Mycosporine-like amino acid analogue compounds and use thereof
Patent Information
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- SYMRISE GMBH & CO KG
- Filing Date
- 2023-08-04
- Publication Date
- 2026-06-10
AI Technical Summary
Existing UV filters, including mycosporine-like amino acids, are either insoluble in water, thermolabile, or not stable in alkaline conditions, limiting their effectiveness in protecting against UV radiation.
Development of novel mycosporine-like amino acid analogue compounds that are water-soluble, stable across a broader pH range, and effective in absorbing UV radiation, thereby enhancing their use in sunscreen formulations and other applications.
The new mycosporine-like amino acid analogue compounds provide improved UV protection, stability, and solubility, allowing for higher concentrations in formulations and enhanced protection against photolytic degradation.
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Abstract
Description
230135 Mycosporine-like amino acid analogue compounds and use thereof Technical field
[0001] The present invention refers to the field of protection against ultraviolet (UV) radiation. In particular, the present invention relates to new mycosporine-like amino acid analogues as defined herein. Further, the present invention relates to compositions comprising at least one of said mycosporine-like amino acid analogues, such as food, cosmetic or pharmaceutical preparations, in particular sunscreen formulations, or homecare products. Still further, the present invention relates to the use of said mycosporine-like amino acid analogues for the preparation of said food, cosmetic or pharmaceutical preparations, in particular sunscreen formulations, or homecare products, and for the use of other purposes. Background Art
[0002] The negative effects of exposure of UV light are well-known. Prolonged exposure to sunlight causes damage such as sunburn to the skin and dries out hair making it brittle. When skin is exposed to UV light having a wavelength of from 290 nm to 400 nm, long term damage can lead to serious conditions such as skin cancer, the type of damage depending on the wavelength of the radiation.
[0003] UV light also contributes to aging by causing free radicals to form in the skin. Free radicals include, for example, singlet oxygen, hydroxyl radical, the superoxide anion, nitric oxide and hydrogen radicals. Free radicals attack DNA, membrane lipids and proteins, generating carbon radicals. These in turn react with oxygen to produce a peroxyl radical that can attack adjacent fatty acids to generate new carbon radicals. This cascade leads to a chain reaction producing lipid peroxidation products. Damage to the cell membrane results in loss of cell permeability, increased intercellular ionic concentration, and decreased ability to excrete or detoxify waste products. The end result is a loss of skin elasticity and the appearance of wrinkles. This process is commonly referred to as photo- aging.230135
[0004] Moreover, UVA radiation can trigger phototoxic or photo allergic skin reactions.
[0005] UV rays are classified according to their wavelength as UVA rays (320 to 400 nm) or UVB rays (280 to 320 nm).
[0006] To attenuate these negative effects of UV-radiation, i.e. for the purpose of protecting the skin and keratin materials against UV-radiation, anti-sun / sunscreen compositions comprising screening agents that are active in the UVA range and in the UVB range, i.e. within the full range of 280 nm to 400 nm, are generally used.
[0007] UV-filters are compounds which have a pronounced absorption capacity for ultraviolet radiation. They are used especially in sunscreen products, cosmetic, dermatological and pharmacological preparations or sunscreen products, but also to improve the light fastness of industrial products, such as paints, varnishes, plastics, textiles, polymers such as, for example, polymers and copolymers of mono- and di- olefins, polystyrenes, polyurethanes, polyamides, polyesters, polyureas and polycarbonates, packaging materials and rubbers.
[0008] The UV-filters are classified as UVA and UVB filters depending on the location of their absorption maxima; if a UV-filter absorbs both UVA and UVB, it is referred to as a UVA / UVB broadband absorber or UVA / UVB broadband filter.
[0009] In order to achieve the desired maximum protection from UV-radiation sunscreen products, cosmetic, especially dermatological, and pharmacological preparations or homecare products are formulated to contain a mixture of UV-filters with varying concentrations and the choice of UV-filters used is determined by the legislation within the country or economic area. For example, UV-filters which can be used for the protection of skin are regulated in the USA by the America FDA via their OTC monograph system and are regulated in the European Union by the Cosmetic Regulation. Regulations covering the use of UV-filters exist in other countries and regions as well. These regulations not only stipulate the filters which can be used but also fix a maximum230135 usage level for each UV-filter. Thus, there are limited UV-filters available to achieve high efficacy with respect to both SPF and UVA or UVB protection.
[0010] Accordingly, there is generally a need for further effective UV filters.
[0011] However, UV filters known in the prior art, which are used in e.g. cosmetic or pharmaceutical composition, such as sunscreen compositions, have certain disadvantages. One of the disadvantages is that the vast majority of cosmetic registered organic UV filters are only miscible or soluble in oil, i.e. they are only suitable to be added to the oil phase of a sunscreen emulsion. The solubility of each UV filter is thereby dependent on the oils used. Hence, the formulation of a sunscreen is limited by the choice of certain oils and thus also limited by choosing exemplary emollients to improve the sensory. This may affect the compliance of the consumer.
[0012] Mycosporine-like amino acids (MAAs) have been associated with the potential to protect organisms against UV radiation. MAAs consists of a family of compounds with a cyclohexanone or cyclohexenimine core structure. The MAA compounds are capable of electron delocalization. Analogues of MAA are known to be suitable UV filters in terms of absorption and photostability, which are however nearly insoluble in water.
[0013] Another disadvantage of the known mycosporine-like amino acids (MAAs) having an ester function is that they tend to be thermolabile and not stable under alkaline conditions.
[0014] Hence, there is an ongoing need for novel water soluble compounds that are stable and sufficiently protect against UV radiation.
[0015] The object of the present invention was therefore to provide novel mycosporine- like amino acid analogue compounds that overcome the disadvantages of the prior art, which are water soluble, stable and sufficiently protect against UV radiation.230135
[0016] This object is solved by the subject matter of the present invention which is the provision of mycosporine-like amino acid analogue compounds as defined herein.
[0017] Surprisingly it has been found that mycosporine-like amino acid analogue compounds as defined herein are water soluble and stable.
[0018] Especially, the mycosporine-like amino acid compounds as defined herein have a better pH stability in a broader pH-range compared to their respective ester compounds which hydrolize, and, thus, are not stable in alkaline solutions having a pH higher than 9.
[0019] In particular, it has been found that the mycosporine-like amino acid analogue compounds effectively absorb light in the UV range relevant of UV protection, thus prevent skin, hair, or nail of a human or animal against harmful effect of UV radiations or stabilise food, a cosmetic or pharmaceutical preparation or a homecare product against degradation through UV radiation.
[0020] In addition, it has been found that the mycosporine-like amino acid analogue compounds - stabilize a photo-unstable UV filter in a food, a cosmetic or pharmaceutical preparation or a homecare product, preferably in a sunscreen product; or - improve the SPF and boosting the UVA photoprotection of a food, a cosmetic or pharmaceutical preparation or a homecare product, preferably in a sunscreen product, comprising an organic UV filter and / or an inorganic UV filter; or - boost the antimicrobial efficacy of an antioxidant in food, a cosmetic or pharmaceutical preparation or a homecare product; or - stabilize a fragrance or aroma / flavour compound, preferably a fragrance or aroma / flavour composition in a food, a cosmetic or pharmaceutical preparation or a homecare product; or - boost the antioxidative effect of an antioxidant in a food, a cosmetic or pharmaceutical preparation or a homecare product. Summary of the invention230135
[0021] In order to accomplish the above problem, the present invention relates in a first aspect to a mycosporine-like amino acid analogue compound represented either by the general formula (I)formula (I), as defined herein, or a stereoisomer or tautomer or a salt thereof.
[0022] In a second aspect, the present invention provides for food, cosmetic or pharmaceutical preparations or homecare products, comprising at least one of said mycosporine-like amino acid analogue compound and as defined herein.
[0023] In a further aspect, the present invention relates to the use of said mycosporine- like amino acid analogue compound for - preparing food, a cosmetic or pharmaceutical preparation, preferably a sunscreen product, or a homecare product; or - stabilizing food, a cosmetic or pharmaceutical preparation or a homecare product against light, in particular against UV light; or - for stabilizing a photo-unstable UV filter in a food, a cosmetic or pharmaceutical preparation or a homecare product, preferably in a sunscreen product; or - for improving the SPF and boosting the UVA photoprotection of a food, a cosmetic or pharmaceutical preparation or a homecare product, preferably in a sunscreen product, comprising an organic UV filter and / or an inorganic UV filter; or - for boosting the antimicrobial efficacy of an antimicrobial in a food, a cosmetic or pharmaceutical preparation or a homecare product; or230135 - for stabilizing a fragrance or aroma / flavour compound, preferably a fragrance or aroma / flavour composition in a food, a cosmetic or pharmaceutical preparation or a homecare product; or - for boosting the antioxidative effect of an antioxidant in a food, a cosmetic or pharmaceutical preparation or a homecare product.
[0024] The present invention is specified in the appended claims. The invention itself, and its preferred variants, other objects and advantages, are however also apparent from the following detailed description in conjunction with the accompanying examples and figures. Description of the Figures
[0025] Figure 1 is the LC-MS chromatogram of the MAA-20 compound according to the present invention.
[0026] Figure 2 is a graph showing the UV absorption spectrum of the MAA compound ethyl 2-[[5,5-dimethyl-3-phenylimino-cyclohexen-1-yl]amino]acetate (prior art)
[0027] Figure 3 is a graph showing the UV absorption spectrum of MAA-20
[0028] Figure 3 a are absorption spectra showing the photostability E1% / cm measurement of MAA-20 (mycosporine-like amino acid compound)
[0029] Figure 4 is a graph showing the UV absorptions spectrum of MAA-28
[0030] Figure 4 a are absorption spectra showing the photostability E1% / cm measurement of MAA-28
[0031] Figure 5 are absorption spectra showing the photostability E1% / cm measurement of Ethylhexyl Methoxycinnamate (UV-filter)230135
[0032] Figure 6 are absorption spectra showing the photostability E1% / cm measurement of Butyl Methoxydibenzoylmethane (UV-filter)
[0033] Figure 7 are absorption spectra showing the photostability E1% / cm measurement of Isoamyl p-Methoxycinnamate (UV-filter)
[0034] Figure 8 are absorption spectra showing the photostability E1% / cm measurement of a mixture of MAA-20 and Iosamyl p-Methoxycinnamate
[0035] Figure 9 are absorption spectra showing the photostability E1% / cm measurement of a mixture of MAA-20 and Ethylhexyl Methoxycinnamate
[0036] Figure 10 are absorption spectra showing the photostability E1% / cm measurement of a mixture of MAA-28 and Isoamyl p-Methoxycinnamate
[0037] Figure 11 are absorption spectra showing the photostability E1% / cm measurement of a mixture of MAA-28 and Ethylhexyl Methoxycinnamate Detailed description of the invention
[0038] In the context of the present invention, the following general meanings apply:
[0039] As used herein, the singular form “a”, “a” and “the” include plural references unless the context clearly dictates otherwise. Thus, for example reference to “cosmetic preparation”, “the cosmetic preparation” or “a cosmetic preparation” also includes a plurality of cosmetic preparations.
