Compositions comprising UV filter stabilizers
By combining the fungicosporin-like amino acid compounds with light-unstable UV filters, the problem of degradation of UV filters in ultraviolet radiation is solved, and the light stability and protection capabilities of UV filters are improved.
Patent Information
- Application Number
- CN202380054654.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2023-08-04
- Filing Date
- 2023-08-07
- Publication Date
- 2025-03-07
AI Technical Summary
Existing UV filters are prone to degradation under ultraviolet radiation, resulting in a decrease in the protection ability of sunscreen products. Some commonly used light stabilizers have toxicological and environmental problems.
A fungicosporin-like amino acid compound is used to combine with a light-unstable UV filter to stabilize the UV filter through its light stability and prevent photodegradation.
The light stability of the UV filter is effectively improved, its UV protection ability is maintained, and the formation of photodegradation products is avoided. The compounds used in this method are toxicologically acceptable.
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Abstract
Description
Technical Field
[0001] The present invention relates to sunscreen products, cosmetic or pharmaceutical preparations or home care products comprising photolabile UV filters and certain mycosporine-like amino acid compounds as stabilizers. In addition, the present invention relates to the use of such mycosporine-like amino acid compounds for improving the photostability of photolabile UV filters. Finally, the present invention relates to a method for stabilizing photolabile UV filters against the degradation effects of UV radiation or enhancing the UV-absorbing properties of UV-absorbing compounds by means of said mycosporine-like amino acid compounds. Background Art
[0002] The negative effects of exposure to UV light are well known. Prolonged exposure to the sun causes damage to the skin, such as sunburn, and makes hair dry and brittle. When the skin is exposed to UV light with a wavelength of 290nm to 400nm, long-term damage can lead to serious conditions such as skin cancer, and the type of damage depends on the wavelength of the radiation.
[0003] UV light also causes aging by causing the formation of free radicals in the skin. Free radicals include, for example, singlet oxygen, hydroxyl radicals, superoxide anions, nitric oxide and hydrogen radicals. Free radicals attack DNA, membrane lipids and proteins, producing carbon free radicals. These then react with oxygen to produce peroxy radicals, which can attack adjacent fatty acids to generate new carbon free radicals. This cascade results in a chain reaction that produces lipid peroxidation products. The damage of the cell membrane results in the loss of cell permeability, an increase in intracellular ion concentrations and a reduction in the ability to excrete or detoxify waste products. The end result is the loss of skin elasticity and the appearance of wrinkles. This process is often referred to as photoaging.
[0004] Furthermore, UVA radiation can trigger phototoxic or photoallergic skin reactions.
[0005] UV rays are classified into UVA rays (320 nm to 400 nm) or UVB rays (280 nm to 320 nm) according to their wavelengths.
[0006] In order to attenuate these negative effects of UV radiation, i.e. for the purpose of protecting the skin and keratin materials from UV radiation, sunscreen / sunscreen compositions are generally used which contain sunscreens active in the UVA range and in the UVB range, i.e. in the entire range from 280 nm to 400 nm.
[0007] UV filters are compounds with a pronounced ability to absorb ultraviolet radiation. They are used, inter alia, in sunscreen products, cosmetics, dermatological and pharmacological preparations or sunscreen products, but also for improving the lightfastness of industrial products such as paints, varnishes, plastics, textiles, polymers (such as, for example, polymers and copolymers of mono- and diolefins, polystyrene, polyurethanes, polyamides, polyesters, polyureas and polycarbonates), encapsulating materials and rubbers.
[0008] UV filters are classified according to the position of their absorption maximum as UVA and UVB filters; if a UV filter absorbs both UVA and UVB, the UV filter is called a UVA / UVB broadband absorber or UVA / UVB broadband filter.
[0009] In order to achieve the maximum protection expected from UV radiation sunscreen products, cosmetics, especially dermatological and pharmacological preparations or home care products are formulated to contain mixtures of UV filters with different concentrations, and the choice of the UV filters used is determined by legislation in the country or economic region. For example, UV filters that can be used to protect the skin are regulated in the USA by the US FDA via its OTC monograph system, and in the EU by cosmetic regulations. Regulations covering the use of UV filters also exist in other countries and regions. These regulations not only specify the filters that can be used, but also determine the maximum use level of each UV filter. Therefore, with respect to SPF and UVA or UVB protection, the UV filters available to achieve high efficacy are limited.
[0010] However, some of the approved and used UV filters are known in the art, such as ethylhexyl methoxycinnamate (Neo AV), butyl methoxydibenzoylmethane (Avobenzone; Neo 357), Isoamyl p-methoxycinnamate (Neo E1000), diethylamino-hydroxy-benzoyl hexyl benzoate (UVinulA plus) are relatively sensitive to ultraviolet radiation (UVR), i.e., they are likely to chemically degrade after exposure to UVR, especially after prolonged exposure. More specifically, these UV filters have an unpleasant tendency to degrade more or less rapidly under the action of such UV.
[0011] Exposure to UVR depletes the available concentration of UV filters in the formulation, resulting in a reduction in the efficacy of the product in terms of protection level and duration. Therefore, the labeled SPF of a sunscreen formulation containing such photolabile UV filters is not necessarily effective for the UVR protection of the product.
[0012] According to photophysics, UVR exposure causes organic UV absorbing molecules to leave the ground state and enter a single excited state. Excited state filters can return to the ground state by singlet quenching and thereby be preserved to continue to provide UVR protection or transfer from the singlet state to a triplet excited state. In the triplet state, the UV filter molecules can undergo triplet quenching and return to the ground state. However, if triplet quenching or another photophysical pathway does not restore the sunscreen molecules to the ground state, the filter undergoes photodegradation by one or more photochemical reactions. Therefore, the photodegraded filter loses the ability to filter UVR, thereby severely reducing the effectiveness of the entire formulation, i.e., the UV protection ability.
[0013] This substantial lack of photochemical stability of the photolabile UV filters towards the UV radiation to which they are essentially subjected therefore makes it impossible to ensure constant protection during prolonged exposure to the sun and therefore requires repeated applications at regular and frequent intervals in order to obtain effective protection of the skin against UV rays.
[0014] Furthermore, it is believed that photodegradation of photolabile UV filters formed by photoisomerization or photolysis can lead to phototoxic or photoallergic degradation products, such as free radicals, which are associated with a risk of adverse health effects when in direct contact with the skin.
[0015] These UV light absorbing filters need to be stabilized by one or more compounds or materials in the formulation.
[0016] In order to increase the photostability of the photolabile UV filters, the use in combination with photostabilizers has been proposed. For example, when avobenzone is combined with zinc oxide, an increase in the photostability of avobenzone can be observed, or the photostability of avobenzone can be enhanced by adding octocrylene or phenylbenzimidazole sulfonic acid.
[0017] However, the use of some photostabilizers is controversial. For example, octocrylene and benzophenone have recently been suggested to induce adverse effects on the endocrine system in addition to their allergic and / or photoallergic potential and may be harmful to corals.
[0018] Therefore, there is still a continuing need to provide further substances which stabilize photolabile UV filters against photodegradation. The sunscreen, cosmetic or pharmaceutical industry or the home care products business is constantly looking for ingredients which can counteract this negative effect.
[0019] Another disadvantage is that the vast majority of cosmetically registered organic UV filters are only miscible or soluble in oil, i.e. they are only suitable for addition to the oil phase of a sunscreen formulation. Thus, the solubility of each UV filter depends on the oil used. Thus, the formulation of sunscreens is limited by the choice of certain oils and, therefore, also by the choice of exemplary emollients to improve the sensory perception. This can affect consumer compliance. Oil-soluble, photolabile UV filters are mainly stabilized using oil-soluble substances in the oil phase.
[0020] Therefore, there is a need for new water-soluble compounds which are themselves photostable and provide stabilization of oil-soluble photolabile UV filters towards photodegradation, for example in the aqueous phase of a formulation.
[0021] When looking for agents for improving the photostability of UV filters, it must be taken into account that the substances used in the sunscreen, cosmetics or pharmaceutical or home care sectors must be toxicologically acceptable, well tolerated by the skin, in particular stable in customary cosmetic and / or pharmaceutical preparations, essentially and preferably odorless and can be prepared inexpensively, i.e. using standard processes.
[0022] It was therefore an object of the present invention to provide photostable sunscreen products, cosmetic or pharmaceutical preparations, in particular dermatological preparations or home care products comprising or consisting of photostable UV filters, wherein the UV filters are stabilized against photodegradation in order to retain the UV protective capacity and thus provide constant protection during prolonged exposure to the sun.
[0023] Another object of the present invention is to provide substances which are able to stabilize photolabile UV filters against photodegradation or at least reduce the losses of photolabile UV filters in photodegradation during exposure to UV radiation and prevent the formation of reactive intermediates of photolabile filter substances which behave as photooxidants when in direct contact with the skin.
[0024] Another object of the present invention is to provide a method for stabilizing photolabile UV filters against the degradation effects of UV radiation or for enhancing the UV absorbing properties of photolabile UV absorbing compounds.
[0025] This problem is solved by the subject matter of the independent patent claims. However, further aspects of the invention are also apparent from the wording of the dependent patent claims, from the following detailed description in conjunction with the accompanying embodiments and drawings. Summary of the invention
[0026] In order to achieve the above problems, in a first aspect, the present invention provides a sunscreen product, a cosmetic or pharmaceutical preparation or a home care product, which comprises or consists of:
[0027] (a) at least one photolabile UV filter; and
[0028] (b) at least one mycosporin-like amino acid compound,
[0029] The at least one mycosporin-like amino acid compound is represented by the general formula (V) as defined herein
[0030]
[0031] or a tautomer or stereoisomer or a salt thereof;
[0032] or
[0033] Represented by the general formula (VI) as defined herein
[0034]
[0035] or a tautomer or stereoisomer or a salt thereof;
[0036] or any mixture of the foregoing compounds.
[0037] In a second aspect, the present invention provides the use of at least one mycosporin-like amino acid compound as defined herein, or a mixture thereof, for stabilizing the photostability of photostable UV filters.
[0038] Finally, in another aspect, the present invention relates to a method for stabilizing a photolabile UV filter against the degradative effects of UV radiation or for enhancing the UV absorbing properties of a photolabile UV absorbing compound, which method comprises mixing the photolabile UV filter with an effective amount of at least one mycosporin-like amino acid or compound as defined herein, or a mixture thereof.
[0039] The present invention is described in detail in the appended claims. However, the invention itself and its preferred variations, other objects and advantages are also apparent from the following detailed description taken in conjunction with the accompanying examples and drawings. BRIEF DESCRIPTION OF THE DRAWINGS
[0040] FIG. 1 is an absorption spectrum showing the photostability E1% / cm measurement of MAA-1 (mycosporin-like amino acid compound).
[0041] FIG. 2 is an absorption spectrum showing the photostability E1% / cm measurement of MAA-13 (a mycosporin-like amino acid compound).
[0042] FIG. 3 is an absorption spectrum showing the photostability E1% / cm measurement of MAA-20 (a mycosporin-like amino acid compound).
[0043] FIG. 4 is an absorption spectrum showing the photostability E1% / cm measurement of MAA-28 (a mycosporin-like amino acid compound).
[0044] FIG. 5 is an absorption spectrum showing the photostability E1% / cm measurement of ethylhexyl methoxycinnamate (UV filter).
[0045] FIG. 6 is an absorption spectrum showing the photostability E1% / cm measurement of butyl methoxydibenzoylmethane (UV filter).
[0046] FIG. 7 is an absorption spectrum showing the photostability E1% / cm measurement of isoamyl p-methoxycinnamate (UV filter).
[0047] FIG. 8 is an absorption spectrum showing photostability E1% / cm measurement of a mixture of MAA-1 and ethylhexyl methoxycinnamate.
[0048] FIG. 9 is an absorption spectrum showing photostability E1% / cm measured for a mixture of MAA-1 and butyl methoxydibenzoylmethane.
[0049] FIG. 10 is an absorption spectrum showing the photostability E1% / cm measurement of a mixture of MAA-1 and isoamyl p-methoxycinnamate.
[0050] FIG. 11 is an absorption spectrum showing the photostability E1% / cm measurement of a mixture of MAA-13 and isoamyl p-methoxycinnamate.
[0051] FIG. 12 is an absorption spectrum showing the photostability E1% / cm measurements of MAA-13 and ethylhexyl methoxycinnamate.
[0052] FIG. 13 is an absorption spectrum showing photostability E1% / cm measured for a mixture of MAA-20 and isoamyl p-methoxycinnamate.
[0053] FIG. 14 is an absorption spectrum showing photostability E1% / cm measurements of a mixture of MAA-20 and ethylhexyl methoxycinnamate.
[0054] FIG. 15 is an absorption spectrum showing photostability E1% / cm measured for a mixture of MAA-28 and isoamyl p-methoxycinnamate.
[0055] 16 is an absorption spectrum showing photostability E1% / cm measurements of a mixture of MAA-28 and ethylhexyl methoxycinnamate.
[0056] FIG. 17 is an absorption spectrum showing the photostability E1% / cm measurement of a mixture of MAA-1 and MAA-13.
[0057] FIG. 18 is an absorption spectrum showing the photostability E1% / cm measurement of a mixture of MAA-20 and MAA-13. DETAILED DESCRIPTION
[0058] In the context of the present invention, the following general meanings apply:
[0059] As used herein, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a cosmetic formulation", "the cosmetic formulation" or "a cosmetic formulation" also includes a plurality of cosmetic formulations.
[0060] The terms "comprising," "including," and "containing" should be understood as open-ended terms, and mean that the named components following the term are essential but not "limited to," and other components may be added and still be encompassed by the invention.
[0061] The term "consisting of" as used in accordance with 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 or cosmetic or pharmaceutical formulation, and indicates that the subject matter is closed and may include only the limitations explicitly recited.
[0062] Unless the context dictates otherwise, whenever "comprising" is mentioned, it is intended to cover both meanings as alternatives, ie the meaning may be "including" or "consisting of".
[0063] The term "optionally" means that the subsequently described compound may but need not be present in the composition, and that the description includes variations in which the compound is included and variations in which the compound is not present.
[0064] The terms "or" or "and / or" are used as function words to indicate that two words or phrases are to be used together or separately.
[0065] All range endpoints directed to the same component or property are inclusive and independently combinable.
[0066] The term "compound" or "compound of the present invention" refers to all compounds covered by structural formula (V) and / or formula (VI) and / or formula (VII) and / or formula (XIII) and / or formula (IX) and / or formula (X) and / or formula (A) and their subformulae disclosed herein, and includes each subclass and all specific compounds whose structures are within the formulae disclosed herein.
[0067] A compound can be identified by its chemical structure and / or chemical name. When the chemical structure and chemical name conflict, the chemical structure determines the identity of the compound.
[0068] The term "at least one compound of ..." means that the food or cosmetic or pharmaceutical preparation according to the invention, in particular a sunscreen product or a home care product may contain any one of the subsequently described individual compounds or a mixture of two, three, four, five, six or even more different subsequently described compounds.
[0069] The term "effective amount of a compound" means an amount of the compound sufficient to achieve the desired effect or improvement.
[0070] In the context of the present invention, the term "cosmetic or pharmaceutical preparation" is a composition for cosmetic or pharmaceutical use, which contains a UV absorber to protect the skin or hair from UV radiation. In addition to providing photoprotection, the cosmetic or pharmaceutical preparation according to the present invention is used to provide anti-aging benefits to the skin, whiten or prevent darkening of the skin, improve the appearance of the skin, reduce visible signs of skin aging and improve the radiance and firmness of the skin.
[0071] The term "sunscreen composition" or "sunscreen" or "skin care product", also known as "sunblock", "suncream" or "suntan lotion", refers to any topical product which reflects and / or absorbs a certain portion of the UV radiation and thus contributes to the protection against sun spots and, most importantly, against skin cancer. The term "sunscreen composition" is therefore to be understood as including not only sunscreen compositions but also any cosmetic composition providing UV protection. According to the invention, a sunscreen composition may comprise one or more active agents, such as organic UV filters, and other ingredients or additives, such as emulsifiers, emollients, viscosity regulators, stabilizers, preservatives or fragrances. Sunscreens come in lotions, sprays, gels, foams (such as expanding foam lotions or whipping lotions), sticks, powders and other topical products. UV absorbing compounds are used not only in sunscreens but also in other personal care products, such as lipsticks, shampoos, hair sprays, body washes, toilet soaps and insect repellents.
[0072] In the context of the present invention, the term "home care product" is a necessity for daily care and cleaning purposes in a home. The home care product is used to maintain the hygiene and good atmosphere of the home. The home care product generally includes laundry detergents (powders, liquids and tablets), fabric conditioners, dishwashing (liquids and tablets), 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 liquids, powders, sprays, granules, etc. Preparations containing sunscreens prevent premature light damage and photobleaching of surfaces and the home care formulations themselves.
[0073] As used herein, the term "light stabilizer" is a compound suitable for protecting body care and household cleaners and treatments from photolytic degradation.
[0074] The term "photostability" refers to the ability of a UV filter or any other molecule exposed to sunlight to remain stable upon irradiation. In particular, this means that the compound does not undergo degradation processes under UV radiation.
[0075] As used herein, the term "sun protection factor (SPF)" indicates the degree of protection provided by a sunscreen composition to the skin. In particular, the factor indicates how long the protected skin can be exposed to the sun without sunburn compared to untreated skin. For example, if a sunscreen composition with SPF 15 is evenly applied to the skin, the sunscreen allows the technician to stay in the sun 15 times longer. In other words, SPF 15 means that 1 / 15 of the burning UV radiation will reach the skin, assuming that the sunscreen is applied at 2 mg / cm2 (mg / cm 2 ) is applied evenly in thick doses.
[0076] The term "critical wavelength" is defined as the wavelength at which the area under the UV protection curve (% protection vs. wavelength) represents 90% of the total area under the curve in the UV region (280 nm to 400 nm). For example, a critical wavelength of 370 nm indicates that the protection of the sunscreen composition is not limited to wavelengths of UV-B, i.e. wavelengths from 280 nm to 320 nm, but extends to 370 nm in such a way that 90% of the total area under the protection curve in the UV region is reached at 370 nm. The higher the critical wavelength, the better the protection against UV radiation.
[0077] According to the present invention, the main object of the invention is solved by a sunscreen product or a cosmetic, in particular a dermatological or pharmaceutical preparation comprising or consisting of:
[0078] (a) at least one photolabile UV filter; and
[0079] (b) at least one mycosporin-like amino acid compound,
[0080] The at least one mycosporin-like amino acid compound is represented by the general formula (V)
[0081]
[0082] in
[0083] -Z is selected from the group consisting of O-R2' or amide';
[0084] -R1' is selected from the group consisting of: CH2, unsubstituted or substituted CH(alkyl), unsubstituted or substituted C(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-spiro;
[0085] -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, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl;
[0086] -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), and unsubstituted or substituted NR9'R10', unsubstituted or substituted -N(O-alkyl)(alkyl)(Weinreb amide), -N(OH)(H)(hydroxamic acid), and unsubstituted or substituted -N(OH)(alkyl)(alkylated hydroxamic acid);
[0087] -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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=O)-OY, 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-spiro;
[0088] - the substituents R4', R5' and R6' may be identical or different and are independently 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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted substituted or substituted heteroaryl, SO, SO2, -S(=O)2OH, sulfonyl, 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-spiro;
[0089] -R7' and R8' may be identical or different and are independently 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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=O)-OY, 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';
[0090] - R9' and R10' may be identical or different and are independently 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 RC(=O)-, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heteroaryl;
[0091] -Y is selected from the group consisting of H and unsubstituted or substituted alkyl; and
[0092] -R is unsubstituted or substituted alkyl;
[0093] or a tautomer or stereoisomer or salt of the aforementioned compound;
[0094] Or represented by general formula (VI)
[0095]
[0096] in
[0097] -R1" is selected from the group consisting of CH2, unsubstituted or substituted CH(alkyl), unsubstituted or substituted C(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-spiro;
[0098] -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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -C(=O)-amide", unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2, -S(=O)2OH, sulfonyl, NH2, unsubstituted or substituted NH unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), 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-spiro;
[0099] -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), -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-spiro;
[0100] - the substituents R4", R5" and R6" may be identical or different and are independently 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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted substituted or substituted heteroaryl, SO, SO2, -S(=O)2OH, sulfonyl, 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-spiro;
[0101] -R7" and R8" may be identical or different and are independently 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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted
[0102] 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";
[0103] -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)(hydroxamic acid), and unsubstituted or substituted -N(OH)(alkyl)(alkylated hydroxamic acid);
[0104] - R9" and R10" may be identical or different and are independently 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 RC(=O)-, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heteroaryl;
[0105] -Y is selected from the group consisting of H and unsubstituted or substituted alkyl; and
[0106] -R is unsubstituted or substituted alkyl;
[0107] or a tautomer or stereoisomer or salt of the aforementioned compound;
[0108] or any mixture of the foregoing compounds.
[0109] Component (a) of the sunscreen product or cosmetic or pharmaceutical preparation according to the first aspect of the invention relates to at least one photolabile UV filter, which is usually used in sunscreen products or cosmetic or pharmaceutical preparations.
[0110] UV filters are compounds or mixtures of compounds that block or absorb ultraviolet (UV) light. UV classification includes UVA (320nm to 400nm), UVB (290nm to 320nm) and UVC (200nm to 280nm). UV absorbing compounds are not only used in sunscreens, but also in other personal care products, such as lipsticks, shampoos, hair sprays, bath preparations, hand soaps and insect repellents. Chemical filters protect against UV radiation by absorption, reflection or scattering. Reflection and scattering are achieved by inorganic physical UV filters, such as titanium dioxide (TiO2) and zinc oxide (ZnO). Absorption, mainly the absorption of UVB, is accomplished by organic UV filters, which are referred to as chemical UV filters. Sunscreen products or cosmetics or pharmaceutical preparations according to the present invention provide broad-spectrum light protection, i.e. protection against UVA and UVB.
[0111] Many different organic compounds can be used as UV filters. They are divided into several structural types:
[0112] (1) Benzophenone
[0113] a. Benzophenone-3 (BP3)
[0114] b. Benzophenone-4 (BP4)
[0115] (2) Salicylate
[0116] a. Homosalate (HMS)
[0117] b.2-Ethylhexyl salicylate (EHS)
[0118] (3) p-Aminobenzoic acid and its derivatives
[0119] a. Dimethyl PABA ethylhexyl ester (OD-PABA)
[0120] b.4-para-aminobenzoic acid (PABA)
[0121] (4) Benzimidazole derivatives
[0122] a. Phenylbenzimidazole sulfonic acid (PMDSA)
[0123] b. Disodium phenyl dibenzimidazole tetrasulfonate (disodium bisbenzimidazole)
[0124] (5) Triazines
[0125] a. Ethylhexyl triazone (OT)
[0126] b. Diethylhexyl butyramido triazone (DBT)
[0127] c. Bis-ethylhexyloxyphenol methoxyphenyl triazine (EMT)
[0128] (6) Benzotriazoles
[0129] a. Dromtriazole trisiloxane (DRT)
[0130] b. Methylene bis-benzotriazolyl tetramethylbutylphenol (MBP, bistriazole)
[0131] (7) Dibenzoylmethane derivatives
[0132] a.4-tert-Butyl-4'-methoxydibenzoylmethane (BM-DBM, avobenzone)
[0133] (8) Cinnamate
[0134] a. Ethylhexyl methoxycinnamate (OMC)
[0135] b. Isoamyl p-methoxycinnamate (IMC, amiloxate)
[0136] (9) Camphor derivatives
[0137] a.Para-terephthalylidene camphorsulfonic acid (PDSA)
[0138] b.3-Benzalcamphor (3BC)
[0139] c. Benzylidene camphorsulfonic acid (BCSA)
[0140] d.4-Methylbenzylidene camphor (4-MBC)
[0141] e. Polyacrylamide methylbenzylidene camphor (PBC)
[0142] (10) Camphor benzalkonium bromide methyl sulfate (CBM)
[0143] In the context of the present invention, the term "photolabile UV filter" means a UV filter which is photolabile and does not retain its integrity when exposed to light. In other words, photolabile UV filters degrade more or less rapidly when exposed to light, i.e. lose their essential qualities for a sunscreen. This characteristic reduces the ability of the UV filter to protect against UV radiation. Exposure to UV radiation depletes the available concentration of organic UV filters in the sunscreen formulation, resulting in a reduction in the efficacy of the product, i.e. the UV protection capacity, in terms of protection level and protection duration.
[0144] The photostability of UV filters can be determined in vitro using an absorbance measurement method by which the absorbance loss of the UV filter before and after irradiation with, for example, 5 MED is measured. The absorbance loss of the UV filter is accompanied by degradation of the UV filter by one or more photochemical reactions (including photocleavage, isomerization, tautomerization, photoaddition, etc.). UV filters with an absorbance loss of ≥ 20% after irradiation are classified as photounstable. Alternatively, the photostability of UV filters can be determined by analytical measurement, i.e. by quantitatively determining the amount (i.e. concentration) of filter degradation.
[0145] The photolabile UV filter component in the sunscreen product or cosmetic or pharmaceutical preparation according to the first aspect of the present invention is selected from the group consisting of ethylhexyl methoxycinnamate (Neo AV), butyl methoxy dibenzoylmethane (Avobenzone; Neo 357), Isoamyl p-methoxycinnamate (Neo E1000), diethylamino-hydroxybenzoyl-hexyl-benzoate (UVinul A plus) and any mixture thereof.
[0146] Ethylhexyl methoxycinnamate
[0147]
[0148] are UVB filter substances which provide protection against UVB radiation in the wavelength range of 280 nm to 320 nm.
[0149] Butyl methoxydibenzoylmethane or avobenzone
[0150]
[0151] It is a dibenzoylmethane derivative. Avobenzone exists in the ground state as a mixture of enol and keto forms, favoring the chelation of the enol. This enol form is stabilized by intramolecular hydrogen bonding within the β-diketone. The ability of the enol form to absorb UV light over a wider wavelength range of 320 nm to 380 nm than many other sunscreens leads to its use in many commercial formulations marketed as broad spectrum sunscreens. Avobenzone has a maximum absorption of 357 nm. Avobenzone has been shown to degrade significantly in light exposure, resulting in less protection over time. One day of sunlight in a temperate climate is sufficient to break down most compounds.
[0152] Isoamyl p-methoxycinnamate
[0153]
[0154] are UVB filter substances which provide protection against UVB radiation in the wavelength range of 280 nm to 320 nm.
[0155] Diethylamino-hydroxybenzoyl-hexyl-benzoate
[0156]
[0157] It is a UV filter with high absorption in the UVA range within the wavelength range of 320nm to 380nm.
[0158] The aforementioned photostability UV filters are used as individual components or in mixtures with two, three or more of said photostability UV filters as specified above in sunscreens, cosmetic or pharmaceutical preparations or household care products.
[0159] Component (b) in the sunscreen product, cosmetic or pharmaceutical preparation according to the first aspect of the present invention is at least one mycosporin-like amino acid compound, and the at least one mycosporin-like amino acid compound is represented by the general formula (V):
[0160]
[0161] As defined herein;
[0162] Or represented by general formula (VI)
[0163]
[0164] As defined herein.
[0165] Mycosporine-like amino acids (MAAs) are small secondary metabolites produced by organisms living in environments with a lot of sunlight, usually marine environments. MAAs are imine derivatives of mycosporines and contain an amino-cyclohexene-imine ring attached to an amino acid, amino alcohol or amino group. The compounds are capable of electron delocalization. In addition, the compounds exhibit antioxidant properties.
[0166] Unless otherwise indicated, in the context of the present invention, in particular for the definition of mycosporin-like amino acid compounds represented by any general formula, the following general meanings apply:
[0167] According to the present invention, the term "halogen" residue / moiety or group alone or as part of another substituent refers to F, Cl, Br or I.
[0168] According to the present invention, the term "alkyl" alone or as part of another substituent refers to a saturated or mono- or poly-unsaturated straight or branched chain monovalent hydrocarbon radical obtained by removing a hydrogen atom from a single carbon atom of the corresponding parent alkane.
[0169] In preferred variations, the term "alkyl" also includes any alkyl moiety in a radical derived therefrom, such as alkoxy, alkylthio, alkylsulfonyl saturated straight or branched chain hydrocarbon radicals having 1 to 10, 1 to 8, 1 to 6 or 1 to 4 carbon atoms.
[0170] If the alkyl group is further bonded to another atom, the alkyl group becomes an alkylene radical or an alkylene group. In other words, the term "alkylene" also refers to a divalent straight or branched chain alkyl group. For example, -CH2CH3 is an ethyl group, while -CH2CH2- is an ethylene group.
[0171] The term "alkylene" by itself or as part of another substituent refers to a saturated straight or branched chain divalent hydrocarbon radical derived by the removal of two hydrogen atoms from a single carbon atom or from two different carbon atoms of a starting alkane.
[0172] In a preferred variant according to the invention, the linear or branched alkyl group or alkylene group contains 1 to 10 carbon atoms. In a further still more preferred variant, the linear or branched alkyl group or alkylene group contains 1 to 6 carbon atoms.
[0173] More preferred according to the invention are saturated straight-chain or branched C1 to C6 alkyl groups or saturated straight-chain or branched C1 to C6 alkylene groups.
[0174] Most preferably the straight or branched chain alkyl or alkylene group has 1 to 4 carbon atoms.
[0175] Preferred alkyl groups / moieties or alkyl groups include, but are not limited to, C1 to C6 alkyl, including 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.
[0176] In a preferred variant, the alkyl group / moiety is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, a more preferred form being the group consisting of methyl and ethyl.
[0177] The alkyl or alkylene groups as defined above may be further substituted.
[0178] The term "alkyl" or "alkylene" also includes radicals or groups having any degree of saturation, i.e., radicals having only carbon-carbon single bonds ("alkyl" or "alkylene"), radicals having one or more carbon-carbon double bonds ("alkenyl"), radicals having one or more carbon-carbon triple bonds ("alkynyl"), and radicals having mixtures of carbon-carbon single bonds, carbon-carbon double bonds, and / or carbon-carbon triple bonds.
[0179] According to the present invention, the term "alkenyl" alone or as part of another substituent refers to an unsaturated straight or branched monovalent hydrocarbon group having at least one carbon-carbon double bond (C=C double bond). The group can be in the cis or trans conformation around the double bond. Therefore, the term "alkenyl" also includes the corresponding cis / trans isomers.
[0180] In a preferred variant according to the invention, the straight-chain or branched alkenyl group contains 2 to 10 carbon atoms. In a further preferred variant, the straight-chain or branched alkenyl group contains 2 to 6 carbon atoms.
[0181] In a still more preferred variation, the straight-chain or branched alkenyl group contains 2 to 4 carbon atoms.
[0182] According to the invention, mono- or di-unsaturated, straight-chain or branched C1 to C6 alkenyl radicals are preferred.
[0183] Typical alkenyl radicals or alkenyl groups include, but are not limited to, vinyl; propenyl 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; butenyl 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, etc.
[0184] Alkenyl groups as defined above may be further substituted.
[0185] According to the present invention, the term "alkenyl" alone or as part of another substituent refers to an unsaturated straight or branched chain monovalent hydrocarbon group having at least one carbon-carbon triple bond (C≡C triple bond).
[0186] In preferred variants according to the invention, the straight-chain or branched alkynyl group contains 2 to 10 carbon atoms. In other preferred variants, the alkynyl group contains 2 to 6 carbon atoms. In a more preferred variant, the alkynyl group contains 2 to 4 carbon atoms.
[0187] Most preferred according to the invention are mono- or di-unsaturated straight-chain or branched C1 to C6 alkynyl groups.
[0188] Typical alkenyl radicals / moieties or alkenyl groups include, but are not limited to, ethynyl; propynyl, such as prop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butynyl, such as but-1-yn-1-yl, but-1-yn-3-yl, but-3-yn-1-yl, etc.
[0189] An alkynyl group as defined above may be further substituted. An alkyl group or an alkylene group as defined above may be further substituted.
[0190] According to the present invention, the term "alkoxy" by itself or as part of another substituent refers to a straight or branched chain radical of the formula -OR, wherein R is alkyl or substituted alkyl as defined herein.
[0191] In preferred variants according to the invention, the straight-chain or branched alkoxy group contains 2 to 10 carbon atoms. In other preferred variants, the straight-chain or branched alkoxy group contains 2 to 6 carbon atoms. In a more preferred variant, the straight-chain or branched alkoxy group contains 2 to 4 carbon atoms.
