inflammatory diseases. [0334] In order to be used, the sunscreen product or cosmetic or pharmaceutical, in particular dermatological preparation according to the first aspect of the present invention is applied to the skin, hair, scalp and/or nails in an adequate amount in such manner as is customary with sunscreen products or cosmetics and dermatological products. [0335] In addition, the products and preparations according to the present invention are homecare products. The home care products generally include laundry detergents (powder, liquid and tablet), fabric conditioners, dishwashing detergents (liquid and tablet), hard floor and surface cleaners, glass cleaners, carpet cleaners, oven cleaners, air fresheners, disinfectants, stain removers, car wash products. These products are usually manufactured in the form of a liquid, powder, spray, granules and others.
220082 [0336] Surprisingly, it was found that the addition of a mycosporine-like amino acid compound or its salt as defined in the present application have the effect of improving SPF and boosting the UVA photoprotection. The higher the SPF or the UVA-PF the more protective the sunscreen is. [0337] Furthermore, with the addition of a mycosporine-like amino acid compound or its salt, the critical wavelength of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product can be increased to provide a broad-spectrum coverage having a critical wavelength greater than 370 nm. [0338] These effects have the advantage that sunscreen products or cosmetic or pharmaceutical products can be provided having a broader spectrum protection covering UVA and UVB. In addition, an improved UV-filter performance, in particular UVA photoprotection, allows to reduce the amount of organic UV-filter agent without affecting the envisaged SPF. [0339] As it is demonstrated by the following examples, the SPF and the UVA photoprotection is highly improved, i.e. increased by the addition of a mycosporine-like amino acid compound as defined therein. The control samples containing none mycosporine-like amin acid compound exhibited average or lower SPF. [0340] An improvement in SPF and UVA photoprotection can be observed when a mycosporine-like amino acid compound according to general formula (I) or general formula (II) as defined herein is added to a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an organic UV-filter or a mixture thereof. A pronounced SPF improving effect is especially observed for the mycosporine-like amino acid compounds according to general formula (II). [0341] With the addition of a mycosporine-like amino acid compound according to general formula (II), wherein X is S, a particular pronounced SPF and UVA photoprotection boosting effect can be obtained.
220082 [0342] Particular beneficial are the mycosporine-like amino acid compounds according to the general formula (V) or (VI) when added to a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an organic UV-filter or a mixture thereof. [0343] Surprisingly, the mycosporine-like amino acid compounds are particularly effective in improving the SPF and UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product when they are in the form of an acid or in salt form as described above in detail. [0344] With the addition of a mycosporine-like amino acid compound as defined herein, the SPF of a sunscreen product, a cosmetic or pharmaceutical preparation or homecare product comprising an organic UV-filter or a mixture of organic UV-filters can be increased by at least 5 %, preferably by at least 10 %, and more preferred by at least 10 % as it is demonstrated in the following examples. [0345] The addition of a MAA-2 salt in an amount of 1.0 % by weight to a sunscreen composition comprising a modern UV-filter mixture results in an in vitro SPF of 53.4 which is 68.5 % higher than the in vitro SPF of the reference sample, i.e. the sample without the addition of the mycosporine-like amino acid compound. The addition of MAA-9 acid in an amount of 1.0 % to said sunscreen composition results in an in vitro SPF of 34.4 which is 8.52 % higher than the in vitro SPF of the reference sample, i.e. the sample without the addition of the mycosporine-like amin acid compound. The addition of MAA-2 salt in an amount of 3.0 % by weight to said sunscreen composition even results in an in vitro SPF of 86.1 which is 171.6 % higher than the in vitro SPF of the control sample, i.e. containing none mycosporine-like amino acid compound. The addition of MAA-9 salt in an amount of 3.0 % by weight results in an in vitro SPF of 39.8 which is 25.6 % higher compared to the in vitro SPF of the reference sample, i.e. the sample without the addition of the mycosporine-like amino acid compound. [0346] In addition, not only an improved SPF results from the addition of a certain mycosporine-like amino acid compound in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising a mixture of organic UV-