[0040] The terms “comprising”, “including”, and “containing” are to be understood as open-ended terms and mean that the named components following said term are essential but not “limited to”, and other components may be added and are still embraced by the present invention.230135
[0041] The term “consisting of” as used according to the present invention means that the total amount of components (a) and (b) adds up to 100 % by weight, based on the total weight of the food, cosmetic or pharmaceutical preparation or homecare product, and signifies that the subject matter is closed-ended and can only include the limitations that are expressly recited.
[0042] Whenever reference is made to “comprising” it is intended to cover both meanings as alternatives, that is the meaning can be either “comprising” or “consisting of” unless the context dictates otherwise.
[0043] The term "or" or "and / or" is used as a function word to indicate that two words or phrases are to be taken together or separately.
[0044] The term “optionally” means that the subsequently described compound may but need not to be present in the composition, and that the description includes variants, where the compound is included or variants, where the compound is absent.
[0045] The endpoints of all ranges directed to the same component or property are inclusive and independently combinable.
[0046] The term "compound(s)" or "compound(s) of the present invention" refers to all compounds encompassed by the structural formula (I) and / or formula (lI) and / or formula (III) as well as their preferred embodiments disclosed herein and includes each subgenus and all specific compounds within the formula whose structure is disclosed herein. In addition, the term "compound(s)" or "compound(s) of the present invention" comprises also a tautomer, a stereoisomer or a salt thereof.
[0047] The compounds may be identified by either their chemical structure and / or chemical name. When the chemical structure and chemical name are in conflict, the chemical structure determines the identity of the compound.230135
[0048] The term “at least one …compound” means that the food or cosmetic or pharmaceutical preparation, in particular sunscreen product, or homecare product according to the present invention, in the following also referred to as “composition”, can comprise either one of said subsequently described individual compound or a mixture of two, three, four, five, six or even more different of said subsequently compounds.
[0049] The term “effective amount of a compound” means the amount of compound, that is sufficient to achieve the desired effect or improvement.
[0050] With respect to the aroma / flavour or fragrance compound, an effective amount is the amount to impart a perceptible odour or flavour in the fragrance or aroma / flavour composition or in the ready-to-use product. When applied to a combination of aroma / flavour or fragrance substances, the term refers to the total amount of the combination of aroma / flavour or fragrance substances resulting in the flavour or odour.
[0051] With respect to the mycosporine-like amino-acid analogoue compounds, an effective amount is the amount which is necessary for resulting in the stabilizing the fragrance or aroma / flavour compounds and protect the composition against degradation.
[0052] The term “synergistic effect” is an effect achieved when two different chemical substances or biological structures interact resulting in accumulative overall effect that is greater than the sum of individual effects of any of them. In the present invention, the synergistic effect relates to a synergistic stabilizing or antioxidative effect.
[0053] The term “food” in the context of the present invention is any substance or formulation consumed to provide nutritional support for an organism. Food is usually of plant, animal, or fungal origin, and contains essential nutrients, such as carbohydrates, fats, proteins, vitamins or minerals. The substance or formulation is ingested by an organism and assimilated by the organism’s cells to provide energy, maintain life, or stimulate growth. The term “food” also encompass food for animals.230135
[0054] The term “cosmetic or pharmaceutical preparations” in the context of the present invention are compositions for cosmetic or pharmaceutical purposes. The term “cosmetic or pharmaceutical preparations” also encompasses sunscreen products, i.e. a photoprotective topical product for the skin including UV-filter compounds that absorbs or reflects some of the sun’s ultraviolet (UV) radiation and thus helps protect against sunburn and most importantly prevent skin cancer.
[0055] The term “sunscreen composition” or “sunscreen” or “skin-care product”, also known as “sunblock”, “sun cream” or “suntan lotion”, refers to any topical product, which reflects and / or absorbs certain parts of UV radiation and thus helps protect against sunburn and most importantly prevent skin cancer. Thus, the term “sunscreen composition” is to be understood as not only including sunscreen compositions, but also any cosmetic compositions that provide UV protection. According to the present invention the sunscreen composition may comprise one or more active agents, e.g., organic UV- filters, as well as other ingredients or additives, e.g., emulsifiers, emollients, viscosity regulators, stabilizers, preservatives, or fragrances. Sunscreens come as lotions, sprays, gels, foams (such as an expanded foam lotion or whipped lotion), sticks, powders and other topical products. UV-absorbing compounds are used not only in sunscreen, but also in other personal care products, such as lipstick, shampoo, hair spray, body wash, toilet soap, and insect repellent.
[0056] The term “homecare products” in the context of the present invention are the essentials for daily care and cleaning purpose in households. They are used for maintaining hygiene and a good aura of the homes. The home care products generally include laundry detergents (powder, liquid and tablet), fabric conditioners, dishwashing detergents (liquid and tablet), hard floor and surface cleaners, glass cleaners, carpet cleaners, oven cleaners, air fresheners, disinfectants, stain removers, car wash products. These products are usually manufactured in the form of a liquid, powder, spray, granules and others. The sunscreen containing formulations prevent premature photodamage and photobleaching to surfaces and the homecare formulation itself.230135
[0057] The term “light stabilizers” as used herein are compounds suitable for protecting body-care and household cleaning and treating agents against photolytic degradation.
[0058] The term “photostability” refers to the ability of a UV filter or any other molecule, which is exposed to sunlight, to stay stable upon irradiation. In particular, this means that the compound does not undergo a degradation process upon UV radiation.
[0059] The term “sun protection factor (SPF)” as used herein indicates how well the skin is protected by a sunscreen composition. In particular, the factor indicates how much longer the protected skin may be exposed to the sun without getting a sunburn in comparison to untreated skin. For example, if a sunscreen composition with an SPF of 15 is evenly applied to the skin of a person usually getting a sunburn after 10 minutes in the sun, the sunscreen allows the skilled person to stay in the sun 15 times longer. In other words, SPF 15 means that 1 / 15 of the burning UV radiation will reach the skin, assuming sunscreen is applied evenly at a thick dosage of 2 milligrams per square centimeter (mg / cm2).
[0060] The term “critical wavelength” is defined as the wavelength at which the area under the UV protection curve (% protection versus wavelength) represents 90 % of the total area under the curve in the UV region (280-400 nm). For example, a critical wavelength of 370 nm indicates that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e. wavelengths from 280-320 nm, but extends to 370 nm in such a way that 90 % of the total area under the protective curve in the UV region are reached at 370 nm.
[0061] According to the present invention, the primary object of the present invention is solved by a mycosporine-like amino acid analogue compound, represented by the general formula (I)230135formula (I), wherein - Z is selected from the group consisting of O-R2’ and amide’; - R1’ is selected from the group consisting of CH2, unsubstituted or substituted CH(alkyl), and unsubstituted or substituted C(alkyl)2; - R2’ is H; - amide’ is NH2 or N(alkyl)2; - R3’ is selected from the group consisting of H, OH, halogen, and unsubstituted or substituted alkyl; - the substituents R4’, R5’ and R6’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy; - S(=O)2OH, and sulfonyl; or a tautomer or a stereoisomer or a salt of the afore-mentioned compounds; or any mixture of the afore-mentioned compounds.
[0062] Unless stated otherwise, in the context of the present invention, especially for the definition of the mycosporine-like amino acid analogue compounds represented by any of the general formulae the following general meanings apply:
[0063] The term “halogen” residue / moiety or group alone or as part of another substituent according to the present invention refers to F, Cl, Br or I.
[0064] The term "alkyl" alone or as part of another substituent according to the present invention refers to a saturated or mono- or polyunsaturated linear or branchedmonovalent hydrocarbon radical obtained by removing a hydrogen atom from a single carbon atom of a corresponding parent alkane.
[0065] In a preferred variation, the term "alkyl" also includes any alkyl moieties in radicals derived therefrom, such as alkoxy, alkylthio, alkylsulphonyl saturated linear or branched hydrocarbon radicals having 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms.
[0066] If the alkyl radical is further bonded to another atom, it becomes an alkylene radical or alkylene group. In other words, the term "alkylene" also refers to a divalent linear or branched alkyl. For example, -CH2CH3 is an ethyl, while -CH2CH2- is an ethylene.
[0067] In preferred variants according to the present invention, the linear or branched alkyl group or alkylene group comprises 1 to 10 carbon atoms. In other still more preferred variants, the linear or branched alkyl group or alkylene group comprises 1 to 6 carbon atoms.
[0068] More preferred according to the invention are saturated linear or branched C1 to C6 alkyl groups.
[0069] Most preferred the linear or branched alkyl groups have 1 to 4 carbon atoms.
[0070] Preferred alkyl radicals / moieties or alkyl groups include, but are not limited to: C1 to C6 alkyl comprising methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1- methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2- dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1- methylpropyl and 1-ethyl-2-methylpropyl.
[0071] In a preferred variant, the alkyl radical / moiety is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferred from the group consisting of methyl and ethyl.
[0072] The alkyl group or alkylene group as defined above may further be substituted.
[0073] The term "alkyl" or "alkylene" further includes radicals or groups having any degree of saturation, i.e., groups having only single carbon-carbon bonds ("alkyl" or "alkylene"), groups having one or more double carbon-carbon bonds ("alkenyl"), radicals having one or more triple carbon-carbon bonds ("alkynyl"), and groups having a mixture of single, double and / or triple carbon-carbon bonds.
[0074] The term "alkenyl" alone or as part of another substituent according to the present invention refers to an unsaturated linear or branched monovalent hydrocarbon radical having at least one carbon-carbon double bond (C=C double bond). The radical may be in either the cis or trans conformation around the double bond(s). So that the term "alkenyl" also includes the corresponding cis / trans isomers.
[0075] In preferred variants according to the present invention, the linear or branched alkenyl group comprises 2 to 10 carbon atoms. In other preferred variants, the linear or branched alkenyl group comprises 2 to 6 carbon atoms.
[0076] In still further preferred variants, the linear or branched alkenyl group comprises 2 to 4 carbon atoms.
[0077] Preferred according to the invention are mono- or di-unsaturated linear or branched C1 to C6 alkenyl groups.