[0192] Most preferred according to the invention are straight-chain or branched C1 to C6 alkoxy groups.
[0193] Typical alkoxy radicals / moieties or alkoxy groups include C1 to C6 alkoxy groups including C1 to C4 alkoxy groups such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy; and pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexyloxy, 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.
[0194] In a preferred variation, the alkoxy radical or alkoxy group is methoxy (-O-methyl), ethoxy (-O-ethyl), propoxy (-O-propyl) or butoxy (-O-butyl), more preferably selected from the group consisting of methoxy (-O-methyl) and ethoxy (-O-ethyl).
[0195] The alkoxy groups or alkylene groups as defined above may be further substituted.
[0196] According to the present invention, the term "alkylthio" or "thioalkoxy" by itself or as part of another substituent refers to a radical of formula -SR, wherein R is alkyl or substituted alkyl as defined herein.
[0197] According to the present invention, the term "alkyl" or "alkylene" also includes heteroalkyl radicals or heteroalkyl groups. The term "heteroalkyl" itself or as a part of other substituents refers to an alkyl group, one or more carbon atoms in the alkyl group being independently replaced by the same or another heteroatom or by the same or another heteroatom group. Typical heteroatoms or heteroatom groups of replaceable carbon atoms include, but are not limited to: -O-, -S-, -N-, -Si-, -NH-, -S(O)-, -S(O)2-, -S(O)NH-, -S(O)2NH-, etc. and combinations thereof. Heteroatoms or heteroatom groups can be positioned at any internal position of an alkyl group.
[0198] Typical heteroatom groups that may be included in these groups include, but are not limited to, -O-, -S-, -OO-, -SS-, -OS-, -NRR-, =NN=, -N=N-, -N=N-NRR, -PR-, -P(O)2-, -POR-, -OP(O)2-, -SO-, -SO2-, -SR2OR-, and the like, where 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.
[0199] The alkyl or alkylene groups as defined above may be further substituted.
[0200] According to the present invention, the term "acyl" or "alkanoyl" by itself or as part of another substituent refers to the group RC(=O)-, wherein R is hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, arylalkyl, unsubstituted or substituted arylalkyl, unsubstituted or substituted heteroalkyl, unsubstituted or substituted heteroarylalkyl as defined herein.
[0201] Representative examples include, but are not limited to, formyl, acetyl, propionyl, butyryl, valeryl, benzoyl, cyclohexylcarbonyl, cyclohexylmethylcarbonyl, benzylcarbonyl, and the like.
[0202] According to the present invention, the term "cycloalkyl" alone or as part of another substituent refers to a saturated or mono- or polyunsaturated non-aromatic cyclic monovalent hydrocarbon radical, wherein the carbon atoms are ring-linked and having no heteroatoms.
[0203] The carbocycle may occur as a monocyclic compound having only a single ring, or as a polycyclic compound having two or more rings.
[0204] In a 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 variations, the cycloalkyl moiety includes a five-, six- or seven-membered monocyclic cycloalkyl moiety or a nine- to twelve-membered bicyclic cycloalkyl moiety.
[0205] In a preferred embodiment according to the present invention, the cycloalkyl radical or group comprises 3 to 20 carbon atoms. In an even more preferred embodiment, the cycloalkyl radical comprises 6 to 15 carbon atoms. In a most preferred embodiment, the cycloalkyl radical comprises 6 to 10 carbon atoms. Most preferably, the monocyclic C3 to C7 cycloalkyl radical.
[0206] Typical cycloalkyl radicals or cycloalkyl groups include, but are not limited to, saturated carbocyclic groups having 3 to 20 carbon atoms, such as C3 to C12 carbocyclic groups, including cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl, cycloheptyl, and cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl-methyl, cyclobutyl-ethyl, cyclopentyl-methyl, cyclopentyl-ethyl, cyclohexyl-methyl, or C3- To C7-carbocyclic group, the C3- To C7-carbocyclic groups include 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.
[0207] Preferred polycyclic cycloalkyl radicals or cycloalkyl groups according to the present invention include, but are not limited to, naphthyl, indenyl, cycloalkyl radicals, and the like.
[0208] According to the invention, the term "cycloalkyl" also includes cycloalkenyl, i.e. an unsaturated cyclic hydrocarbon group containing a C=C double bond between two carbon atoms of the ring molecule. In a broader sense, cycloalkenyl is a compound with one, two or more double bonds, wherein the number of possible, most conjugated double bonds in the molecule depends on the ring size.
[0209] Typical cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, and the like.
[0210] According to the invention, the term "cycloalkyl" also includes cycloalkynyl groups containing a cyclic hydrocarbon group between two carbon atoms of the ring molecule, ie an unsaturated -C≡C- triple bond which, due to ring strain, depends on the ring size.
[0211] Typical cycloalkynes include cyclooctyne.
[0212] The cycloalkyl, cycloalkenyl or cycloalkynyl moieties or groups as defined above may be further substituted.
[0213] According to the present invention, the term "aryl" alone or as part of another substituent refers to a monovalent aromatic hydrocarbon radical derived by removing a hydrogen atom from a single carbon atom of an aromatic ring SY-stem.
[0214] In a 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 variations, the carboaryl group includes a five-, six- or seven-membered monocyclic carboaryl group or a nine- to twelve-membered bicyclic carboaryl group.
[0215] In a preferred embodiment according to the invention, the aryl group comprises 3 to 20 carbon atoms. In a preferred variant, the aryl moiety comprises 6 to 15 ring atoms. In an even more preferred embodiment, the aryl group comprises 6 to 10 carbon atoms.
[0216] According to the present invention, most preferred is a monocyclic C3 to C10 aryl group.Most preferred is a monocyclic C3 to C7 aryl group.
[0217] Typical aryl groups include, but are not limited to, benzene, phenyl, biphenyl, naphthyl such as 1-naphthyl or 2-naphthyl, tetrahydronaphthyl, fluorenyl, indenyl, and phenanthrenyl. Typical carboaryl moieties also include, but are not limited to, groups derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene, hexalene, as-indacene, S-indacene, indane, indene, naphthalene, octaphene, octalene, ovalene, pentadiene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene, etc.
[0218] According to the present invention, preferred aromatic polycyclic aryl radicals or aryl groups include, but are not limited to, naphthalene, biphenyl, and the like.
[0219] The aryl moieties or groups as defined above may be further substituted.
[0220] According to the present invention, the term "arylalkyl" alone or as a part of another substituent refers to an acyclic alkyl group, wherein one of the hydrogen atoms attached to a carbon atom (usually a terminal or sp carbon atom) is replaced by an aryl group as defined herein. In other words, arylalkyl may also be considered as an alkyl substituted with aryl. Typical arylalkyl groups include but are not limited to benzyl, 2-phenylethyl-1-yl, 2-phenylethene-1-yl, naphthylmethyl, 2-naphthylethyl-1-yl, 2-naphthylethene-1-yl, naphthobenzyl, 2-naphthobenzylethyl-1-yl etc.
[0221] 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 the 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 group, for example, the alkyl group, alkenyl group or alkynyl group of the heteroarylalkyl group is a C1 to C6 alkyl group and the heteroaryl group is a 5- to 15-membered heteroaryl group. In other embodiments, the heteroarylalkyl group is a 6- to 13-membered heteroarylalkyl group, for example, the alkyl group, alkenyl group or alkynyl group is a C1 to C3 alkyl group and the heteroaryl group is a 5- to 10-membered heteroaryl group.
[0222] According to the present invention, the term "heterocycloalkyl" alone or as part of another substituent refers to a saturated or mono- or polyunsaturated non-aromatic cyclic monovalent hydrocarbon group in which one or more carbon atoms are independently replaced by the same or different heteroatoms. Typical heteroatoms replacing carbon atoms include, but are not limited to, N, P, O, S, Si, etc. Typical heterocycloalkyl groups include, but are not limited to, groups derived from epoxides, aziridines, thiiranes, imidazolidines, morpholine, piperazine, piperidine, pyrazolidine, pyrrolidone, quinuclidine, etc.
[0223] In a preferred embodiment according to the invention, the heterocycloalkyl moiety or group comprises 3 to 20 carbon atoms. In a preferred variant, the heterocycloalkyl moiety comprises 6 to 15 ring atoms. In an even more preferred embodiment, the heterocycloalkyl moiety comprises 6 to 10 carbon atoms.
[0224] The heterocycloalkyl moiety may occur as a monocyclic compound having only a single ring, or as a polycyclic (such as a bicyclic, tricyclic or spirocyclic) compound having two or more rings.
[0225] Preferably, the term "heterocycloalkyl" includes a three- to seven-membered saturated or mono- or polyunsaturated heterocycloalkyl moiety containing one, two, three or four heteroatoms selected from the group consisting of O, N and S. The one or more heteroatoms may occupy any position in the heterocycloalkyl ring.
[0226] In a preferred variation, the term "heterocycloalkyl" includes a three-membered to ten-membered monocyclic heterocycloalkyl group or a nine-membered to twelve-membered polycyclic heterocycloalkyl group. In other still more preferred variations, the heterocycloalkyl moiety comprises a five-membered, six-membered or seven-membered monocyclic heterocycloalkyl moiety or a nine-membered to twelve-membered bicyclic heterocycloalkyl moiety.
[0227] According to the invention, most preferred are monocyclic heterocycloalkyl groups containing 3 to 12 carbon atoms.Most preferred are monocyclic heterocycloalkyl groups having 5 to 7 ring atoms.
[0228] Typical heterocycloalkyl moieties include, but are not limited to, five-membered or six-membered saturated or monounsaturated heterocycloalkyl groups containing one or two nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members, including 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2- Oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolidin-2-yl, 2-pyrrolidin-3-yl, 3-pyrrolidin-2-yl, 3-pyrrolidin-3-yl, 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 2-tetrahydropyranyl, 1,3-dioxane-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyridazinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, and the like.
[0229] The heterocycloalkyl moieties or groups as defined above may be further substituted.
[0230] According to the present invention, the term "heteroaryl" alone or as part of another substituent refers to a monovalent heteroaromatic group obtained by removing a hydrogen atom from a single atom of a heteroaromatic ring SY-stem. Typical heteroaryl groups or heteroaryl groups include, but are not limited to, those derived from acridine, β-carboline, chroman, chromium, cinnoline, furan, imidazole, indazole, indole, dihydroindole, indolizine, isobenzofuran, isochromene, 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, etc.
[0231] The heteroaryl moiety may occur as a monocyclic compound having only a single ring or as a polycyclic compound having two or more rings.
[0232] In a preferred variation, the term "heteroaryl" includes a three- to ten-membered monocyclic heteroaryl group or a nine- to twelve-membered polycyclic heteroaryl group. In other still more preferred variations, the heteroaryl moiety comprises a five-, six- or seven-membered monocyclic heteroaryl moiety or a nine- to twelve-membered bicyclic heteroaryl moiety.
[0233] Preferably, the term "heteroaryl" includes three- to seven-membered monocyclic heteroaryl groups containing one, two, three or four heteroatoms selected from the group consisting of O, N and S. The one or more heteroatoms may occupy any position in the heteroaryl ring.
[0234] In a preferred embodiment according to the invention, the heteroaryl moiety or group comprises 3 to 20 carbon atoms. In an even more preferred variation, the heteroaryl moiety comprises 6 to 15 ring atoms. In a most preferred embodiment, the heteroaryl group comprises 6 to 10 ring atoms. According to the invention, most preferably a monocyclic C3 to C7 heteroaryl group.
[0235] Particularly preferred heteroaryl moieties or 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.
[0236] Five-membered aromatic heteroaryl groups 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-imidazolyl, 4-imidazolyl and 1,3,4-triazol-2-yl.
[0237] Five-membered aromatic heteroaryl groups containing one, two, three or four nitrogen atoms as ring atoms include 1-pyrrolyl, 2-pyrrolyl or 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl or 4-pyrazolyl, 1-imidazolyl, 2-imidazolyl or 4-imidazolyl, 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]-tetrazole-1-yl, [1H]-tetrazole-5-yl, [2H]-tetrazole-2-yl, [2H]-tetrazole-5-yl, and the like.
[0238] Five-membered aromatic heteroaryl groups containing as ring atoms a heteroatom selected from oxygen or sulfur and optionally one, two or three nitrogen atoms include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 3- or 4-isoxazolyl, 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.
[0239] In addition to carbon atoms, six-membered heteroaryl groups contain one or two or one, two or three nitrogen atoms as ring atoms and include, for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 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.
[0240] Heteroaryl moieties or groups as defined above may be further substituted.
[0241] In the context of the present application, the term "C-spiro" means a compound having at least two molecular rings with only one common atom. The simplest spiro compound is a bicyclic ring (having only two rings) or has a bicyclic moiety as part of a larger ring system, in either case, the two rings are connected by a single common atom defined. A common atom connected to the participating rings distinguishes spiro compounds from other bicyclic structures: from isolated ring compounds (such as biphenyl) without connecting atoms, from condensed ring compounds (such as decahydronaphthalene) with two rings connected by two adjacent atoms, and from bridged ring compounds (such as norbornane) with two rings connected by two non-adjacent atoms. Spiro compounds can be completely carbocyclic (all carbon) or heterocyclic (with one or more non-carbon atoms, such as N, O and S). The common atom connecting two (or sometimes three) rings is called a spiro atom. Preferably, the spiro atom is a carbon atom. More preferably, C-spiro compounds mean a compound of a complete carbocyclic (all carbon).
[0242] In the context of the present invention, the term "substituted" means that one or more hydrogen atoms of the indicated radical or group are independently replaced by identical or different substituents. In addition, the term "substituted" explicitly provides one or more, i.e. two, three or even more, substitutions commonly used in the art. However, it is well known that substituents should be selected so that they do not have an adverse effect on the usable properties of the compound or its function.
[0243] In the context of the present invention, suitable substituents preferably include halogen, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl groups or heteroaryl groups, aryloxy groups or heteroaryloxy groups, arylalkyl groups or heteroarylalkyl groups, arylalkoxy groups or heteroarylalkoxy groups, amino groups, alkyl groups and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, carboxyl groups, 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, borate or boryl groups, phosphate or phosphonyl groups, sulfamoyl groups, sulfonyl groups, sulfinyl groups and combinations thereof.
[0244] Substituents or substituent groups suitable for replacing saturated carbon atoms in the indicated group or radical more preferably include, but are not limited to, halogen, hydroxy, alkyl, alkenyl, alkynyl, alkoxy, -NH2, amino (primary, secondary or tertiary), nitro, thiol, thioether, imine, cyano, amido, phosphonate, phosphine, carboxyl, thiocarbonyl, sulfonyl, sulfonamide, ketone, aldehyde, ester, acetyl, acetoxy, carbamoyl, oxygen (O); haloalkyl (e.g., trifluoromethyl); aminoacyl and aminoalkyl, carbocyclic cycloalkyl, which carbocyclic cycloalkyl can be a monocyclic or fused or non-fused polycyclic (e.g., cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), or heterocycloalkyl, which heterocyclic group can be monocyclic or fused or non-fused polycyclic (for example pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl or thiazinyl), carbocyclic or heterocyclic, monocyclic or fused or non-fused polycyclic aromatic (for example phenyl, naphthyl, pyrrolyl, indolyl, furanyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, benzimidazolyl, benzothienyl or benzofuranyl), -CO2CH3, -CONH2, -OCH2CONH2; -SO2NH2, -OCHF2, -CF3, -OCF3.
[0245] According to the present invention, the substituents used to replace a particular group or groups may in turn be further substituted, typically by one or more identical or different groups 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 alkyl groups may be substituted, or both the aryl and alkyl groups may be substituted by one or more substituents.
[0246] In a preferred variant, Z in the general formula (V) is -O-R2' or amide'.
[0247] In a further preferred variant, R1' in the general formula (V) is CH2.
[0248] In a further preferred variant, R1' in the general formula (V) is C(alkyl)2.
[0249] In a further preferred variant, R1′ in the general formula (V) is O.
[0250] In a further preferred variant, R1′ in general formula (V) is S.
[0251] In a further preferred variant, R1' in the general formula (V) is SO.
[0252] In a further preferred variant, R1' in the general formula (V) is SO2.
[0253] In a further preferred variant, R1' in the general formula (V) is NH.
[0254] In yet another preferred variant, R1' in the general formula (V) is N(alkyl)
[0255] Most preferably, R1' in formula (V) is CH2 or C(alkyl)2.
[0256] In a preferred variant, R2' in general formula (V) is H.
[0257] In a further preferred variant, R2' in the general formula (V) is methyl.
[0258] In a further preferred variant, R2' in the general formula (V) is ethyl.
[0259] In a further preferred variant, R2' in the general formula (V) is propyl.
[0260] In a further preferred variant, R2' in the general formula (V) is isopropyl.
[0261] In a further preferred variant, R2' in the general formula (V) is butyl.
[0262] In a further preferred variant, R2' in the general formula (V) is isobutyl.
[0263] In a further preferred variant, R2' in the general formula (V) is tert-butyl.
[0264] In another preferred variant, R2' in the general formula (V) is
[0265] In another preferred variant, R2' in the general formula (V) is
[0266] In another preferred variant, R2' in the general formula (V) is (2-ethylhexyl).
[0267] In yet another preferred variant, R2′ in the general formula (V) is phenyl.
[0268] Most preferably, R2' in the general formula (V) is H or ethyl or isopropyl or 2-ethylhexyl or phenyl.
[0269] In a preferred variant, amide' in general formula (V) is NH2.
[0270] In a further preferred variant, the amide' in the general formula (V) is NH(alkyl), wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0271] In a further preferred variant, the amide' in the general formula (V) is N(alkyl)2, wherein the alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0272] In a further preferred variant, the amide' in formula (V) is -N(O-alkyl)(alkyl)(Weinreb amide), wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0273] In yet another preferred variant, the amide of general formula (V) is -N(OH)(H)(hydroxamic acid).
[0274] Most preferably, the amide' in formula (V) is NH2, N(methyl)2 or N(ethyl)2 or -N(O-alkyl)(alkyl) (Weinreb amide), wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl or -N(OH)(H) (hydroxamic acid).
[0275] In a preferred variant, R3' in general formula (V) is H.
[0276] In a further preferred variant, R3' in the general formula (V) is methyl.
[0277] In a further preferred variant, R3' in the general formula (V) is ethyl.
[0278] In a further preferred variant, R3' in general formula (V) is -O-methyl.
[0279] In a further preferred variant, R3' in general formula (V) is -C(=O)-OH.
[0280] In another preferred variant, R3' in general formula (V) is -C(=O)-CH3.
[0281] In another preferred variant, R3' in the general formula (V) is -C(=O)-C3H 7。
[0282] In yet another preferred variant, R3' in general formula (V) is -C(=O)-O-methyl.
[0283] Most preferably, R3' in the general formula (V) is H or methyl or -O-methyl.
[0284] In a preferred variation according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) of general formula (V) is an acid compound or an ester compound represented by general formula (VII):
[0285]
[0286] wherein R1′, R2′, R3′, R4′, R5′ and R6′ have the same meanings as defined herein for Formula (V).
[0287] In a preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) of general formula (V) is an acid compound represented by general formula (VII-acid)
[0288]
[0289] wherein R1′, R3′, R4′, R5′ and R6′ have the same meanings as defined herein for Formula (V).
[0290] The mycosporin-like amino acid compounds according to the general formula (VII-acid) are particularly light-stable and temperature-stable compounds and show stability in pH solutions or in different emulsion types and do not degrade.
[0291] In particular, the mycosporin-like amino acid compounds as defined herein have better pH stability over a wider pH range than their corresponding ester compounds, which hydrolyze and are therefore unstable in alkaline solutions above pH 9.
[0292] In addition, the mycosporin-like amino acid compound also has better solubility in water than its corresponding ester compound. Due to the better solubility of the mycosporin-like amino acid compound in water, the mycosporin-like amino acid compound can be incorporated into the aqueous phase of the formulation at a higher concentration, resulting in a better photostabilization effect and thus having an improved sunscreen in sunscreen products, cosmetic or pharmaceutical formulations or home care products.
[0293] In a preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) of general formula (V) is an ester compound represented by general formula (VII-ester):
[0294]
[0295] wherein R1′, R3′, R4′, R5′ and R6′ have the same meanings as defined herein for Formula (V).
[0296] Preferably, the alkyl residue in the general formula (VII-ester) is methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl. Most preferably, the alkyl residue in the general formula (VII-ester) is methyl. Such ester compounds are particularly stable.
[0297] In an alternative preferred variation according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) of general formula (V) is an amide compound represented by general formula (VIII):
[0298]
[0299]
[0300] wherein R1′, Amide′, R3′, R4′, R5′ and R6′ have the same meanings as defined herein for Formula (V).
[0301] In a more preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) of general formula (V) is an amide compound represented by general formula (VIII-amide):
[0302]
[0303] wherein R1′, R3′, R4′, R5′ and R6′ have the same meanings as defined herein for formula (V), and R11′ and R12′ are independently selected from the group consisting of H, OH and alkyl.
[0304] In a preferred variant according to the first aspect of the invention, in the general formula (VIII-amide), R11′ and / or R12′ is H.
[0305] In a further preferred variant, R11′ alkyl and / or R12′ alkyl in the general formula (VIII-amide) are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0306] Preferably, R11′ and / or R12′ in the general formula (VIII-amide) are each H or are each methyl.
[0307] In a still more preferred variation, the mycosporin-like amino acid compound (b) of formula (V) is a Weinreb amide compound represented by the formula (VIII-Weinreb amide)
[0308]
[0309] wherein R1′, R3′, R4′, R5′ and R6′ have the same meanings as defined herein for Formula (V).
[0310] In a preferred variant, the alkyl residue in the general formula (VIII-Weinreb amide) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferably the alkyl residue is methyl.
[0311] Alternatively, in a still more preferred variation, the mycosporin-like amino acid compound (b) of general formula (V) is a hydroxamic acid compound represented by general formula (VIII-hydroxamate derivative)
[0312]
[0313] Formula (VIII-hydroxamic acid derivative)
[0314] wherein R1′, R3′, R4′, R5′ and R6′ have the same meanings as defined herein for Formula (V).
[0315] Alternatively, in yet another preferred variation, the mycosporin-like amino acid compound (b) of the amide compound (VIII-amide) general formula (V) is an alkylated hydroxamic acid compound represented by the general formula (VIII-alkylated hydroxamic acid derivative)
[0316]
[0317] Formula (VIII - alkylated hydroxamic acid derivative),
[0318] wherein R1′, R3′, R4′, R5′ and R6′ have the same meanings as defined herein for Formula (V).
[0319] In a preferred variant, the alkyl residue in the general formula (VIII - alkylated hydroxamic acid derivative) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferably the alkyl group is methyl.
[0320] In a preferred alternative variant, the mycosporin-like amino acid compound (b) is an alcohol compound represented by the general formula (A):
[0321]
[0322] wherein R1′, R3′, R4′, R5′ and R6′ have the same meanings as defined herein for Formula (V).
[0323] In the present invention, the same preferred variants as defined herein for the mycosporin-like amino acid compounds according to general formula (V) apply analogously to the mycosporin-like amino acid compounds according to general formula (VII), (VIII) and variants thereof or general formula (A).
[0324] In a further preferred variant, R1″ in the general formula (VI) is CH2.
[0325] In a further preferred variant, R1″ in the general formula (VI) is C(alkyl)2.
[0326] In a further preferred variant, R1″ in the general formula (VI) is O.
[0327] In a further preferred variant, R1″ in the general formula (VI) is S.
[0328] In a further preferred variant, R1″ in the general formula (VI) is SO.
[0329] In a further preferred variant, R1″ in the general formula (VI) is SO2.
[0330] In a further preferred variant, R1″ in the general formula (VI) is NH.
[0331] In yet another preferred variant, R1″ in the general formula (VI) is N(alkyl).
[0332] The most preferred R1" in formula (VI) is CH2 or C(alkyl)2.
[0333] In a further preferred variant, R2" in the general formula (VI) is -CH2-OH.
[0334] In a further preferred variant, R2″ in the general formula (VI) is —C(═O)—OY.
[0335] In a further preferred variant, R2" in the general formula (VI) is -C(=O)-amide".
[0336] Most preferably, R2" in the general formula (VI) is -C(=O)-OY or -C(=O)-amide".
[0337] In a further preferred variant, X in the general formula (VI) is CH2.
[0338] In a further preferred variant, X in the general formula (VI) is C═O.
[0339] In a further preferred variant, X in the general formula (VI) is O.
[0340] In a further preferred variant, X in the general formula (VI) is S.
[0341] In a further preferred variant, X in the general formula (VI) is SO.
[0342] In a further preferred variant, X in the general formula (VI) is SO2.
[0343] In a further preferred variant, X in the general formula (VI) is NH.
[0344] In yet another preferred variation, X in formula (VI) is N(alkyl), wherein alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0345] Most preferably, X in formula (VI) is S, SO or SO2.
[0346] In a preferred variant, Y in the general formula (VI) is H.
[0347] In a further preferred variant, Y in the general formula (VI) is methyl.
[0348] In a further preferred variant, Y in the general formula (VI) is ethyl.
[0349] In a further preferred variant, Y in the general formula (VI) is propyl.
[0350] In a further preferred variant, Y in the general formula (VI) is isopropyl.
[0351] In a further preferred variant, Y in the general formula (VI) is butyl.
[0352] In a further preferred variant, Y in the general formula (VI) is isobutyl.
[0353] In a further preferred variant, Y in the general formula (VI) is tert-butyl.
[0354] In another preferred variant, Y in the general formula (VI) is
[0355] In another preferred variant, Y in the general formula (VI) is
[0356] In a preferred variant, Y in the general formula (VI) is (2-ethylhexyl).
[0357] In yet another preferred variant, Y in the general formula (VI) is phenyl.
[0358] Most preferably, Y in the general formula (VI) is H or ethyl or isopropyl or 2-ethylhexyl or phenyl.
[0359] In a preferred variant, "amide" in general formula (VI) is NH2.
[0360] In a further preferred variant, the "amide" in the general formula (VI) is NH(alkyl), wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0361] In a further preferred variant, the "amide" in the general formula (VI) is N(alkyl)2, wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0362] In a further preferred variant, the "amide" in the general formula (VI) is -N(O-alkyl)(alkyl)(Weinreb amide), wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0363] In yet another preferred variant, the "amide" in general formula (V) is -N(OH)(H)(hydroxamic acid).
[0364] The most preferred "amide" in general formula (V) is NH2, N(methyl)2 or N(ethyl)2 or -N(O-alkyl)(alkyl) (Weinreb amide), wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl or -N(OH)(H) (hydroxamic acid).
[0365] In a more preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) is an alcohol compound represented by the general formula (IX-alcohol):
[0366]
[0367] wherein R1", X, R4", R5" and R6" have the same meanings as defined herein for formula (VI).
[0368] Alternatively, in a more preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) of the general formula (VI) is an acid compound represented by the general formula (IX-acid):
[0369]
[0370] wherein R1", X, R4", R5" and R6" have the same meanings as defined herein for formula (VI).
[0371] Alternatively, in a more preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) of the general formula (VI) is an ester compound represented by the general formula (VII-ester):
[0372]
[0373] wherein R1", X, R4", R5" and R6" have the same meanings as defined herein for formula (VI).
[0374] Preferably, the alkyl residue in the general formula (VII-ester) is methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl, more preferably the alkyl residue is methyl.
[0375] In an alternative more preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) of general formula (VI) is an amide compound represented by general formula (X):
[0376]
[0377] wherein R1", amide", X, R4", R5" and R6" have the same meanings as defined herein for formula (VI).
[0378] In a more preferred alternative variant according to the first aspect of the present invention, the mycosporin-like amino acid compound (b) of the general formula (VI) is an amide compound represented by the general formula (X-amide):
[0379]
[0380] wherein R1″, X, R4″, R5″ and R6″ have the same meanings as defined herein for formula (VI), and R11′ and R12′ are independently selected from the group consisting of H, OH and alkyl.
[0381] In a preferred variant according to the first aspect of the present invention, in the general formula (X-amide), R11″ and / or R12″ is H.
[0382] Preferably, R11" alkyl and / or R12" alkyl in the general formula (X-amide) is methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl.
[0383] Preferably, R11" and / or R12" in the general formula (X-amide) are each H or are each methyl.
[0384] In a still more preferred variation, the mycosporin-like amino acid compound (b) of formula (VI) is a Weinreb amide compound represented by the formula (X-Weinreb amide):
[0385]
[0386] wherein R1", X, R4", R5" and R6" have the same meanings as defined herein for formula (VI).
[0387] In a preferred variant, the alkyl residue in the general formula (X-Weinreb amide) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferably the alkyl residue is methyl.
[0388] Alternatively, in a still more preferred variation, the mycosporin-like amino acid compound (b) of general formula (VI) is a hydroxamic acid compound represented by the general formula (X-hydroxamic acid derivative):
[0389]
[0390] wherein R1", X, R4", R5" and R6" have the same meanings as defined herein for formula (VI).
[0391] Alternatively, in yet another preferred variation, the mycosporin-like amino acid compound (b) of general formula (VI) is an alkylated hydroxamic acid compound represented by general formula (VIII-alkylated hydroxamic acid derivative)
[0392]
[0393] wherein R1", X, R4", R5" and R6" have the same meanings as defined herein for formula (VI).
[0394] In a preferred variant, the alkyl residue in the general formula (X-alkylated hydroxamic acid derivative) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and butyl, more preferably the alkyl residue is methyl.
[0395] In the present invention, the same preferred variants as defined herein for the mycosporin-like amino acid compounds according to general formula (VI) apply analogously to the mycosporin-like amino acid compounds according to general formula (IX) or (X) and variants thereof.
[0396] In the following and throughout the specification, the term "according to the general formula YZ and variants thereof" includes any subformula (e) of said general formula as disclosed herein. Thus, variants of the general formulas (V) and (VI) as defined herein include formulas (VII), (VIII), (IX) and (X) as defined herein. Variants of the general formulas (VII) and (VIII) as defined herein include subformula (VII-acid), subformula (VII-ester), subformula (VIII-amide), subformula (VIII-Weinreb amide), subformula (VIII-hydroxamic acid derivative) and subformula (VIII-alkylated hydroxamic acid derivative) as defined herein. Variants of the general formulas (IX) and (X) as defined herein include formula (IX-acid), formula (IX-ester), formula (X-amide), formula (X-Weinreb amide), formula (X-hydroxamic acid derivative) and formula (X-alkylated hydroxamic acid derivative) as defined herein.