220082 filter, but also a boosted UVA-PF. In particular, the addition of MAA-9 acid in an amount of 1.0 % results in an improvement of the UVA-PF of 14.8 % compared to the control sample, i.e. containing none mycosporine-like amino acid compound. The addition of MAA-9 acid in an amount of 3.0 % even results in an improvement of the UVA-PF of 30.75 % compared to the control sample, i.e. containing none mycosporine-like amino acid compound. compared to the control sample, i.e. containing none mycosporine-like amino acid compound. Also the MAA-2 salt in an amount of 3.0 % enhances the UVA-PF by 9.35 %. [0347] The addition of MAA-9 acid in an amount of 3.0 % also increases the broad- spectrum protection of said modern sunscreen composition from a critical wavelength of 378 nm to a critical wavelength of 379 nm. [0348] Hence, as demonstrated by the above test samples, the addition of MAA-9 leads to a considerable improvement of the SPF and/or of the UVA-PF in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising a modern organic UV-filter composition. [0349] The addition of MAA-2 salt in an amount of 1.0 % by weight to a sunscreen composition comprising a classic organic UV filter or a mixture of classic organic UV- filters results in an in vitro SPF of 35.4 which is 5.0 % higher than the in vitro SPF of the reference sample, i.e. the sample without the addition of the mycosporine-like amino acid compound. The addition of MAA-2 salt in an amount of 3.0 % by weight to said sunscreen composition even results in an in vitro SPF of 54.4 which is 61.4 % higher than the in vitro SPF of the control sample, i.e. containing none mycosporine-like amino acid compound. The addition of MAA-9 acid in an amount of 1.0 % to said sunscreen composition results in an in vitro SPF of 36.3 which is 7.7 % higher than the in vitro SPF of the reference sample, i.e. the sample without the addition of the mycosporine-like amin acid compound. The addition of MAA-9 salt in an amount of 3.0 % by weight to said sunscreen composition even results in an in vitro SPF of 63.1 which is 87.2 % higher compared to the in vitro SPF of the reference sample, i.e. the sample without the addition of the mycosporine-like amino acid compound.
220082 [0350] In addition, not only an improved SPF results from the addition of a certain mycosporine-like amino acid compound in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an organic UV-filter, but also a boosted UVA-PF. In particular, the addition of MAA-9 acid in an amount of 1.0 % results in an improvement of the UVA-PF of 3.2 % compared to the control sample, i.e. containing none mycosporine-like amino acid compound. The addition of MAA-9 acid in an amount of 3.0 % even results in an improvement of the UVA-PF of 5.2 % compared to the control sample, i.e. containing none mycosporine-like amino acid compound. compared to the control sample, i.e. containing none mycosporine-like amino acid compound. [0351] The addition of MAA-9 acid in an amount of 1.0 % and 3.0 % also increases the broad-spectrum protection of said classic sunscreen composition from a critical wavelength of 380 nm to a critical wavelength of 381 nm. [0352] Hence, as demonstrated by the above test samples, the addition of MAA-9 leads to an improvement of the SPF and/or of the UVA-PF in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising a classic organic UV-filter composition. [0353] Similar SPF and UVA photoprotection improving effects can be shown for the mycosporine-like amino acid compounds MAA-1, MAA-3, MAA-4, MAA-5, MAA-6, MAA- 7, MAA-8, MAA-10 and MAA-11. Said compounds show an increase in SPF by at least 10 % compared to the SPF of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product without the combination with said mycosporine-like amino acid compounds. [0354] Pronounced SPF and UVA photoprotection improving effects can be demonstrated for the mycosporine-like amino acid compounds MAA-12, MAA-13 and MAA-14. Said compounds show an increase in SPF by at least 10 % compared to the SPF of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product without the combination with said mycosporine-like amino acid compounds.