[0078] Typical alkenyl radicals or alkenyl groups include, but are not limited to, ethenyl; propenyls such as prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl (allyl), prop-2-en-2-yl, cycloprop-1-en-1-yl, cycloprop-2-en-1-yl; butenyls such as but-1-en-1-yl, but-1-en-2-yl, 2-230135 methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-2-yl, buta-1,3-dien-1-yl, buta-1,3-dien-2-yl and the like.
[0079] The alkenyl group as defined above may further be substituted.
[0080] The term "alkynyl" alone or as part of another substituent according to the present invention refers to an unsaturated linear or branched monovalent hydrocarbon radical having at least one carbon-carbon triple bond (C≡C triple bond).
[0081] In preferred variants according to the present invention, the linear or branched alkynyl group comprises 2 to 10 carbon atoms. In other preferred variants, the alkynyl group comprises 2 to 6 carbon atoms. In still further preferred variants, the alkynyl group comprises 2 to 4 carbon atoms.
[0082] Most preferred according to the invention are mono- or di-unsaturated linear or branched C1 to C6 alkynyl groups.
[0083] Typical alkynyl radicals / moieties or alkynyl groups include, but are not limited to, ethynyl; propynyls such as prop-1-yn-1-yl, prop-2-in-1-yl, etc.; butynyls such as but-1-in- 1-yl, but-1-in-3-yl, but-3-in-1-yl, and the like.
[0084] The alkynyl group as defined above may further be substituted. The alkyl group or alkylene group as defined above may further be substituted.
[0085] The term "alkoxy" alone or as part of another substituent according to the present invention refers to a linear or branched radical of the formula -O-R, where R is alkyl or substituted alkyl, as defined herein.
[0086] In preferred variants according to the present invention, the linear or branched alkoxy group comprises 2 to 10 carbon atoms. In other preferred variants, the linear or branched alkoxy group comprises 2 to 6 carbon atoms. In still further preferred variants, the linear or branched alkoxy group comprises 2 to 4 carbon atoms.230135
[0087] Most preferred according to the invention are linear or branched C1 to C6 alkoxy groups.
[0088] Typical alkoxy radicals / moieties or alkoxy groups include C1 to C6 alkoxy comprising C1 to C4 alkoxy such as. methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy; as well as pentoxy, 1- methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2- dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2- methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2- dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3- dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2- trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.
[0089] In a preferred variant, the alkoxy radical or alkoxy group is selected from the group consisting of methoxy (-O-methyl), ethoxy (-O-ethyl), propoxy (-O-propyl) and butoxy (-O-butyl), more preferred from the group consisting of methoxy (-O-methyl) and ethoxy (-O-ethyl).
[0090] The alkoxy group as defined above may further be substituted.
[0091] According to the invention, the term "alkyl" or "alkylene" also includes heteroalkyl radicals or heteroalkyl groups. The term "heteroalkyl" by itself or as part of other substituents refers to alkyl groups in which one or more of the carbon atom(s) is / are independently replaced by the same or another heteroatom or by the same or another heteroatomic group(s). Typical heteroatoms or heteroatomic groups that may replace the carbon atoms include, but are not limited to, -O-, -S-, -N-, -Si-, -NH-, -S(O)- , -S(O)2-, -S(O)NH-, -S(O)2NH-, and the like, and combinations thereof. The heteroatoms or heteroatomic groups may be located at any internal position of the alkyl group.230135
[0092] Typical heteroatomic groups that may be included in these groups include, but are not limited to, -O-, -S-, -O-O-, -S-S-, -O-S-, -NRR-, =NN=, -N=N-, -N=N-NRR, -PR-, - P(O)2-, -POR-, -O-P(O)2-, -SO-, -SO2-, -SR2OR-, and the like, wherein R is independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, substituted arylalkyl, cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted cycloheteroalkyl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, heteroarylalkyl or substituted heteroarylalkyl as defined herein.
[0093] The term "substituted" in the context of the present invention means that one or more hydrogen atoms of the indicated radical or group is / are independently replaced by the same or a different substituent(s). Additionally, the term "substituted" specifically provides for one or more, i.e., two, three, four, five, six or more, substitutions commonly used in the art. However, it is generally known that the substituents should be selected so that they do not adversely affect the useful properties of the compound or its function.
[0094] Suitable substituents in the context of the present invention preferably include halogen, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy groups or heteroaryloxy groups, arylalkyl or heteroarylalkyl groups, arylalkoxy or heteroarylalkoxy groups, amino groups, alkyl and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, carboxyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, cycloalkyl groups, cyano groups, C1 to C6 alkylthio groups, arylthio groups, nitro groups, keto groups, acyl groups, boronate or boronyl groups, phosphate or phosphonyl groups, sulfamyl groups, sulfonyl groups, sulfinyl groups, and combinations thereof.
[0095] Substituents or substituent groups useful for substituting saturated carbon atoms in the indicated group or radical more preferably include, but are not limited to, halogen, hydroxyl, alkyl, alkenyl, alkynyl, alkoxyl, -NH2, amino (primary, secondary, or tertiary), nitro, thiol, thioether, imine, cyano, amido, phosphonato, phosphine, carboxyl, thiocarbonyl, sulfonyl, sulfonamide, ketone, aldehyde, ester, acetyl, acetoxy, carbamoyl,230135 oxygen (O); haloalkyl (e.g., trifluoromethyl); aminoacyl and aminoalkyl, carbocyclic cycloalkyl, which may be monocyclic or fused or non-fused polycyclic (e.g., cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl), or a heterocycloalkyl, which may be monocyclic or fused or non-fused polycyclic (e.g. pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, or thiazinyl), carbocyclic or heterocyclic, monocyclic or fused or non-fused polycyclic aryl (e.g., phenyl, naphthyl, pyrrolyl, indolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridinyl, quinolinyl, isoquinolinyl, acridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, benzimidazolyl, benzothiophenyl, or benzofuranyl), -CO2CH3, -CONH2, -OCH2CONH2; -SO2NH2, -OCHF2, -CF3, -OCF3.
[0096] According to the invention, the substituents used to replace a particular radical or radical may in turn be further substituted, typically with one or more of the same or different radicals selected from the various groups indicated above and as defined in detail above. In the case of substituted combinations such as substituted arylalkyl, either the aryl or the alkyl group may be substituted, or both the aryl and the alkyl group may be substituted with one or more substituents.
[0097] In a preferred variant, Z in the general formula (I) is either -O-R2’ or amide’, preferably -O-R2’.
[0098] In a further preferred variant, R1’ in the general formula (I) is CH2.
[0099] In a further preferred variant, R1’ in the general formula (I) is C(alkyl)2.
[0100] Preferably, the alkyl residue in C(alkyl)2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferred methyl or ethyl.
[0101] In a further preferred variant, R1’ in the general formula (I) is C(methyl)2.
[0102] In a further preferred variant, R1’ in the general formula (I) is C(ethyl)2.230135
[0103] In a further preferred variant, R1’ in the general formula (I) is C(propyl)2.
[0104] In a further preferred variant, R1’ in the general formula (I) is C(isopropyl)2.
[0105] In a further preferred variant, R1’ in the general formula (I) is C(butyl)2.
[0106] In a further preferred variant, R1’ in the general formula (I) is C(isobutyl)2.
[0107] In a further preferred variant, R1’ in the general formula (I) is C(tert-butyl)2.
[0108] Most preferred the R1’ in the general formula (I) is either CH2 or C(methyl)2.
[0109] In a preferred variant, R2’ in the general formula (I) is H.
[0110] In a preferred variant, amide’ in the general formula (I) is NH2 or N(alkyl)2.
[0111] Preferably, the alkyl residue in N(alkyl)2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferred methyl or ethyl.
[0112] Most preferred, that amide’ in the general formula (I) is NH2.
[0113] In a preferred variant, R3’ in the general formula (I) is H.
[0114] In a further preferred variant, R3’ in the general formula (I) is OH.
[0115] In a further preferred variant, R3’ in the general formula (I) is methyl.
[0116] In a further preferred variant, R3’ in the general formula (I) is ethyl.
[0117] In a further preferred variant, R3’ in the general formula (I) is propyl.230135
[0118] In a further preferred variant, R3’ in the general formula (I) is isopropyl.
[0119] In a further preferred variant, R3’ in the general formula (I) is butyl.
[0120] In a further preferred variant, R3’ in the general formula (I) is isobutyl.
[0121] In a further preferred variant, R3’ in the general formula (I) is tert-butyl.
[0122] Most preferred the R3’ in the general formula (V) is either H or methyl.
[0123] In a preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound of the general formula (I) is an acid compound represented by the general formula (II)formula (II), wherein R1’, R3’, R4’, R5’ and R6’ have the same meaning as defined herein for the general formula (I).
[0124] Such mycosporine-like amino acid compounds are particularly photo-stable and temperature-stable compounds and show stability in pH solution or in different emulsion types and do not degrade. In addition, said mycosporine-like amino acid compounds have a better solubility in water compared to their corresponding ester compounds. Due to their better solubility in water, said mycosporine-like amino acid compounds can be incorporated into the water-phase of emulsions in higher concentrations, resulting in an230135 improved sunscreen in food, cosmetic or pharmaceutical preparations or homecare products, in particular in sunscreen products.
[0125] In an alternative preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound of the general formula (I) is an amide compound represented by the general formula (III) 'formula (III), wherein R1’, amide’, R3’, R4’, R5’ and R6’ have the same meaning as defined herein for the general formula (I).
[0126] In a preferred variant, amide’ in the general formula (III) is NH2 or N(alkyl)2.
[0127] Preferably, the alkyl residue in N(alkyl)2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferred methyl or ethyl.
[0128] Within the present invention, the same preferred variants as defined herein for the mycosporine-like amino acid compounds according to general formula (I) apply analogously for the mycosporine-like amino acid compounds according to the general formulae (II) or (III).
[0129] It is to be understood that each preferred variant is relevant on its own as well as in combination with other preferred embodiments as defined herein. Furthermore, it is to230135 be understood that the preferences in each case also apply to the tautomer, stereoisomer or salt of the mycosporine-like amino acid compound.
[0130] In a further preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound is a compound according to general formula (I), wherein - 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 H; or - amide’ is NH2 or N(alkyl)2; and / or - R3’ is selected from the group consisting of H, OH, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl; and / or - the substituents R4’, R5’ and R6’ have the same meaning as defined for formula (I); wherein the alkyl residue in N(alkyl)2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferred methyl or ethyl. .