[0397] In further preferred variations of the general formula (VI), (IX), (X) and variations thereof, X is selected from the group consisting of CH2, unsubstituted or substituted CH(alkyl), unsubstituted or substituted C(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), -CR7"R8", C=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-spiro;
[0398] In further preferred variants according to the first aspect of the invention, the mycosporin-like amino acid compound is a compound according to general formula (V), wherein
[0399] -Z is -O-R2' or amide'; and / or
[0400] - R1' is selected from the group consisting of: CH2, C(alkyl)2, O, S, SO, SO2, NH and N(alkyl); and / or
[0401] -R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethyl-hexyl) and phenyl; or
[0402] -amide' is selected from the group consisting of: NH2, NH(alkyl), N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and / or
[0403] -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
[0404] - the substituents R4', R5' and R6' have the same meanings as defined for formula (V);
[0405] - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0406] In another preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound is a compound according to general formula (VII) or (VIII), wherein
[0407] - R1' is selected from the group consisting of: CH2, C(alkyl)2, O, S, SO, SO2, NH and N(alkyl); and / or
[0408] -R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,
[0409] (2-ethyl-hexyl) and phenyl; or
[0410] -amide' is selected from the group consisting of: NH2, NH(alkyl), N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and / or
[0411] -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
[0412] - the substituents R4', R5' and R6' have the same meanings as defined for formula (V);
[0413] - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0414] In another preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound is a compound according to general formula (VI), wherein
[0415] -R1" is selected from the group consisting of CH2, C(alkyl)2, O, S, SO, SO2, NH and N(alkyl); and / or
[0416] -R2" is selected from the group consisting of: -CH2-OH, -C(=O)-OY and -C(=O)-amide"; and / or
[0417] -X is selected from the group consisting of CH2, C=O, O, S, SO, SO2, NH and N(alkyl); and / or
[0418] -Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethyl-hexyl) and phenyl; and / or
[0419] -amide" is selected from the group consisting of: NH2, NH(alkyl), N(alkyl), -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and / or
[0420] - the substituents R4", R5" and R6" have the same meanings as defined for formula (VI);
[0421] - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0422] In further preferred variants according to the first aspect of the invention, the mycosporin-like amino acid compound is a compound according to general formula (V), wherein
[0423] -Z is -O-R2' or amide'; and / or
[0424] - R1' is selected from the group consisting of: CH2 and C(methyl)2; and / or
[0425] -R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethyl-hexyl) and phenyl; or
[0426] -amide' is selected from the group consisting of: NH2, NH(alkyl), N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and / or
[0427] -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
[0428] - the substituents R4', R5' and R6' have the same meanings as defined for formula (V);
[0429] - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0430] In another preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound is a compound according to general formula (VII) or (VIII), wherein
[0431] - R1' is selected from the group consisting of: CH2 and C(methyl)2; and / or
[0432] -R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethyl-hexyl) and phenyl; or
[0433] -amide' is selected from the group consisting of: NH2, NH(alkyl), N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and / or
[0434] -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
[0435] - the substituents R4', R5' and R6' have the same meanings as defined for formula (V);
[0436] - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0437] In another preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound is a compound according to general formula (VI), wherein
[0438] -R1" is selected from the group consisting of: CH2 and C(methyl)2; and / or
[0439] -R2" is selected from the group consisting of: -CH2-OH, -C(=O)-OY and -C(=O)-amide"; and / or
[0440] -X is selected from the group consisting of CH2, C=O, O, S, SO, SO2, NH and N(alkyl); and / or
[0441] -Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethyl-hexyl) and phenyl; and / or
[0442] -amide" is selected from the group consisting of: NH2, NH(alkyl), N(alkyl), -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and / or
[0443] - the substituents R4", R5" and R6" have the same meanings as defined for formula (VI);
[0444] - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0445] In a still more preferred variant according to the invention, the sunscreen product, cosmetic or pharmaceutical preparation or home care product comprises at least one mycosporin-like amino acid compound selected from the group consisting of the following compounds I-1 to I-128 according to general formula (V) and compounds II-1 to II-192 according to general formula (VI):
[0446] Table 1 :
[0447]
[0448]
[0449]
[0450]
[0451]
[0452]
[0453]
[0454]
[0455] or a tautomer or stereoisomer or salt of the aforementioned compound or any mixture of the aforementioned compounds.
[0456] In the mycosporin-like amino acid compounds of Table 1, the benzene ring may be unsubstituted or substituted. The substituents R4', R5', R6', R4", R5", R6", amide', Y, amide" and alkyl have the same meanings as defined for the mycosporin-like amino acid compounds according to the aforementioned general formula (V) or general formula (VI).
[0457] Particularly preferred are those mycosporin-like amino acid compounds, wherein in the general formula (V) R1' is CH2 or C(methyl)2, or wherein in the general formula (VI) R1" is CH2 or C(methyl)2:
[0458] Table 2 :
[0459]
[0460]
[0461]
[0462] or a tautomer or stereoisomer or salt of the aforementioned compound or any mixture of the aforementioned compounds.
[0463] In the mycosporin-like amino acid compounds of Table 2, the benzene ring may be unsubstituted or substituted. The substituents R4', R5', R6', R4", R5", R6", amide', Y, amide" and alkyl have the same meanings as defined for the mycosporin-like amino acid compounds according to the aforementioned general formula (V) or general formula (VI).
[0464] Preferably, among the mycosporin-like amino acid compounds according to the specified general formula (V) and formula (VI) in Table 1 and Table 2
[0465] -R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl;
[0466] -amide' is selected from the group consisting of: NH2, NH(alkyl), N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid);
[0467] -Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl;
[0468] -amide" is selected from the group consisting of: NH2, NH(alkyl), N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide), and -N(OH)(H)(hydroxamic acid); and
[0469] - Alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0470] In the most preferred variant according to the first aspect of the present invention, the mycosporin-like amino acid compound is a compound according to general formula (V) and its variants or formula (VI) and its variants, wherein R1' or R1" is CH2. Such mycosporin-like amino acid compounds have particularly good solubility in water.
[0471] In yet further preferred variants according to the first aspect of the invention, the mycosporin-like amino acid compound is a compound according to general formula (VI), (IX), (X) and variants thereof, wherein X is selected from the group consisting of S, SO and SO2.
[0472] Such mycosporin-like amino acid compounds change the UV absorption profile of sunscreen products or cosmetic or pharmaceutical preparations and broaden the UV absorption spectrum of the preparations over the UV radiation spectrum.
[0473] In still more preferred variations according to the first aspect of the invention, the mycosporin-like amino acid compound is a compound according to general formula (VI), (IX), (X) and variations thereof, wherein X is S. However, the S atom in said compound is easily oxidized.
[0474] In the most preferred variants according to the first aspect of the present invention, the mycosporin-like amino acid compound is a compound according to the general formula (VI), (IX), (X) and variants thereof, wherein X is SO or SO2. Such mycosporin-like amino acid compounds are particularly stable due to their oxidation state.
[0475] In yet further preferred variants according to the invention, in the general formulae (V) to (X) and their variants, n is 1.
[0476] In yet more preferred variations according to the first aspect of the invention, the mycosporin-like amino acid compound is a compound according to general formula (V), wherein
[0477] -Z is -O-R2' or amide'; and / or
[0478] - R1' is CH2 or C(methyl)2; and / or
[0479] - R2' is H or ethyl or isopropyl or 2-ethylhexyl or phenyl; or
[0480] -amide' is NH2 or N(methyl)2 or N(ethyl)2 or -N(O-alkyl)(alkyl)(Weinreb amide) or -N(OH)(H)(hydroxamic acid); and / or
[0481] -R3' is H or -O-methyl or -C(=O)-OH or -C(=O)-CH3 or -C(=O)-O-methyl; and / or
[0482] - the substituents R4', R5' and R6' have the same meanings as defined for formula (V);
[0483] - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0484] In a more preferred variant according to the first aspect of the invention, the mycosporin-like amino acid compound is a compound according to formula (VII) or formula (VIII), wherein
[0485] - R1' is CH2 or C(methyl)2; and / or
[0486] - R2' is H or ethyl or isopropyl or 2-ethylhexyl or phenyl; or
[0487] -amide' is NH2 or N(methyl)2 or N(ethyl)2 or -N(O-alkyl)(alkyl)(Weinreb amide) or -N(OH)(H)(hydroxamic acid); and / or
[0488] -R3' is H or -O-methyl or -C(=O)-OH or -C(=O)-CH3 or -C(=O)-O-methyl; and / or
[0489] - the substituents R4', R5' and R6' have the same meanings as defined for formula (V);
[0490] - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
[0491] In a more preferred variant according to the first aspect of the invention, the mycosporin-like amino acid compound is a compound according to general formula (VI), wherein
[0492] -R1" is CH2 or C(methyl)2; and / or
[0493] -R2" is -C(=O)-OY or -C(=O)-amide"; and / or
[0494] - X is S, SO or SO2; and / or
[0495] -Y is H or ethyl or isopropyl or 2-ethylhexyl or phenyl; or
[0496] "-amide" is NH2 or N(methyl)2 or N(ethyl)2 or -N(O-alkyl)(alkyl)(Weinreb amide) or -N(OH)(H)(hydroxamic acid); and / or
[0497] - the substituents R4", R5" and R6" have the same meanings as defined for formula (VI);
[0498] - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and butyl.
[0499] The benzene ring in the mycosporin-like amino acid compounds according to general formula (V) to (X) and variations thereof may be unsubstituted or substituted.
[0500] In preferred variants, the benzene ring in the mycosporin-like amino acid compounds according to general formulae (V) to (X) and their variants is unsubstituted, i.e., the substituents R4′, R5′ and R6′ on the benzene ring in general formula (V) are H; or the substituents R4″, R5″ and R6″ on the benzene ring in general formula (VI) are H.
[0501] In a further preferred variant, the benzene ring in the mycosporin-like amino acid compounds according to general formulae (V) to (X) and variants thereof is substituted.
[0502] Most preferably, the benzene ring in the mycosporin-like amino acid compound according to general formula (V), (VII), (VIII) and variants thereof is unsubstituted, i.e., the substituents R4', R5' and R6' are each H. Alternatively, most preferably, the benzene ring in the mycosporin-like amino acid compound according to general formula (VI), (IX), (X) and variants thereof is unsubstituted, i.e., the substituents R4", R5" and R6" are each H. The compounds have improved solubility in water.
[0503] Preferably, the benzene ring in the mycosporin-like amino acid compounds according to general formula (V) to (X) and variants thereof is mono-substituted, di-substituted or tri-substituted.
[0504] In still more preferred variants according to the first aspect of the invention, the mycosporin-like amino acid is a compound according to the general formula (V), (VII), (VIII) and variants thereof, wherein the substituents R4', R5' and R6' may be identical or different and are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O)2OH and sulfonyl.
[0505] Still more preferably, the substituents R4', R5' and R6' in the general formula (V), (VII), (VIII) and their variants may be identical or different and independently selected from the group consisting of: H, OH, methyl, O-methyl, -S(=O)2OH and sulfonyl.
[0506] Alternatively, the mycosporin-like amino acid compound is a compound according to the general formula (VI), (IX), (X) and variants thereof, wherein the substituents R4", R5" and R6" may be identical or different and are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O)2OH and sulfonyl.
[0507] Still more preferably, the substituents R4", R5" and R6" in the general formula (VI), (IX), (X) and their variants may be identical or different and independently selected from the group consisting of: H, OH, methyl, O-methyl, -S(=O)2OH and sulfonyl.
[0508] In the general formulae (V) to (X) and their variants, the following substitution patterns are particularly preferred:
[0509] R4′=H and R5′=H and R6′=H; or
[0510] R4′=H and R5′=H and R6′=OH; or
[0511] R4'=H and R5'=H and R6'=methyl; or
[0512] R4′=H and R5′=H and R6′=O-methyl; or
[0513] R4′=H and R5′=H and R6′=-S(=O)2OH; or
[0514] R4'=H and R5'=H and R6'=sulfonyl; or
[0515] R4′=H and R5′=OH and R6′=H; or
[0516] R4′=H and R5′=OH and R6′=OH; or
[0517] R4'=H and R5'=OH and R6'=methyl; or
[0518] R4'=H and R5'=OH and R6'=O-methyl; or
[0519] R4′=H and R5′=OH and R6′=-S(=O)2OH; or
[0520] R4'=H and R5'=OH and R6'=sulfonyl; or
[0521] R4'=H and R5'=methyl and R6'=H; or
[0522] R4'=H and R5'=methyl and R6'=OH; or
[0523] R4'=H and R5'=methyl and R6'=methyl; or
[0524] R4'=H and R5'=methyl and R6'=O-methyl; or
[0525] R4'=H and R5'=methyl and R6'=-S(=O)2OH; or
[0526] R4'=H and R5'=methyl and R6'=sulfonyl; or
[0527] R4'=H and R5'=O-methyl and R6'=H; or
[0528] R4'=H and R5'=O-methyl and R6'=OH; or
[0529] R4'=H and R5'=O-methyl and R6'=methyl; or
[0530] R4′=H and R5′=O-methyl and R6′=O-methyl; or
[0531] R4'=H and R5'=O-methyl and R6'=-S(=O)2OH; or
[0532] R4'=H and R5'=O-methyl and R6'=sulfonyl; or
[0533] R4′=H and R5′=-S(=O)2OH and R6′=H; or
[0534] R4'=H and R5'=-S(=O)2OH and R6'=OH; or
[0535] R4'=H and R5'=-S(=O)2OH and R6'=methyl; or
[0536] R4'=H and R5'=-S(=O)2OH and R6'=O-methyl; or
[0537] R4′=H and R5′=-S(=O)2OH and R6′=-S(=O)2OH; or
[0538] R4'=H and R5'=-S(=O)2OH and R6'=sulfonyl; or
[0539] R4'=H and R5'=sulfonyl and R6'=H; or
[0540] R4'=H and R5'=sulfonyl and R6'=OH; or
[0541] R4'=H and R5'=sulfonyl and R6'=methyl; or
[0542] R4'=H and R5'=sulfonyl and R6'=O-methyl; or
[0543] R4'=H and R5'=sulfonyl and R6'=-S(=O)2OH; or
[0544] R4'=H and R5'=sulfonyl and R6'=sulfonyl; or
[0545] R4′=OH and R5′=H and R6′=H; or
[0546] R4′=OH and R5′=H and R6′=OH; or
[0547] R4'=OH and R5'=H and R6'=methyl; or
[0548] R4'=OH and R5'=H and R6'=O-methyl; or
[0549] R4′=OH and R5′=H and R6′=-S(=O)2OH; or
[0550] R4'=OH and R5'=H and R6'=sulfonyl; or
[0551] R4′=OH and R5′=OH and R6′=H; or
[0552] R4′=OH and R5′=OH and R6′=OH; or
[0553] R4'=OH and R5'=OH and R6'=methyl; or
[0554] R4′=OH and R5′=OH and R6′=O-methyl; or
[0555] R4′=OH and R5′=OH and R6′=-S(=O)2OH; or
[0556] R4'=OH and R5'=OH and R6'=sulfonyl; or
[0557] R4'=OH and R5'=methyl and R6'=H; or
[0558] R4'=OH and R5'=methyl and R6'=OH; or
[0559] R4'=OH and R5'=methyl and R6'=methyl; or
[0560] R4'=OH and R5'=methyl and R6'=O-methyl; or
[0561] R4'=OH and R5'=methyl and R6'=-S(=O)2OH; or
[0562] R4'=OH and R5'=methyl and R6'=sulfonyl; or
[0563] R4'=OH and R5'=O-methyl and R6'=H; or
[0564] R4'=OH and R5'=O-methyl and R6'=OH; or
[0565] R4'=OH and R5'=O-methyl and R6'=methyl; or
[0566] R4′=OH and R5′=O-methyl and R6′=O-methyl; or
[0567] R4'=OH and R5'=O-methyl and R6'=-S(=O)2OH; or
[0568] R4'=OH and R5'=O-methyl and R6'=sulfonyl; or
[0569] R4'=OH and R5'=-S(=O)2OH and R6'=H; or
[0570] R4′=OH and R5′=-S(=O)2OH and R6′=OH; or
[0571] R4'=OH and R5'=-S(=O)2OH and R6'=methyl; or
[0572] R4'=OH and R5'=-S(=O)2OH and R6'=O-methyl; or
[0573] R4′=OH and R5′=-S(=O)2OH and R6′=-S(=O)2OH; or
[0574] R4'=OH and R5'=-S(=O)2OH and R6'=sulfonyl; or
[0575] R4'=OH and R5'=sulfonyl and R6'=H; or
[0576] R4'=OH and R5'=sulfonyl and R6'=OH; or
[0577] R4'=OH and R5'=sulfonyl and R6'=methyl; or
[0578] R4'=OH and R5'=sulfonyl and R6'=O-methyl; or
[0579] R4'=OH and R5'=sulfonyl and R6'=-S(=O)2OH; or
[0580] R4'=OH and R5'=sulfonyl and R6'=sulfonyl; or
[0581] R4'=methyl and R5'=H and R6'=H; or
[0582] R4'=methyl and R5'=H and R6'=OH; or
[0583] R4'=methyl and R5'=H and R6'=methyl; or
[0584] R4'=methyl and R5'=H and R6'=O-methyl; or
[0585] R4'=methyl and R5'=H and R6'=-S(=O)2OH; or
[0586] R4'=methyl and R5'=H and R6'=sulfonyl; or
[0587] R4'=methyl and R5'=OH and R6'=H; or
[0588] R4'=methyl and R5'=OH and R6'=OH; or
[0589] R4'=methyl and R5'=OH and R6'=methyl; or
[0590] R4'=methyl and R5'=OH and R6'=O-methyl; or
[0591] R4'=methyl and R5'=OH and R6'=-S(=O)2OH; or
[0592] R4'=methyl and R5'=OH and R6'=sulfonyl; or
[0593] R4'=methyl and R5'=methyl and R6'=H; or
[0594] R4'=methyl and R5'=methyl and R6'=OH; or
[0595] R4'=methyl and R5'=methyl and R6'=methyl; or
[0596] R4'=methyl and R5'=methyl and R6'=O-methyl; or
[0597] R4'=methyl and R5'=methyl and R6'=-S(=O)2OH; or
[0598] R4'=methyl and R5'=methyl and R6'=sulfonyl; or
[0599] R4'=methyl and R5'=O-methyl and R6'=H; or
[0600] R4'=methyl and R5'=O-methyl and R6'=OH; or
[0601] R4'=methyl and R5'=O-methyl and R6'=methyl; or
[0602] R4'=methyl and R5'=O-methyl and R6'=O-methyl; or
[0603] R4'=methyl and R5'=O-methyl and R6'=-S(=O)2OH; or
[0604] R4'=methyl and R5'=O-methyl and R6'=sulfonyl; or
[0605] R4'=methyl and R5'=-S(=O)2OH and R6'=H; or
[0606] R4'=methyl and R5'=-S(=O)2OH and R6'=OH; or
[0607] R4'=methyl and R5'=-S(=O)2OH and R6'=methyl; or
[0608] R4'=methyl and R5'=-S(=O)2OH and R6'=O-methyl; or
[0609] R4'=methyl and R5'=-S(=O)2OH and R6'=-S(=O)2OH; or
[0610] R4'=methyl and R5'=-S(=O)2OH and R6'=sulfonyl; or
[0611] R4'=methyl and R5'=sulfonyl and R6'=H; or
[0612] R4'=methyl and R5'=sulfonyl and R6'=OH; or
[0613] R4'=methyl and R5'=sulfonyl and R6'=methyl; or
[0614] R4'=methyl and R5'=sulfonyl and R6'=O-methyl; or
[0615] R4'=methyl and R5'=sulfonyl and R6'=-S(=O)2OH; or
[0616] R4'=methyl and R5'=sulfonyl and R6'=sulfonyl; or
[0617] R4′=O-methyl and R5′=H and R6′=H; or
[0618] R4'=O-methyl and R5'=H and R6'=OH; or
[0619] R4'=O-methyl and R5'=H and R6'=methyl; or
[0620] R4'=O-methyl and R5'=H and R6'=O-methyl; or
[0621] R4'=O-methyl and R5'=H and R6'=-S(=O)2OH; or
[0622] R4'=O-methyl and R5'=H and R6'=sulfonyl; or
[0623] R4'=O-methyl and R5'=OH and R6'=H; or
[0624] R4'=O-methyl and R5'=OH and R6'=OH; or
[0625] R4'=O-methyl and R5'=OH and R6'=methyl; or
[0626] R4'=O-methyl and R5'=OH and R6'=O-methyl; or
[0627] R4'=O-methyl and R5'=OH and R6'=-S(=O)2OH; or
[0628] R4'=O-methyl and R5'=OH and R6'=sulfonyl; or
[0629] R4'=O-methyl and R5'=methyl and R6'=H; or
[0630] R4'=O-methyl and R5'=methyl and R6'=OH; or
[0631] R4'=O-methyl and R5'=methyl and R6'=methyl; or
[0632] R4'=O-methyl and R5'=methyl and R6'=O-methyl; or
[0633] R4'=O-methyl and R5'=methyl and R6'=-S(=O)2OH; or
[0634] R4'=O-methyl and R5'=methyl and R6'=sulfonyl; or
[0635] R4'=O-methyl and R5'=O-methyl and R6'=H; or
[0636] R4'=O-methyl and R5'=O-methyl and R6'=OH; or
[0637] R4'=O-methyl and R5'=O-methyl and R6'=methyl; or
[0638] R4′=O-methyl and R5′=O-methyl and R6′=O-methyl; or
[0639] R4'=O-methyl and R5'=O-methyl and R6'=-S(=O)2OH; or
[0640] R4'=O-methyl and R5'=O-methyl and R6'=sulfonyl; or
[0641] R4'=O-methyl and R5'=-S(=O)2OH and R6'=H; or
[0642] R4'=O-methyl and R5'=-S(=O)2OH and R6'=OH; or
[0643] R4'=O-methyl and R5'=-S(=O)2OH and R6'=methyl; or
[0644] R4'=O-methyl and R5'=-S(=O)2OH and R6'=O-methyl; or
[0645] R4'=O-methyl and R5'=-S(=O)2OH and R6'=-S(=O)2OH; or
[0646] R4'=O-methyl and R5'=-S(=O)2OH and R6'=sulfonyl; or
[0647] R4'=O-methyl and R5'=sulfonyl and R6'=H; or
[0648] R4'=O-methyl and R5'=sulfonyl and R6'=OH; or
[0649] R4'=O-methyl and R5'=sulfonyl and R6'=methyl; or
[0650] R4'=O-methyl and R5'=sulfonyl and R6'=O-methyl; or
[0651] R4'=O-methyl and R5'=sulfonyl and R6'=-S(=O)2OH; or
[0652] R4'=O-methyl and R5'=sulfonyl and R6'=sulfonyl; or
[0653] R4′=-S(=O)2OH and R5′=H and R6′=H; or
[0654] R4′=-S(=O)2OH and R5′=H and R6′=OH; or
[0655] R4'=-S(=O)2OH and R5'=H and R6'=methyl; or
[0656] R4'=-S(=O)2OH and R5'=H and R6'=O-methyl; or
[0657] R4′=-S(=O)2OH and R5′=H and R6′=-S(=O)2OH; or
[0658] R4'=-S(=O)2OH and R5'=H and R6'=sulfonyl; or
[0659] R4′=-S(=O)2OH and R5′=OH and R6′=H; or
[0660] R4′=-S(=O)2OH and R5′=OH and R6′=OH; or
[0661] R4'=-S(=O)2OH and R5'=OH and R6'=methyl; or
[0662] R4'=-S(=O)2OH and R5'=OH and R6'=O-methyl; or
[0663] R4′=-S(=O)2OH and R5′=OH and R6′=-S(=O)2OH; or
[0664] R4'=-S(=O)2OH and R5'=OH and R6'=sulfonyl; or
[0665] R4'=-S(=O)2OH and R5'=methyl and R6'=H; or
[0666] R4'=-S(=O)2OH and R5'=methyl and R6'=OH or
[0667] R4'=-S(=O)2OH and R5'=methyl and R6'=methyl; or
[0668] R4'=-S(=O)2OH and R5'=methyl and R6'=O-methyl; or
[0669] R4′=-S(=O)2OH and R5′=methyl and R6′=-S(=O)2OH; or
[0670] R4'=-S(=O)2OH and R5'=methyl and R6'=sulfonyl; or
[0671] R4'=-S(=O)2OH and R5'=O-methyl and R6'=H; or
[0672] R4'=-S(=O)2OH and R5'=O-methyl and R6'=OH or
[0673] R4'=-S(=O)2OH and R5'=O-methyl and R6'=methyl; or
[0674] R4'=-S(=O)2OH and R5'=O-methyl and R6'=O-methyl; or
[0675] R4′=-S(=O)2OH and R5′=O-methyl and R6′=-S(=O)2OH; or
[0676] R4'=-S(=O)2OH and R5'=O-methyl and R6'=sulfonyl; or
[0677] R4′=-S(=O)2OH and R5′=-S(=O)2OH and R6′=H; or
[0678] R4′=-S(=O)2OH and R5′=-S(=O)2OH and R6′=OH; or
[0679] R4'=-S(=O)2OH and R5'=-S(=O)2OH and R6'=methyl; or
[0680] R4'=-S(=O)2OH and R5'=-S(=O)2OH and R6'=O-methyl; or
[0681] R4'=-S(=O)2OH and R5'=sulfonyl and R6'=H; or
[0682] R4'=-S(=O)2OH and R5'=sulfonyl and R6'=OH; or
[0683] R4'=-S(=O)2OH and R5'=sulfonyl and R6'=methyl; or
[0684] R4'=-S(=O)2OH and R5'=sulfonyl and R6'=O-methyl; or
[0685] R4'=sulfonyl and R5'=H and R6'=H; or
[0686] R4'=sulfonyl and R5'=H and R6'=OH; or
[0687] R4'=sulfonyl and R5'=H and R6'=methyl; or
[0688] R4'=sulfonyl and R5'=H and R6'=O-methyl; or
[0689] R4'=sulfonyl and R5'=H and R6'=-S(=O)2OH; or
[0690] R4'=sulfonyl and R5'=H and R6'=sulfonyl; or
[0691] R4'=sulfonyl and R5'=OH and R6'=H; or
[0692] R4'=sulfonyl and R5'=OH and R6'=OH; or
[0693] R4'=sulfonyl and R5'=OH and R6'=methyl; or
[0694] R4'=sulfonyl and R5'=OH and R6'=O-methyl; or
[0695] R4'=sulfonyl and R5'=OH and R6'=-S(=O)2OH; or
[0696] R4'=sulfonyl and R5'=OH and R6'=sulfonyl; or
[0697] R4'=sulfonyl and R5'=methyl and R6'=H; or
[0698] R4'=sulfonyl and R5'=methyl and R6'=OH; or
[0699] R4'=sulfonyl and R5'=methyl and R6'=methyl; or
[0700] R4'=sulfonyl and R5'=methyl and R6'=O-methyl; or
[0701] R4'=sulfonyl and R5'=methyl and R6'=-S(=O)2OH; or
[0702] R4'=sulfonyl and R5'=methyl and R6'=sulfonyl; or
[0703] R4'=sulfonyl and R5'=O-methyl and R6'=H; or
[0704] R4'=sulfonyl and R5'=O-methyl and R6'=OH; or
[0705] R4'=sulfonyl and R5'=O-methyl and R6'=methyl; or
[0706] R4'=sulfonyl and R5'=O-methyl and R6'=O-methyl; or
[0707] R4'=sulfonyl and R5'=O-methyl and R6'=-S(=O)2OH; or
[0708] R4'=sulfonyl and R5'=O-methyl and R6'=sulfonyl; or
[0709] R4'=sulfonyl and R5'=-S(=O)2OH and R6'=H; or
[0710] R4'=sulfonyl and R5'=-S(=O)2OH and R6'=OH; or
[0711] R4'=sulfonyl and R5'=-S(=O)2OH and R6'=methyl; or
[0712] R4'=sulfonyl and R5'=-S(=O)2OH and R6'=O-methyl; or
[0713] R4'=sulfonyl and R5'=sulfonyl and R6'=H; or
[0714] R4'=sulfonyl and R5'=sulfonyl and R6'=OH; or
[0715] R4'=sulfonyl and R5'=sulfonyl and R6'=methyl; or
[0716] R4'=sulfonyl and R5'=sulfonyl and R6'=O-methyl; or
[0717] R4"=H and R5"=H and R6"=H; or
[0718] R4"=H and R5"=H and R6"=OH; or
[0719] R4"=H and R5"=H and R6"=methyl; or
[0720] R4"=H and R5"=H and R6"=O-methyl; or
[0721] R4"=H and R5"=H and R6"=-S(=O)2OH; or
[0722] R4"=H and R5"=H and R6"=sulfonyl; or
[0723] R4"=H and R5"=OH and R6"=H; or
[0724] R4"=H and R5"=OH and R6"=OH; or
[0725] R4" = H and R5" = OH and R6" = methyl; or
[0726] R4"=H and R5"=OH and R6"=O-methyl; or
[0727] R4"=H and R5"=OH and R6"=-S(=O)2OH; or
[0728] R4"=H and R5"=OH and R6"=sulfonyl; or
[0729] R4"=H and R5"=methyl and R6"=H; or
[0730] R4"=H and R5"=methyl and R6"=OH; or
[0731] R4"=H and R5"=methyl and R6"=methyl; or
[0732] R4"=H and R5"=methyl and R6"=O-methyl; or
[0733] R4"=H and R5"=methyl and R6"=-S(=O)2OH; or
[0734] R4" = H and R5" = methyl and R6" = sulfonyl; or
[0735] R4"=H and R5"=O-methyl and R6"=H; or
[0736] R4"=H and R5"=O-methyl and R6"=OH; or
[0737] R4" = H and R5" = O-methyl and R6" = methyl; or
[0738] R4"=H and R5"=O-methyl and R6"=O-methyl; or
[0739] R4"=H and R5"=O-methyl and R6"=-S(=O)2OH; or
[0740] R4" = H and R5" = O-methyl and R6" = sulfonyl; or
[0741] R4"=H and R5"=-S(=O)2OH and R6"=H; or
[0742] R4"=H and R5"=-S(=O)2OH and R6"=OH; or
[0743] R4"=H and R5"=-S(=O)2OH and R6"=methyl; or
[0744] R4"=H and R5"=-S(=O)2OH and R6"=O-methyl; or
[0745] R4"=H and R5"=-S(=O)2OH and R6"=-S(=O)2OH; or
[0746] R4"=H and R5"=-S(=O)2OH and R6"=sulfonyl; or
[0747] R4"=H and R5"=sulfonyl and R6"=H; or
[0748] R4"=H and R5"=sulfonyl and R6"=OH; or
[0749] R4" = H and R5" = sulfonyl and R6" = methyl; or
[0750] R4" = H and R5" = sulfonyl and R6" = O-methyl; or
[0751] R4"=H and R5"=sulfonyl and R6"=-S(=O)2OH; or
[0752] R4"=H and R5"=sulfonyl and R6"=sulfonyl; or
[0753] R4"=OH and R5"=H and R6"=H; or
[0754] R4"=OH and R5"=H and R6"=OH; or
[0755] R4" = OH and R5" = H and R6" = methyl; or
[0756] R4" = OH and R5" = H and R6" = O-methyl; or
[0757] R4"=OH and R5"=H and R6"=-S(=O)2OH; or
[0758] R4" = OH and R5" = H and R6" = sulfonyl; or
[0759] R4"=OH and R5"=OH and R6"=H; or
[0760] R4″=OH and R5″=OH and R6″=OH; or
[0761] R4"=OH and R5"=OH and R6"=methyl; or
[0762] R4"=OH and R5"=OH and R6"=O-methyl; or
[0763] R4"=OH and R5"=OH and R6"=-S(=O)2OH; or
[0764] R4"=OH and R5"=OH and R6"=sulfonyl; or
[0765] R4"=OH and R5"=methyl and R6"=H; or
[0766] R4"=OH and R5"=methyl and R6"=OH; or
[0767] R4" = OH and R5" = methyl and R6" = methyl; or
[0768] R4" = OH and R5" = methyl and R6" = O-methyl; or
[0769] R4"=OH and R5"=methyl and R6"=-S(=O)2OH; or
[0770] R4" = OH and R5" = methyl and R6" = sulfonyl; or
[0771] R4"=OH and R5"=O-methyl and R6"=H; or
[0772] R4"=OH and R5"=O-methyl and R6"=OH; or
[0773] R4" = OH and R5" = O-methyl and R6" = methyl; or
[0774] R4″=OH and R5″=O-methyl and R6″=O-methyl; or
[0775] R4"=OH and R5"=O-methyl and R6"=-S(=O)2OH; or
[0776] R4" = OH and R5" = O-methyl and R6" = sulfonyl; or
[0777] R4"=OH and R5"=-S(=O)2OH and R6"=H; or
[0778] R4"=OH and R5"=-S(=O)2OH and R6"=OH; or
[0779] R4"=OH and R5"=-S(=O)2OH and R6"=methyl; or
[0780] R4"=OH and R5"=-S(=O)2OH and R6"=O-methyl; or
[0781] R4"=OH and R5"=-S(=O)2OH and R6"=-S(=O)2OH; or
[0782] R4" = OH and R5" = -S(=O)2OH and R6" = sulfonyl; or
[0783] R4"=OH and R5"=sulfonyl and R6"=H; or
[0784] R4"=OH and R5"=sulfonyl and R6"=OH; or
[0785] R4" = OH and R5" = sulfonyl and R6" = methyl; or
[0786] R4" = OH and R5" = sulfonyl and R6" = O-methyl; or
[0787] R4"=OH and R5"=sulfonyl and R6"=-S(=O)2OH; or
[0788] R4" = OH and R5" = sulfonyl and R6" = sulfonyl; or
[0789] R4"=methyl and R5"=H and R6"=H; or
[0790] R4" = methyl and R5" = H and R6" = OH; or
[0791] R4" = methyl and R5" = H and R6" = methyl; or
[0792] R4" = methyl and R5" = H and R6" = O-methyl; or
[0793] R4" = methyl and R5" = H and R6" = -S(=O)2OH; or
[0794] R4" = methyl and R5" = H and R6" = sulfonyl; or
[0795] R4" = methyl and R5" = OH and R6" = H; or
[0796] R4"=methyl and R5"=OH and R6"=OH; or
[0797] R4" = methyl and R5" = OH and R6" = methyl; or
[0798] R4" = methyl and R5" = OH and R6" = O-methyl; or
[0799] R4" = methyl and R5" = OH and R6" = -S(=O)2OH; or
[0800] R4" = methyl and R5" = OH and R6" = sulfonyl; or
[0801] R4" = methyl and R5" = methyl and R6" = H; or
[0802] R4" = methyl and R5" = methyl and R6" = OH; or
[0803] R4" = methyl and R5" = methyl and R6" = methyl; or
[0804] R4" = methyl and R5" = methyl and R6" = O-methyl; or
[0805] R4" = methyl and R5" = methyl and R6" = -S(=O)2OH; or
[0806] R4" = methyl and R5" = methyl and R6" = sulfonyl; or
[0807] R4" = methyl and R5" = O-methyl and R6" = H; or
[0808] R4" = methyl and R5" = O-methyl and R6" = OH; or
[0809] R4" = methyl and R5" = O-methyl and R6" = methyl; or
[0810] R4" = methyl and R5" = O-methyl and R6" = O-methyl; or
[0811] R4" = methyl and R5" = O-methyl and R6" = -S(=O)2OH; or
[0812] R4" = methyl and R5" = O-methyl and R6" = sulfonyl; or
[0813] R4"=methyl and R5"=-S(=O)2OH and R6"=H; or
[0814] R4" = methyl and R5" = -S(=O)2OH and R6" = OH or
[0815] R4" = methyl and R5" = -S(=O)2OH and R6" = methyl; or
[0816] R4" = methyl and R5" = -S(=O)2OH and R6" = O-methyl; or
[0817] R4" = methyl and R5" = -S(=O)2OH and R6" = -S(=O)2OH; or
[0818] R4" = methyl and R5" = -S(=O)2OH and R6" = sulfonyl; or
[0819] R4" = methyl and R5" = sulfonyl and R6" = H; or
[0820] R4" = methyl and R5" = sulfonyl and R6" = OH; or
[0821] R4" = methyl and R5" = sulfonyl and R6" = methyl; or
[0822] R4" = methyl and R5" = sulfonyl and R6" = O-methyl; or
[0823] R4" = methyl and R5" = sulfonyl and R6" = -S(=O)2OH; or
[0824] R4" = methyl and R5" = sulfonyl and R6" = sulfonyl; or
[0825] R4"=O-methyl and R5"=H and R6"=H; or
[0826] R4" = O-methyl and R5" = H and R6" = OH; or
[0827] R4" = O-methyl and R5" = H and R6" = methyl; or
[0828] R4" = O-methyl and R5" = H and R6" = O-methyl; or
[0829] R4" = O-methyl and R5" = H and R6" = -S(=O)2OH; or
[0830] R4" = O-methyl and R5" = H and R6" = sulfonyl; or
[0831] R4" = O-methyl and R5" = OH and R6" = H; or
[0832] R4"=O-methyl and R5"=OH and R6"=OH; or
[0833] R4" = O-methyl and R5" = OH and R6" = methyl; or
[0834] R4" = O-methyl and R5" = OH and R6" = O-methyl; or
[0835] R4" = O-methyl and R5" = OH and R6" = -S(=O)2OH; or
[0836] R4" = O-methyl and R5" = OH and R6" = sulfonyl; or
[0837] R4" = O-methyl and R5" = methyl and R6" = H; or
[0838] R4" = O-methyl and R5" = methyl and R6" = OH; or
[0839] R4" = O-methyl and R5" = methyl and R6" = methyl; or
[0840] R4" = O-methyl and R5" = methyl and R6" = O-methyl; or
[0841] R4" = O-methyl and R5" = methyl and R6" = -S(=O)2OH; or
[0842] R4" = O-methyl and R5" = methyl and R6" = sulfonyl; or
[0843] R4" = O-methyl and R5" = O-methyl and R6" = H; or
[0844] R4" = O-methyl and R5" = O-methyl and R6" = OH; or
[0845] R4" = O-methyl and R5" = O-methyl and R6" = methyl; or
[0846] R4" = O-methyl and R5" = O-methyl and R6" = O-methyl; or
[0847] R4" = O-methyl and R5" = O-methyl and R6" = -S(=O)2OH; or
[0848] R4" = O-methyl and R5" = O-methyl and R6" = sulfonyl; or
[0849] R4"=O-methyl and R5"=-S(=O)2OH and R6"=H; or
[0850] R4" = O-methyl and R5" = -S(=O)2OH and R6" = OH or
[0851] R4" = O-methyl and R5" = -S(=O)2OH and R6" = methyl; or
[0852] R4" = O-methyl and R5" = -S(=O)2OH and R6" = O-methyl; or
[0853] R4" = O-methyl and R5" = -S(=O)2OH and R6" = -S(=O)2OH; or
[0854] R4" = O-methyl and R5" = -S(=O)2OH and R6" = sulfonyl; or
[0855] R4" = O-methyl and R5" = sulfonyl and R6" = H; or
[0856] R4" = O-methyl and R5" = sulfonyl and R6" = OH; or
[0857] R4" = O-methyl and R5" = sulfonyl and R6" = methyl; or
[0858] R4" = O-methyl and R5" = sulfonyl and R6" = O-methyl; or
[0859] R4" = O-methyl and R5" = sulfonyl and R6" = -S(=O)2OH; or
[0860] R4" = O-methyl and R5" = sulfonyl and R6" = sulfonyl; or
[0861] R4"=-S(=O)2OH and R5"=H and R6"=H; or
[0862] R4"=-S(=O)2OH and R5"=H and R6"=OH; or
[0863] R4"=-S(=O)2OH and R5"=H and R6"=methyl; or
[0864] R4"=-S(=O)2OH and R5"=H and R6"=O-methyl; or
[0865] R4"=-S(=O)2OH and R5"=H and R6"=-S(=O)2OH; or
[0866] R4"=-S(=O)2OH and R5"=H and R6"=sulfonyl; or
[0867] R4"=-S(=O)2OH and R5"=OH and R6"=H; or
[0868] R4"=-S(=O)2OH and R5"=OH and R6"=OH; or
[0869] R4"=-S(=O)2OH and R5"=OH and R6"=methyl; or
[0870] R4"=-S(=O)2OH and R5"=OH and R6"=O-methyl; or