220082 [0355] Hence, the addition of a mycosporine-like amino acid compound as defined herein leads to an improvement of the SPF as well as of the UVA-PF in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an inorganic UV-filter. [0356] With the formulations according to the present invention it is therefore possible to offer sunscreen products or cosmetic or pharmaceutical products having a significant increase in SPF, a significant increase in UVA-PF as well as an increase in the critical wavelength, and thus, offer a broad-spectrum protection which is by far higher than the minimum critical wavelength of 370 nm compared to products or preparations without the addition of the specified mycosporine-like amino acid compounds. [0357] The improved UV-filter performance in terms of SPF and UVA-PF allows to reduce the amount of the primary organic UV-filter agent without affecting the envisaged sun protection factor. [0358] Hence, the present invention provides for a sunscreen product, cosmetic or pharmaceutical preparation or homecare product wherein the SPF is increased by at least 5 % compared to a sunscreen product, cosmetic or pharmaceutical preparation or homecare product without the mycosporine-like amino acid compound (b), preferred by at least 10 %, and more preferred by at least 20 %. [0359] Furthermore, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention provides an increase in UVA-PF of at least 5 % relative to an otherwise identical formulation without the mycosporine-like amino acid compound (b). In some instances, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product provides an increase in UVA-PF of at least 10 %, more preferred by at least 15 %, relative to an otherwise identical formulation without the mycosporine-like amino acid compound. [0360] Due to this beneficial effect as described before, the present invention relates in a further aspect to the use of a mycosporine-like amino acid compound (b) as defined herein or a mixture thereof for improving the SPF and the UVA photoprotection of a
220082 sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising at least one inorganic UV-filter. [0361] By the admixture of a mycosporine-like amino acid compound (b) as defined herein or a mixture thereof the SPF of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an inorganic UV-filter can be boosted by at least 5 % relative to a sunscreen product, cosmetic or pharmaceutical preparation or homecare product without the mycosporine-like amino acid compound (b), preferred by at least 10 %, and more preferred even by at least 20 %. Additionally, the UVA-PF in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an inorganic UV-filter can be boosted by at least 5 %, preferred by at least 10 %, and most preferred by at least 15 %, relative to an otherwise identical formulation without the mycosporine-like amino acid compound. [0362] In a further aspect, the present invention relates to a method of enhancing or boosting the SPF performance and the UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product. In the method an effective amount of at least one mycosporine-like amino acid (b) as defined herein or a mixture thereof is added to said sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an inorganic UV-filter. [0363] Due to its enhanced SPF and UVA photoprotection, the present invention relates in a further aspect to a method of providing anti-aging benefits to skin, whitening or preventing darkening of skin, improving the appearance of skin, diminishing the visible signs of skin aging and improving skin’s radiance and firmness by topically applying the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention. [0364] The present invention shall now be described in detail with reference to the following examples, which are merely illustrative of the present invention, such that the content of the present invention is not limited by or to the following examples.
220082 Examples [0365] Determination of the in-vitro SPFs and UVA-PF [0366] The SPF boosting and UVA-PF boosting test is carried out as in-vitro determination of SPFs. [0367] Principle: The formulation to be tested (emulsion, solution) is weighed on PMMA plates with the help of an analytical balance. The formulation if distributed and incorporated on the plate using a method corresponding to the formulation. The thus prepared plates are then measured on a Labsphere device and the results are calculated as SPF with a suitable software. [0368] 1. Sample preparation: [0369] PMMA plates (Polymethylmethacrylate), measuring 3 cm x 8.5 cm (WW5 plates based on ISOethA 24443:2012 “Determination of UVA photoprotection in vitro” with 5 µ roughness by Schönberg GmbH & Co. AG) are used to perform an SPF measurement. [0370] 1.1 Preparation of reference samples: [0371] A reference sample is obtained by distributing 25 to 28 mg glycerin (99.5 %) with the index finger on the roughened side of the PMMA plate. The glycerin film must be very thin and uniform. Subsequently, this plate is stored for at least 2 hours. [0372] The reference plate is measured with the following transmission values: 290 nm > 60 % transmission; 300 nm > 69 % transmission; and 320 nm > 82 % transmission. [0373] 1.2 Application of the sample to be measured:
220082 [0374] The sample to be measured should be homogeneously mixed with a spatula before application.1.2 mg/cm2 of sample is evenly distributed in several rows of dots on the PMMA plate. In order to minimise the evaporation of the sample during weighing, this process must be carried out quickly. The sample is then evenly distributed by hand with a finger previously saturated with the sample material. The distribution takes place in two phases: Phase 1: Fast and uniform distribution with a slight pressure until the emulsion is broken. Phase 2: The sample is massaged into the rough surface with strong pressure and the process should last 30 seconds. In this context under strong pressure means that when massaged on a scale, this indicates at least 200 m. [0375] Exceptions: Sun oils: The product quantity is generally 1.3 mg/cm². For strongly spreading oils, less product is applied, as the amount of oil cannot be "absorbed" from the plate. Then the amount of application should be reduced to 1.0-0.75 mg/cm². Application method here is also the 30 s fast/light and 30 s strong method". Sun sprays: The "30/30 method" applies here (especially for thicker sprays). For very liquid sprays (similar to water): Fast and uniform distribution with a slight pressure, until the emulsion "breaks". The process should take 45 s. [0376] The finished sample plates are stored dust-free and measured at the earliest after 15 minutes. [0377] 2. Measurement on the Labsphere: [0378] The samples are measured using the UV-200S device, using the specified Colipa method. The Labsphere user manual also applies. [0379] 2.1 Basic settings in the software:
220082 [0380] A new "Study" is opened via File and then the "Colipa Guideline 2011" method is selected under the heading "Study". In the new window "Colipa Method Options" the number of plates (3 plates), the measuring points per plate (5 measuring points) and the in vivo SPF and, if necessary, the irradiance intensity of the external irradiance device (Solar Simulator Irradiance) entered. The irradiance set on the external device is 765 W/m2 as standard. The complete naming of the sample is done via Study", "Study Information". [0381] 2.2 Sample measurement: [0382] At the beginning of the measurement, a blank value of the glycerin reference sample is measured ("scan blank plate"). In order to determine the SPF of a sample, a total of 15 measuring points (3 plates of 5 measuring points) are then created ("Scan Location"). The already scanned plates and measuring points are checked in the upper right window, while the absorbance of the currently measured plate is displayed in the middle window. [0383] With irradiation: After the first measurement run, the device calculates an irradiation dose (Irradiation Dose/J/cm2) and the duration (exposure time) for each plate. The plates are irradiated in the external irradiation device (irradiation duration = average value of the 3 plates). [0384] The calculation of irradiation dose and exposure time is based on the irradiance (765 W/m
2) set on the external device. [0385] Without irradiation: If no irradiation device is available or irradiation is not desired, the first plate is started again after completion of the 15 individual scans and the measurements are repeated (Background: Without the second measurement, no UVA/UVB balance calculation is performed by the software.)
220082 [0386] After completion of the measurements, the "Study" is recorded and the data can be printed/exported as a "Report". [0387] 3. Tested samples: [0388] Example 1: Sunscreen product with modern organic UV-filter combination: The formulation samples A to E as specified in the following Table 3 were prepared as follows: [0389] Phase A: The ingredients of phase A without Keltrol® CG-BT and Pemulen® were heated to 85 °C in order to dissolve the ingredients. After dissolution of the ingredients, Keltrol® CG-BT and Pemulen® were added and the solutions was homogenized for a short time (Ultra Turrax® T25: 15,000rpm/10 sec). [0390] Phase B: The ingredients of phase B were mixed while stirring until the ingredients were dissolved. The water phase will be cloudy in combination with the sodium hydroxide solution. Afterwards, the water phase B was heated to 80 °C. Afterwards, the hot phase B was added to the hot phase A and homogenized (Ultra Turrax® T25: 13,000 rpm/3 min). Finally, the mixture was cooled down to ambient temperature while stirring. [0391] The results of the in vitro SPFs and UVA-PF determination are presented in Table 3.