[0131] In another preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound is a compound according to general formulae (II) or (III), wherein - R1’ is selected from the group consisting of CH2 and C(methyl)2; and / or - R2’ H; or - amide’ is NH2 or N(alkyl)2; and / or - R3’ is selected from the group consisting of H, OH, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl; and / or - the substituents R4’, R5’ and R6’ have the same meaning as defined for formula (I); wherein the alkyl residue in N(alkyl)2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferred methyl or ethyl.
[0132] In a still further preferred variant according to the present invention, in the general formulae (I) to (III) n is 1.
[0133] In a more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound is a compound according to general formula (I), wherein - Z is -O-R2’ or amide’; and / or - R1’ is either CH2 or C(methyl)2; and / or - R2’ is H; or - amide’ is NH2 or N(alkyl)2; and / or - R3’ is either H or OH or halogen or methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl; and / or - the substituents R4’, R5’ and R6’ have the same meaning as defined for formula (I); wherein the alkyl residue in N(alkyl)2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferred methyl or ethyl.
[0134] In a more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid compound is a compound according to general formulae (II) or (III), wherein - R1’ is either CH2 or C(methyl)2; and / or - R2’ is H; or - amide’ is NH2 or N(alkyl)2; and / or - R3’ is either H or OH or halogen or methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl; and / or - the substituents R4’, R5’ and R6’ have the same meaning as defined for formula (I); wherein the alkyl residue in N(alkyl)2 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferred methyl or ethyl.
[0135] In a preferred variant, R1’ in the general formula (I) to (III) is CH2. Said compounds are particularly water soluble.
[0136] The phenyl ring in the mycosporine-like amino acid compounds according to the general formulae (I) to (III) can be unsubstituted or substituted.
[0137] In a preferred variant, the phenyl ring in the mycosporine-like amino acid compounds according to the general formulae (I) to (III) is unsubstituted, i.e. the substituents R4’, R5’ and R6’ on the phenyl ring in the general formulae (I) to (III) are each H.
[0138] In a further preferred variant, the phenyl ring in the mycosporine-like amino acid compounds according to the general formulae (I) to (III) and their variants is substituted.
[0139] Preferably, the phenyl ring in the mycosporine-like amino acid compounds according to the general formulae (I) to (III) and their variants are monosubstituted, disubstituted or trisubstituted.
[0140] In a still more preferred variant according to the first aspect of the present invention, the mycosporine-like amino acid is a compound according to general formulae (I) to (III), wherein the substituents R4’, R5’ and R6’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, alkyl, preferably methyl, ethyl, propyl, iso-propyl, butyl, isobutyl or tert.-butyl, alkoxy, preferably, O-methyl, O-ethyl, or O-butyl, -S(=O)2OH, and sulfonyl.
[0141] Still more preferred, the substituents R4’, R5’ and R6’ in the general formulae (I) to (III), which may be identical or different, are independently from each other selected from the group consisting of H, OH, methyl, O-methyl, -S(=O)2OH, and sulfonyl.
[0142] Most preferred, in the general formulae (I) to (III), the phenyl ring is unsubstituted, i.e. the substituents R4’, R5’ and R6’ are each H, or one or two substituents R4’, R5’ and R6’ are -S(=O)2OH. Said compounds have an improved water solubility.
[0143] In the general formulae (I) to (III), the following substitution patterns are particularly preferred: R4’ = H and R5’ = H and R6’ = H; or R4’ = H and R5’ = H and R6’ = OH; or230135 R4’ = H and R5’ = H and R6’ = methyl; or R4’ = H and R5’ = H and R6’ = O-methyl; or R4’ = H and R5’ = H and R6’ = -S(=O)2OH; or R4’ = H and R5’ = H and R6’ = sulfonyl; or R4’ = H and R5’ = OH and R6’ = H; or R4’ = H and R5’ = OH and R6’ = OH; or R4’ = H and R5’ = OH and R6’ = methyl; or R4’ = H and R5’ = OH and R6’ = O-methyl; or R4’ = H and R5’ = OH and R6’ = -S(=O)2OH; or R4’ = H and R5’ = OH and R6’ = sulfonyl; or R4’ = H and R5’ = methyl and R6’ = H; or R4’ = H and R5’ = methyl and R6’ = OH; or R4’ = H and R5’ = methyl and R6’ = methyl; or R4’ = H and R5’ = methyl and R6’ = O-methyl; or R4’ = H and R5’ = methyl and R6’ = -S(=O)2OH; or R4’ = H and R5’ = methyl and R6’ = sulfonyl; or R4’ = H and R5’ = O-methyl and R6’ = H; or R4’ = H and R5’ = O-methyl and R6’ = OH; or R4’ = H and R5’ = O-methyl and R6’ = methyl; or R4’ = H and R5’ = O-methyl and R6’ = O-methyl; or R4’ = H and R5’ = O-methyl and R6’ = -S(=O)2OH; or R4’ = H and R5’ = O-methyl and R6’ = sulfonyl; or R4’ = H and R5’ = -S(=O)2OH and R6’ = H; or R4’ = H and R5’ = -S(=O)2OH and R6’ = OH; or R4’ = H and R5’ = -S(=O)2OH and R6’ = methyl; or R4’ = H and R5’ = -S(=O)2OH and R6’ = O-methyl; or R4’ = H and R5’ = -S(=O)2OH and R6’ = -S(=O)2OH; or R4’ = H and R5’ = -S(=O)2OH and R6’ = sulfonyl; or230135 R4’ = H and R5’ = sulfonyl and R6’ = H; or R4’ = H and R5’ = sulfonyl and R6’ = OH; or R4’ = H and R5’ = sulfonyl and R6’ = methyl; or R4’ = H and R5’ = sulfonyl and R6’ = O-methyl; or R4’ = H and R5’ = sulfonyl and R6’ = -S(=O)2OH; or R4’ = H and R5’ = sulfonyl and R6’ = sulfonyl; or R4’ = OH and R5’ = H and R6’ = H; or R4’ = OH and R5’ = H and R6’ = OH; or R4’ = OH and R5’ = H and R6’ = methyl; or R4’ = OH and R5’ = H and R6’ = O-methyl; or R4’ = OH and R5’ = H and R6’ = -S(=O)2OH; or R4’ = OH and R5’ = H and R6’ = sulfonyl; or R4’ = OH and R5’ = OH and R6’ = H; or R4’ = OH and R5’ = OH and R6’ = OH; or R4’ = OH and R5’ = OH and R6’ = methyl; or R4’ = OH and R5’ = OH and R6’ = O-methyl; or R4’ = OH and R5’ = OH and R6’ = -S(=O)2OH; or R4’ = OH and R5’ = OH and R6’ = sulfonyl; or R4’ = OH and R5’ = methyl and R6’ = H; or R4’ = OH and R5’ = methyl and R6’ = OH; or R4’ = OH and R5’ = methyl and R6’ = methyl; or R4’ = OH and R5’ = methyl and R6’ = O-methyl; or R4’ = OH and R5’ = methyl and R6’ = -S(=O)2OH; or R4’ = OH and R5’ = methyl and R6’ = sulfonyl; or R4’ = OH and R5’ = O-methyl and R6’ = H; or R4’ = OH and R5’ = O-methyl and R6’ = OH; or R4’ = OH and R5’ = O-methyl and R6’ = methyl; or230135 R4’ = OH and R5’ = O-methyl and R6’ = O-methyl; or R4’ = OH and R5’ = O-methyl and R6’ = -S(=O)2OH; or R4’ = OH and R5’ = O-methyl and R6’ = sulfonyl; or R4’ = OH and R5’ = -S(=O)2OH and R6’ = H; or R4’ = OH and R5’ = -S(=O)2OH and R6’ = OH; or R4’ = OH and R5’ = -S(=O)2OH and R6’ = methyl; or R4’ = OH and R5’ = -S(=O)2OH and R6’ = O-methyl; or R4’ = OH and R5’ = -S(=O)2OH and R6’ = -S(=O)2OH; or R4’ = OH and R5’ = -S(=O)2OH and R6’ = sulfonyl; or R4’ = OH and R5’ = sulfonyl and R6’ = H; or R4’ = OH and R5’ = sulfonyl and R6’ = OH; or R4’ = OH and R5’ = sulfonyl and R6’ = methyl; or R4’ = OH and R5’ = sulfonyl and R6’ = O-methyl; or R4’ = OH and R5’ = sulfonyl and R6’ = -S(=O)2OH; or R4’ = OH and R5’ = sulfonyl and R6’ = sulfonyl; or R4’ = methyl and R5’ = H and R6’ = H; or R4’ = methyl and R5’ = H and R6’ = OH; or R4’ = methyl and R5’ = H and R6’ = methyl; or R4’ = methyl and R5’ = H and R6’ = O-methyl; or R4’ = methyl and R5’ = H and R6’ = -S(=O)2OH; or R4’ = methyl and R5’ = H and R6’ = sulfonyl; or R4’ = methyl and R5’ = OH and R6’ = H; or R4’ = methyl and R5’ = OH and R6’ = OH; or R4’ = methyl and R5’ = OH and R6’ = methyl; or R4’ = methyl