[0871] R4"=-S(=O)2OH and R5"=OH and R6"=-S(=O)2OH; or
[0872] R4"=-S(=O)2OH and R5"=OH and R6"=sulfonyl; or
[0873] R4"=-S(=O)2OH and R5"=methyl and R6"=H; or
[0874] R4"=-S(=O)2OH and R5"=methyl and R6"=OH or
[0875] R4" = -S(=O)2OH and R5" = methyl and R6" = methyl; or
[0876] R4"=-S(=O)2OH and R5"=methyl and R6"=O-methyl; or
[0877] R4"=-S(=O)2OH and R5"=methyl and R6"=-S(=O)2OH; or
[0878] R4" = -S(=O)2OH and R5" = methyl and R6" = sulfonyl; or
[0879] R4"=-S(=O)2OH and R5"=O-methyl and R6"=H; or
[0880] R4"=-S(=O)2OH and R5"=O-methyl and R6"=OH or
[0881] R4" = -S(=O)2OH and R5" = O-methyl and R6" = methyl; or
[0882] R4"=-S(=O)2OH and R5"=O-methyl and R6"=O-methyl; or
[0883] R4"=-S(=O)2OH and R5"=O-methyl and R6"=-S(=O)2OH; or
[0884] R4" = -S(=O)2OH and R5" = O-methyl and R6" = sulfonyl; or
[0885] R4"=-S(=O)2OH and R5"=-S(=O)2OH and R6"=H; or
[0886] R4"=-S(=O)2OH and R5"=-S(=O)2OH and R6"=OH; or
[0887] R4" = -S(=O)2OH and R5" = -S(=O)2OH and R6" = methyl; or
[0888] R4"=-S(=O)2OH and R5"=-S(=O)2OH and R6"=O-methyl; or
[0889] R4"=-S(=O)2OH and R5"=sulfonyl and R6"=H; or
[0890] R4"=-S(=O)2OH and R5"=sulfonyl and R6"=OH; or
[0891] R4" = -S(=O)2OH and R5" = sulfonyl and R6" = methyl; or
[0892] R4" = -S(=O)2OH and R5" = sulfonyl and R6" = O-methyl; or
[0893] R4"=sulfonyl and R5"=H and R6"=H; or
[0894] R4"=sulfonyl and R5"=H and R6"=OH; or
[0895] R4" = sulfonyl and R5" = H and R6" = methyl; or
[0896] R4" = sulfonyl and R5" = H and R6" = O-methyl; or
[0897] R4" = sulfonyl and R5" = H and R6" = -S(=O)2OH; or
[0898] R4" = sulfonyl and R5" = H and R6" = sulfonyl; or
[0899] R4"=sulfonyl and R5"=OH and R6"=H; or
[0900] R4"=sulfonyl and R5"=OH and R6"=OH; or
[0901] R4" = sulfonyl and R5" = OH and R6" = methyl; or
[0902] R4" = sulfonyl and R5" = OH and R6" = O-methyl; or
[0903] R4" = sulfonyl and R5" = OH and R6" = -S(=O)2OH; or
[0904] R4" = sulfonyl and R5" = OH and R6" = sulfonyl; or
[0905] R4" = sulfonyl and R5" = methyl and R6" = H; or
[0906] R4" = sulfonyl and R5" = methyl and R6" = OH; or
[0907] R4" = sulfonyl and R5" = methyl and R6" = methyl; or
[0908] R4" = sulfonyl and R5" = methyl and R6" = O-methyl; or
[0909] R4" = sulfonyl and R5" = methyl and R6" = -S(=O)2OH; or
[0910] R4" = sulfonyl and R5" = methyl and R6" = sulfonyl; or
[0911] R4" = sulfonyl and R5" = O-methyl and R6" = H; or
[0912] R4" = sulfonyl and R5" = O-methyl and R6" = OH; or
[0913] R4" = sulfonyl and R5" = O-methyl and R6" = methyl; or
[0914] R4" = sulfonyl and R5" = O-methyl and R6" = O-methyl; or
[0915] R4" = sulfonyl and R5" = O-methyl and R6" = -S(=O)2OH; or
[0916] R4" = sulfonyl and R5" = O-methyl and R6" = sulfonyl; or
[0917] R4"=sulfonyl and R5"=-S(=O)2OH and R6"=H; or
[0918] R4"=sulfonyl and R5"=-S(=O)2OH and R6"=OH; or
[0919] R4" = sulfonyl and R5" = -S(=O)2OH and R6" = methyl; or
[0920] R4" = sulfonyl and R5" = -S(=O)2OH and R6" = O-methyl; or
[0921] R4"=sulfonyl and R5"=sulfonyl and R6"=H; or
[0922] R4"=sulfonyl and R5"=sulfonyl and R6"=OH; or
[0923] R4" = sulfonyl and R5" = sulfonyl and R6" = methyl; or
[0924] R4" = sulfonyl and R5" = sulfonyl and R6" = O-methyl.
[0925] In the general formula (V), (VI), (VII), (VIII), (IX), formula (X) and variants thereof, the substituted benzene ring bonded to the imino functional group is preferably selected from the group consisting of:
[0926]
[0927] The dotted line indicates the binding site to the cyclohexene imine ring.
[0928] In a further more preferred variant according to the first aspect of the invention, in the general formula (V), (VII), (VIII) and their variants, the substituents R4', R5' and R6' may be identical or different and are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O)2OH and sulfonyl; provided that, if the substituted benzene ring is monosubstituted, the substituent is in the ortho or meta position but not in the para position to the imino function of the general formula (V), (VII) and (VIII).
[0929] Alternatively, in an even more preferred variant according to the first aspect of the present invention, in the general formula (VI), (IX), (X) and their variants, the substituents R4", R5" and R6" may be identical or different and are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O)2OH and sulfonyl; provided that, if the substituted benzene ring is monosubstituted, the substituent is in the ortho or meta position, but not in the para position, to the imino functionality of the general formula (VI), (IX) and (X).
[0930] Still more preferably according to the first aspect of the present invention, the sunscreen product, cosmetic or pharmaceutical preparation or home care product comprises at least one mycosporin-like amino acid compound selected from the group consisting of:
[0931] Table 3 :
[0932]
[0933]
[0934]
[0935]
[0936]
[0937] or its tautomers or stereoisomers or salts, or any mixture of the foregoing compounds.
[0938] Among the mycosporin-like amino acid compounds specified in Table 3 above, compounds MAA-1 and MAA-13 are particularly preferred because they have a significant light stabilization effect. Most preferred are acid compounds MAA-20, MAA-21, MAA-22, MAA-23, MAA-24, MAA-24, MAA-26, MAA-27, MAA-28, MAA-29, MAA-30, MAA-31 and amide compounds MAA-32, MAA-33, MAA-34, MAA-35, MAA-36, MAA-37, MAA-38 and MAA-39. The compounds having acid or amide functional groups are light-stable and temperature-stable, and show stability in pH solutions or oil-in-water emulsions, and do not degrade compared to the corresponding ester analogs. Particularly preferred are the acid compounds MAA-20, MAA-21, MAA-22, MAA-23, MAA-24, MAA-24, MAA-26, MAA-27, MAA-28, MAA-29, MAA-30 and MAA-31 due to their stability and their improved solubility in water.
[0939] In particular, the mycosporin-like amino acid compounds MAA-20, MAA-21, MAA-22, MAA-23, MAA-24, MAA-24, MAA-26, MAA-27, MAA-28, MAA-29, MAA-30 and MAA-31 have better stability over a wider pH range than their corresponding ester compounds, which hydrolyze and are therefore unstable in alkaline solutions / formulations above pH 9.
[0940] Due to the better solubility of the mycosporin-like amino acid compound in water compared to its corresponding ester compound, the mycosporin-like amino acid compound can be incorporated into the aqueous phase of the formulation at a higher concentration, resulting in a better photostabilization effect and thus an improved sunscreen in sunscreen products, cosmetic or pharmaceutical formulations or home care products.
[0941] Still more preferably according to the first aspect of the present invention, the sunscreen product, cosmetic or pharmaceutical preparation or home care product comprises at least one mycosporin-like amino acid compound selected from the group consisting of:
[0942] MAA-A:
[0943]
[0944] MAA-B:
[0945]
[0946] MAA-C:
[0947]
[0948] or its tautomer or stereoisomer or salt, or any mixture of the aforementioned compounds, wherein the alkyl group is preferably methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl, most preferably methyl.
[0949] The mycosporin-like amino acid compounds according to the invention and as defined herein are used as individual substances or in mixtures with one, two or more different mycosporin-like amino acid compounds as defined herein.
[0950] Particularly preferred are mixtures of two mycosporin-like amino acid compounds according to the invention and as defined herein. Such mixtures show a particularly enhanced photostabilization effect, as demonstrated in the following examples.
[0951] The sunscreen product, cosmetic or pharmaceutical preparation or home care 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 mycosporin-like amino acid compounds:
[0952] Compound 1:
[0953]
[0954] Compound 2:
[0955]
[0956] Compound 3:
[0957]
[0958] Compound 4:
[0959]
[0960] Compound 5:
[0961]
[0962] Compound 6:
[0963]
[0964] Compound 7:
[0965]
[0966] Compound 8:
[0967]
[0968] As described herein, various mycosporin-like amino acid compounds (b) contain one or more chiral centers and may therefore exist as racemic mixtures of enantiomers, mixtures of diastereomers, or enantiomerically or optically pure compounds. It should also be noted that the compounds of the present invention include E and Z isomers or mixtures thereof, as well as cis and trans isomers or mixtures thereof.
[0969] Therefore, the chemical structures of the mycosporin-like amino acid compounds according to general formula (V) to (X) and variants thereof and the compounds explicitly disclosed herein include all possible enantiomers and diastereomers or stereoisomers thereof.
[0970] In certain embodiments, the mycosporin-like amino acid compounds (b) of the present invention are isolated as E or Z isomers. In other embodiments, the compounds of the present invention are mixtures of E and Z isomers.
[0971] Alternatively, stereoisomerically pure compounds are used in sunscreen products or cosmetic or pharmaceutical preparations according to the present invention. As used herein and unless otherwise indicated, the term "stereoisomerically pure" means that one stereoisomer of a compound is substantially free of other stereoisomers of the compound, or one geometric isomer (e.g., about double bonds) is substantially free of other geometric isomers. For example, a stereoisomerically pure compound of the present invention with one chiral center will be substantially free of the opposite enantiomer of the compound. A stereoisomerically pure compound of the present invention with two chiral centers or its composition will be substantially free of other diastereomers of the compound. A stereoisomerically pure compound of the present invention or its composition with a double bond capable of E / Z isomerism will be substantially free of one of the E / Z isomers.
[0972] A typical stereomerically pure compound contains 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 isomers 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 other stereoisomers or E / Z isomers 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 other stereoisomers or E / Z isomers 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 other stereoisomers or E / Z isomers of the compound.
[0973] As used herein and unless otherwise indicated, the term "stereoisomerically enriched" means a compound of the invention, or composition thereof, containing 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.
[0974] Thus, it should be noted that the terms mycosporin-like amino acid compounds and variants thereof according to the general formulae (I) to (X) as well as the individual mycosporin-like amino acid compounds specified herein should be interpreted as covering racemic mixtures of enantiomers, mixtures of diastereomers or enantiomerically or optically pure compounds, unless otherwise indicated.
[0975] Due to their aminocyclohexene imine structure and their electron delocalization capabilities, the mycosporin-like amino acid compounds according to general formulae (V) to (X) and variants thereof are in equilibrium with their tautomeric structures, wherein the hydrogen of the amino group changes its position with the double bond of the cyclohexene ring.
[0976] Tautomerism is defined as each of two or more isomers of a compound that exist together in equilibrium and are readily interchangeable by migration of atoms or groups within the molecule. A tautomerically pure or enriched system will readily exchange to an equilibrium state over time.
[0977] The tautomers of the general formula (V) are represented by the general formula (V-tau):
[0978]
[0979] The tautomers of the general formula (VI) are represented by the general formula (VI-tau):
[0980]
[0981] The above-mentioned tautomerism and redispersion principles explained based on the mycosporin-like amino acid compounds according to general formula (V) and (VI) are equally applicable to any mycosporin-like amino acid compounds defined by general formula (VII), (VIII), (IX), (X) and variants thereof, or to any individual mycosporin-like amino acid compound specified herein.
[0982] Therefore, in the following and throughout the specification, references to mycosporin-like amino acid compounds represented by any of the general formulae (V) to (X) and variants thereof, or references to individual mycosporin-like amino acid compounds specified herein, also encompass tautomeric isomers thereof.
[0983] According to a first aspect of the invention, the mycosporin-like amino acid compounds according to the general formulae (V) to (X) and variants thereof as well as the individual mycosporin-like amino acid compounds specified herein are used in neutral (i.e. uncharged form) or in the form of their salts (such as acid addition salts of inorganic or organic acids).
[0984] In the context of the present invention, the term "salt" refers to a salt of a compound that has the desired effect or pharmacological activity of the parent compound. Such salts include:
[0985] (1) an acid addition salt formed with an inorganic acid, or an acid addition salt formed with an organic acid, preferably a monovalent or polyvalent carboxylic acid; or
[0986] (2) A salt formed when an acidic proton present in the starting compound is replaced by a metal ion such as an alkali metal ion, an alkaline earth metal ion or an aluminum ion; or a salt formed by coordination with an organic base.
[0987] Among the salts, acid addition salts are also particularly preferred, since the mycosporin-like amino acid compounds according to the general formulae (V) to (X) and variants thereof or the mycosporin-like amino acid compounds specified herein contain a protonated N atom.
[0988] The inorganic acid used according to the present invention to form an acid addition salt with the mycosporin-like amino acid compound is preferably selected from the group consisting of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, etc. Particularly preferred are hydrochlorides, sulfates or phosphates.
[0989] Even more preferred are acid addition salts with organic mono- or polycarboxylic acids. Also 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 C10 dicarboxylic acids or tricarboxylic acids. The carboxylic acids may be mono- or polysubstituted by hydroxyl groups, preferably α-hydroxycarboxylic acids, wherein the hydroxyl groups are located on carbon atoms adjacent to the carboxyl groups. Many representative substances 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.
[0990] The organic acid used according to the invention which forms an acid addition salt with the mycosporin-like amino acid compound is preferably selected from the group consisting of amino acids, acetic acid, trifluoroacetic acid, propionic acid, hexanoic acid, cyclopentanepropionic 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 acid), gluconic acid, glutamic acid, hydroxynaphthoic acid, salicylic acid, stearic acid, muconic acid, 4-hydroxybutyric acid, etc.
[0991] Suitable anionic counterions are, in particular, chloride, bromide, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, hydrogencarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C1- to C4-alkanoic acids, preferably formate, acetate, trifluoroacetate, propionate and butyrate, furthermore lactate, gluconate and the anions of polyacids such as succinate, oxalate, maleate, fumarate, malate, tartrate and citrate, furthermore sulfonate anions such as besylate (benzenesulfonate), toluenesulfonate (p-toluenesulfonate), naphthalenesulfonate (naphthalene-2-sulfonate), mesylate (methanesulfonate), esylate (ethanesulfonate) and edisulphonate. They can be formed by reacting compounds according to the invention having basic functional groups with acids of the corresponding anions.Preferred salts of the compounds of formula (I) to (III) and of the individual mycosporin-like amino acid compounds specified herein are chloride salts.
[0992] The metal ion used to form the salt replacing the acidic proton present in the starting compound is selected from the group consisting of alkali metal ions (preferably Na+, K+ or Li+), alkaline earth metal ions (preferably Ca++ or Mg++), aluminum+++ or NH4+.
[0993] The coordinating organic base used to form the salt is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N-methylglucamine, triethylamine and the like.
[0994] In the following specification and claims and unless otherwise indicated, the term mycosporin-like amino acid compound includes the neutral, uncharged form of the compound / molecule and the salt form of the same.
[0995] Mycosporin-like amino acid compounds in salt form result in lower logP OW , and thus make the compound more hydrophilic, which leads to better solubility in water. In particular, the cationic salts of mycosporin-like amino acid compounds support the emulsification process in emulsions due to their surface reducing activity, i.e., co-emulsifying properties. In addition, the cationic salt forms of mycosporin-like amino acid compounds show excellent affinity behavior on skin and hair and other inanimate surfaces: most conditioning active substances are cationic; the conditioning effect leads to a softer skin feel, which makes the final product more acceptable to consumers. In addition, mycosporin-like amino acid compounds in cationic salt form exhibit antimicrobial activity.
[0996] In a particularly advantageous variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the first aspect of the invention comprises one of the following combinations of components (a) and (b):
[0997] ethylhexyl methoxycinnamate plus at least one mycosporin-like amino acid compound according to any one of formula (V) as defined herein; or
[0998] ■ butyl-methoxydibenzoylmethane plus at least one mycosporin-like amino acid compound according to any one of formula (V) as defined herein; or
[0999] ■ isoamyl p-methoxycinnamate plus at least one mycosporin-like amino acid compound according to any one of formula (V); or
[1000] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus at least one mycosporin-like amino acid compound according to any one of formula (V) as defined herein; or
[1001] ■ ethylhexyl methoxycinnamate plus at least one mycosporin-like amino acid compound according to any one of formula (VI) as defined herein; or
[1002] ■ butyl-methoxydibenzoylmethane plus at least one mycosporin-like amino acid compound according to any one of formula (VI) as defined herein; or
[1003] ■ isoamyl p-methoxycinnamate plus at least one mycosporin-like amino acid compound according to any one of formula (VI); or
[1004] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus at least one mycosporin-like amino acid compound according to any one of formula (VI) as defined herein; or
[1005] ■ ethylhexyl methoxycinnamate plus at least one mycosporin-like amino acid compound according to any one of formula (VII) as defined herein; or
[1006] ■ butyl-methoxydibenzoylmethane plus at least one mycosporin-like amino acid compound according to any one of formula (VII) as defined herein; or
[1007] ■ isoamyl p-methoxycinnamate plus at least one mycosporin-like amino acid compound according to any one of formula (VII); or
[1008] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus at least one mycosporin-like amino acid compound according to any one of formula (VII) as defined herein; or
[1009] ■ ethylhexyl methoxycinnamate plus at least one mycosporin-like amino acid compound according to any one of formula (VIII) as defined herein; or
[1010] ■ butyl-methoxydibenzoylmethane plus at least one mycosporin-like amino acid compound according to any one of formula (VIII) as defined herein; or
[1011] ■ isoamyl p-methoxycinnamate plus at least one mycosporin-like amino acid compound according to any one of formula (VIII); or
[1012] ■ Diethylamino-hydroxybenzoyl-hexyl-benzoate plus at least one mycosporin-like amino acid compound according to any one of formula (VIII) as defined herein.
[1013] A more preferred combination of components (a) and (b) in the sunscreen product or cosmetic or pharmaceutical preparation according to the first aspect of the present invention is:
[1014] ■ ethylhexyl methoxycinnamate plus compound MAA-1, as depicted in Table 3; or
[1015] ■ Butyl-methoxydibenzoylmethane plus compound MAA-1, as depicted in Table 3; or
[1016] ■ isoamyl p-methoxycinnamate plus compound MAA-1, as depicted in Table 3; or
[1017] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-1, as depicted in Table 3; or
[1018] ■ ethylhexyl methoxycinnamate plus compound MAA-2, as depicted in Table 3; or
[1019] ■ Butyl-methoxydibenzoylmethane plus compound MAA-2, as depicted in Table 3; or
[1020] ■ isoamyl p-methoxycinnamate plus compound MAA-2, as depicted in Table 3; or
[1021] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-2, as depicted in Table 3; or
[1022] ■ ethylhexyl methoxycinnamate plus compound MAA-3, as depicted in Table 3; or
[1023] ■ Butyl-methoxydibenzoylmethane plus compound MAA-3, as depicted in Table 3; or
[1024] ■ isoamyl p-methoxycinnamate plus compound MAA-3, as depicted in Table 3; or
[1025] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-3, as depicted in Table 3; or
[1026] ■ ethylhexyl methoxycinnamate plus compound MAA-4, as depicted in Table 3; or
[1027] ■ Butyl-methoxydibenzoylmethane plus compound MAA-4, as depicted in Table 3; or
[1028] ■ isoamyl p-methoxycinnamate plus compound MAA-4, as depicted in Table 3; or
[1029] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-4, as depicted in Table 3; or
[1030] ■ ethylhexyl methoxycinnamate plus compound MAA-5, as depicted in Table 3; or
[1031] ■Butyl-methoxydibenzoylmethane plus compound MAA-5, as depicted in Table 3; or
[1032] ■ isoamyl p-methoxycinnamate plus compound MAA-5, as depicted in Table 3; or ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-5, as depicted in Table 3; or
[1033] ■ ethylhexyl methoxycinnamate plus compound MAA-6, as depicted in Table 3; or
[1034] ■Butyl-methoxydibenzoylmethane plus compound MAA-6, as depicted in Table 3; or
[1035] ■ isoamyl p-methoxycinnamate plus compound MAA-6, as depicted in Table 3; or
[1036] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-6, as depicted in Table 3; or
[1037] ■ ethylhexyl methoxycinnamate plus compound MAA-7, as depicted in Table 3; or
[1038] ■Butyl-methoxydibenzoylmethane plus compound MAA-7, as depicted in Table 3; or
[1039] ■ isoamyl p-methoxycinnamate plus compound MAA-7, as depicted in Table 3; or
[1040] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-7, as depicted in Table 3; or
[1041] ■ ethylhexyl methoxycinnamate plus compound MAA-8, as depicted in Table 3; or
[1042] ■Butyl-methoxydibenzoylmethane plus compound MAA-8, as depicted in Table 3; or
[1043] ■ isoamyl p-methoxycinnamate plus compound MAA-8, as depicted in Table 3; or
[1044] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-8, as depicted in Table 3; or
[1045] ■ ethylhexyl methoxycinnamate plus compound MAA-9, as depicted in Table 3; or
[1046] ■Butyl-methoxydibenzoylmethane plus compound MAA-9, as depicted in Table 3; or
[1047] ■ isoamyl p-methoxycinnamate plus compound MAA-9, as depicted in Table 3; or
[1048] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-9, as depicted in Table 3; or
[1049] ■ ethylhexyl methoxycinnamate plus compound MAA-11, as depicted in Table 3; or
[1050] ■Butyl-methoxydibenzoylmethane plus compound MAA-11, as depicted in Table 3; or
[1051] ■ isoamyl p-methoxycinnamate plus compound MAA-11, as depicted in Table 3; or
[1052] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-11, as depicted in Table 3; or
[1053] ■ ethylhexyl methoxycinnamate plus compound MAA-12, as depicted in Table 3; or
[1054] ■Butyl-methoxydibenzoylmethane plus compound MAA-12, as depicted in Table 3; or
[1055] ■ isoamyl p-methoxycinnamate plus compound MAA-12, as depicted in Table 3; or
[1056] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-12, as depicted in Table 3; or
[1057] ■ ethylhexyl methoxycinnamate plus compound MAA-13, as depicted in Table 3; or
[1058] ■Butyl-methoxydibenzoylmethane plus compound MAA-13, as shown in Table 3; or
[1059] ■ isoamyl p-methoxycinnamate plus compound MAA-13, as depicted in Table 3; or
[1060] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-13, as depicted in Table 3; or
[1061] ■ ethylhexyl methoxycinnamate plus compound MAA-14, as depicted in Table 3; or
[1062] ■Butyl-methoxydibenzoylmethane plus compound MAA-14, as shown in Table 3; or
[1063] ■ isoamyl p-methoxycinnamate plus compound MAA-14, as shown in Table 3; or
[1064] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-14, as depicted in Table 3; or
[1065] ■ ethylhexyl methoxycinnamate plus compound MAA-16, as depicted in Table 3; or
[1066] ■Butyl-methoxydibenzoylmethane plus compound MAA-16, as shown in Table 3; or
[1067] ■ isoamyl p-methoxycinnamate plus compound MAA-16, as shown in Table 3; or
[1068] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-16, as depicted in Table 3; or
[1069] ■ ethylhexyl methoxycinnamate plus compound MAA-17, as depicted in Table 3; or
[1070] ■Butyl-methoxydibenzoylmethane plus compound MAA-17, as depicted in Table 3; or
[1071] ■ isoamyl p-methoxycinnamate plus compound MAA-17, as depicted in Table 3; or
[1072] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-17, as depicted in Table 3; or
[1073] ■ ethylhexyl methoxycinnamate plus compound MAA-20, as depicted in Table 3; or
[1074] ■Butyl-methoxydibenzoylmethane plus compound MAA-20, as shown in Table 3; or
[1075] ■ isoamyl p-methoxycinnamate plus compound MAA-20, as shown in Table 3; or
[1076] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-20, as depicted in Table 3; or
[1077] ■ ethylhexyl methoxycinnamate plus compound MAA-21, as depicted in Table 3; or
[1078] ■Butyl-methoxydibenzoylmethane plus compound MAA-21, as depicted in Table 3; or
[1079] ■ isoamyl p-methoxycinnamate plus compound MAA-21, as depicted in Table 3; or
[1080] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-21, as depicted in Table 3; or
[1081] ■ ethylhexyl methoxycinnamate plus compound MAA-22, as depicted in Table 3; or
[1082] ■Butyl-methoxydibenzoylmethane plus compound MAA-22, as depicted in Table 3; or
[1083] ■ isoamyl p-methoxycinnamate plus compound MAA-22, as depicted in Table 3; or
[1084] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-22, as depicted in Table 3; or
[1085] ■ ethylhexyl methoxycinnamate plus compound MAA-23, as depicted in Table 3; or
[1086] ■Butyl-methoxydibenzoylmethane plus compound MAA-23, as depicted in Table 3; or
[1087] ■ isoamyl p-methoxycinnamate plus compound MAA-23, as depicted in Table 3; or
[1088] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-23, as depicted in Table 3; or
[1089] ■ ethylhexyl methoxycinnamate plus compound MAA-24, as depicted in Table 3; or
[1090] ■Butyl-methoxydibenzoylmethane plus compound MAA-24, as depicted in Table 3; or
[1091] ■ isoamyl p-methoxycinnamate plus compound MAA-24, as depicted in Table 3; or
[1092] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-24, as depicted in Table 3; or
[1093] ■ ethylhexyl methoxycinnamate plus compound MAA-25, as depicted in Table 3; or
[1094] ■Butyl-methoxydibenzoylmethane plus compound MAA-25, as depicted in Table 3; or
[1095] ■ isoamyl p-methoxycinnamate plus compound MAA-25, as depicted in Table 3; or
[1096] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-25, as depicted in Table 3; or
[1097] ■ ethylhexyl methoxycinnamate plus compound MAA-26, as depicted in Table 3; or
[1098] ■Butyl-methoxydibenzoylmethane plus compound MAA-26, as depicted in Table 3; or
[1099] ■ isoamyl p-methoxycinnamate plus compound MAA-26, as depicted in Table 3; or
[1100] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-26, as depicted in Table 3; or
[1101] ■ ethylhexyl methoxycinnamate plus compound MAA-27, as depicted in Table 3; or
[1102] ■Butyl-methoxydibenzoylmethane plus compound MAA-27, as depicted in Table 3; or
[1103] ■ isoamyl p-methoxycinnamate plus compound MAA-27, as depicted in Table 3; or
[1104] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-27, as depicted in Table 3; or
[1105] ■ ethylhexyl methoxycinnamate plus compound MAA-28, as depicted in Table 3; or
[1106] ■Butyl-methoxydibenzoylmethane plus compound MAA-28, as depicted in Table 3; or
[1107] ■ isoamyl p-methoxycinnamate plus compound MAA-28, as depicted in Table 3; or
[1108] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-28, as depicted in Table 3; or
[1109] ■ ethylhexyl methoxycinnamate plus compound MAA-29, as depicted in Table 3; or
[1110] ■Butyl-methoxydibenzoylmethane plus compound MAA-29, as depicted in Table 3; or
[1111] ■ isoamyl p-methoxycinnamate plus compound MAA-29, as depicted in Table 3; or
[1112] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-29, as depicted in Table 3; or
[1113] ■ ethylhexyl methoxycinnamate plus compound MAA-30, as depicted in Table 3; or
[1114] ■Butyl-methoxydibenzoylmethane plus compound MAA-30, as depicted in Table 3; or
[1115] ■ isoamyl p-methoxycinnamate plus compound MAA-30, as depicted in Table 3; or
[1116] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-30, as depicted in Table 3; or
[1117] ■ ethylhexyl methoxycinnamate plus compound MAA-31, as depicted in Table 3; or
[1118] ■Butyl-methoxydibenzoylmethane plus compound MAA-31, as depicted in Table 3; or
[1119] ■ isoamyl p-methoxycinnamate plus compound MAA-31, as depicted in Table 3; or
[1120] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-31, as depicted in Table 3; or
[1121] ■ ethylhexyl methoxycinnamate plus compound MAA-32, as depicted in Table 3; or
[1122] ■Butyl-methoxydibenzoylmethane plus compound MAA-32, as depicted in Table 3; or
[1123] ■ isoamyl p-methoxycinnamate plus compound MAA-32, as depicted in Table 3; or
[1124] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-32, as depicted in Table 3; or
[1125] ■ ethylhexyl methoxycinnamate plus compound MAA-33, as depicted in Table 3; or
[1126] ■Butyl-methoxydibenzoylmethane plus compound MAA-33, as depicted in Table 3; or
[1127] ■ isoamyl p-methoxycinnamate plus compound MAA-33, as depicted in Table 3; or
[1128] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-33, as depicted in Table 3; or
[1129] ■ ethylhexyl methoxycinnamate plus compound MAA-34, as depicted in Table 3; or
[1130] ■Butyl-methoxydibenzoylmethane plus compound MAA-34, as depicted in Table 3; or
[1131] ■ isoamyl p-methoxycinnamate plus compound MAA-34, as depicted in Table 3; or
[1132] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-34, as depicted in Table 3; or
[1133] ■ ethylhexyl methoxycinnamate plus compound MAA-35, as depicted in Table 3; or
[1134] ■Butyl-methoxydibenzoylmethane plus compound MAA-35, as depicted in Table 3; or
[1135] ■ isoamyl p-methoxycinnamate plus compound MAA-35, as depicted in Table 3; or
[1136] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-35, as shown in Table 3; or
[1137] ■ Ethylhexyl methoxycinnamate plus compound MAA-36, as shown in Table 3; or
[1138] ■Butyl-methoxydibenzoylmethane plus compound MAA-36, as depicted in Table 3; or
[1139] ■ isoamyl p-methoxycinnamate plus compound MAA-36, as depicted in Table 3; or
[1140] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-36, as depicted in Table 3; or
[1141] ■ Ethylhexyl-methoxycinnamate plus compound MAA-37, as depicted in Table 3; or
[1142] ■ Butyl-methoxydibenzoylmethane plus compound MAA-37, as depicted in Table 3; or
[1143] ■ isoamyl p-methoxycinnamate plus compound MAA-37, as depicted in Table 3; or
[1144] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-37, as depicted in Table 3; or
[1145] ■ Ethylhexyl-methoxycinnamate plus compound MAA-38, as depicted in Table 3; or
[1146] ■Butyl-methoxydibenzoylmethane plus compound MAA-38, as depicted in Table 3; or
[1147] ■ isoamyl p-methoxycinnamate plus compound MAA-38, as depicted in Table 3; or
[1148] ■ diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-38, as depicted in Table 3; or
[1149] ■ Ethylhexyl-methoxycinnamate plus compound MAA-39, as depicted in Table 3; or
[1150] ■Butyl-methoxydibenzoylmethane plus compound MAA-39, as depicted in Table 3; or
[1151] ■ isoamyl p-methoxycinnamate plus compound MAA-39, as depicted in Table 3; and
[1152] ■Diethylamino-hydroxybenzoyl-hexyl-benzoate plus compound MAA-39, as depicted in Table 3.