and R5’ = OH and R6’ = O-methyl; or R4’ = methyl and R5’ = OH and R6’ = -S(=O)2OH; or R4’ = methyl and R5’ = OH and R6’ = sulfonyl; or230135 R4’ = methyl and R5’ = methyl and R6’ = H; or R4’ = methyl and R5’ = methyl and R6’ = OH; or R4’ = methyl and R5’ = methyl and R6’ = methyl; or R4’ = methyl and R5’ = methyl and R6’ = O-methyl; or R4’ = methyl and R5’ = methyl and R6’ = -S(=O)2OH; or R4’ = methyl and R5’ = methyl and R6’ = sulfonyl; or R4’ = methyl and R5’ = O-methyl and R6’ = H; or R4’ = methyl and R5’ = O-methyl and R6’ = OH; or R4’ = methyl and R5’ = O-methyl and R6’ = methyl; or R4’ = methyl and R5’ = O-methyl and R6’ = O-methyl; or R4’ = methyl and R5’ = O-methyl and R6’ = -S(=O)2OH; or R4’ = methyl and R5’ = O-methyl and R6’ = sulfonyl; or R4’ = methyl and R5’ = -S(=O)2OH and R6’ = H; or R4’ = methyl and R5’ = -S(=O)2OH and R6’ = OH; or R4’ = methyl and R5’ = -S(=O)2OH and R6’ = methyl; or R4’ = methyl and R5’ = -S(=O)2OH and R6’ = O-methyl; or R4’ = methyl and R5’ = -S(=O)2OH and R6’ = -S(=O)2OH; or R4’ = methyl and R5’ = -S(=O)2OH and R6’ = sulfonyl; or R4’ = methyl and R5’ = sulfonyl and R6’ = H; or R4’ = methyl and R5’ = sulfonyl and R6’ = OH; or R4’ = methyl and R5’ = sulfonyl and R6’ = methyl; or R4’ = methyl and R5’ = sulfonyl and R6’ = O-methyl; or R4’ = methyl and R5’ = sulfonyl and R6’ = -S(=O)2OH; or R4’ = methyl and R5’ = sulfonyl and R6’ = sulfonyl; or R4’ = O-methyl and R5’ = H and R6’ = H; or R4’ = O-methyl and R5’ = H and R6’ = OH; or R4’ = O-methyl and R5’ = H and R6’ = methyl; or R4’ = O-methyl and R5’ = H and R6’ = O-methyl; or230135 R4’ = O-methyl and R5’ = H and R6’ = -S(=O)2OH; or R4’ = O-methyl and R5’ = H and R6’ = sulfonyl; or R4’ = O-methyl and R5’ = OH and R6’ = H; or R4’ = O-methyl and R5’ = OH and R6’ = OH; or R4’ = O-methyl and R5’ = OH and R6’ = methyl; or R4’ = O-methyl and R5’ = OH and R6’ = O-methyl; or R4’ = O-methyl and R5’ = OH and R6’ = -S(=O)2OH; or R4’ = O-methyl and R5’ = OH and R6’ = sulfonyl; or R4’ = O-methyl and R5’ = methyl and R6’ = H; or R4’ = O-methyl and R5’ = methyl and R6’ = OH; or R4’ = O-methyl and R5’ = methyl and R6’ = methyl; or R4’ = O-methyl and R5’ = methyl and R6’ = O-methyl; or R4’ = O-methyl and R5’ = methyl and R6’ = -S(=O)2OH; or R4’ = O-methyl and R5’ = methyl and R6’ = sulfonyl; or R4’ = O-methyl and R5’ = O-methyl and R6’ = H; or R4’ = O-methyl and R5’ = O-methyl and R6’ = OH; or R4’ = O-methyl and R5’ = O-methyl and R6’ = methyl; or R4’ = O-methyl and R5’ = O-methyl and R6’ = O-methyl; or R4’ = O-methyl and R5’ = O-methyl and R6’ = -S(=O)2OH; or R4’ = O-methyl and R5’ = O-methyl and R6’ = sulfonyl; or R4’ = O-methyl and R5’ = -S(=O)2OH and R6’ = H; or R4’ = O-methyl and R5’ = -S(=O)2OH and R6’ = OH; or R4’ = O-methyl and R5’ = -S(=O)2OH and R6’ = methyl; or R4’ = O-methyl and R5’ = -S(=O)2OH and R6’ = O-methyl; or R4’ = O-methyl and R5’ = -S(=O)2OH and R6’ = -S(=O)2OH; or R4’ = O-methyl and R5’ = -S(=O)2OH and R6’ = sulfonyl; or R4’ = O-methyl and R5’ = sulfonyl and R6’ = H; orR4’ = O-methyl and R5’ = sulfonyl and R6’ = OH; or R4’ = O-methyl and R5’ = sulfonyl and R6’ = methyl; or R4’ = O-methyl and R5’ = sulfonyl and R6’ = O-methyl; or R4’ = O-methyl and R5’ = sulfonyl and R6’ = -S(=O)2OH; or R4’ = O-methyl and R5’ = sulfonyl and R6’ = sulfonyl; or R4’ = -S(=O)2OH and R5’ = H and R6’ = H; or R4’ = -S(=O)2OH and R5’ = H and R6’ = OH; or R4’ = -S(=O)2OH and R5’ = H and R6’ = methyl; or R4’ = -S(=O)2OH and R5’ = H and R6’ = O-methyl; or R4’ = -S(=O)2OH and R5’ = H and R6’ = -S(=O)2OH; or R4’ = -S(=O)2OH and R5’ = H and R6’ = sulfonyl; or R4’ = -S(=O)2OH and R5’ = OH and R6’ = H; or R4’ = -S(=O)2OH and R5’ = OH and R6’ = OH; or R4’ = -S(=O)2OH and R5’ = OH and R6’ = methyl; or R4’ = -S(=O)2OH and R5’ = OH and R6’ = O-methyl; or R4’ =-S(=O)2OH and R5’ = OH and R6’ = -S(=O)2OH; or R4’ = -S(=O)2OH and R5’ = OH and R6’ = sulfonyl; or R4’ = -S(=O)2OH and R5’ = methyl and R6’ = H; or R4’ = -S(=O)2OH and R5’ = methyl and R6’ = OH; or R4’ = -S(=O)2OH and R5’ = methyl and R6’ = methyl; or R4’ = -S(=O)2OH and R5’ = methyl and R6’ = O-methyl; or R4’ = -S(=O)2OH and R5’ = methyl and R6’ = -S(=O)2OH; or R4’ = -S(=O)2OH and R5’ = methyl and R6’ = sulfonyl; or R4’ = -S(=O)2OH and R5’ = O-methyl and R6’ = H; or R4’ = -S(=O)2OH and R5’ = O-methyl and R6’ = OH; or R4’ = -S(=O)2OH and R5’ = O-methyl and R6’ = methyl; or R4’ = -S(=O)2OH and R5’ = O-methyl and R6’ = O-methyl; or R4’ = -S(=O)2OH and R5’ = O-methyl and R6’ = -S(=O)2OH; orR4’ = -S(=O)2OH and R5’ = O-methyl and R6’ = sulfonyl; or R4’ = -S(=O)2OH and R5’ = -S(=O)2OH = and R6’ = H; or R4’ = -S(=O)2OH and R5’ = -S(=O)2OH and R6’ = OH; or R4’ = -S(=O)2OH and R5’ = -S(=O)2OH and R6’ = methyl; or R4’ = -S(=O)2OH and R5’ = -S(=O)2OH and R6’ = O-methyl; or R4’ = -S(=O)2OH and R5’ = sulfonyl = and R6’ = H; or R4’ = -S(=O)2OH and R5’ = sulfonyl and R6’ = OH; or R4’ = -S(=O)2OH and R5’ = sulfonyl and R6’ = methyl; or R4’ = -S(=O)2OH and R5’ = sulfonyl and R6’ = O-methyl; or R4’ = sulfonyl and R5’ = H and R6’ = H; or R4’ = sulfonyl and R5’ = H and R6’ = OH; or R4’ = sulfonyl and R5’ = H and R6’ = methyl; or R4’ = sulfonyl and R5’ = H and R6’ = O-methyl; or R4’ = sulfonyl and R5’ = H and R6’ = -S(=O)2OH; or R4’ = sulfonyl and R5’ = H and R6’ = sulfonyl; or R4’ = sulfonyl and R5’ = OH and R6’ = H; or R4’ = sulfonyl and R5’ = OH and R6’ = OH; or R4’ = sulfonyl and R5’ = OH and R6’ = methyl; or R4’ = sulfonyl and R5’ = OH and R6’ = O-methyl; or R4’ = sulfonyl and R5’ = OH and R6’ = -S(=O)2OH; or R4’ = sulfonyl and R5’ = OH and R6’ = sulfonyl; or R4’ = sulfonyl and R5’ = methyl and R6’ = H; or R4’ = sulfonyl and R5’ = methyl and R6’ = OH; or R4’ = sulfonyl and R5’ = methyl and R6’ = methyl; or R4’ = sulfonyl and R5’ = methyl and R6’ = O-methyl; or R4’ = sulfonyl and R5’ = methyl and R6’ = -S(=O)2OH; or R4’ = sulfonyl and R5’ = methyl and R6’ = sulfonyl; or230135 R4’ = sulfonyl and R5’ = O-methyl and R6’ = H; or R4’ = sulfonyl and R5’ = O-methyl and R6’ = OH; or R4’ = sulfonyl and R5’ = O-methyl and R6’ = methyl; or R4’ = sulfonyl and R5’ = O-methyl and R6’ = O-methyl; or R4’ = sulfonyl and R5’ = O-methyl and R6’ = -S(=O)2OH; or R4’ = sulfonyl and R5’ = O-methyl and R6’ = sulfonyl; or R4’ = sulfonyl and R5’ = -S(=O)2OH and R6’ = H; or R4’ = sulfonyl and R5’ = -S(=O)2OH and R6’ = OH; or R4’ = sulfonyl and R5’ = -S(=O)2OH and R6’ = methyl; or R4’ = sulfonyl and R5’ = -S(=O)2OH and R6’ = O-methyl; or R4’ = sulfonyl and R5’ = sulfonyl and R6’ = H; or R4’ = sulfonyl and R5’ = sulfonyl and R6’ = OH; or R4’ = sulfonyl and R5’ = sulfonyl and R6’ = methyl; or R4’ = sulfonyl and R5’ = sulfonyl and R6’ = O-methyl; or
[0144] In the general formulae (I) to (III), the substituted phenyl ring bonded to the imino functionality is preferably selected from the group consisting of; wherein the dotted line designates the binding site to the cyclohexene imine ring.230135
[0145] In a more preferred variant according to the first aspect of the present invention, in the general formulae (I), (II) and (III), the substituents R4’, R5’ and R6’, which may be identical or different, are independently from each other selected from the group consisting of H, OH, alkyl, preferably methyl, ethyl, propyl, iso-propyl, butyl, isobutyl or tert.-butyl, alkoxy, preferably, O-methyl, O-ethyl, or O-butyl, with the proviso, that if the substituted phenyl ring is monosubstituted, the substituent is either in the ortho or meta- position to the imino-functionality of the general formulae (I), (II) and (III), but not in the para position to the imino-functionality.