[1153] Most preferred are the photolabile UV filters ethylhexyl methoxycinnamate, butyl methoxydibenzoylmethane, isoamyl p-methoxycinnamate or diethylamino-hydroxybenzoyl-hexyl-benzoate in combination with one of the MAA compounds MAA-20 to MAA-39.
[1154] In the above-specified combinations, the photolabile UV filters are particularly stabilized against photodegradation by the mycosporin-like amino acid compound. In some cases, the combination of photolabile UV filters and mycosporin-like amino acid compounds has a synergistic stabilizing effect. The photostabilizing effect of mycosporin-like amino acid compounds with an acid function is particularly pronounced compared to the corresponding ester analogs.
[1155] In the preparation of sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention, the compounds defined herein can be used in combination with other UV absorbers other than the at least one photolabile UV filter (a) in order to further optimize the SPF, i.e. to obtain a high SPF in the range of 6 to 100, preferably in the range of 6 to 70, and to cover a wide UVA and UVB range.
[1156] Therefore, the photolabile UV filter (a) in the sunscreen product, cosmetic or pharmaceutical preparation or home care product as defined herein is advantageously combined with at least one additional primary sunscreen UV filter different from the photolabile UV filter (a) and / or with at least one additional secondary sunscreen ingredient or secondary sunscreen UV filter. The combination of different classes of effective sunscreen UV filters such as UVA filters, UVB filters, broadband filters, inorganic pigments provides reliable protection against different UV rays in the wavelength range from 290 nm to 400 nm.
[1157] In the context of the present invention, primary sunscreen UV filters are, for example, organic substances (photofilters) which are liquid or crystalline at room temperature and are able to absorb ultraviolet radiation and to release the absorbed energy (eg heat) in the form of longer-wave radiation.
[1158] The sunscreen products or cosmetic or pharmaceutical preparations according to the invention advantageously contain at least one additional UVA filter and / or at least one additional UVB filter and / or a broadband filter and / or at least one inorganic pigment, preferably at least one UVA filter and at least one UVB filter, for their use in protecting against UV radiation.
[1159] For example, the UV filter may be one or more organic UV filters and / or one or more inorganic UV filters. Non-limiting examples of UV filters include:
[1160] (i) Sparingly soluble UV filters (insoluble in water or oil), such as methylenebis-benzotriazolyltetramethylbutylphenol, terphenyltriazine, ketone, 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl-]phenyl];
[1161] (ii) oil-soluble organic UV filters (at least partially soluble in oil or organic solvents), such as bis-ethylhexyloxyphenol methoxyphenyl triazine, butyl methoxydibenzoylmethane (BMBM), oxymethoxybenzophenone, sulisobenzone, diethylhexyl butyramido 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 diethylaminohydroxybenzoyl hexyl benzoate (DHHB);
[1162] (iii) inorganic UV filters such as titanium and zinc oxides, iron oxide, zirconium oxide and cerium oxide; and
[1163] (iv) water-soluble UV filters such as phenylbenzimidazole sulfonic acid (PBSA), sulfisobenzone-sodium salt, benzalkonium camphorsulfonic acid, camphorbenzalkonium methyl sulfate, Cinoxate, disodium phenyldibenzylimidazole tetrasulfonate, terephthalylidene dicamphorsulfonic acid, PABA and PEG-25PAB; and any mixtures thereof.
[1164] In some cases, the UV filter is one or more of the following: p-aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone or aminobenzophenone, anthranilic acid derivatives, b,b-diphenylacrylate derivatives, benzylidene camphor derivatives, phenylbenzimidazole derivatives, benzotriazole derivatives, triazine derivatives, bisresorcinol triazine, imidazoline derivatives, benzylidene malonate derivatives, 4,4-diarylbutadiene derivatives, benzoxazole derivatives, merocyanine, malononitrile or malonate diphenylbutadiene derivatives, chalcone, and any mixtures thereof.
[1165] Inorganic UV filters used as further primary UV filters are selected from the group of pigments consisting of titanium dioxide (TiO2) (amorphous or crystalline in rutile and / or anatase form), zinc oxide (ZnO), iron oxide (Fe2O3), zirconium oxide (ZrO2), silicon dioxide (SiO2), manganese oxide (e.g. MnO), aluminum oxide (Al2O3), cerium oxide (Ce2O3), barium carbonate (BaCO3), calcium carbonate (CaCO3) and mixtures thereof.
[1166] Preferably, the inorganic UV filter is titanium dioxide, zinc oxide and mixtures thereof, more preferably at least one inorganic UV filter is titanium dioxide and / or zinc oxide, and most preferably at least one inorganic UV filter is zinc oxide. ZnO has a broad UVA / UVB absorption curve, while TiO2 provides better UVB protection.
[1167] According to another variant, the inorganic UV filter has a weight average particle size d of 1 nm to 1000 nm. 50 The particle form of the present invention is preferably 3 nm to 800 nm, more preferably 5 nm to 600 nm, and most preferably 10 nm to 400 nm.
[1168] Inorganic UV filters also include nanopigments of untreated or treated metal oxides (average size of the primary particles: generally 1 nm to 100 nm, preferably 3 nm to 90 nm, more preferably 5 nm to 80 nm, and most preferably 10 to 70 nm), such as, for example, nanopigments of titanium dioxide (TiO2) (amorphous or crystalline in rutile and / or anatase form), zinc oxide (ZnO), iron oxide (Fe2O3), zirconium oxide (ZrO2), silicon dioxide (SiO2), manganese oxide (e.g. MnO), aluminum oxide (Al2O3), cerium oxide (Ce2O3), barium carbonate (BaCO3), calcium carbonate (CaCO3) or mixtures thereof.
[1169] Treated nanopigments and non-nanopigments are pigments that have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature using compounds such as amino acids, beeswax, fatty acids, fatty acid esters, fatty alcohols, anionic surfactants, lecithin, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal (titanium or aluminum) alcoholates, polyethylene, silicone, protein (collagen or elastin), alkanolamines, silica, metal oxides, sodium hexametaphosphate, alumina or glycerol, hydrated silica, stearic acid, jojoba esters or glutamic acid derivatives.
[1170] The treated nanopigments and non-nanopigments may more particularly be titanium oxide treated with silica and alumina, alumina and aluminum stearate, alumina and aluminum laurate, aluminum hydroxide, iron oxide and iron stearate, silica, alumina and silicone, sodium hexametaphosphate, octyl trimethoxy silane, alumina and stearic acid, alumina and glycerol, or alumina and silicone or polyhydroxy stearic acid, silica hydrate, jojoba esters, stearoyl glutamic acid, glutamic acid and derivatives, trimethoxy caprylyl silane, glycerol, polydimethylsiloxane, hydrogenated polydimethylsiloxane, dimethicone or a combination thereof. Other titanium oxide nanopigments treated with silicone are preferably TiO2 treated with octyl trimethoxy silane, preferably with an average size of 25 nm to 40 nm of elementary particles; TiO2 treated with polydimethylsiloxane, preferably with an average size of 21 nm of elementary particles; or TiO2 treated with polydimethylsiloxane, preferably with an average size of 25 nm of elementary particles.
[1171] The coated zinc oxide nanopigments and zinc oxide non-nanopigments are, for example, ZnO coated with polymethylhydrogensiloxane; ZnO dispersions in cyclomethicone / oxyethylated polydimethylsiloxane containing 30% or 80% of nano or non-nano zinc oxide coated with silica and polymethylhydrogensiloxane; ZnO coated with perfluoroalkyl phosphate and perfluoroalkylethyl-based copolymers as dispersions in cyclopentasiloxane; ZnO coated with dimethoxydiphenylsilane triethoxyoctanoylsilane crosspolymer; ZnO coated with glutamic acid; ZnO coated with octyltriethoxysilane; ZnO coated with polydimethylsiloxane; ZnO coated with methylsiloxane; ZnO coated with a siloxane grafted polymer and dispersed in cyclodimethicone; ZnO coated with triethoxycaprylylsilane; ZnO coated with polyhydroxystearic acid; ZnO treated with alumina dispersed in a mixture of ethylhexyl methoxycinnamate / PVP-hexadecene / polymethicone copolymer; ZnO coated with silica and polymethylsilsesquioxane; ZnO dispersed in a hydroxystearic acid polycondensate; or ZnO coated with a mixture of stearoyl glutamic acid, jojoba esters, polyhydroxypivalic acid, isopropyl titanium triisostearate, hydrogenated olive oil stearyl esters, cetearyl nonanoate, white beeswax (cera alba), polydimethylsiloxane, dimethoxydiphenylsilane triethoxycaprylylsilane crosspolymer, octyl triethoxysilane, glutamic acid and sodium stearoyl lactylate.
[1172] Also preferred are particulate UV filters or inorganic pigments, which may optionally be hydrophobized, such as iron oxide (Fe2O3), zirconium oxide (ZrO2), silicon dioxide (SiO2), manganese oxide (e.g. MnO), aluminum oxide (Al2O3), cerium oxide (e.g. Ce2O3), barium carbonate (BaCO3), calcium carbonate (CaCO3), or mixtures thereof.
[1173] Preferably, the one, two, three or more additional primary organic and / or inorganic UV filters different from the photolabile UV filters (a) are selected from the group consisting of: camphor benzalkonium bromide methyl sulfate, homosalate, benzophenone-3, phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, benzalkonium sulfonic acid, octocrylene, polyacrylamidomethylbenzylidene camphor, PEG-25 PABA, 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, titanium dioxide, titanium dioxide (nano), tris-biphenyl triazine (nano), zinc oxide, zinc oxide (nano), phenylene bis-diphenyl triazine, methoxypropylaminocyclohexenylene ethoxyethyl cyanoacetate, bis-(diethylaminohydroxybenzoylbenzoyl)piperazine, TEA-salicylate, benzophenone-8, PABA, dimethyl PABA ethylhexyl ester, menthyl anthranilate, and any mixture thereof.
[1174] More preferably, the one, two, three or more additional primary organic and / or inorganic UV filters are selected from the group consisting of camphor benzalkonium methyl sulfate, benzophenone-3, terephthaloyl dicamphor sulfonic acid, benzylidene camphor sulfonic acid, polyacrylamidomethylbenzylidene camphor, PEG-25 PABA, drometrizole trisiloxane, dimethyl PABA ethylhexyl ester, benzophenone-4, benzophenone-5, methylene bis-benzotriazolyl tetramethylbutylphenol, polysilicone-15, titanium dioxide (nano), terphenyl triazine (nano), phenylene bis-diphenyl triazine, methoxypropylaminocyclohexenyl ethoxyethyl cyanoacetate, bis-(diethylaminohydroxybenzoylbenzoyl)piperazine, benzophenone-8, ethylhexyl dimethyl PABA, homosalate, phenylbenzimidazole sulfonic acid, butyl methoxydibenzoylmethane, octocrylene, isoamyl methoxycinnamate, ethylhexyl triazone, diethylhexyl butyramido triazone, 4-methylbenzylidene camphor, ethylhexyl salicylate, disodium phenyl dibenzimidazole tetrasulfonate, bis-ethylhexyloxyphenol methoxyphenyl triazine, titanium dioxide, diethylaminohydroxybenzoyl hexyl benzoate, zinc oxide, zinc oxide (nano), menthyl anthranilate, and any mixture thereof.
[1175] Most preferably, the one, two, three or more additional primary organic and / or inorganic UV filters are 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, titanium dioxide, diethylaminohydroxybenzoyl phenhexyl carboxylate, zinc oxide, zinc oxide (nano) and any mixtures thereof.
[1176] In a preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention comprises a combination with one or more broadband filters selected from the group consisting of 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, sodium hydroxymethylbenzophenonesulfonate, 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfonate. Sodium, phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(1,3,3,3-tetramethyl-1-(trimethylsilyl)oxy)disiloxyphenyl)propyl), 2,2'-methylene-bis-(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)phenol (methylene-bis-benzotriazolyltetramethylbutylphenol), 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: Asymmetric Triazine (Aniso Triazine), 2,4-bis-[{(4-(3-sulfonato)-2-hydroxypropoxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine sodium salt, 2,4-bis-[{(3-(2-propoxy)-2-hydroxypropoxy)-2-hydroxy}phenyl]-6-(4-methoxy-phenyl)-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-propoxy)-2-hydroxypropoxy)-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-(trimethylsilyloxysilylpropoxy)-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'-heptamethylsilyloxy-2"-methylpropoxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, dioctylbutyramidotrione (INCI: dioctylbutyrylaminotriazone), 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)tribenzoic acid tris(2-ethylhexyl) (also known as: 2,4,6-tris[anilino(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazine (INCI: octyl triazone)), 2,4,6-terphenyl- 4-amino-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 (dimethyl PABA ethylhexyl ester), N,N,N-trimethyl-4-(2-oxobornyl-3-ylmethyl)anilinium methylsulfate (camphorbenzalkonium bromide methylsulfate), dimethicone diethylbenzylidenemalonate (polysilicone-15) and any mixture thereof.
[1177] The additional essential organic and / or inorganic UV filters other than the photolabile UV filters (a) are generally present in the compositions according to the invention in a proportion of 0.01 to 80.0% by weight relative to the total weight of the composition, preferably 0.1 to 75.0% by weight relative to the total weight of the ready-to-use preparation, more preferably 0.5 to 70% by weight and most preferably 1.0 to 60.0% by weight.
[1178] In a further preferred variant, the sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention contain primary UV filters, i.e. in particular organic filters and / or inorganic pigments (UV filter pigments), in a total amount such that the products or preparations according to the invention have 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.
[1179] In addition to the abovementioned primary groups of organic and inorganic UV filters, secondary sunscreen ingredients of the antioxidant type can also advantageously be used in the sunscreen products, cosmetic or pharmaceutical preparations or household care products according to the invention in order to further optimize the UV protection.
[1180] Secondary sunscreen ingredients of the antioxidant type interrupt the photochemical reaction chain that is initiated when UV rays penetrate the skin.
[1181] Typical examples of secondary sunscreen ingredients are amino acids (e.g. arginine, lysine, glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D,L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. alpha-carotene, beta-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g. dihydrolipoic acid), aurothiocan, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, Cystine, cystamine and its glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, α-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (e.g. buthionine sulfate imine, homocysteine sulfate imine, buthionine sulfone, pentathionine sulfate imine, hexylthioether sulfate imine, heptathionine sulfate imine), also (metal) chelating agents (e.g. α-hydroxy fatty acids, palmitic acid, phytosteryl acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. gamma-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherol and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and coniferyl benzoate of benzoin resin, rutin Citronellol and its derivatives, glycosides rutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguaiaretic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, sinapinic acid, sinapinic acid malate, sinapinic acid ester derivatives, selenium and its derivatives (e.g. selenomethionine), stilbene and its derivatives (e.g. stilbene oxide, trans-stilbene oxide) and derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances suitable for the purposes of the present invention.
[1182] The group of protective ingredients for secondary sun protection also includes plant-based extracts. These plant-based extracts have antioxidant and generally photoprotective properties and interrupt the photochemical reaction chain that is initiated when UV rays penetrate the skin, thus effectively preventing skin aging. The plant extract with UV protection properties is selected from the group consisting of lignin / cellulose, lignin, hydrolyzed lignin, propolis and green propolis, galangal extract, macroalgae and microalgae (Porphyra, red algae (Porphyra umbilicus), Palmaria palmata, Saccharina latissimi, Corallina pilulifera, Eckloina cava, Sargassum sagamianum, Porphyra rosengurttii, Sargassum siliquastrum, Thalassiosira weissflogii, green microalgae (e.g. Interfilum and Klebsormidium), seaweed (e.g. Padina australis), Eucheuma, Kappaphycus cottonii), Pongamia glabrous seed oil, Karanja Oil (Pongamia millettiapinnata), Rhatania extract (Krameria lappacea), Lichen, Soybean, Caper (Capparis spinosa), Bamboo, Green Coffee Oil, Buriti Oil (Mauritia flexuosa), Black Sea Cucumber (Holothuria atra), Cyanobacteria, Fern (Polypodium leucotomos), Green Tea, Black Tea (Camellia sinensis), Aloe, Walnut, Borage Oil, Evening Primrose Oil, Avocado Oil, Tea Tree Oil, Red Clover (Trifolium pratense L.), Soybean (Glycine max L.), Caper (Capparis spinosa), Almond, Flame of the forest (Spathodea campanulata), Milk Thistle (Silybum marianum L.), Cashew nut shell, Grapes, Oranges, 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), Brassicas (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), black currant seed oil (Ribes nigrum), sesame oil (Sesamumindicum), carrot root (Daucus carota sativa), raspberry seed oil (Rubusidaeus), traditional medicinal plants from Sri Lanka (Aporosa lindleyana (Euphorbiaceae), Atalantia ceylanica (Rutaceae), Hibiscus furcatus (Malvaceae), Olax zeylanica (Oleaceae), Ophiorrhiza mungos (Rubiaceae), Argyreia populifolia (Convolvulaceae), Ipomoea mauritiana (Convolvulaceae), Lasiaspinosa (Araceae), Leucas zeylanica (Lamiaceae), Plectranthus zeylanicus (Lamiaceae)), and traditional medicinal plants of Brazil (D. gardneriana seeds, L. larix leaves (L.microphylla leaves), Amburana cearensis, Aspidosperma cuspa, Aspidosperma pyrifolium, Crotonsonderianus, Curatella americana, Dimophandragardneriana, Lippia microphylla, Luehea paniculata, Sida galheirensis) and any mixtures thereof.
[1183] Preferably, the extract having UV protection properties is selected from the group consisting of lignin / cellulose, lignin, hydrolyzed lignin, galangal extract, Porphyra, red algae (Porphyra umbilicus), green microalgae (e.g. Endothella and Creatia), seaweed (e.g. Padilla, Eucheuma, Kappaphycus auriculata), Pongamia glabrous seed oil, Karanja oil (Pongamia glabrata), Rhatania extract (Krameria lappacea), soy, bamboo, Bridgeberry oil (Palmi pubescens), cyanobacteria, fern mass (Polypodium leucophyllum), green tea, black tea (Camellia sinensis), evening primrose oil, cashew nut shell, pomegranate (Punica granatum) and any mixture thereof.
[1184] Advantageously, the amount of secondary sunscreen substances in the sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention is advantageously from 0.005 to 5.0% by weight, preferably from 0.01 to 4.0% by weight and most preferably from 0.05 to 3.0% by weight, based on the total weight of the ready-to-use preparation.
[1185] The UV filters can be incorporated into the aqueous part or the lipophilic part of the sunscreen product, cosmetic or pharmaceutical preparation or home care product, depending on whether the UV filter is a water or oil (fat) soluble / miscible UV filter, or even added to the final product by standard methods known to those skilled in the art.
[1186] The photolabile UV filter (a) according to the first aspect of the invention is present in the sunscreen product or the cosmetic or pharmaceutical preparation in an amount of 0.01% to 35.0% by weight, based on the total weight of the final preparation. In a preferred variant, the sunscreen product or the cosmetic or pharmaceutical preparation comprises the photolabile UV filter (a) in an amount of 0.1% to 30.0% by weight, based on the total weight of the final preparation. In a more preferred variant, the photolabile UV filter (a) is advantageously used in the sunscreen product or the cosmetic or pharmaceutical preparation in an amount of 0.5% to 25.0% by weight, based on the total weight of the final preparation. In a most preferred variant, the photolabile UV filter is advantageously used in the sunscreen product or the cosmetic or pharmaceutical preparation in an amount of 1.0% to 20.0% by weight, based on the total weight of the final preparation.
[1187] For mixtures of photolabile UV filters, the amounts mentioned above relate to the total content of photolabile UV filters in the mixture, ie the amount is the sum of the contents of all photolabile UV filters in the mixture.
[1188] The photolabile UV filter (a) and the additional UV filter components, such as the primary organic and / or inorganic UV filters and the secondary sunscreen ingredients as defined herein, i.e. the total amount of all UV filters, are present in the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention in an amount of 0.1% to 85.0% by weight, based on the total weight of the final preparation. In a preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product comprises the photolabile UV filter (b) as defined herein and the additional UV filter components in an amount of 0.3% to 80.0% by weight, based on the total weight of the final preparation. In a more preferred variant, the photolabile UV filter (b) as defined herein and the additional UV filter components are advantageously used in the sunscreen product or the cosmetic or pharmaceutical preparation or home care product in an amount of 0.5% to 75.0% by weight, based on the total weight of the final preparation. The above amounts therefore relate to the sum of the contents of all UV filters present in the sunscreen, cosmetic or pharmaceutical preparation or home care product.
[1189] At least one mycosporin-like amino acid compound (b) according to the first aspect of the invention is present in a sunscreen product, a cosmetic or pharmaceutical preparation or a home care product in an amount of 0.001% to 15.0% by weight based on the total weight of the final preparation. In a preferred variant, the sunscreen product, the cosmetic or pharmaceutical preparation or the home care product comprises at least one mycosporin-like amino acid compound (b) in an amount of 0.01% to 10.0% by weight based on the total weight of the final preparation. In a more preferred variant, at least one mycosporin-like amino acid compound (b) is advantageously used in a sunscreen product or a cosmetic or pharmaceutical preparation or a home care product in an amount of 0.05% to 7.5% by weight based on the total weight of the final preparation. In a most preferred variant, at least one mycosporin-like amino acid compound is advantageously used in a sunscreen product or a cosmetic or pharmaceutical preparation or a home care product in an amount of 0.1% to 5.0% by weight based on the total weight of the final preparation.
[1190] For a mixture of mycosporin-like amino acid compounds (b), the above amount relates to the total content of mycosporin-like amino acid compounds in the mixture, ie the amount is the sum of the contents of all mycosporin-like amino acid compounds (b) in the mixture.
[1191] The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the present invention provides broad spectrum light protection for the skin and therefore provides protection against UVA and UVB radiation. The sun protection factor (SPF) is a measure of UVB protection. Typically, the composition of the present invention has an SPF of at least 6. However, the SPF can be varied as desired. The type and amount of UVB filter can be varied to obtain the desired level of SPF. Preferably, the SPF of the sunscreen product or cosmetic or pharmaceutical preparation 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 higher.
[1192] In the context of the present invention, it is also possible and in some cases advantageous to combine the sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the first aspect of the invention with other conventional active substances, adjuvants or additives (as further described below, commonly used in sunscreen products, cosmetic or pharmaceutical compositions or home care products) in order to obtain a ready-to-use preparation or formulation.
[1193] Other active agents and / or adjuvants and / or additives or auxiliaries are, for example, abrasives, anti-acne agents, anti-skin aging agents, anti-cellulite agents, anti-dandruff agents, anti-inflammatory agents, anti-irritants, anti-irritants, antioxidants, alkanediols, astringents, odor absorbers, antiperspirants, bactericides, antistatic agents, antimicrobial agents, binders, buffers, carrier materials, chelating agents, oil components, cell stimulants, cleaning agents, depilatories, surfactants, deodorants, antiperspirants, softeners, emulsifiers, enzymes, enzyme inhibitors, Essential oils, fibers, film formers, water resistance improvers, color fixatives, foam formers, foam stabilizers, defoamers, foam boosters, gelling agents, gel formers, hair care agents, hair fixatives, hair straighteners, moisturizers, moisturizing substances, water-retaining substances, whitening agents, strengthening agents, detergents, optical brighteners, impregnants, antifouling agents, dyes, friction reducers, lubricants, moisturizing creams, ointments, sunscreens, plasticizers, covering agents, polishes, preservatives, glossing agents, green and synthetic polymers, powders, proteins, refatting agents, abrasives, silicones, skin soothing agents, skin cleansers, skin care agents, skin healing agents, skin lightening agents, skin protectants, skin softeners, hair promoters, coolants, skin coolants, warming agents, skin warming agents, stabilizers, surfactants, antimicrobial agents, detergents / surfactants, fabric conditioners, suspending agents, skin tanning agents, active substances that regulate skin or hair pigmentation, matrix metalloproteinase inhibitors, skin moisturizers, mucopolysaccharide stimulators, TRPV1 antagonists, peeling agents, anti-cellulite or fat-enhancing agents, hair growth activators or inhibitors, thickeners, rheological additives, vitamins, oils, waxes, pearlescent waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, alpha-hydroxy acids, polyhydroxy fatty acids, liquefiers, dyes, color protection agents, pigments, anti-corrosion agents, fragrance or fragrance oils, fragrance substances, flavoring substances, odor substances, polyols, electrolytes, organic solvents and mixtures of two or more of the foregoing, as further described below.
[1194] The above-mentioned cosmetic or pharmaceutical excipients and / or active substances and / or additives and / or auxiliary carriers, oil components, rheological additives, hydrotropes, solubilizers, powders, film formers, water resistance improvers, skin moisturizing and / or moisturizing substances, soothing substances, physiological cooling agents, alkanediols, antioxidants, anti-skin aging agents, matrix metalloproteinase inhibitors (MMPI), anti-inflammatory agents, TRPV1 antagonists, emulsifiers, antimicrobial agents, preservatives, antibacterial or antifungal active substances, chelating agents, surfactants, fragrances / fragrance substances or fragrance oils and any mixtures of two or more of the aforementioned substances are particularly preferred in the preparation of sunscreen products, cosmetic and pharmaceutical preparations or home care products.
[1195] Carrier: sunscreen products, cosmetics or medicines as defined herein, particularly dermatological preparations or home care products, in the form of ointments, pastes, creams and gels, are preferred based on carriers. The most common acceptable carrier is water. Acceptable carriers other than water include glycerol, C1-4 alcohols, organic solvents, fatty alcohols, fatty ethers, fatty esters, polyols, glycols, vegetable oils, mineral oils, liposomes, thin layer lipid materials, water or mixtures thereof. Non-limiting examples of organic solvents include monohydric alcohols and polyols, such as ethanol, isopropanol, propanol, benzyl alcohol and phenylethyl alcohol, or glycols or glycol ethers, such as monomethyl ether, monoethyl ether and monobutyl ether of ethylene glycol, propylene glycol or its ethers, such as monomethyl ether, butanediol, hexanediol, dipropylene glycol and alkyl ethers of diethylene glycol, such as monoethyl ether or monobutyl ether of diethylene glycol. Other suitable examples of organic solvents are ethylene glycol, propylene glycol, butanediol, hexanediol, propylene glycol and glycerol. The organic solvent may be a volatile or non-volatile compound.The total amount of carrier in the composition may vary but is typically from 40% to 90% by weight based on the total weight of the composition.
[1196] Composition of the present invention can comprise at least one water-soluble or organic solvent.The non-limiting example of organic solvent comprises monohydric alcohol and polyhydric alcohol, such as ethanol, isopropanol, propanol, benzyl alcohol and phenylethyl alcohol, or glycol or glycol ether, such as monomethyl ether, monoethyl ether and monobutyl ether, propylene glycol or its ether of for example ethylene glycol, such as the alkyl ether of monomethyl ether, butylene glycol, hexylene glycol, dipropylene glycol and diethylene glycol of for example propylene glycol, for example monoethyl ether or monobutyl ether of diethylene glycol.Other suitable examples of organic solvent are ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, propylene glycol and glycerine.Organic solvent can be volatile or non-volatile compound.