[0146] Still more preferred according to the first aspect of the present invention, the food, cosmetic or pharmaceutical preparation, especially the sunscreen product, or homecare product comprises at least one mycosporine-like amino acid compound selected from the group consisting of:
[0147] Table 1: Com- Structure INCI / chemical name pound MAA-20 2-[(5,5-dimethyl-3-phenylimino- cyclohexen-1-yl)amino]acetic acid230135 MAA-21 2-[(3-phenyliminocyclohexen-1- yl)amino]acetic acid MAA-22 2,5,5-trimethyl-3- (phenylimino)cyclohex-1-en-1-yl- glycine MAA-23 2-[(2-methyl-3-phenylimino- cyclohexen-1-yl)amino]acetic acid MAA-24 3-((3,4-dimethoxyphenyl)imino)- 5,5-dimethylcyclohex-1-en-1-yl- glycineMAA-25 3-((3,4- dimethoxyphenyl)imino)cyclohex- 1-en-1-yl-glycine MAA-26 3-((3,4-dimethoxyphenyl)imino)- 2,5,5-trimethylcyclohex-1-en-1-yl- glycine MAA-27 2-[(3-(3,4-dimethoxyphenyl)imino- 2-methyl-cyclohexen-1- yl)amino]acetic acid MAA-28 2-[(5,5-dimethyl-3-(4- sulfophenyl)imino-cyclohexen-1- yl)amino]acetic acidMAA-29 2-[(3-(4- sulfophenyl)iminocyclohexen-1- yl)amino]acetic acid MAA-30 2,5,5-trimethyl-3-((4- sulfophenyl)imino)cyclohex-1-en- 1-yl-glycine MAA-31 2-methyl-3-((4- sulfophenyl)imino)cyclohex-1-en- 1-yl-glycine MAA-32 2-[(5,5-dimethyl-3-phenylimino- cyclohexen-1-yl)amino]acetamide230135 MAA-33 2-[(3-phenyliminocyclohexen-1- yl)amino]acetamide MAA-34 2-((2,5,5-trimethyl-3- (phenylimino)cyclohex-1-en-1- yl)amino)acetamide MAA-35 2-((2-methyl-3- (phenylimino)cyclohex-1-en-1- yl)amino)acetamide MAA-36 2-((3-((3,4- dimethoxyphenyl)imino)-5,5- dimethylcyclohex-1-en-1- yl)amino)acetamide230135 MAA-37 2-[(3-(3,4- dimethoxyphenyl)iminocyclohexen -1-yl)amino]acetamide MAA-38 2-((3-((3,4- dimethoxyphenyl)imino)-2,5,5- trimethylcyclohex-1-en-1- yl)amino)acetamide MAA-39 2-((3-((3,4- dimethoxyphenyl)imino)-2- methylcyclohex-1-en-1- yl)amino)acetamide or a tautomer or a stereoisomer or a salt of the afore-mentioned compounds, or any mixture of the afore-mentioned compounds.
[0148] Among the above specified mycosporine-like amino acid compounds the compounds 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, MAA-31 are most preferred. Said compounds having an acid functionality are particularly photo-stable and temperature- stable and show stability in pH solution or in different emulsion types and does not degrade.230135
[0149] Especially, the mycosporine-like amino acid compounds as defined herein have a better pH stability in a broader pH-range compared to their respective ester compounds which hydrolize, and, thus, are not stable in alkaline solutions having a pH higher than 9.
[0150] Due to their better solubility in water, said mycosporine-like amino acid compounds can be incorporated into the water-phase of formulations in higher concentrations, resulting in an improved sunscreen in sunscreen product, compared to their known ester compounds. In addition, the higher concentration also results in better protection against photolytic degradation of food, cosmetic or pharmaceutical preparations or homecare products, in particular in sunscreen compositions.
[0151] Due to their better solubility in water, the mycosporine-like amino acid compounds remain in the water phase where usually microbial contamination takes place. This is in particular beneficial for the development of the antimicrobial boosting effect of the mycosporine-like amino acid compounds in the water phase.
[0152] Various mycosporine-like amino acid compounds as described herein contain one or more chiral centers, and, thus, can exist as racemic mixtures of enantiomers, mixtures of diastereomers or enantiomerically or optically pure compounds. It should also be noted the compounds of the invention include E and Z isomers, or a mixture thereof, and cis and trans isomers or a mixture thereof.
[0153] Accordingly, the chemical structures of the mycosporine-like amino acid compounds according to the general formulae (I) to (III) and compounds explicitly disclosed herein include all possible enantiomers and diastereomers or stereoisomers thereof.
[0154] In certain embodiments, the mycosporine-like amino acid compounds (b) of the invention are isolated as either the E or Z isomer. In other embodiments, the compounds of the invention are a mixture of the E and Z isomers.230135
[0155] Alternatively, stereomerically pure compounds are used in the food, cosmetic or pharmaceutical preparation or homecare product according to the present invention. As used herein and unless otherwise indicated, the term " stereomerically pure" means that one stereoisomer of a compound is substantially free of other stereoisomers of that compound or one geometric isomer (e.g., about a double bond) is substantially free of the other geometric isomer. For example, a stereomerically pure compound of the invention having one chiral center, will be substantially free of the opposite enantiomer of the compound. A stereomerically pure compound of the invention having two chiral centers, or a composition thereof, will be substantially free of other diastereomers of the compound. A stereomerically pure compound of the invention having a double bond capable of E / Z isomerism, or a composition thereof, will be substantially free of one of the E / Z isomers.
[0156] A typical stereomerically pure compound comprises greater than about 80 % by weight of one stereoisomer or E / Z isomer of the compound and less than about 20 % by weight of other stereoisomers or E / Z isomer of the compound, more preferably greater than about 90 % by weight of one stereoisomer or E / Z isomer of the compound and less than about 10 % by weight of the other stereoisomers or E / Z isomer of the compound, even more preferably greater than about 95 % by weight of one stereoisomer or E / Z isomer of the compound and less than about 5 % by weight of the other stereoisomers or E / Z isomer of the compound, and most preferably greater than about 97 % by weight of one stereoisomer or E / Z isomer of the compound and less than about 3 % by weight of the other stereoisomers or E / Z isomer of the compound.
[0157] As used herein and unless otherwise indicated, the term "stereomerically enriched" means a compound of the invention, or a composition thereof, that comprises greater than about 60 % by weight of one stereoisomer or E / Z isomer of a compound of the invention, preferably greater than about 70 % by weight, more preferably greater than about 80 % by weight of one stereoisomer or E / Z isomer of a compound of the invention.
[0158] Thus, it should be noted that unless stated otherwise, the term mycosporine-like amino acid compound according to general formulae (I) to (III) as well as individual230135 mycosporine-like amino acid compounds specified herein, are to be interpreted as encompassing racemic mixtures of enantiomers, mixtures of diastereomers or enantiomerically or optically pure compounds.
[0159] Due to their amino cyclohexene imine structure and their capability of electron delocalization, the mycosporine-like amino acid compounds according to general formulae (I) to (III) are in equilibrium with their tautomer structures, in which the hydrogen of the amino group changes its places with the double bond of the cyclohexene ring.
[0160] Tautomerism is defined as each of two or more isomers of a compound which exist together in equilibrium and are readily interchanged by migration of an atom or group within the molecule. Tautomeric pure or enriched systems will readily interchange into the equilibrium state over time.
[0161] The tautomers of general formula (I) are represented by general formulae (I-tau):
[0162] The above principles of tautomerism and redeposition explained on the basis of the mycosporine-like amino acid compounds according to the general formula (I) are likewise applicable with respect to any of the mycosporine-like amino acid compounds defined by the general formula (II) or (III) or with respect to any individual mycosporine- like amino acid compounds specified herein.230135
[0163] Thus, in the following and throughout the description, the reference to a mycosporine-like amino acid compound represented by any of the general formulae (I) to (III) or to an individual mycosporine-like amino acid compound specified herein encompasses likewise its tautomer isomer(s).
[0164] The mycosporine-like amino acid compounds according to the general formulae (I) to (III) as well as individual mycosporine-like amino acid compounds specified herein are used according to the first aspect of the present invention either in neutral, i.e. uncharged form, or in the form of their salts, such as an acid addition salt, with inorganic or organic acids.
[0165] The term "salt" in the context of the present invention refers to a salt of a compound that possesses the desired effect or pharmacological activity of the parent compound. Such salts include: (1) acid addition salts formed with inorganic acids, or formed with organic acids, preferably monovalent or polyvalent carboxylic acids; or (2) salts formed when an acidic proton present in the starting compound is replaced by a metal ion, e.g., an alkali metal ion, an alkaline earth ion, or an aluminium ion; or coordinated with an organic base.
[0166] Among the salts, acid addition salts are again particularly preferred, since the mycosporine-like amino acid compounds according to the general formulae (I) to (III) or the mycosporine-like amino acid compounds specified herein comprise a protonable N atom.
[0167] The inorganic acids that form acid addition salts with the mycosporine-like amino acid compounds used according to the present invention are preferably selected from the group consisting of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like. Particularly preferred is the hydrochloride salt or the sulfate salt or the phosphate salt.230135
[0168] Even more preferred are acid addition salts with organic mono- or polycarboxylic acids. Further preferred are acid addition salts with organic mono- or polycarboxylic acids, wherein the carboxylic acid is selected from saturated or mono- or polyunsaturated C1 to C30 monocarboxylic acids, saturated or mono- or polyunsaturated C3 to 10 di- or tricarboxylic acids. The carboxylic acid may be mono- or poly-substituted with hydroxy groups, preferably α-hydroxycarboxylic acids in which the hydroxy group is located on the carbon atom adjacent to the carboxy group. Many representatives occur naturally as so- called fruit acids. Preferred α-hydroxycarboxylic acids are malic acid, citric acid, 2- hydroxy-4-methylmercaptobutyric acid, glycolic acid, isocitric acid, mandelic acid, lactic acid, tartronic acid, or tartaric acid.
[0169] The organic acids that form acid addition salts with the mycosporine-like amino acid compounds used according to the present invention are preferably selected from the group consisting of amino acids, acetic acid, trifluoroacetic acid, propionic acid, hexanoic acid, cyclopentane propionic acid, glycolic acid, pyruvic acid, lactic acid, malonic acid, oxalic acid, succinic acid, malic acid, maleic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, 3-(4-hydroxybenzoyl)benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, 1,2-ethanedisulfonic acid, 2- hydroxyethanesulfonic acid, benzenesulfonic acid, 4-chlorobenzenesulfonic acid, 2- naphthalenesulfonic acid, 4-toluenesulfonic acid, camphorsulfonic acid, 4- methylbicyclo[2. 2.2]-oct-2-ene-1-carboxylic acid, glucoheptonic acid, 3-phenylpropionic acid, trimethylacetic acid, tert. butylacetic acid, laurylsulfuric acid, gluconic acid, glutamic acid, hydroxynaphthoic acid, salicylic acid, stearic acid, muconic acid, 4-hydroxybutanoic acid, and the like.
[0170] Suitable anionic counterions are in particular chloride, bromide, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, 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 poly acids such as succinate, oxalate, maleate, fumarate, malate, tartrate and citrate, furthermore sulfonate anions such as besylate (benzenesulfonate), tosylate (p-toluenesulfonate), napsylate (naphthalene-2-230135 sulfonate), mesylate (methanesulfonate), esylate (ethanesulfonate), and ethanedisulfonate. They can be formed by reacting compounds according to the invention that have a basic functionality with an acid of the corresponding anion. Preferred salts of the compounds of formulae (I) to (III) as well as of the individual mycosporine-like amino acid compounds specified herein are chloride salts.