[1197] Additional non-limiting examples of water-soluble solvents include alkanols (polyhydric alcohols such as diols and polyols) such as glycerol, 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-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl 1,2-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, isobutyl alcohol, Propanol; 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 monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-tert-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-tert-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, ethylene ... propylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether and dipropylene glycol monoisopropyl ether; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbitan, sorbitan, acetic acid glycerol, diacetic acid glycerol, triacetic acid glycerol, sulfolane and any mixture thereof. The total amount of water-soluble or organic solvent in the composition according to the present invention may vary, but is generally 0.1% to 50% by weight based on the total weight of the composition.
[1198] Solubilizer: The composition of the present invention may include at least one solubilizer. A solubilizer is a compound that helps dissolve the UV filters and / or other components in the composition. A particularly useful but non-limiting example of a solubilizer is a hydrotrope. Hydrotropes (or hydrotropic agents) are a variety of typical water-soluble compounds characterized by an amphiphilic molecular structure and the ability to significantly increase the solubility of poorly soluble organic molecules in water. Non-limiting examples of hydrotropes include sodium 1,3-benzenedisulfonate, sodium benzoate, sodium 4-pyridinecarboxylate, sodium salicylate, sodium benzenesulfonate, caffeine, sodium p-toluenesulfonate, sodium butyl monoethylene glycol sulfate, 4-aminobenzoic acid HCl, sodium isopropylbenzenesulfonate, N,N-diethylnicotinamide, N-pyridylnicotinamide, N-allylnicotinamide, 2-methacryloyloxyethylphosphatidylcholine, resorcinol, butyl urea, pyrogallol, N-pyridineacetamide 3.5, procaine HCl, proline HCl, nicotinamide, pyridine, 3-pyridinamine, sodium ibuprofen, sodium xylenesulfonate, ethyl carbamate, pyridoxal hydrochloride, sodium benzoate, 2-pyrrolidone, ethyl urea, N,N-dimethylacetamide, N-methylacetamide and isoniazid and any mixtures thereof. In some cases, particularly useful hydrotropes include nicotinamide (niacinamide), caffeine, sodium PCA, sodium salicylate, urea and hydroxyethyl urea, especially nicotinamide (niacinamide) and / or caffeine. Combinations of two or more, three or more, or four or more hydrotropes may also be used in the compositions according to the invention. The total amount of solubilizer in the compositions of the invention may vary, but is typically in an amount of 0.01% to 20% by weight, based on the total weight of the composition.
[1199] Oil component: Sunscreen products or cosmetics or pharmaceutical preparations may include at least one oil phase or at least one oil component, wax, starch, tragacanth, cellulose derivatives, polyethylene glycol, silicone, bentonite, silicon dioxide, talc and zinc oxide or any mixture thereof. Powders include carriers such as lactose, talc, silicon dioxide, aluminum hydroxide, calcium silicate and polyamide powders 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 based only on water are also possible. Oil, oil-in-water and water-in-oil emulsions, etc. are preferred.
[1200] Possible suitable oily phases or oil components in the sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention are, for example, vegetable oils, hydrocarbons, fatty alcohols, fatty acid esters or mixtures of two or more of the aforementioned oil components.
[1201] The oil phase or oil component in the cosmetic or pharmaceutical preparation is preferably a vegetable oil, and even more preferably a liquid vegetable oil. Mixtures of two or more vegetable oil components, especially liquid vegetable oil mixtures, may also be advantageous.
[1202] Plant oils or vegetable oils are oils extracted from seeds, or less frequently from other parts of fruit. Similar to animal fats, vegetable oils are mixtures of triglycerides. Soybean oil, rapeseed oil, and cocoa butter are examples of vegetable oils from seeds. Olive oil, palm oil, and rice bran oil are examples of oils from other parts of fruit. In common use, vegetable oil or vegetable oil may refer only to plant fats that are liquid at room temperature or at a skin temperature of 35°C to 37°C. Vegetable oils are generally edible.
[1203] The term "vegetable oil" also includes unsaturated vegetable oils. Unsaturated oils or vegetable oils can be converted into higher melting point oils by partial or complete "hydrogenation". The hydrogenation process includes "spraying" the oil with hydrogen at high temperature and high pressure in the presence of a catalyst (usually a powdered nickel compound). When each carbon-carbon double bond is chemically reduced to a single bond, two hydrogen atoms each form a single bond with two carbon atoms. Eliminating double bonds by adding hydrogen atoms is called saturation; when the saturation increases, the oil progresses to complete hydrogenation. The oil can be hydrogenated to increase resistance to rancidity (oxidation) or to change the physical characteristics of the oil. When the saturation increases, the viscosity and melting point of the oil increase.
[1204] In a preferred variant, the vegetable oil is selected from the group consisting of: Avocado (Persea Gratissima / Avocado) Oil, European Fir (Abies Alba) Seed Oil, Acacia Victoriae Seed Oil, Actinidia Chinensis Kiwi Seed Oil, Amaranthus Hypochondriacus Seed Oil, Peanut (Arachis Hypogaea / Peanut) Oil, Astrocaryum Murumuru Seed Butter, Astrophicum Tucuma Seed Butter, Astrophicum 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, Hemp 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 AurantiumDulcis (Orange) Seed Oil, Citrus Grandis (Grapefruit) Seed Oil, Coconut (Cocos Nucifera / Coconut) Oil, Coconut (Cocos Nucifera / Coconut) Seed Butter, Coffea Arabica Seed Oil, Chlorella Vulgaris Oil (Biotech), CorylusAmericana (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 (Lime Balm) Officinalis Seed Oil, Microalgae Oil, Moringa Oleifera Seed Oil, Moringa Oleifera 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, Rice Bran Oil, Rice Germ Oil, Rice Lipids, Rice Seed Oil, Poppy (Papaver Somniferum) Seed Oil, Passiflora Edulis Seed Oil, Avocado (Persea Gratissima / Avocado) Butter, Avocado Oil, Sweet Almond (Prunus Amygdalus Dulcis) Sweet Almond Oil, Apricot (Prunus Armeniaca / Apricot) Kernel Oil, Prunus Persica / Peach) Kernel Oil, Punica Granatum Seed Oil, Pyrheat Malus / Apple Seed Oil, Ricinoleic / Caproic / Caprylic / Capric Triglyceride, Ricinus communis (Ricinus communis)Communis (Castor) Seed Oil, Rosa Canina Fruit Oil, Rosa Moschata Seed Oil, Rubus Idaeus (Raspberry) Seed Oil, Sesame (Sesame) Seed Butter, Soybean Glycerides, Theobroma Cacao (Cocoa) Seed Butter, Theobroma Grandiflorum Seed Butter, Triticum Vulgare (Wheat) Bran Oil, Triticum Vulgare (Wheat) Germ Oil, Vitis Vinifera (Grape) Seed Oil, Corn (Zea Mays) Germ Oil and Corn (Zea Mays) Oil.
[1205] The above-specified vegetable oils are the most common natural lipid components serving as base substances for the production of cosmetic or pharmaceutical preparations.
[1206] Hydrocarbons (mineral oils) are generally organic compounds composed entirely of hydrogen and carbon. As defined by IUPAC nomenclature or organic chemistry, hydrocarbons are classified as follows:
[1207] 1. Saturated hydrocarbons are the simplest hydrocarbon substances. They are composed entirely of single bonds and are saturated with hydrogen. The formula of acyclic saturated hydrocarbons (i.e. alkanes) is C n H 2n+2 The most general form of saturated hydrocarbons is C n H 2n+2(1-r) , where r is the number of rings. Those saturated hydrocarbons with exactly one ring are cycloalkanes. Saturated hydrocarbons are the basis of petroleum fuels and are found as straight or branched chain substances.
[1208] 2. Unsaturated hydrocarbons have one or more double or triple bonds between carbon atoms. Those unsaturated hydrocarbons with double bonds are called olefins. Those unsaturated hydrocarbons with one double bond have the formula C n H 2n (Assuming a non-cyclic structure). Those unsaturated hydrocarbons containing a triple bond are called alkynes. Those unsaturated hydrocarbons with one triple bond have the formula C n H 2n-2 .
[1209] 3. Aromatic hydrocarbons, also called arenes, are hydrocarbons having at least one aromatic ring.
[1210] Hydrocarbons can be liquids (e.g., hexane and benzene), waxes, or low melting point solids (e.g., paraffin and naphthalene) in particular. The term 'aliphatic' refers to non-aromatic hydrocarbons. Saturated aliphatic hydrocarbons are sometimes referred to as "paraffins". Mineral oils and waxes are mixtures of saturated hydrocarbons consisting mainly of straight, branched, and ring structures having a carbon chain length greater than C14. Mineral oils and waxes are chemicals prepared from naturally occurring crude oil. They are mainly composed of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). Due to the excellent skin tolerance of hydrocarbons and the high protection and cleaning properties of hydrocarbons and the wide viscosity selection, hydrocarbons have been used in skin and lip care cosmetics for decades. Compared with vegetable oils, mineral oils are non-allergenic because mineral oils are highly stable and not prone to oxidation or rancidity.
[1211] Fatty alcohols (or long-chain alcohols) derived from natural fats and oils are typically high molecular weight, straight-chain primary alcohols, but can range from as few as 4 to 6 carbons to as many as 22 to 26 carbons. The exact chain length varies with the source. Some important commercial fatty alcohols are lauryl alcohol, stearyl alcohol, and oleyl alcohol. They are colorless oily liquids (for smaller carbon numbers) or waxy solids, although impure samples may appear yellow. Fatty alcohols generally 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 are found in nature as waxes, which are esters of fatty acids and fatty alcohols. The traditional sources of fatty alcohols are mostly various vegetable oils, and these are still large-scale raw materials. Alcohols are obtained from triglycerides (triglycerides of fatty acids) that form the bulk of the oil. The process involves transesterification of triglycerides to obtain methyl esters, which are then hydrogenated to obtain fatty alcohols. Fatty alcohols are also prepared from petrochemical sources. In the Ziegler process, ethylene is oligomerized using triethylaluminum and subsequently oxidized with air. Alternatively, ethylene can be oligomerized to obtain a mixture of olefins, which is subjected to hydroformylation, a process that gives odd-numbered aldehydes, which are subsequently hydrogenated. Fatty alcohols are primarily used in the production of detergents and surfactants. They are also a component of cosmetic solvents. They can be used as co-emulsifiers, emollients and thickeners in cosmetics.
[1212] In a preferred variant, the fatty alcohol is selected from the group consisting of phenyl propanol, dimethylbenzylbutanol, cetyl alcohol, octyldodecanol, octyldodecanol, tridecanol, isostearyl alcohol, phenylisohexanol, phenyl propanol, trimethylphenylpropanol, isopentanol, isostearyl alcohol and isotridecanol. In a more preferred variant, the fatty alcohol is selected from the group consisting of cetyl alcohol, octyldodecanol, phenyl propanol, isopentanol and mixtures of two or more of the aforementioned fatty alcohols. The fatty alcohol can be used as a single component or in a mixture with one or more further different fatty alcohols as specified above.
[1213] Fatty acid esters are a class of esters produced by the combination of fatty acids and alcohols. When the alcohol component is glycerol, the fatty acid ester produced can be a monoglyceride, a diglyceride, or a triglyceride. Fatty acid esters have a conditioning effect that softens the skin to produce a smooth feel. They are also added to cosmetics to dissolve highly polar active ingredients and UV absorbers. Esters of straight-chain fatty acids and lower alcohols can effectively dissolve the slightly soluble components of oils with a light touch during application. Isostearic acid and other liquid oils with branched fatty acids and unsaturated fatty acids are often used as emollients. Esters of higher fatty acids and higher alcohols with relatively high melting points are added to skin creams to adjust the feel of application.
[1214] Oil bodies and emollients: Sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention advantageously include one or more oil bodies or emollients. Emollients are greasy or oily substances which contribute to smoothing and softening the skin and which may also reduce skin roughness, cracking or irritation. In particular, in sunscreen products, emollients keep crystalline and oil-soluble organic and inorganic UV filters dissolved and prevent them from recrystallizing. In addition, emollients act as wetting agents for inorganic UV filters in order to disperse them uniformly in the formulation. Suitable oil bodies are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, linear C6-C 22 -Fatty acids with straight or branched C6-C 22 - esters of fatty alcohols, or branched C6-C 13 -Carboxylic acid with straight or branched C6-C 22 - esters of 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, myristyl stearate, palmitostearate, stearyl stearate, isostearyl stearate, oleyl stearate, behenyl stearate, erucyl stearate, myristyl isostearate, palmitostearate, stearyl stearate, Isostearic acid ester, isostearic acid isostearic acid ester, oleic acid isostearic acid ester, behenic acid isostearic acid ester, oleic acid isostearic acid ester, myristic acid oleic acid ester, palmitic acid oleic acid ester, stearic acid oleic acid ester, isostearic acid oleic acid ester, oleic acid oleic acid ester, behenic acid oleic acid ester, erucic acid oleic acid ester, myristic acid behenic acid ester, palmitic acid behenic acid ester, stearic acid behenic acid ester, isostearic acid behenic acid ester, oleic acid behenic acid ester, behenic acid behenic acid ester, behenic acid erucic acid ester, myristic acid sinapic acid ester, palmitic acid sinapic acid ester, stearic acid sinapic acid ester, isostearic acid sinapic acid ester, oleic acid sinapic acid ester, behenic acid sinapic acid ester and erucic acid sinapic acid ester. Also suitable are straight chain C6-C 22 - Esters of fatty acids with branched alcohols, especially 2-ethylhexanol, C 18 -C38 -alkyl hydroxycarboxylic acid with a straight or branched C6-C 22 - esters of fatty alcohols, in particular dioctyl malate, esters of linear and / or branched fatty acids with polyols (such as, for example, propylene glycol, dimer or trimer) and / or Guerbet alcohols, based on C6-C 10 Triglycerides of fatty acids, based on C6-C 18 -Liquid mono- / di- / triglyceride mixtures of fatty acids, C6-C 22 - esters of fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, C2-C 12 - esters of dicarboxylic acids with straight-chain 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, straight-chain and branched C6-C 22 - fatty alcohol carbonates such as, for example, dicaprylyl carbonate ( CC), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, having linear and / or branched C6-C 22 -Alcohol benzoate (e.g. TN), a linear or branched, symmetrical or asymmetrical dialkyl ether having 6 to 22 carbon atoms per alkyl group, such as, for example, dioctyl ether ( OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.) and / or aliphatic or cycloparaffinic hydrocarbons such as, for example, squalane, squalene or dialkylcyclohexanes and any mixtures thereof.
[1215] Powder: The composition as defined herein may optionally comprise a powder. The optional powder provides a smoother and softer formulation on the skin. Representative powders include talc, mica, magnesium carbonate, calcium carbonate, magnesium silicate, magnesium aluminum silicate, silicon dioxide, titanium dioxide, zinc oxide, red iron oxide, yellow iron oxide, black iron oxide, polyethylene powder, methacrylate powder, polystyrene powder, silk powder. Preferred solid powdered materials that can be a component of the composition according to the invention are hydrocolloids such as starch, degraded starch, chemically or physically modified starch, dextrin, (powdered) maltodextrin (preferably having a dextrose equivalent value of 5 to 25, preferably 10 to 20), lactose, silicon dioxide, glucose, modified celluloses, gum arabic, ghatti gum, traganth, karaya, carrageenan, pullulan, curdlan, xanthan gum, gellan gum, guar gum powder, locust bean powder, alginates, agar, pectin, inulin and mixtures of two or more of these solids, in particular maltodextrin (preferably having a dextrose equivalent value of 15 to 20), lactose, silicon dioxide and / or glucose.
[1216] Rheology modifier: Sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the present invention advantageously include one or more thickeners and / or rheology modifiers. The rheology modifier is present in an amount to prevent the composition from dripping or pooling significantly after application to the skin or surface. 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, stearyl alcohol polyglycol ethers having an average of about 1 to about 21 ethylene oxide units, cetyl alcohol polyglycol ethers having an average of about 1 to about 5 ethylene oxide units, and mixtures thereof.
[1217] Additional examples of rheology modifiers include thickeners or gelling agents, including materials that can increase the viscosity of the composition. Thickeners include those that can increase the viscosity of the composition without substantially changing the efficacy of the active ingredient in the formulation. Thickeners can also increase the stability of the formulation of the present application. In certain aspects of the present application, thickeners include hydrogenated polyisobutylene or trihydroxystearin or a mixture of the two. Additional non-limiting examples of additional thickeners that can be used in the context of the present application include carboxylic acid polymers, cross-linked polyacrylate polymers, polyacrylamide polymers, polysaccharides and gums. Examples of carboxylic acid polymers include cross-linked compounds containing one or more monomers derived from acrylic acid, substituted acrylic acid, and salts and esters of these acrylic acid and substituted acrylic acid, wherein the cross-linking agent contains two or more carbon-carbon double bonds and is derived from polyols (see CTFA International Cosmetic Ingredient Dictionary, Fourth Edition, 1991, pages 12 and 80). Examples of commercially available carboxylic acid polymers include homopolymers of acrylic acid crosslinked with allyl ethers of sucrose or pentaerythritol, carbomers (e.g., Carbopol from BF Goodrich). TM 900 Series). Non-limiting examples of cross-linked polyacrylate polymers include cationic and nonionic polymers.
[1218] 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 acrylamide and substituted acrylamides with acrylic acid and substituted acrylic acid.
[1219] The non-limiting examples of polysaccharides include cellulose, carboxymethyl hydroxyethyl cellulose, cellulose acetate propionate carboxylate, hydroxyethyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl hydroxyethyl cellulose, microcrystalline cellulose, sodium cellulose sulfate and mixtures thereof. Another example is alkyl-substituted cellulose, in which the hydroxyl groups of the cellulose polymer are hydroxyalkylated (preferably hydroxyethylated or hydroxypropylated) to form hydroxyalkylated cellulose, which is then further modified with C10-C30 straight or branched alkyl groups. Typically, these polymers are ethers of C10-C30 straight or branched alcohols and hydroxyalkyl cellulose. Other useful polysaccharides include scleroglucan, which comprises a straight chain of (1 to 3) connected glucose units, with every three units having (1 to 6) connected glucose.
[1220] Non-limiting examples of gums that can be used with the compositions of the present invention include gum arabic, agar, algin, alginic acid, ammonium alginate, pullulan, calcium alginate, calcium carrageenan, carnitine, carrageenan, dextrin, gelatin, gellan gum, guar gum, guar hydroxypropyltrimonium chloride, hectorite, hyaluronic acid, silica hydrate, hydroxypropyl chitosan, hydroxypropyl guar, karaya gum, seaweed, 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 thickener is Chondrus crispus (carrageenan) extract.
[1221] Film formers: The sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention may advantageously contain one or more film formers or film forming agents. Film formers are hydrophobic materials which impart water resistance and film-forming properties to the sunscreen products, cosmetic or pharmaceutical preparations or home care products. Standard film formers are preferably chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid and its salts and similar compounds. Preferred film formers for improving the water resistance of the composition are selected from the group consisting of: polyamide-8 (such as Oleocraft LP 20PA (MV)), polyamide-3 (such as Oleocraft MP g322432PA (MV)), trimethylpentanediol / adipic acid / glycerin crosspolymer (such as WetFilm), octyldodecyl citrate crosspolymer (such as CosmoSurf CE 100), polyglyceryl-3 methylglucose distearate (such as TegoCare450), C28-52 olefin / undecenoic acid copolymer (such as Performa V6112), hydrolyzed jojoba esters, jojoba esters, aqua (such as Floraester jojoba oil K100), cyclopentasiloxane acrylate / dimethicone copolymer (such as KP545), acrylates / beheneth-25 methacrylate 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 SymEffect Sun), pullulan, xanthan gum, hydrogenated palm oil, sugar cane extract (SymEffect TM UV), microcrystalline cellulose (and) Sphingomonas ferment extract (and) cellulose gum (such as PemuPur TM START polymers), Senegalese gum arabic and xanthan gum (such as SOLAGUM TM AX), microcrystalline cellulose (and) cellulose gum (such as Natpure Cellgum Plus), sodium stearoyl glutamate (such as HS-11P), hydrogenated polycyclopentadiene (and) caprylic / capric triglyceride (such as 5400CCT), Glyceryl Hydrogenated Rosinate (and) Caprylic / Capric Triglyceride (and) Tocopherol (such as NATURAL 2063-CCT), galactoarabinan (such as A 200), C26-28 alkyl dimethicone (and) (such as Wacker CDM3526VP), Caprylyl Methicone (such as Silsoft034), Stearyl Dimethicone (and) Octadecene (such as Dowsil 2503 Cosmetic Wax), VP / Hexadecene (such as Antaron TM V 216), triacontanol PVP (such as Antaron TM WP-660), caprylylglycerol / sebacic acid copolymer (such as LexFilm TM Sun Natural MB), poly C10-30 alkyl acrylate (such as Tego SP 13 Sun Up), microcrystalline cellulose (such as Sunspheres TM BIO SPF Booster) and any mixture thereof. The aforementioned film formers are used in sunscreen, cosmetic or pharmaceutical preparations or home care products as a single component or preferably in a mixture with two or more of the film formers specified above. The film former is used in an effective amount to allow the final preparation to remain on the skin or surface after exposure to circulating water for at least 40 minutes, preferably 80 minutes. The film former is present in the sunscreen product, cosmetic or pharmaceutical preparation or home care 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 preparation.
[1222] Water resistance improving agent: The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the present invention may advantageously contain one or more agents for improving water resistance. The agent for improving water resistance is a hydrophobic material that imparts film-forming and water-resistant characteristics to the emulsion. Typical suitable water resistance improving agents include copolymers derived from the polymerization of octadecene-1 and maleic anhydride. Preferably, the 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 is used in an amount 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. Based on the total weight of the final formulation, one or more water resistance improving agents may optionally be included in the final formulation in an amount of 0.01% to 10.0% by weight, preferably 0.05% to 8.0% by weight, and more preferably 0.1% to 5.0% by weight.
[1223] Silicones: In order to impart a silky, spreadable and luxurious texture and to make the skin look and feel smoother, and additionally to improve processability (anti-foaming), the sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention preferably comprise one or more silicones or silicone derivatives. The total amount of silicone compounds in the composition according to the invention may vary, but is generally from 0.1 to 35.0% by weight, based on the total weight of the composition.
[1224] Dry feel modifiers: The sunscreen product or cosmetic or pharmaceutical formulation according to the present invention is preferably combined with a dry feel modifier. A dry feel modifier is an agent that, when incorporated into an emulsion, imparts a "dry feel" to the skin when the emulsion dries. Dry feel modifiers may also reduce migration of sunscreens onto the skin. Dry feel modifiers may include starch, talc, kaolin, chalk, zinc oxide, hydroxyapatite (such as Tinomax CC), 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 available from Degussa Inc. of New York, NY USA or mixtures thereof; polydimethylsiloxane, a mixture of methylated linear siloxane polymer mixtures, available as DC200 fluid, trade name Dow Corning, Midland, Mich. USA. One or more dry touch modifiers may optionally be included in the sunscreen in an amount of 0.01% to 20% by weight, more preferably 0.1% to 10.0% by weight.
[1225] Emollients: The sunscreen products or cosmetic or pharmaceutical preparations according to the invention may also advantageously contain one or more emollients, wherein any emollient suitable or conventional in cosmetic or pharmaceutical applications may be used, such as alpha-bisabolol, azulene, guaiac, 18-beta-glycyrrhetinic acid, allantoin, aloe juice or gel, Hamamelisvirginiana (witch hazel) extract, extracts of Echinacea species, Centella asiatica, chamomile, Arnica montana, liquorice species, algae, seaweed and Calendula officinalis, and plant oils such as sweet almond oil, baobab oil, olive oil and panthenol, laureth-9, trideceth-9 and 4-tert-butyl cyclohexanol.
[1226] Physiological cooling agents: The sunscreen products or cosmetic or pharmaceutical preparations according to the invention can be combined with one or more physiological cooling agents with particular advantage. The use of cooling agents can relieve itching. Preferred individual cooling agents for use within the scope of the present invention are listed below. A 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, and these cooling agents are preferably selected from the following list: menthol and menthol derivatives (e.g. L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol), menthyl ethers (e.g. (l-menthoxy)-1,2-propanediol, (l-menthoxy)-2-methyl-1,2-propanediol, l-menthyl-methyl ether), menthone glycerol acetal, menthone glycerol ketal or mixtures of the two, menthyl esters (e.g. menthyl formate, menthyl acetate, menthyl isobutyrate, menthyl hydroxyisobutyrate, menthyl lactone, menthyl methyl ether ...methyl ether, menthone glycerol acetal, menthone glycerol ketal or mixtures of the two, menthyl esters (e.g. menthyl formate, menthyl acetate, menthyl isobutyrate, menthyl hydroxyisobutyrate, menthyl lactone, menthyl methyl ether, menthyl methyl ether, menthyl methyl ether, menthone glycerol acetal, menthone glycerol ketal or mixtures of the two, menthyl esters (e.g. menthyl formate, menthyl acetate, menthyl isobutyrate, menthyl hydroxyisobutyrate Menthyl carbonate (e.g. propylene glycol carbonate, ethylene glycol carbonate, menthyl glycerol carbonate or mixtures thereof), half esters of menthol with dicarboxylic acids or derivatives thereof (e.g. monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthyl succinate-N,N-(dimethyl)amide, O-menthyl succinate amide), menthanecarboxylic acid amide (in this case preferably menthanecarboxylic acid- N -acetamide [WS3] or N αWS5], menthanecarboxylic acid-N-(4-cyanophenyl)amide or menthanecarboxylic acid-N-(-4-cyanomethylphenyl)amide, menthanecarboxylic acid-N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g. L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butyric acid derivatives (e.g. 2,3-dimethyl-2-(2-propyl)-butyric acid-N-methylamide [WS23]), isopulegol or its esters (1-(-)-isopulegol, 1-(-)-isopulegol acetate), menthane derivatives (e.g. p-menthane-3,8-diol), cubebol or synthetic or natural mixtures containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (e.g. 3-methyl-2(1-pyrrolidinyl)-2-cyclopenten-1-one) or tetrahydropyrimidin-2-one (e.g. WO 2004 / 026840), further carboxamides (e.g. N-(2-(pyridin-2-yl)ethyl)-3-p-menthanecarboxamide or related compounds), (1R,2S,5R)-N-(4-methoxyphenyl)-5-methyl-2-(1-isopropyl)cyclohexanecarboxamide [WS12], oxalates and [(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl]2-(ethylamino)-2-oxo-acetate (X Cool). Preferred coolants due to their particular synergistic effects are l-menthol, d-menthol, racemic menthol, menthone glycerol acetal (trade name: MGA), menthyl lactate (preferably l-menthyl lactate, especially l-menthyl lactate (trade name: ML)), substituted menthyl-3-carboxamides (such as menthyl-3-carboxylic acid N-ethylamide), 2-isopropyl-N-2,3-trimethylbutyramide, substituted cyclohexanecarboxamides, 3-menthoxypropane-1,2-diol, 2-hydroxyethyl menthyl carbonate, 2-hydroxypropyl menthyl carbonate and isopulegol. Particularly preferred coolants are l-menthol, racemic menthol, menthone glycerol acetal (trade name: MGA), menthyl lactate (preferably l-menthyl lactate, especially l-menthyl lactate (trade name: 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: MGA) and menthyl lactate (preferably l-menthyl lactate, especially l-menthyl lactate (trade name: ML)).
[1227] Alkanediols: In a further preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention comprises one or more linear alkanediols having a carbon chain of 5 to 12 carbon atoms. Preferably, the one or more linear alkanediols are selected from the group consisting of 1,2-alkanediol, 2,3-alkanediol, 3,4-alkanediol and 1,3-alkanediol, more preferably 2,3-alkanediol and 1,3-alkanediol. Most preferably, the linear alkanediol is selected from the group consisting of 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 2,3-octanediol, 2,3-nonanediol, 2,3-decanediol, 2,3-undecanediol and 2,3-dodecanediol.
[1228] Surprisingly, it has been found that the photostability in general, and in particular the photostability of UV filters, is improved by adding the abovementioned alkanediols.
[1229] Initial observations by the inventors surprisingly indicated that compositions according to the invention comprising linear alkanediols having a carbon chain of 5 to 12 carbon atoms, preferably alkanediols as defined herein, show particularly advantageous emulsifying properties. In particular, it was surprisingly found that one or more of said linear alkanediols (if not the emulsion itself) support the formation of water or oil droplets having a particularly small average size in the emulsion, or (if the emulsion itself) contain water or oil droplets having a particularly small average size.
[1230] In addition, it was found that the presence of alkanediols, in particular 1,2-alkanediol or 2,3-alkanediol, improves the solubility of oil components, such as one or more oil bodies or waxes in the sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention. Preferably, the oil bodies or waxes are selected from the group consisting of natural fats and oils, fatty alcohols and alcohols, alcohols, glycerides and derivatives thereof, esters, ethers, silicones and silanes, waxes and cycloalkanes, preferably from the group consisting of squalene, dialkylcyclohexanes, tetradecane, isohexadecane, dodecane, docosane, paraffins and mineral oils, and are further described below.
[1231] The combination of one or more of said alkanediols with 4-hydroxyacetophenone, typically in an amount of 0.1 to 2% by weight, more preferably 0.1 to 1% by weight, even improves the solubility of the oil component in a synergistic manner.
[1232] Preferably, the composition comprises from 0.01% to 10% by weight, more preferably from 0.1% to 5% by weight, still more preferably from 0.3% to 3% by weight, most preferably from 0.5% to 1% by weight of said linear alkanediol as defined herein and having a carbon chain of 5 to 12 carbon atoms, based on the total weight of the composition.
[1233] Antioxidants: Sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention advantageously contain one or more antioxidants. Suitable antioxidants include amino acids (preferably glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (preferably urocanic acid) and their derivatives, peptides, preferably D,L-carnosine, D-carnosine, L-carnosine and their derivatives (preferably anserine), carnitine, creatine, matrikine peptides (preferably lysyl-threonyl-threonyl-lysyl-serine) and palmitoylated pentapeptides, carotenoids, carotenes (preferably α-carotene, β-carotene, lycopene) and their derivatives, lipoic acid and its derivatives (preferably dihydrolipoic acid), thioglucosinolates, propylthiouracil and other thiols (preferably thioredoxin, glutathione, cysteine, cystine, cystamine and its glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauric acid) in very small tolerated doses (e.g. pmol to μmol / kg). thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (preferably esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (preferably buthionine sulfate imine, homocysteine sulfate imine, buthionine sulfone, pentathionine sulfate imine, hexyl thioether sulfate imine, heptathionine sulfate imine), and (metal) chelating agents (preferably α-hydroxy fatty acids acid, palmitic acid, phytic acid, lactoferrin, α-hydroxy acids (preferably citric acid, lactic acid, malic acid), humic acid, bile acid, bile extract, tannin, bilirubin, biliverdin, EDTA, EGTA and its derivatives), unsaturated fatty acids and their derivatives (preferably γ-linolenic acid, linolenic acid, oleic acid), folic acid and its derivatives, ubiquinone and its derivatives, panthenol and its derivatives, vitamin C and its derivatives (preferably ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate, ascorbyl glucosylceramide, thiazolinone and its derivatives), glycosides), tocopherol and derivatives (preferably vitamin E acetate), vitamin A and derivatives (preferably vitamin A palmitate) and coniferyl benzoate of benzoin resin, rutinic acid and its derivatives, flavonoids and their glycosylated precursors, in particular quercetin and its derivatives, preferably α-glucosylrutin, rosmarinic acid, carnosic acid, resveratrol, caffeic acid and its derivatives, sinapinic acid and its derivatives, ferulic acid and its derivatives, curcumin, chlorogenic acid and its derivatives, retinoids,Preferably retinyl palmitate, retinyl palmitate, retinol or retinoic acid, ursolic acid, levulinic acid, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguaiaretic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (preferably ZnO, ZnSO4), selenium and its derivatives (preferably selenomethionine), superoxide dismutase, stilbene and its derivatives (preferably stilbene oxide, trans-stilbene oxide) and suitable according to the present invention. Derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these cited active ingredients or plant extracts or fractions with antioxidant effect, preferably green tea, rooibos, honeybush, grape, rosemary, sage, melissa, thyme, lavender, olive, oat, cocoa, ginkgo, ginseng, liquorice, honeysuckle, sophora japonica, kudzu root, pine, citrus, emblica or St. John's wort, grape seed, malt extract, emblica, coenzyme, preferably coenzyme Q10, plastoquinone and menaquinone. Preferably the antioxidant is selected from the group consisting of vitamin A and derivatives, vitamin C and derivatives, tocopherol and derivatives, preferably tocopheryl acetate and ubiquinone. ,
[1234] Emulsifiers: Furthermore, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention may advantageously contain one or more emulsifiers. Emulsifiers include amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsifier is selected in a suitable manner depending on the emulsion to be obtained. Preferred examples include:
[1235] - Add 2 mol to 30 mol of ethylene oxide and / or 0 mol to 5 mol of propylene oxide to the linear C 8-22 Fatty alcohol, C 12-22 Products of fatty acids and alkylphenols containing 8 to 15 carbon atoms in the alkyl group;
[1236] -1 mol to 30 mol of ethylene oxide addition product on glycerol C 12 / 18 Fatty acid monoesters and diesters;
[1237] - mono- and di-glycerides, mono- and di-sorbitan esters and ethylene oxide addition products thereof of saturated and unsaturated fatty acids containing from 6 to 22 carbon atoms;
[1238] - addition products of 15 to 60 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil;
[1239] - polyol esters, and in particular polyglycerol esters, such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimethyl isostearate. Mixtures of compounds from several of these classes are also suitable;
[1240] - products of 2 to 15 mol of ethylene oxide added to castor oil and / or hydrogenated castor oil;
[1241] - Based on straight chain, branched, unsaturated or saturated C 6 / 22 Fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
[1242] - mono-, di- and tri-alkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
[1243] -Wool wax alcohol;
[1244] - polysiloxane / polyalkyl polyether copolymers and corresponding derivatives;
[1245] - pentaerythritol, fatty acids, citric acid and fatty alcohols and / or C 6-22 Mixed esters of fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol,
[1246] -polyalkylene glycol and
[1247] -Glyceryl carbonate.
[1248] The addition products of ethylene oxide and / or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol monoesters and diesters and sorbitan monoesters and diesters of fatty acids or onto castor oil are known commercially available products. They are homologous mixtures whose average degree of alkoxylation corresponds to the ratio between the amount of ethylene oxide and / or propylene oxide and the amount of substrate subjected to the addition reaction. The C of the addition products of ethylene oxide onto glycerol is 12 / 18 Fatty acid monoesters and diesters are known as lipid layer enhancers for cosmetic preparations. Preferred emulsifiers are described in more detail below:
[1249] 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, linolenic 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 amounts of triglycerides from the production process. Also suitable are addition products of 1 to 30 mol and preferably 5 to 10 mol of ethylene oxide onto the partial glycerides mentioned.
[1250] 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 hemierucate, sorbitan glycerol dierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan hemierucate, sorbitan glycerol dierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monooleate, sorbitan Sugar alcohol 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 trimalate and technical mixtures thereof. Also suitable are addition products of 1 to 30 mol and preferably 5 to 10 mol of ethylene oxide onto the sorbitan esters mentioned.
[1251] Polyglycerol esters: A typical example of a suitable polyglycerol ester is polyglyceryl-2 dipolyhydroxystearate ( PGPH), polyglyceryl-3 diisostearate ( TGI), polyglyceryl-4 isostearate ( GI 34), polyglyceryl-3 oleate, diisostearoyl polyglyceryl-3 diisostearate ( PDI), polyglyceryl-3 methyl glucose distearate (Tego 450), Polyglyceryl-3 Beeswax (Cera )、Polyglyceryl-4 Caprate (Polyglyceryl Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether ( NL), polyglyceryl-3 distearate ( GS 32) and polyglyceryl polyricinoleate ( WOL 1403), polyglyceryl dimethyl ether isostearate and mixtures thereof. Other examples of suitable polyol esters are monoesters, diesters and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like, optionally reacted with 1 mol to 30 mol of ethylene oxide.
[1252] Anionic emulsifiers: Typical anionic emulsifiers are aliphatic C12 to C22 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, potassium cetyl phosphate, and hydrogenated palm glycerides (Emulsiphos / Emulsiphos F).
[1253] 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 N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinates, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinates, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines and cocoacylaminoethylhydroxyethylcarboxymethylglycinates containing 8 to 18 carbon atoms in the alkyl or acyl group. The fatty acid amide derivatives known under the CTFA name cocoacylaminopropyl betaine are particularly preferred. Amphoteric surfactants are also suitable emulsifiers. Amphoteric surfactants are compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. 8 / 18 A surface-active compound which contains at least one free amino group and at least one -COOH- or -SO3H- group in addition to the alkyl group or acyl group and is capable of forming an inner salt. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid containing about 8 to 18 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-coconut alkylaminopropionate, cocoacylaminoethylaminopropionate and C12 / 18 acylsarcosine.
[1254] Anti-aging active substances: The compositions according to the invention are preferably combined with one or more anti-aging active substances. In the context of the present invention, anti-aging agents or biogenic agents are, for example, antioxidants, matrix metalloproteinase inhibitors (MMPIs), skin moisturizers, glycosaminoglycan stimulators, anti-inflammatory agents, TRPV1 antagonists and plant extracts.
[1255] Matrix metalloproteinase inhibitors (MMPI): The composition according to the invention is preferably combined with one or more matrix metalloproteinase inhibitors selected from the group consisting of ursolic acid, retinyl palmitate, propyl gallate, precocenes, 6-hydroxy-7-methoxy-2,2-dimethyl-1(2H)-benzopyran, 3,4-dihydroxy-6-hydroxy-7-methoxy-2,2-dimethyl-1(2H)-benzopyran, benzamidine hydrochloride, cysteine protease inhibitor N-ethylmaleimide and ε-amino-n-hexanoic acid of the serine protease inhibitors: phenylmethylsulfonyl fluoride, collhibin (Pentapharm; INCI: hydrolyzed rice protein), oenotherol (Solliance; INCI: propylene glycol, water, evening primrose root extract, ellagic acid and ellagitannins, for example from pomegranate), phosphoramidone hinokitiol), EDTA, MGDA (trisodium dicarboxymethylalanine), galardin, EquiStat (Collaborative Group; malus ursolic acid, soy isoflavones and soy protein), sage extract, MDI (Atrium; INCI: glycosaminoglycans), fermiskin (Silab / Mawi; INCI: water and shiitake mushroom extract), actimp 1.9.3 (Expanscience / Rahn; INCI: hydrolyzed lupin protein), lipobelle soyaglycone (Mibelle; INCI: alcohol, polysorbate 80, lecithin and soy isoflavones), extracts from green and black tea and further plant extracts, proteins or glycoproteins from soy, hydrolyzed proteins from rice, pea or lupin, plant extracts that inhibit MMPs, preferably extracts from shiitake mushrooms, extracts from the leaves of the Rosaceae, subfamily Rosaceae, very particularly extracts from blackberry leaves, such as SymMatrix (Symrise, INCI: maltodextrin, Rubus fruticosus (blackberry) leaf extract). Preferred active substances are selected from the group consisting of retinyl palmitate, ursolic acid, extracts from the leaves of the Rosaceae, subfamily Rosaceae, genistein and daidzein.
[1256] Skin moisturizing and / or humectant substances: The sunscreen product or cosmetic or pharmaceutical preparation according to the invention advantageously comprises one or more skin moisturizing and / or humectant substances. Preferred skin moisturizing and / or humectant substances are selected from the group consisting of oils: alkanediols or alkantriols containing 3 to 12 carbon atoms, preferably C3-C 10- Alkanediols and C3-C 10- Alkantriols. More preferred skin moisturizers 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-heptanediol, 1,2-octanediol, and 1,2-decanediol. Additional skin moisturizing and / or humectant substances include sodium lactate, urea, urea derivatives, alcohols, glycerol, glycols 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, α-hydroxy acids (such as citric acid, lactic acid, malic acid) and derivatives thereof, mono-, disaccharides and oligosaccharides such as glucose, galactose, fructose, mannose, fructose and lactose, polysaccharides such as R-glucans, in particular 1,3-1,4-β-glucans from oats, α-hydroxy fatty acids, triterpene acids such as betulinic acid or ursolic acid, and algae extracts.
[1257] Glycosaminoglycan stimulators: Preferred compositions according to the invention comprise one or more substances stimulating the synthesis of glycosaminoglycans selected from the group consisting of: hyaluronic acid and derivatives or salts, Subliskin (Sederma, INCI: Sinorhizobium Meliloti Ferment Filtrate, Cetyl Hydroxyethylcellulose, Lecithin), Hyalufix (BASF, INCI: Water, Butylene Glycol, Alpinia Alpinia Extract, Xanthan Gum, Caprylic / Capric Triglyceride), Stimulhyal (Soliance, INCI: Calcium Ketogluconate), Syn-Glycan (DSM, INCI: Tetradecyl Aminobutyroylvalylaminobutyric UreaTrifluoroacetate, Glycerin, Magnesium Chloride), Kalpariane (Biotech Marine), DC Upregulex (Distinctive Cosmetic Ingredients, INCI: water, butylene glycol, phospholipids, hydrolyzed sericin), glucosamine, N-acetylglucosamine, retinoids (preferably retinol and vitamin A), burdock fruit extract, loquat extract, genkwain, N-methyl-L-serine, (-)-α-bisabolol or synthetic α-bisabolol, such as, for example, Dragosantol and Dragosantol 100 from Symrise, oat glucan, echinacea extract, and soy protein hydrolyzate. Preferred active substances are selected from the group consisting of hyaluronic acid and derivatives or salts, retinol and derivatives, (-)-α-bisabolol or synthetic α-bisabolol, such as, for example, Dragoantol and Dragoantol 100 from Symrise, oat glucan, Echinacea extract, Sinorhizobium meliloti ferment filtrate, calcium ketogluconate, Alpinia galanga leaf extract and tetradecylaminobutyrylvalylaminobutyric acid urea trifluoroacetate.
[1258] Anti-inflammatory agents: The compositions according to the invention are preferably combined with anti-inflammatory and / or redness and / or itching improving ingredients, in particular steroidal substances of the corticosteroid type selected from the group consisting of: hydrocortisone, dexamethasone, dexamethasone phosphate, methylprednisolone or cortisone, advantageously used as anti-inflammatory active ingredients or active ingredients for reducing redness and itching, the list of which can be expanded by adding other steroidal anti-inflammatory agents. Non-steroidal anti-inflammatory agents can also be used. More specifically:
[1259] (i) steroidal anti-inflammatory substances of the corticosteroid type, in particular hydrocortisone, hydrocortisone derivatives such as hydrocortisone 17-butyrate, dexamethasone, dexamethasone phosphate, methylprednisolone or cortisone,
[1260] (ii) nonsteroidal anti-inflammatory substances, in particular oxicams such as piroxicam or tenoxicam; salicylates such as aspirin, disalicylic acid, soluble aspirin or fendosal, acetic acid derivatives such as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or clindanac, fenamates such as mefenamic acid, meclofenamic acid, flufenamic acid or niflumic acid, propionic acid derivatives such as ibuprofen, naproxen or benoxaprofen, pyrazoles such as phenylbutazone, oxyphenylbutazone, febrazone or azapropazone,
[1261] (iii) natural or naturally occurring anti-inflammatory substances or substances which relieve redness and / or itching, in particular extracts or fractions thereof from chamomile, aloe vera, Commiphora species, Rubia species, willow, fireweed, oats, calendula, arnica, St John's wort, honeysuckle, rosemary, pink passionflower (Passiflora incarnata), witch hazel, ginger or Echinacea, or their individual active compounds,
[1262] (iv) histamine receptor antagonists, serine protease inhibitors (e.g., soybean extracts), TRPV1 antagonists (e.g., 4-tert-butylcyclohexanol), NK1 antagonists (e.g., aprepitant, hydroxyphenylpropionamide benzoic acid), cannabinoid receptor agonists (e.g., palmitoylethanolamine), and TRPV3 antagonists.
[1263] Examples that may be cited here are oxicams, such as piroxicam or tenoxicam; salicylates, such as aspirin, disalicylic acid, soluble aspirin or fendosal; acetic acid derivatives, such as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or clorinac; fenamates, such as mefenamic acid, meclofenamic acid, flufenamic acid or niflumic acid; propionic acid derivatives, such as ibuprofen, naproxen, benoxaprofen or pyrazoles, such as phenylbutazone, oxyphenylbutazone, feprazone or azapropazone. Anthranilic acid derivatives are preferred anti-itch ingredients in the composition according to the invention.
[1264] Also useful are natural or naturally occurring anti-inflammatory substance mixtures or substance mixtures which relieve redness and / or itching, in particular extracts or fractions from chamomile, aloe, Commiphora species, Rubia species, willow, willow herb, oats, calendula, arnica, St. John's wort, honeysuckle, rosemary, pink passionflower, witch hazel, ginger or echinacea; preferably selected from the group consisting of extracts or fractions from chamomile, aloe, oats, calendula, arnica, honeysuckle, rosemary, witch hazel, ginger or echinacea, and / or pure substances, preferably alpha-bisabolol, apigenin, apigenin-7-glucoside, gingerol, shogaol, gingerdiol, dehydrogingerdione, hydrogingerdione), paradol, a natural or naturally occurring avenanthramide, preferably tranilast, avenanthramide A, avenanthramide B, avenanthramide C, non-natural or non-naturally occurring avenanthramide, preferably dihydroavenanthramide D, dihydroavenanthramide E, avenanthramide D, avenanthramide E, avenanthramide F, boswellic acid, phytosterols, glycyrrhizin, glabridin and licoricechalcone A; preferably selected from the group consisting of α-bisabolol, natural avenanthramide, non-natural avenanthramide, preferably dihydroavenanthramide D (such as WO 2004 047833A1), boswellic acid, phytosterols, glycyrrhizin and glycyrrhizic chalcone A, and / or allantoin, panthenol, lanolin, (pseudo)ceramides [preferably ceramide 2, hydroxypropyl bispalmitamide MEA, hexadecyloxypropylglyceryl methoxypropyl myristamide, N-(1-hexadecyl)-4-hydroxy-L-proline (1-hexadecyl) ester, hydroxyethyl palmitoyloxyhydroxypropyl palmitamide], glycosphingolipids, phytosterols, chitosan, mannose, lactose and β-glucans, in particular 1,3->1,4-β-glucans from oats.
[1265] TRPV1 antagonists: Preferred compositions according to the invention comprise one or more TRPV1 antagonists. Suitable compounds which reduce skin nerve hypersensitivity due to their action as TRPV1 antagonists include, for example, trans-4-tert-butylcyclohexanol, or indirect modulators of TRPV1 via activation of μ-receptors, such as acetyl tetrapeptide-15, are preferred.
[1266] Antimicrobial agents: Sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the present invention can advantageously be combined with an antimicrobial agent, which acts primarily on microorganisms, in particular bacteria, yeasts and / or fungi, and includes one or more antimicrobial agents such as caprylhydroxamic acid, O-cymene-5-ol, isopropylparaben, capryloylglycine, phenoxyethanol, tropolone, PCA cocoyl arginine ethyl ester salt, 2-methyl 5-cyclohexylphenol, 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, caprylic glyceryl, sodium phytate or phytic acid, sodium levulinate or levulinic acid and its esters and / or ketals, chlorhexidine, glyceryl laurate, anisic acid and its salts, chlorhexidine digluconate, TE A-Salicylate, Phenethyl Alcohol, Glyceryl Caprate, Sorbitan Caprylate, Tetrasodium Glutamate Diacetate, Trisodium Ethylenediamine Disuccinate, Hydroxyethoxyphenyl Butanone, Hydroxyethoxyphenyl Butanol, Itaconic Acid, Hydroxymethoxyoctopirox, Propylene Glycol Caprylate, Climbazole, Undecylenoyl Glycine, Thymol, 4-Hydroxyacetophenone, Lactic Acid, Sodium Lactate, Trisodium Dicarboxymethyl Alanine, Raspberry Ketone, Xylitol Caprylate, 3-Hydroxypropyl Benzoate, 3-Hydroxypropyl Anisate, 3-Hydroxypropyl 1,2-hydroxybenzoic acid esters, 1,3-propylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 2,3-octanediol, 2,3-nonanediol, 2,3-decanediol, 2,3-undecanediol, 2,3-dodecanediol, and any mixture thereof.
[1267] Preferably, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention comprises one or more antimicrobial agents selected from the group consisting of 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 2,3-octanediol, 2,3-nonanediol, 2,3-decanediol, 2,3-undecanediol, 2,3-dodecanediol, 2-benzylheptanol, 2-hydroxyacetophenone, 2-methyl 5-cyclohexylphenol, 3-hydroxypropyl 2-hydroxybenzoate, 4-hydroxyacetophenone and any mixtures thereof. More preferably, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention comprises one or more antimicrobial agents selected from the group consisting of 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 1,2-tridecanediol, 4-hydroxyacetophenone and any mixture thereof.
[1268] In order to further enhance the antimicrobial efficacy, the sunscreen product, cosmetic or pharmaceutical preparation or household care product as defined herein is advantageously combined with at least one additional antimicrobial agent different from the antimicrobial agent specified above. The combination with additional antimicrobial agents provides a reliable protection against microbial degradation and deterioration of the preparation, particularly during storage. In addition, other different antimicrobial agents provide a solid protection against other microorganisms as described above, such as Corynebacterium, Anaerococcus, Finegoldia, Moraxella, Porphyromonas, Fusobacterium, Malassezia, Peptoniphilus, Streptococcus, Lactobacillus, Gardnerella, Fannyhessea, Epidermophyton, Trichophyton, Cutibacterium. Therefore, the combination with other different antimicrobial agents allows the antimicrobial protection against different groups of microorganisms, and therefore allows a wider spectrum of microorganisms. In the context of the present invention, the further different antimicrobial agents are preferably selected from the group consisting of: 2-benzylheptanol, alkyl (C 12-22) trimethylammonium bromides and chlorides, ascorbic acid and its salts, benzalkonium bromide, benzalkonium chloride, benzalkonium saccharinate, isooctylphenoxyethoxyethylbenzyldimethylammonium chloride, benzoic acid, camphor, cetylpyridinium chloride, chlorhexidine diacetate, chlorhexidine dihydrochloride, chlorocresol, chloroxylenol, cyclohexylglycerol, dimethylphenylbutanol, dimethylphenylpropanol, ethanol, lauroyl arginine ethyl ester HCl, lauroyl arginine ethyl ester laurate, eucalyptol, gluconic acid and its salts, glycerol, hexamidine, hexamidine diisothionate, hexylglycerol, iodopropargyl butylcarbamate, jasmone, lauryl alcohol, acetyl Sodium propionate or levulinic acid and its esters and / or ketals, 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, xylitol sesquioctanoate, zinc citrate, octyl pyrithione, zinc ricinoleate, and any mixture thereof.
[1269] The aforementioned antimicrobial agents are used in sunscreen products, cosmetic or pharmaceutical preparations or household care products as individual components or preferably in mixtures with two or more of said antimicrobial agents as specified above.
[1270] The antimicrobial agent is present in the sunscreen product, cosmetic or pharmaceutical formulation or home care product in an amount of 0.01 to 25.0% by weight, preferably 0.02 to 15.0% by weight, more preferably 0.05 to 6.0% by weight, based on the total weight of the final formulation.
[1271] Advantageously, at least one antimicrobial agent is present in the sunscreen product, cosmetic or pharmaceutical preparation or home care product in an amount of 0.1% to 5% by weight, based on the total weight of the final preparation, and / or 4-hydroxyacetophenone is present in the sunscreen product, cosmetic or pharmaceutical preparation or home care product in an amount of 0.01% to 2% by weight, based on the total weight of the final preparation.
[1272] Preservatives: For preservation purposes, the sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention preferably contain one or more preservatives which are suitable or customary in sunscreen products, cosmetic or pharmaceutical preparations or home care products. Suitable and advantageous preservatives are, for example, benzoic acid, sodium benzoate, ammonium benzoate, butyl benzoate, calcium benzoate, ethyl benzoate, isobutyl benzoate, isopropyl benzoate, magnesium benzoate, tetrabutyl 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, monoethanolamine salicylate, mesalamine, salicylate, salicylic acid, salicylate ... Sodium, potassium salicylate, triethanolamine salicylate (teasalicylate), sorbate, calcium sorbate, sodium sorbate, potassium sorbate, o-phenylphenol, sodium sulfite, ammonium bisulfite, ammonium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, chlorobutanol, 4-hydroxybenzoic acid, methylparaben, potassium ethylparaben, potassium paraben, sodium methylparaben, ethylparaben Sodium parahydroxybenzoate, ethyl parahydroxybenzoate, sodium parahydroxybenzoate, potassium methyl parahydroxybenzoate, calcium parahydroxybenzoate, butyl parahydroxybenzoate, propyl parahydroxybenzoate, sodium propyl parahydroxybenzoate, sodium butyl parahydroxybenzoate, potassium butyl parahydroxybenzoate, potassium propyl parahydroxybenzoate, dehydroacetic acid, sodium dehydroacetate, formic acid, sodium formate, dibromohexamidine isethionate, thimerosal, phenylmercuric phenylacetate, phenylmercuric benzoate, undecylenic acid, potassium undecylenate, undecylenic acid Sodium undecylenate, calcium undecylenate, monoethanolamine undecylenate (mea-undecylenate), triethanolamine undecylenate (tea-undecylenate), hexetidine, 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, dichlorobenzyl alcohol, triclocarban, para-chlorometa-cresol, triclosan, chloroxylenol, imidazolidinyl urea, polyaminopropyl;Biguanide, phenoxyethanol, hexamethylenetetramine, climbazole, DMDM hydantoin, benzyl alcohol, 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-pyridone, hydroxymethyloctopiroxolamine, bromochlorobenzene, o-cymene-5-ol, methylchloroisothiazolinone and methylisothiazolinone, chlorhexidine, chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidine dihydrochloride, phenoxyisopropyl alcohol, docosane trimethylammonium chloride (1), cetyltrimethylammonium bromide, cetyltrimethylammonium chloride (2), lauryltrimethylammonium bromide, lauryltrimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride (2), dimethyloxazolidine, diimidazolidinyl urea, hexamidine, hexamidine dihydroxyethyl ether, hexamidine, hexamidine dihydroxyethyl sulfonate, hexamidine paraben, glutaraldehyde, 7-ethylbicyclic oxazolidine, chlorphenesin, sodium hydroxymethylglycinate, silver chloride, isooctylphenoxyethoxyethylbenzyldimethylammonium chloride, benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate, benzyl hemiformal, iodopropargyl butylcarbamate, methylisothiazolinone, citric acid, citric silver, hydroxyethoxyphenyl butyrrolidone (HEPB) and any mixture thereof.
[1273] Drugs: The sunscreen product or cosmetic or pharmaceutical preparation according to the present invention is preferably combined with one or more drugs. In certain such embodiments, the pharmaceutical active agent is selected from the group consisting of: anti-acne agents, agents for treating rosacea, analgesics, anesthetics, anorectics, antihistamines, anti-inflammatory agents (including non-steroidal anti-inflammatory drugs), antibiotics, antifungal agents, antivirals, antimicrobials, anticancer active ingredients, scabicides, pediculicides, antitumor agents, antiperspirants, antipruritics, antipsoriatic agents, antiseborrheic agents, biologically active proteins and peptides, burn treatment agents, cautery agents, depigmenting agents, depilatories, diaper rash treatment agents, enzymes, hair growth stimulants, hair growth retardants (including eflornithine and its salts and analogs), hemostats, keratolytics, canker sore treatment agents (canker sore treatment agents agents), herpes labialis treatment agents, dental and periodontal treatment agents, photosensitizing active substances, skin protectants / barrier agents, steroids (including hormones and corticosteroids), sunburn treatment agents, sunscreens, transdermal active ingredients, nasal active ingredients, vaginal active ingredients, wart treatment agents, wound treatment agents, wound healing agents, etc.
[1274] Particularly useful are natural or naturally occurring anti-inflammatory substance mixtures, in particular extracts or fractions from chamomile, aloe, Commiphora species, Rubia species, willow, willow herb, oats, calendula, arnica, St. John's wort, honeysuckle, rosemary, pink passionflower, witch hazel, ginger or echinacea; preferably selected from the group consisting of extracts or fractions from chamomile, aloe, oats, calendula, arnica, honeysuckle, rosemary, witch hazel, ginger or echinacea, and / or pure substances, preferably α-bisabolol, apigenin, apigenin-7-glucoside, gingerol, shogaol, gingerdiol, dehydrogingerdione, shogaol, natural or naturally occurring avenant alkaloids, preferably tranilast, avenant alkaloid A, avenant alkaloid B, avenant alkaloid C, non-natural or non-naturally occurring avenant alkaloids, preferably dihydroavenant alkaloid D, dihydroavenant alkaloid oat alkaloids, preferably selected from the group consisting of α-bisabolol, natural avenant alkaloids, unnatural avenant alkaloids, preferably dihydroavenant alkaloids D, boswellic acid, phytosterols, glycyrrhizin, glabridin and licorice chalcone A, and / or allantoin, panthenol, lanolin, (pseudo)ceramides, preferably ceramide 2, hydroxypropyl bispalmitamide MEA, hexadecyloxypropyl glyceryl methoxypropyl myristamide, N-(1-hexadecyl)-4-hydroxy-L-proline (1-hexadecyl) ester, hydroxyethyl palmitoyloxyhydroxypropyl palmitamide, glycosphingolipids, phytosterols, chitosan, mannose, lactose and β-glucan, in particular 1,3->1,4-β-glucan from oats.
[1275] In addition to the substances mentioned above, it is also possible to use further ingredients customary in sunscreen products, cosmetic or pharmaceutical preparations or household care products which are suitable or conventional in the compositions according to the invention.
[1276] The sunscreen product or cosmetic or pharmaceutical preparation, in particular dermatological preparation according to the first aspect of the invention is intended for topical application. The term "topical" is understood to mean external application on the skin or mucous membranes of mammals, which is particularly used for protecting, treating, caring for and cleaning the skin, scalp, eyelashes, eyebrows, nails, mucous membranes and hair. The mammal is preferably a human.
[1277] For topical application, the cosmetic or pharmaceutical preparations are rinse-off preparations or leave-on preparations.
[1278] Sunscreen products according to the present invention may be in the form of aqueous solutions, dispersions, hydroalcoholic carriers, sticks, ointments, gels, aerosols (foams, sprays, propellant pumps), and the like.
[1279] The sunscreen product, cosmetic or pharmaceutical preparation, in particular dermatological preparation or home care product according to the first aspect of the present invention can be present in different forms, for example in the form of a dispersion, in the form of anhydrous preparation, or in the form of a water-based solution, a water-based solution / alcohol-based solution, in particular a water-based solution / ethanol-based solution, a water-based solution / glycol-based solution or an alcohol-based solution / glycol-based solution, in particular an ethanol-based solution / glycol-based solution.
[1280] In a preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care 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 home care product is a dispersed two-phase system consisting of colloidal particles (dispersed phase) and a medium (dispersion medium) in which the colloidal particles are suspended. The two phases are immiscible with each other and are only miscible with emulsifiers. Such dispersions, such as emulsions, contain at least one oil component (without UV filters) in an amount preferably ≥1% by weight, more preferably ≥3% by weight.
[1281] Preferably, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the first aspect of the invention takes various forms, such as emulsions, in particular O / W emulsions, W / O emulsions, multiple emulsions, water-dispersible gels, balms, water-in-oil (W / O / WO) or oil-in-water (O / W / O) multiple emulsions, PIT emulsions, Pickering emulsions, microemulsions, liquids, lotions, suspensions, milks, ointments, pastes, gels, cream-based, oil-based or liposome-based preparations, or aerosols such as foams and sprays, including all types of silicone-based emulsions.
[1282] In a most preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention is in the form of an emulsion as defined herein, advantageously 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.
[1283] If the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the 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. In a preferred variant, the cosmetic or pharmaceutical preparation contains an amount of 0.1% to 45.0% by weight of the oil component, based on the total weight of the composition. In a particularly preferred variant, the oil component is advantageously used in the cosmetic or pharmaceutical preparation in an amount of 1.0% to 40% by weight, based on the total weight of the composition.
[1284] In a further variant, the sunscreen product, cosmetic or pharmaceutical formulation, preferably dermatological formulation or home care product according to the first aspect of the invention is an anhydrous formulation, ie an oil formulation.
[1285] If the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention is an anhydrous preparation, i.e. an oil preparation, the oil component is present in the cosmetic or pharmaceutical preparation in an amount of ≥60% by weight, preferably ≥75% by weight, more preferably ≥90% by weight, based on the total weight of the composition.
[1286] Such anhydrous formulations include, for example, oils, skin fats, powders, lipsticks, antiperspirants / deo sticks and decorative cosmetics.
[1287] Furthermore, further anhydrous preparations are likewise ethanol / diol / triol / ethylene glycol based preparations, such as sprays or gels.
[1288] Alternatively, the sunscreen product, cosmetic or pharmaceutical preparation or home care product as disclosed herein is a water-based solution or a water-based solution / alcohol-based solution, preferably a water-based solution / ethanol-based solution, or a water-based solution / glycol-based solution, or an alcohol-based solution / glycol-based solution, preferably an ethanol-based solution / glycol-based solution. Typically, this can be glycerol in a water or alcohol composition. The solution is a homogeneous single-phase system of water / alcohol / glycol and additional components. The water-based solution / alcohol-based solution or the water-based solution / glycol-based solution or the alcohol-based solution / glycol-based solution contains an aliphatic alcohol or diol in an amount of 0.1% to 70.0% by weight, preferably 0.5% to 60.0% by weight, more preferably 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 diol is preferably selected from the group consisting of glycerol, propylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,2-C5 to C10 alkanediol, butylene glycol or dipropylene glycol.
[1289] Preferably, the total water content in the final water-based solution may be ≥ 30% by weight, more preferably ≥ 40% by weight, most preferably ≥ 50% by weight.
[1290] Such water-based solutions / alcohol-based solutions or water-based solutions / glycol-based solutions or alcohol-based solutions / glycol-based solutions include, for example, deo / antiperspirant preparations, aftershaves, cleansing preparations or anti-acne preparations.
[1291] In a preferred variant, the composition of the invention is an impregnation solution in the form of an emulsion spray or an alcohol / oil spray for wet wipes.
[1292] The above-mentioned preparations or compositions are prepared according to conventional and known methods.
[1293] The products and preparations according to the invention are used for cosmetic and / or non-therapeutic uses, for personal care, in particular for skin care, skin protection, sun protection, scalp protection, scalp care, hair care, nail care, in particular for the prevention and treatment of skin disorders, intolerance or sensitive skin, skin irritation, skin redness, rashes, pruritus (itching), skin aging, wrinkle formation, loss of skin volume, loss of skin elasticity, pigment spots, pigment abnormalities, dry skin, flaking, oiliness, skin hypopigmentation and / or skin hyperpigmentation; or preparations for animal care.
[1294] Examples of personal care products are preferably anti-aging preparations, skin care emulsions, body oils, body washes, cleansing washes, facial or body balms, aftershave balms, aftersun balms, deodorant lotions, cationic lotions, body gels, therapeutic creams, skin protection ointments, moisturizing gels, facial and / or body moisturizers, photoprotective preparations (sunscreens), micellar waters, hair sprays, coloring protective hair care products, skin lightening products, anti-dark spot repairs, etc.
[1295] Cosmetic preparations also include make-up, eye care preparations, eye shadows, mascaras, eyeliners, lip care preparations such as lipsticks, lip glosses, nail care preparations such as nail polishes, nail polish removers.
[1296] Alternatively, the preparation according to the invention is a preparation for medical use.
[1297] The pharmaceutical preparations, in particular dermatological preparations, according to the invention are preferably preparations for the prevention and treatment of disorders of the skin, mucous membranes, hair or nails.
[1298] For use, the sunscreen product or cosmetic or pharmaceutical composition, in particular the dermatological composition according to the first aspect of the invention is applied to the skin, hair, scalp and / or nails in a sufficient amount in a conventional manner for sunscreen products or cosmetic and dermatological products.
[1299] Furthermore, the products and formulations according to the invention are home care products. Such home care products typically include laundry detergents (powders, liquids and tablets), fabric conditioners, dishwashing (liquids and tablets), hard floor and surface cleaners, glass cleaners, carpet cleaners, oven cleaners, air fresheners, disinfectants, stain removers, car wash products. These products are typically manufactured in the form of liquids, powders, sprays, granules, etc.