[0171] The metal ions for salt formation that replace an acidic proton present in the starting compound are selected from the group consisting of alkali metal ions, preferably Na+, K+ or Li+, alkaline earth metal ions, preferably Ca++ or Mg++, aluminium+++ and NH4+.
[0172] The coordinating organic base for salt formation is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N-methylglucamine, triethylamine, and the like.
[0173] In the following description and claims, and unless stated otherwise, the term mycosporine-like amino acid compound includes both the neutral, uncharged form of the compound / molecule and equally the salt form of the compound.
[0174] The salt form of the mycosporine-like amino acid compounds leads to a lower logPOW and, thus, making the compounds more hydrophilic, which results in a better water solubility. In particular, the cationic salts of the mycosporine-like amino acid compounds support emulsification processes in emulsions, due to their surface reducing activity, i.e. co-emulsifying, properties. In addition, the cationic salt form of the mycosporine-like compounds shows excellent substantivity behaviour on skin and hair and other non- biological surfaces: most conditioning actives are cationic; the conditioning effect leads to a softer skin feel, which makes the end products more accepted by the consumer. In addition, the mycosporine-like amino acid compounds in the cationic salt form exhibit antimicrobial activity.
[0175] The mycosporine-like amino acid compounds according to the present invention are characterized to be potentially useful in absorbing UV radiations and in blocking UV230135 radiations from penetrating the surface of skin, hair and nails. The harmful effects of UV radiations include sunburn, skin diseases, aggravation of skin diseases, damage to the eyes, indirect DNA damage, melanoma and cancer. In addition, the compounds are also useful in inhibiting or reducing the harmful effects of UV in food, cosmetic or pharmaceutical preparations or homecare products, such as degradation of polymers, degradation of pigments, degradation of color, degradation of dyes, degradation of fragrances, etc.
[0176] The UV absorbance of a sunscreen product can be determined in vitro over the entire UV spectrum (290 nm - 400 nm) using substrate spectrophotometry. The absorbance of that UV radiation is measured according to techniques well known in the art. The UV absorbance curve obtained demonstrates the amplitude and breadth of protection provided across the UV spectrum from 290 nm - 400 nm. The "amplitude" of the absorbance curve reflects the degree of protection. The higher the amplitude of the curve, the greater the absorbance and the more protection provided at that wavelength. Within the UVB portion of the spectrum (290 nm-320 nm) this amplitude correlates with the SPF. The greater the "breadth" of the curve, the more protection provided against longer wave UV radiation. In other words, the greater the "breadth" of the curve, the broader the spectrum of sun protection provided.
[0177] As can be seen from the absorption spectrum in Figure 3, the mycosporine-like amino acid analogue compound MAA-20 absorbs in a range of 290 to 400 nm. In addition, the amplitude of the absorbance of MAA-20 is higher compared to the absorbance of the respective ester compound MAA compound ethyl 2-[[5,5-dimethyl-3-phenylimino- cyclohexen-1-yl]amino]acetate according to the prior art. In addition, the breath of the curve for MAA-20 is broader that the breath of the curve for the comparison compound, i.e. MAA-20 acid compound shows a better UV radiation absorbing capacity than its corresponding ester compound. As can be seen from the absorption spectrum in Figure 4, the mycosporine-like amino acid analogue compound MAA-28 shows an improved UVA protection and an improved broad spectrum protection.230135
[0178] In a further aspect, the present invention relates to the preparation of the mycosporine-like amino acid analogue compounds according to the present invention.
[0179] The mycosporine-like amino acid analogue compounds are synthesized according to the following reaction scheme:Formula Weight: 300,39535 Molecular Formula: C18H24N2O2Formula Weight: 272,3422 Molecular Formula: C16H20N2O22(81 %)
[0180] The starting ethyl ester compound according to formula 1, may be derived by methods according to WO 2023 / 279205 A1. The ethyl ester compound (154 g, 0.514 mol) was dissolved in THF (514 mL) and a solution of an alkali metal hydroxide, preferably NaOH (61.7 g, 1.54 mol) 40 % in water, was added at RT and the mixture was stirred until full conversion.
[0181] After neutralization and aqueous workup, the carboxylic acid 2 was isolated as a pale yellow solid (113 g, 0.415 mol, 81 %) in >95 % purity consisting of a mixture of different E / Z- and double bond isomers.
[0182] LC-MS: tR [min]: 4.15 (MW: 272, C16H20N2O2).
[0183] 1H NMR (400 MHz, MeOD-D4) δ [ppm]: 7.48 (t, J = 7.8 Hz, 2.7H), 7.35 (m, 0.9H), 7.32 (m, 2.6H), 7.24 (m, 0.5H), 5.81 (s, 0.2H), 5.59 (s, 0.2H), 5.54 (s, 1.0H), 3.93 (s, 0.4 H), 3.89 (s, 0.4H), 3.73 (s, 2.0H), 2.61 (s, 2.0H), 2.57 (s, 2.0H), 2.55 (s, 0.3H), 2.53 (s, 0.7H), 1.16 (s, 7.1H), 1.06 (s, 0.9H).230135
[0184] 13C NMR (101 MHz, MeOD-D4) δ [ppm]: 173.0, 172.2, 170.2, 138.1, 131.0, 130.8, 128.9, 128.5, 126.1, 125.8, 87.6, 47.3, 43.9, 43.8, 33.5, 28.1, 27.7.
[0185] Due to their beneficial attributes, the mycosporine-like amino acid compounds according to the present invention are used to absorb UV radiation. Especially, the compounds are used to protect skin, hair, nails or products against damaging effects of UV radiations, in particular against the damaging effects of UVA or UVB or both radiations. For this purpose, at least one mycosporine-like amino acid compound according to the present invention is incorporated into compositons that are suitable for application on the skin, hair, nails or products.
[0186] Hence, the present invention relates in a further aspect to food, cosmetic or pharmaceutical compositions or homecare products comprising at least one mycosporine-like amino acid compound as defined herein or a mixture of two, three or even more mycosporine-like amino acid compounds as defined herein. Preferably, the cosmetic or pharmaceutical compositon is a sunscreen product.
[0187] The mycosporine-like amino acid compound can be formulated in combination with other compounds, in order to obtain formulations or products with the desired characteristics. Such other compounds comprise a wide range of ingredients and compounds that itself are not UV absorbers. Alternatively, the mycosporine-like amino acid compound can be formulated in combination with other compounds that act as UVA or UVB absorbers.
[0188] Especially, in the preparation of sunscreen product, the mycosporine-like amino acid compound as defined herein can be used in combination with other UV absorbing agents known in the art.
[0189] UV-filters: The composition as defined herein, is advantageously combined with at least one primary sun protection factor and / or with at least one secondary sun230135 protection factor, in order to increase the SPF, i.e. to obtain a high SPF and to cover a broad UVA and UVB range.
[0190] The compositions according to the invention advantageously contains at least one UVA filter and / or at least one further 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 stopping UV radiation.
[0191] For example, the at least one primary 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: (i) sparingly soluble UV-filters (not appreciably soluble in either water or oil) such as Methylene Bis-benzotriazolyl Tetramethylbutylphenol, Tris- Biphenyl Triazine, Methanone, 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl- ]phenyl]; (ii) oil soluble organic UV-filters (at least partially soluble in oil or organic solvent), such as Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Butyl Methoxydibenzoylmethane (BMBM), Oxybenzone, Sulisobenzone, Diethylhexyl Butamido Triazone (DBT), Drometrizole Trisiloxane, Ethylhexyl Methoxycinnamate (EHMC), Ethylhexyl Salicylate (EHS), Ethylhexyl Triazone (EHT), Homosalate, Isoamyl p-Methoxycinnamate, 4-Methylbenzylidene Camphor, Octocrylene (OCR), Polysilicone-15, and Diethylamino Hydroxy Benzoyl Hexyl Benzoate (DHHB); (iii) inorganic UV-filters such as titanium oxide and zinc oxide, iron oxide, zirconium oxide and cerium oxide; and (iv) water soluble UV-filters such as Phenylbenzimidazole Sulfonic Acid (PBSA), Sulisobenzone-sodium salt, Benzydilene Camphor Sulfonic Acid, Camphor Benzalkonium Methosulfate, Cinoxate, Disodium Phenyl Dibenzylmidazole Tetrasulfonate, Terephthalylidene Dicamphor Sulfonic Acid, PABA, and PEG-25 PAB; and any mixture thereof.
[0192] Many different organic compounds can serve as UV-filters. They fall into several structural classes: (1) Benzophenones230135 a. Benzophenone-3 (BP3) b. Benzophenone-4 (BP4) (2) Salicylates a. Homosalate (HMS) b. 2-ethylhexyl salicylate (EHS) (3) p-Aminobenzoic acid and derivatives a. Ethylhexyl dimethyl PABA (OD-PABA) b. 4-p-aminobenzoic acid (PABA) (4) Benzimidazole derivatives a. Phenylbenzimidazole sulfonic acid (PMDSA) b. Disodium phenyl dibenzimidazole tetrasulfonate (bisdisulizole disodium) (5) Triazines a. Ethylhexyltriazone (OT) b. Diethylhexyl butamido triazone (DBT) c. Bis-ethylhexyloxyphenol methoxyphenyl triazine (EMT) (6) Benzotriazoles a. Drometrizole trisiloxane (DRT) b. Methylene bis-benzotriazolyl tetramethylbutylphenol (MBP, biscotrizole) (7) Dibenzoylmethane derivatives a. 4-tert-Butyl-4’-methoxydibenzoylmethane (BM-DBM, avobenzone) (8) Cinnamates a. Ethylhexyl methoxycinnamate (OMC) b. Isoamyl p-methoxycinnamate (IMC, amiloxate) (9) Camphor derivatives a. Terephtalydene dicamphor sulfonic acid (PDSA) b. 3-benzylidene camphor (3BC) c. Benzylidene camphor sulfonic acid (BCSA) d. 4-methylbenzylidene camphor (4-MBC) e. Polyacrylamidomethyl benzylidene camphor (PBC) (10) Camphor benzalkonium methosulfate (CBM)230135
[0193] According to the present invention, the at least one inorganic UV-filter (a) is selected from the group of pigments consisting of titanium dioxide (TiO2) (amorphous or crystallized in rutile and / or anatase form), zinc oxide (ZnO), iron oxide (Fe2O3), zirconium oxide (ZrO2), silicon dioxide (SiO2), manganese oxide (e.g. MnO), aluminium oxide (Al2O3), cerium oxide (Ce2O3), barium carbonate (BaCO3), calcium carbonate (CaCO3), and mixtures thereof.