[1300] Surprisingly it has been found that mycosporin-like amino acid compounds or salts thereof have the common property of being effective in stabilizing photolabile UV filters, i.e. acting as stabilizers when combined with photolabile UV filters, making the photolabile UV filters more effective for a longer period of time and providing constant protection during prolonged exposure to the sun. The composition according to the invention exhibits a higher UV absorbance than a composition comprising at least a photolabile UV filter material without the addition of at least one mycosporin-like amino acid compound.
[1301] The mycosporin-like amino acid compound is doped into a sunscreen product or a cosmetic or pharmaceutical preparation and has a stabilizing effect on photolabile UV filters, and the SPF of the sunscreen product, cosmetic or pharmaceutical preparation or home care product remains almost constant even during exposure to the sun, compared to a product or preparation without the addition of the specified mycosporin-like amino acid compound. The higher the SPF, the higher the protection of the sunscreen.
[1302] Furthermore, the sunscreen product, cosmetic or pharmaceutical preparation or home care product has an increased pre-irradiation SPF compared to a composition comprising at least one photostable UV filter without any mycosporin-like amino acid compound.
[1303] Furthermore, by stabilizing the UV filters, their degradation upon exposure to UV radiation can be reduced and the formation of phototoxic or photoallergic degradation products which have the risk of adverse health effects upon direct contact with the skin can be reduced.
[1304] The above combination of a photolabile UV filter with any of the mycosporin-like amino acid compounds defined herein results in a significantly stable sunscreen product or cosmetic or pharmaceutical product, wherein the degradation of the photolabile UV filter is greatly reduced, as demonstrated in the following examples. Thus, the addition of mycosporin-like amino acids results in a highly photostable sunscreen product.
[1305] Furthermore, due to less degradation of the UV filters, the ready-to-use products according to the invention have a higher SPF and thus improved UV protection compared to those ready-to-use products comprising photostable UV filters without any mycosporin-like amino acid stabilizing compound.
[1306] On the contrary, due to the lower degradation of UV filters, in order to obtain the same SPF, smaller amounts of UV filters have to be used in ready-to-use products compared to those comprising photostable UV filters without any mycosporin-like amino acid stabilizing compound.
[1307] Advantageously, the addition of a mycosporin-like amino acid compound to a sunscreen product or cosmetic or pharmaceutical preparation comprising said photolabile UV filter also results in an increase in absorbance, as demonstrated in the following examples. The higher the amplitude of the absorption curve, the greater the absorbance and the more protection provided at that wavelength. This effect results in a higher SPF of the instant product and therefore in improved UV protection compared to those instant products comprising photolabile UV filters without any mycosporin-like amino acid stabilizing compound.
[1308] Furthermore, the addition of mycosporin-like amino acid compounds to sunscreen products or cosmetic or pharmaceutical preparations comprising said photolabile UV filters modifies, ie broadens, the absorption spectrum over the spectrum of ultraviolet radiation. In other words: the wider the width of the absorption curve, the broader the spectrum of sun protection provided.
[1309] The absorption loss of the mixture of MAA-1 and ethylhexyl methoxycinnamate is particularly low: the loss of ethylhexyl methoxycinnamate is reduced from 37.88% to 18.82% in combination with MAA-1, i.e., a reduction of approximately 50% (see Figure 8). In particular, the pre-irradiation SPF of the mixture is increased: mixture: 1.6 relative to the absorbance: MAA-1 alone: 0.9 and ethylhexyl methoxycinnamate alone: 0.8.
[1310] The same effect was observed for the mixture of MAA-1 and butyl methoxydibenzoylmethane, where the combination with MAA-1 reduced the loss of butyl methoxydibenzoylmethane from 7.05% to 5.27%, a reduction of approximately 25% (see Figure 9). The pre-irradiation SPF of the mixture was also increased: mixture: 1.4 relative to the absorbance: MAA-1 alone: 0.9 and butyl methoxydibenzoylmethane alone: 0.8.
[1311] Combining with MAA-1 can reduce the loss of isoamyl p-methoxycinnamate from 30.50% to 18.60%, a reduction of about 39% (see Figure 10). In addition, the pre-irradiation SPF of the mixture increased: mixture: 1.7 relative to the absorbance: MAA-1 alone: 0.9 and isoamyl p-methoxycinnamate alone: 1.0.
[1312] Doping with MAA-13 can reduce the loss of isoamyl p-methoxycinnamate from 30.50% to 20.45%, a reduction of about 32%.
[1313] In addition, the critical wavelength shifts from 324 nm for isoamyl p-methoxycinnamate alone to 371 nm for the above mixture, indicating that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e., wavelengths from 280 nm to 320 nm, but extends to 371 nm in a manner that 90% of the total area under the protection curve in the UV region is reached at 371 nm. Thus, relative to isoamyl p-methoxycinnamate alone, the combination results in a broader protection spectrum across the ultraviolet radiation spectrum, showing UVB and UVA activity (see Figure 11).
[1314] Combining with MAA-13 can reduce the loss of ethylhexyl methoxycinnamate from 37,88.50% to 24.69%, a reduction of approximately 35%. The combination showed UVB and UVA activity relative to ethylhexyl methoxycinnamate alone.
[1315] In addition, the critical wavelength shifts from 324 nm for ethylhexyl methoxycinnamate alone to 372 nm for the above mixture, indicating that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e., wavelengths from 280 nm to 320 nm, but extends to 372 nm in a manner that 90% of the total area under the protection curve in the UV region is reached at 372 nm. Thus, relative to ethylhexyl methoxycinnamate alone, the combination results in a broader protection spectrum across the ultraviolet radiation spectrum, showing UVB and UVA activity (see Figure 12).
[1316] Combining with MAA-20 can reduce the loss of isoamyl p-methoxycinnamate from 30.50% to 14.41%, a reduction of approximately 52%. The combination showed UVB and UVA activity relative to isoamyl p-methoxycinnamate alone.
[1317] In addition, the critical wavelength shifts from 324 nm for isoamyl p-methoxycinnamate alone to 344 nm for the above mixture, indicating that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e., wavelengths from 280 nm to 320 nm, but extends to 344 nm in a manner that 90% of the total area under the protection curve in the UV region is reached at 344 nm. Therefore, relative to isoamyl p-methoxycinnamate alone, the combination results in a broader protection spectrum across the ultraviolet radiation spectrum, showing UVB and UVA activity (see Figure 13).
[1318] Combining with MAA-20 can reduce the loss of ethylhexyl methoxycinnamate from 37.88% to 13.80%, a reduction of approximately 64%. The combination showed UVB and UVA activity relative to ethylhexyl methoxycinnamate alone.
[1319] In addition, the critical wavelength shifts from 324 nm for ethylhexyl methoxycinnamate alone to 346 nm for the above mixture, indicating that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e., wavelengths from 280 nm to 320 nm, but extends to 346 nm in a manner that 90% of the total area under the protection curve in the UV region is reached at 346 nm. Thus, relative to ethylhexyl methoxycinnamate alone, the combination results in a broader protection spectrum across the ultraviolet radiation spectrum, showing UVB and UVA activity (see Figure 14).
[1320] Combining with MAA-28 can reduce the loss of isoamyl p-methoxycinnamate from 30.50% to 19.80%, a reduction of approximately 35%. The combination showed UVB and UVA activity relative to isoamyl p-methoxycinnamate alone.
[1321] In addition, the critical wavelength shifts from 324 nm for isoamyl p-methoxycinnamate alone to 347 nm for the above mixture, indicating that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e., wavelengths from 280 nm to 320 nm, but extends to 347 nm in a manner that 90% of the total area under the protection curve in the UV region is reached at 347 nm. Thus, relative to isoamyl p-methoxycinnamate alone, the combination results in a broader protection spectrum across the ultraviolet radiation spectrum, showing UVB and UVA activity (see Figure 15).
[1322] Combining with MAA-28 reduced the reduction of ethylhexyl methoxycinnamate from 37.88% to 19.54%, a reduction of approximately 48%. The combination showed both UVB and UVA activity relative to ethylhexyl methoxycinnamate alone.
[1323] In addition, the critical wavelength shifts from 324 nm for ethylhexyl methoxycinnamate alone to 349 nm for the above mixture, indicating that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e., wavelengths from 280 nm to 320 nm, but extends to 349 nm in a manner that 90% of the total area under the protection curve in the UV region is reached at 349 nm. Thus, relative to ethylhexyl methoxycinnamate alone, the combination results in a broader protection spectrum across the ultraviolet radiation spectrum, showing UVB and UVA activity (see Figure 16).
[1324] It is evident from the above data that the water-soluble MAA compounds according to the invention show a significant stabilization of oil-soluble photolabile UV filters. Thus, using the water-soluble MAA compounds according to the invention, oil-soluble photolabile UV filters can be stabilized with water-soluble MAA stabilizers via the aqueous phase in the emulsion formulation. From that point on, oil-soluble photolabile UV filters can only be stabilized using oil-soluble stabilizers in the oil phase of the emulsion formulation.
[1325] The mixture of MAA-1 and MAA-13 showed no loss of absorption at 325 nm. However, the absorption spectrum of the mixture was altered compared to the absorption spectra of MAA-1 and MAA-13 alone. The combination covers the complete UVA and UVB spectrum from 284 nm to 396 nm, and the gap between the spectra of MAA-1 alone and MAA-13 alone is closed (see Figure 17).
[1326] The mixture of MAA-13 and MAA-20 showed no loss of absorption at 325 nm. However, the absorption spectrum of the mixture was altered compared to the absorption spectra of MAA-20 and MAA-13 alone. The combination covers the complete UVA and UVB spectrum from 284 nm to 396 nm, and the gap between the spectrum of MAA-13 alone and MAA-20 alone is closed (see Figure 18).
[1327] Thus, using a mixture of two MAA compounds according to the invention an improved photostability can be achieved compared to the photostability of the corresponding individual MAA compounds.
[1328] Thus, the present invention provides a sunscreen product or a cosmetic or pharmaceutical preparation, wherein the reduction in degradation after 5 MED irradiation as determined as described in the present application is reduced by at least 10% compared to a composition comprising at least one photolabile UV filter without a mycosporin-like amino acid compound. More advantageously, in the sunscreen product, cosmetic or pharmaceutical preparation or home care product of the present invention, the reduction in degradation of the photolabile UV filter is at least 15%, more preferably at least 20%, and most preferably at least 25%.
[1329] In particular, this photostability stabilizing effect is observed without the use of additional photostabilizers.
[1330] Without the addition of mycosporin-like amino acid compounds, the photolabile UV filters undergo UV-induced photochemical interactions or reactions, leading to a loss of UV absorption of the UV filters and a severe reduction in the UV protection capability of the sunscreen product, cosmetic or pharmaceutical preparation or household care product.
[1331] By stabilizing the UV filters, their degradation upon exposure to UV radiation can be reduced and the formation of phototoxic or photoallergic degradation products which have the risk of adverse health effects upon direct contact with the skin can be reduced.
[1332] With the stabilization of the photolabile UV filter, the original UV absorption capacity in the sunscreen product, cosmetic or pharmaceutical or home care product is almost retained. Therefore, using the present invention, a sunscreen product, cosmetic or pharmaceutical product or home care product with an almost consistent good SPF can be provided.
[1333] On the other hand, the stabilization of photolabile UV filters by mycosporin-like amino acid compounds as defined herein allows to reduce the amount of UV filters without affecting the envisaged SPF.
[1334] Due to this advantageous effect as described above, another aspect of the present invention relates to the use of a mycosporin-like amino acid compound (b) or a mixture thereof as defined herein for the photostability of photolabile UV filters.
[1335] By doping with a mycosporin-like amino acid compound (b) as defined herein or a mixture thereof, the degradation loss of the photolabile UV filter after 5 MED irradiation as determined as described herein can be reduced by at least 10%. Preferably, the degradation loss of the photolabile UV filter can be reduced by at least 15%, more preferably by at least 20%, and most preferably by at least 25%.
[1336] Advantageously, the photolabile UV absorbing compound to which the mycosporin-like amino acid is added retains greater than 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% or even more of the initial UV absorbing capacity compared to a product or formulation without the addition of at least one mycosporin-like amino acid compound.
[1337] In another aspect, the present invention relates to a method for stabilizing a photolabile UV filter against the degradation effects of UV radiation or for enhancing the UV absorbing properties of a UV absorbing compound. In this method, a photolabile UV filter is doped with an effective amount of at least one mycosporin-like amino acid as defined herein or a mixture thereof.
[1338] The present invention will now be described in detail with reference to the following examples, which are only intended to illustrate the present invention, so that the contents of the present invention are not limited to the following examples.
[1339] Example
[1340] Example 1 - Light stability test
[1341] UV filters are often tested for their photostability to ensure that no degradation occurs to the UV filter itself or in combination with other substances.
[1342] The UV filter stabilizing properties of mycosporin-like amino acid compounds were explored by comparing the behavior of the UV filters alone versus in combination with certain mycosporin-like amino acid compounds.
[1343] In this case, individual photostable UV filters as well as formulations of photostable filters with certain mycosporin-like amino acid compounds were subjected to the photostability test described in detail below to determine the photostability of the samples after exposure to a 5 MED (minimal erythema) dose (1 MED = 250 J / m 2 ) after exposure to UVA and UVB radiation (full spectrum analysis).
[1344] The minimum erythema dose (MED), also called the erythema threshold dose, is a measure of the tolerance of human skin to solar radiation, particularly to the short-wave ultraviolet part of the spectrum around a wavelength of about 300 nm. Dermatologists determine the MED by irradiating a test area (usually on an untanned back) with gradually (the so-called "light step") increasing doses of powerful UV lamps. 1 MED corresponds to the lowest irradiation dose that causes a well-defined erythema (redness) of the skin when read after 24 hours.
[1345] Sample preparation: Dissolve the substance or preparation to be tested in a suitable solvent. To this end, transfer a certain amount of the substance or preparation into a graduated flask by means of an analytical balance / pipette and fill with the chosen solvent. Filling to the calibration mark of the graduated flask is performed only after the substance has been completely dissolved and the temperature has been controlled at 20°C.
[1346] Preparation of solution E1% / cm: 100 mg of the substance or preparation to be tested is weighed into a graduated flask and filled to 100 ml with the corresponding solvent. A clear solution is obtained. If necessary, an ultrasonic bath is used to improve solubility. For further dilution, the sample is adjusted to a temperature of 20°C. 1 ml of the dissolved solution is added to a second 100 ml graduated flask and filled to 100 ml at 20°C. The final concentration of the solution thus obtained is 0.001%. (E1% / cm). This solution is used for absorbance measurement and irradiation. The solution is transferred to a 10 mm quartz cuvette with a cover.
[1347] Irradiation: 700W / m emitted by Atlas SUN Test CPS 2 The sample was irradiated for 32 min. This corresponds to an amount of energy of 5 MED (minimal erythema) dose (=1250 J / m 2). At the same time, the temperature of the apparatus was adjusted to a maximum of 30°C to avoid intense heating of the sample.
[1348] Measurement: Absorbance measurements of samples in quartz cuvettes with caps (10 mm) were performed with a Lambda 25 UV spectrometer in the wavelength range of 200 nm to 700 nm. Blank absorbance tests were performed using the corresponding solvents used to prepare the samples as described above. Absorbance measurements of samples were performed before (before irradiation) and after irradiation emitted by an Atlas SUN Test CPS (see above).
[1349] The UV absorption curves obtained show, as described above, the amplitude and width of protection provided by each sample from 200nm to 700nm on the UV spectrum before irradiation (pre-irradiation) and after irradiation. The amplitude of the absorption curve reflects the degree of protection. The higher the amplitude of the curve, the greater the absorbance, and the more protection provided at this wavelength. In the UVB part of the spectrum (290nm to 320nm), this amplitude is associated with SPF. The greater the width of the curve, the more protection provided for longer-wave UV irradiation. In other words, the wider the width of the curve, the wider the sunscreen spectrum provided.
[1350] The table shows the variation in UV absorption properties of the individual components or in various combinations.
[1351] Samples with a loss of <20% absorbance after irradiation were classified as photostable.
[1352] Test sample:
[1353] a) E1% / cm solution of pure substance:
[1354] 1) MAA-1 (Mycosporine-like amino acid compound)
[1355] 2) MAA-13 (Mycosporine-like amino acid compound)
[1356] 3) MAA-20 (Mycosporin-like amino acid compound)
[1357] 4) MAA-28 (Mycosporine-like amino acid compound)
[1358] 5) Ethylhexyl methoxycinnamate (UV filter)
[1359] 6) Butyl Methoxydibenzoylmethane (UV filter)
[1360] 7) Isoamyl p-methoxycinnamate (UV filter)
[1361] b) E1% / cm solution of the following mixture:
[1362] 1) MAA-1 plus ethylhexyl methoxycinnamate
[1363] 2) MAA-1 plus butyl methoxydibenzoylmethane
[1364] 3) MAA-1 plus isoamyl p-methoxycinnamate
[1365] c) E1% / cm solution of the following mixture:
[1366] 1) MAA-13 plus isoamyl p-methoxycinnamate
[1367] 2) MAA-13 plus ethylhexyl methoxycinnamate
[1368] d) E1% / cm solution of the following mixture:
[1369] 1) MAA-20 plus isoamyl p-methoxycinnamate
[1370] 2) MAA-20 plus ethylhexyl methoxycinnamate
[1371] e) E1% / cm solution of the following mixture:
[1372] 1) MAA-28 plus isoamyl p-methoxycinnamate
[1373] 2) MAA-28 plus ethylhexyl methoxycinnamate
[1374] f) E1% / cm solution of the following mixture:
[1375] 1) MAA-13 plus MAA-1
[1376] 2) MAA-13 plus MAA 20
[1377] result:
[1378] 1) Measurement of photostability E1% / cm of MAA-1 (mycosporine-like amino acid compound):
[1379] Result: 0.53% loss of absorbance at 321 nm. Very photostable molecule (see Figure 1).
[1380] 2) Measurement of photostability E1% / cm of MAA-13 (mycosporine-like amino acid compound):
[1381] Result: 5.13% loss of absorbance at 364 nm. Very photostable molecule (see Figure 2).
[1382] 3) Measurement of photostability E1% / cm of MAA-20 (mycosporine-like amino acid compound):
[1383] Result: 5.95% loss of absorbance at 324 nm. Very photostable molecule (see Figure 3).
[1384] 4) Measurement of photostability E1% / cm of MAA-28 (mycosporine-like amino acid compound):
[1385] Result: 15.03% loss of absorbance at 335 nm. Photostable molecule (see Figure 4).
[1386] 5) Measurement of photostability E1% / cm of ethylhexyl methoxycinnamate (UV filter):
[1387] Result: 37.88% loss of absorbance at 310 nm. Not photostable (see Figure 5).
[1388] 6) Measurement of the photostability of butyl methoxydibenzoylmethane (UV filter) E1% / cm:
[1389] Result: 7.05% loss of absorbance at 358 nm. Butyl methoxydibenzoylmethane is photost...
Claims
1. A sunscreen product, a cosmetic or pharmaceutical preparation or a home care product, comprising or consisting of the following substances: (a) at least one photolabile UV filter; and (b) at least one mycosporin-like amino acid compound, The at least one mycosporin-like amino acid compound is represented by the general formula (V) in -Z is selected from the group consisting of O-R2' or amide'; -R1' is selected from the group consisting of: CH2, unsubstituted or substituted CH(alkyl), unsubstituted or substituted C(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-spiro; -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, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, 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), and unsubstituted or substituted NR9'R10', unsubstituted or substituted -N(O-alkyl)(alkyl)(Weinreb amide), -N(OH)(H)(hydroxamic acid), and unsubstituted or substituted -N(OH)(alkyl)(alkylated hydroxamic acid); -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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=O)-OY, 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-spiro; - the substituents R4', R5' and R6' may be identical or different and are independently 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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted substituted or substituted heteroaryl, SO, SO2, -S(=O)2OH, sulfonyl, 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-spiro; - R7' and R8' may be the same or different and are independently 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)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=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'; - R9' and R10' may be identical or different and are independently 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 RC(=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 stereoisomer or salt of the aforementioned compound; Or represented by general formula (VI) in -R1" is selected from the group consisting of CH2, unsubstituted or substituted CH(alkyl), unsubstituted or substituted C(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-spiro; -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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -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-spiro; -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), -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-spiro; - the substituents R4", R5" and R6" may be identical or different and are independently 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 RC(=O)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted substituted or substituted heteroaryl, SO, SO2, -S(=O)2OH, sulfonyl, 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-spiro; - R7" and R8" may be identical or different and are independently 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)-, -CH2-OH, -R-CH2-OH, -C(=O)-OY, -RC(=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)(hydroxamic acid), and unsubstituted or substituted -N(OH)(alkyl)(alkylated hydroxamic acid); - R9" and R10" may be identical or different and are independently 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 RC(=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 stereoisomer or salt of the aforementioned compound; or any mixture of the foregoing compounds; Provided that the following compounds are not claimed / excluded: Compound 1: Compound 2: Compound 3: Compound 4: Compound 5: Compound 6: Compound 7: as well as Compound 8:
2. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to claim 1, wherein the mycosporin-like amino acid compound (b) is represented by the general formula (VII): wherein R1′, R2′, R3′, R4′, R5′ and R6′ have the same meanings as defined for formula (V); Or represented by general formula (VIII) wherein R1′, Amide′, R3′, R4′, R5′ and R6′ have the same meanings as defined for formula (V).
3. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to claim 1 or claim 2, wherein in the general formula (VI), X is selected from the group consisting of: CH2, unsubstituted or substituted CH(alkyl), unsubstituted or substituted C(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), -CR7"R8", C=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-spiro.
4. The sunscreen product, cosmetic or pharmaceutical preparation or household care product according to any one of claims 1 to 3, wherein in the general formula (V) -Z is -O-R2' or amide'; and / or - R1' is selected from the group consisting of: CH2, C(alkyl)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-ethylhexyl) and phenyl; or -amide' is selected from the group consisting of: NH2, NH(alkyl) and N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); 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 - the substituents R4', R5' and R6' have the same meanings as defined for formula (V); - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; or wherein in the general formula (VII) or (VIII) - R1' is selected from the group consisting of: CH2, C(alkyl)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-ethylhexyl) and phenyl; or -amide' is selected from the group consisting of: NH2, NH(alkyl) and N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); 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 - the substituents R4', R5' and R6' have the same meanings as defined for formula (VII) and formula (VIII); - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; or wherein in the general formula (VI) -R1" is selected from the group consisting of CH2, C(alkyl)2, O, S, SO, SO2, NH and N(alkyl); and / or -R2" is selected from the group consisting of: -CH2-OH, -C(=O)-OY and -C(=O)-amide"; and / or -X is selected from the group consisting of CH2, 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-ethylhexyl) and phenyl; and / or -amide" is selected from the group consisting of: NH2, NH(alkyl) and N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and / or - the substituents R4", R5" and R6" have the same meanings as defined for formula (VI); - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
5. The sunscreen product, cosmetic or pharmaceutical preparation or household care product according to any one of claims 1 to 4, wherein in the general formula (V) -Z is -O-R2' or amide'; and / or - R1' is selected from the group consisting of: CH2 and C(methyl)2; and / or -R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl; or -amide' is selected from the group consisting of: NH2, NH(alkyl) and N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); 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 - the substituents R4', R5' and R6' have the same meanings as defined for formula (V); - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; or wherein in the general formula (VII) or (VIII) -R1' is selected from the group consisting of: CH2 and C(methyl)2; -R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl; or -amide' is selected from the group consisting of: NH2, NH(alkyl) and N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); 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 - the substituents R4', R5' and R6' have the same meanings as defined for formula (VII) and formula (VIII); - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; and / or or wherein in the general formula (VI) -R1" is selected from the group consisting of: CH2 and C(methyl)2; and / or -R2" is selected from the group consisting of: -CH2-OH, -C(=O)-OY and -C(=O)-amide"; and / or -X is selected from the group consisting of CH2, 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-ethylhexyl) and phenyl; and / or -amide" is selected from the group consisting of: NH2, NH(alkyl) and N(alkyl)2, -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and / or - the substituents R4", R5" and R6" have the same meanings as defined for formula (VI); - wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
6. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 5, wherein the mycosporin-like amino acid compound (b) is selected from the group consisting of the following compounds I-1 to I-128 according to the general formula (V) and compounds II-1 to II-192 according to the general formula (VI): wherein in the above-mentioned mycosporin-like amino acid compound, the benzene ring may be unsubstituted or substituted, and R4′, R5′, R6′, R4″, R5″, R6″, amide′, Y, amide″ and alkyl have the same meanings as defined in any one of the preceding claims, or a tautomer or stereoisomer or salt of the aforementioned compound; or wherein the mycosporin-like amino acid is selected from the group consisting of: MAA-A MAA-B and MAA-C wherein alkyl is methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl, preferably methyl, or a tautomer or stereoisomer or salt of the aforementioned compound; or any mixture of the foregoing compounds.
7. A sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 6, wherein in the general formulae (VI), (IX) and (X), X is S, SO or SO2, and / or wherein in the general formulae (V) to (X), n=1.
8. A sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 7, wherein in the general formulae (V), (VII) and (VIII), the substituents R4', R5' and R6' may be identical or different and are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O)2OH and sulfonyl; or In the general formulae (VI), (IX) and (X), the substituents R4", R5" and R6" may be identical or different and are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O)2OH and sulfonyl.
9. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 8, wherein in the general formulae (V) to (X), the substituted phenyl group bonded to the imino functional group is selected from the group consisting of: The dotted lines indicate the binding sites.
10. A sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 9, wherein in the general formulae (V), (VII) and (VIII), the substituents R4', R5', R6' may be identical or different and are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O) 2OH and sulfonyl; provided that, if the substituted phenyl ring is monosubstituted, the substituent is in the ortho or meta position of the imino function; or wherein in the general formulae (VI), (IX) and (X), the substituents R4", R5" and R6" may be identical or different and are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O)2OH and sulfonyl; provided that, if the substituted benzene ring is monosubstituted, the substituent is in the ortho or meta position but not in the para position to the imino functional group of the general formula (VI), (IX) and (X).
11. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 10, wherein the mycosporin-like amino acid compound (b) is selected from the group consisting of: or a tautomer or stereoisomer or salt of the aforementioned compound; or any mixture of the foregoing compounds.
12. Sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 11, wherein the at least one photolabile UV filter (a) is selected from the group consisting of ethylhexyl methoxycinnamate (Neo AV), butyl methoxydibenzoylmethane (Avobenzone; Neo 357), Isoamyl p-methoxycinnamate (Neo E1000), diethylamino-hydroxy-benzoyl hexyl benzoate (UVinul A plus) and any mixture thereof.
13. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 12, further comprising at least one additional primary organic and / or inorganic UV filter different from the at least one photolabile UV filter (a), wherein the additional primary organic and / or inorganic UV filter is selected from the group consisting of camphor benzalkonium methylsulfate, homosalate, benzophenone-3, phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, benzylidene camphor sulfonic acid, octocrylene, polyacrylamidomethylbenzylidene camphor, PEG-25 PABA, ethylhexyl triazone, drometrizole trisiloxane, diethylhexyl butyryl Aminotriazone, 4-methylbenzylidene camphor, ethylhexyl salicylate, dimethyl PABA ethylhexyl ester, benzophenone-4, benzophenone-5, methylene bis-benzotriazolyl tetramethylbutylphenol (nano), disodium phenyl dibenzimidazole tetrasulfonate, bis-ethylhexyloxyphenol methoxyphenyl triazine, polysilicone-15, titanium dioxide, titanium dioxide (nano), tris-biphenyl triazine (nano), zinc oxide, zinc oxide (nano), phenylene bis-diphenyl triazine, methoxypropylaminocyclohexenylene ethoxyethyl cyanoacetate, bis-(diethylaminohydroxybenzoylbenzoyl)piperazine, TEA-salicylate, benzophenone-8, PABA, dimethyl PABA ethylhexyl ester, menthyl anthranilate, and any mixture thereof.
14. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 13, comprising the photolabile UV filter (a) or a mixture thereof in an amount of 0.01 to 35.0% by weight, in particular in an amount of 0.1 to 30.0% by weight, more particularly in an amount of 0.5 to 25.0% by weight, most particularly in an amount of 1.0 to 20.0% by weight, based on the total weight of the product or preparation.
15. The sunscreen product or cosmetic or pharmaceutical preparation according to any one of claims 1 to 14, comprising the mycosporin-like amino acid (b) or a mixture thereof in an amount of 0.001% to 15.0% by weight, in particular in an amount of 0.01% to 10.0% by weight, more particularly in an amount of 0.05% to 7.5% by weight, most particularly in an amount of 0.1% to 5.0% by weight, based on the total weight of the product or preparation.
16. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 15, further comprising at least one 1,2-alkanediol or one 2,3-alkanediol having 5 to 12 carbon atoms, wherein the 1,2-alkanediol is preferably selected from the group consisting of: 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, and wherein the 2,3-alkanediol is selected from the group consisting of 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 2,3-octanediol, 2,3-nonanediol, 2,3-decanediol, 2,3-undecanediol, 2,3-dodecanediol and any mixture thereof.
17. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 16, further comprising one or more antimicrobial agents, preferably wherein the antimicrobial agent is selected from the group consisting of: 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 2,3-octanediol, 2,3-nonanediol, 2,3-decanediol, 2,3-undecanediol, 2,3-dodecanediol, 2-benzylheptanol, 2-hydroxyacetophenone, 2-methyl 5-cyclohexylphenol, 3-hydroxypropyl 2-hydroxybenzoate, 4-hydroxyacetophenone and any mixture thereof.
18. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 17, further comprising at least one excipient and / or active substance selected from the group consisting of: UV filters, carriers, oil components, rheological additives, hydrotropes, solubilizers, powders, film formers, water resistance improvers, skin moisturizing and / or water-retaining substances, soothing substances, physiological cooling agents, alkanediols, antioxidants, anti-skin aging agents, matrix metalloproteinase inhibitors (MMPI), anti-inflammatory agents, TRPV1 antagonists, emulsifiers, antimicrobial agents, preservatives, antibacterial or antifungal active substances, chelating agents, surfactants, fragrances / fragrance substances or perfume oils and any mixtures of two or more of the aforementioned substances.
19. The sunscreen product or cosmetic or pharmaceutical preparation according to any one of claims 1 to 18, which is in the form of (i) dispersions, preferably wherein the cosmetic or pharmaceutical preparation is in the form of an emulsion, in particular an O / W emulsion, a W / O emulsion, a multiple emulsion, an aqueous dispersion gel, a balm, a water-in-oil (W / O / W) or oil-in-water (O / W / O) multiple emulsion, a PIT emulsion, a Pickering emulsion, a microemulsion, 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 an aerosol, in particular a foam and a spray, including all types of silicone-based emulsions; (ii) an anhydrous formulation; or (iii) an aqueous solution or an aqueous solution / alcohol solution, in particular an aqueous solution / ethanol solution, or an aqueous solution / glycol solution, or an alcohol solution / glycol solution, in particular an ethanol solution / glycol solution.
20. The sunscreen product or cosmetic or pharmaceutical preparation according to any one of claims 1 to 19, as a cosmetic, for personal care, in particular for skin care, skin protection, sun protection, scalp protection, scalp care, hair care, nail care, as a medicament, for animal care or household care.
21. A sunscreen product or cosmetic or pharmaceutical formulation according to any one of claims 1 to 20, wherein the degradation losses of the photolabile UV filter (a) after 5 MED irradiation determined as described herein are reduced by at least 10%, preferably at least 15%, more preferably at least 20%, and most preferably at least 25%, compared to a composition comprising the at least one photolabile UV filter without the mycosporin-like amino acid compound.
22. Use of a mycosporin-like amino acid compound as defined in any one of claims 1 to 11 or a mixture thereof for photostabilizing photolabile UV filters.
23. Use according to claim 22, wherein the degradation losses of the photolabile UV filter after 5 MED irradiation determined as described herein are reduced by at least 10%, preferably at least 15%, more preferably at least 20% and most preferably at least 25%.
24. A method for stabilizing a photolabile UV filter against the degradation effects of UV radiation or for enhancing the UV absorbing properties of a UV absorbing compound in a composition, wherein a photolabile UV filter as defined in claim 13 is doped with an effective amount of at least one mycosporin-like amino acid compound as defined in any one of claims 1 to 11 or a mixture thereof.
Citation Information
Patent Citations
Tetrahydropyrimidine-2-one derivatives and their uses
WO2004026840A1
Anthranilic acid amides and the derivatives thereof as cosmetic and pharmaceutical agents
WO2004047833A2