[0194] Preferably, the at least one inorganic UV-filter is titanium dioxide, zinc oxide, and mixtures thereof, more preferably the at least one inorganic UV-filter is titanium oxide and / or zinc oxide, and most preferably, the at least one inorganic UV-filter is zinc oxide. ZnO has a broad UVA / UVB absorption curve, while TiO2 provides better UVB protection.
[0195] According to another variant, the at least one inorganic UV-filter is in form of particles having a weight medium particle size d50 from 1 nm to 1000 nm, preferably from 3 nm to 800 nm, more preferably from 5 nm to 600 nm, and most preferably from 10 nm to 400 nm.
[0196] The inorganic UV-filters also encompass nano pigments (mean size of the primary particles: generally from 1 nm to 100 nm, preferably from 3 nm to 90 nm, more preferred from 5 nm to 80 nm and most preferred from 10 to 70 nm) of untreated or treated metal oxides such as, for example, nano pigments of titanium dioxide (TiO2) (amorphous or crystallized in rutile and / or anatase form), zinc oxide (ZnO), iron oxide (Fe2O3), zirconium oxide (ZrO2), silicon dioxide (SiO2), manganese oxide (e.g. MnO), aluminium oxide (Al2O3), cerium oxide (Ce2O3), barium carbonate (BaCO3), calcium carbonate (CaCO3), or mixtures thereof.
[0197] The treated nano pigments and non-nano pigments are pigments that have undergone one or more surface treatments of chemical, electronic, mechanochemical and / or mechanical nature with compounds, such as amino acids, beeswax, fatty acids, fatty acid esters, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal (titanium or aluminium) alkoxides, polyethylene, silicones, proteins (collagen or elastin), alkanolamines, silicon oxides, metal230135 oxides, sodium hexametaphosphate, alumina or glycerol, hydrated silica, stearic acid, jojoba esters, or glutamic acid derivates,
[0198] The treated nano pigments and non-nano pigments may more particularly be titanium oxides treated with silica and alumina, alumina and aluminium stearate, alumina and aluminium laurate, aluminium hydroxide, iron oxides and iron stearate, silica, alumina and silicone, sodium hexametaphosphate, octyltrimethoxysilane, alumina and stearic acid, alumina and glycerol, or alumina and silicone or polyhydroxy stearic acid, hydrated silica, jojoba esters, steaoryl glutamic acid, glutamic acid and derivates, trimethoxycaprylylsilane, glycerin, dimethicone, hydrogen dimethicone, simethicone or combinations thereof. Other titanium oxide nano pigments treated with a silicone are preferably TiO2 treated with octyltrimethylsilane, preferably for which the mean size of the elementary particles is from 25 to 40 nm; TiO2 treated with a polydimethylsiloxane, preferably for which the mean size of the elementary particles is 21 nm; or TiO2 treated with a polydimethylhydrogenosiloxane, preferably for which the mean size of the elementary particles is 25 nm.
[0199] The coated zinc oxide nano pigments and zinc oxide non-nano pigments are for example ZnO coated with polymethylhydrogenosiloxane; ZnO dispersions in cyclopolymethylsiloxane / oxyethylenated polydimethylsiloxane, containing 30 % or 80 % of nano or non-nano zinc oxides coated with silica and polymethylhydrogenosiloxane; ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl as a dispersion in cyclopentasiloxane; ZnO coated with dimethoxydiphenylsilanetriethoxycaprylylsilane cross-polymer; ZnO coated with glutamic acid; ZnO coated with octyltriethoxy silane; ZnO coated with dimethicone; ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane; ZnO coated with triethoxycaprylylsilane; ZnO coated with polyhydroxystearic acid; alumina-treated ZnO dispersed in an ethylhexyl methoxycinnamate / PVP- hexadecene / methicone copolymer mixture; ZnO coated with silica and polymethylsilsesquioxane; ZnO dispersed in hydroxystearic acid polycondensate; or ZnO coated with a mixture of steaoryl glutamic acid, jojoba esters, polyhydroxystearic acid, isopropyl titanium triisostearate, hydrogenated olive oil stearyl esters, cetearyl230135 nonanoate, cera alba, dimethicone, dimethoxydiphenylsilanetriethoxycaprylylsilane cross- polymer, octyltriethoxysilane, glutamic acid and sodium stearoyl lactylate.
[0200] Also preferred are particulate UV-filters or inorganic pigments, which can optionally be hydrophobed, such as the oxides of iron (Fe2O3), zirconium (ZrO2), silicon (SiO2), manganese (e.g. MnO), aluminium (Al2O3), cerium (e.g. Ce2O3), barium carbonate (BaCO3), calcium carbonate (CaCO3), or mixtures thereof.
[0201] The at least one primary organic and / or inorganic UV-filter is selected from the group consisting of Camphor Benzalkonium Methosulfate, Homosalate, Benzophenone- 3, Phenylbenzimidazole Sulfonic Acid, Terephthalylidene Dicamphor Sulfonic Acid, Butyl Methoxydibenzoylmethane, Benzylidene Camphor Sulfonic Acid, Octocrylene, Polyacrylamidomethyl Benzylidene Camphor, Ethylhexyl Methoxycinnamate, PEG-25 PABA, Isoamyl p-Methoxycinnamate, Ethylhexyl Triazone, Drometrizole Trisiloxane, Diethylhexyl Butamido Triazone, 4-Methylbenzylidene Camphor, Ethylhexyl Salicylate, Ethylhexyl Dimethyl PABA, Benzophenone-4, Benzophenone-5, Methylene Bis- Benzotriazolyl Tetramethylbutylphenol (nano), Disodium Phenyl Dibenzimidazole Tetrasulfonate, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, Polysilicone-15, Titanium Dioxide, Titanium Dioxide (nano), Diethylamino Hydroxy benzoyl Hexyl Benzoate, Tris-biphenyl triazine (nano), Zinc Oxide, Zinc Oxide (nano), Phenylene Bis- Diphenyltriazine, Methoxypropylamino Cyclohexenylidene Ethoxyethylcyanoacetate, Bis- (Diethylaminohydroxybenzoyl Benzoyl) Piperazine, TEA-Salicylate, Benzophenone-8, PABA, Ethylhexyl Dimethyl PABA, Menthyl Anthranilate, and any mixture thereof.
[0202] The aforesaid primary organic or inorganic UV-filters are used in the compositions according to the present invention either as a single component or preferably in a mixture with two, three, four or more further of said UV-filters as specified above.
[0203] In order to optimize the SPF, i.e. to obtain a high SPF in a range of 6 to 100, preferably in a range of 6 to 70, and to cover a broad UVA and UVB range, the compositions comprises at least two, more preferably at least three, most preferably at least four or even more different primary organic and / or inorganic UV-filters, i.e. in230135 particular organic UV-filters and / or inorganic pigments (UV-filtering pigments). The combination of effective sun protection UV-filters of different categories such as UVA filter, UVB, broadband filter, inorganic pigments provides reliable protection against the different UV rays in the wavelength range of 290 to 400 nm.
[0204] Advantageous the amount of primary organic and / or inorganic sun protection substances (UV-filters) in the compositions according to the present invention is advantageously from 0.01 to 80.0 % by weight, preferably from 0.1 to 75.0 % by weight, most preferred from 0.5 to 70.0 % by weight, based on the total weight of the ready-to- use formulation.
[0205] Besides the group of primary organic and / or inorganic sun protection UV-filters mentioned above, secondary sun protection ingredients of the antioxidant type may also be advantageously used in the compositions according to the present invention in order to further optimize the UV protection.
[0206] Secondary sun protection ingredients of the antioxidant type interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin.
[0207] Typical examples of secondary sun protection ingredients are amino acids (for example arginine, lysine, glycine, histidine, tyrosine, tryptophane) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as D,L- carnosine, D-carnosine, L-carnosine and derivatives thereof (for example anserine), carotenoids, carotenes (for example alpha-carotene, beta-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, liponic acid and derivatives thereof (for example dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (for example thioredoxine, glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, alpha-linoleyl, cholesteryl and glyceryl esters thereof) and their salts, dilaurylthiodipropionate, distearyl- thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (for example butionine sulfoximines, homocysteine sulfoximine, butionine sulfones, penta-, hexa- and230135 hepta-thionine sulfoximine) in very small compatible dosages, also (metal) chelators (for example alpha-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrine), alpha-hydroxy acids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (for example linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives thereof (for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, sinapic acid, sinapoyl malate, sinapate ester derivatives, titanium dioxide (for example dispersions in ethanol), zinc and derivatives thereof (for example ZnO, ZnSO4), selenium and derivatives thereof (for example selenium methionine), stilbenes and derivatives thereof (for example stilbene oxide, trans-stilbene oxide) and derivatives of these active substances suitable for the purposes of the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids).
[0208] The group of secondary sun protection ingredients also encompasses plant- based extract(s). Said plant-based extracts have antioxidative and in general photoprotective properties and interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin, and, thus, are effective in preventing skin aging. The plant extracts with UV protection properties are selected from the group consisting of Lignin / Cellulose, Lignin, Lignin Hydrolyzed, Propolis and green propolis, Galanga Extract, macro and micro algae (Porphyra, red algae (Porphyra Umbilicalis), Palmaria 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, Euchema, cottonii), Pongamia Glabra Seed Oil, Karanja oil (Millettia pinnata), Rhatania Extrakt (Krameria lappacea), Lichens, Soybean, Caper (Capparis spinosa), Bamboo, Green Coffee oil, Buriti Oil (Mauritia flexuosa), Black Sea Cucumber (Holothuria atra),230135 Cyanobacteria, Fernblock (Polypodium leucotomos), Green Tee, Black Tea (Camellia sinensis), Aloe vera, Walnut, Borage oil, Evening primrose oil, Avocado oil, Tea tree oil, Red Clover (Trifolium pratense L.), Soybean (Glycine max L.), Caper (Capparis spinosa), Almonds, Flame of the forest (Spathodea campanulata), Milk thistle (Silybum marianum L.), Cashew nut shell, Grape, Red Orange, Pomegranate (Punica granatu), Bilberry (Vaccinium myrtillus L.), Bog blueberry (Vaccinium uliginosum L.), Strawberry (Fragaria ananassa), Foti (Polygonum multiflorum Thunb), Turmeric (Curcuma longa L.), Ginseng (Panax ginseng), English ivy (Hedera helix), Broccoli (Brassica oleracea var italica), Tamarind (Tamarindus indica), Opuntia ficus-indica, Coffee, Basil (Ocimum basilicum, Linn.), pomegranate seed oil(Punica granatum), wheat germ oil (Triticum vulgare), blackcurrant seed oil (Ribes nigrum), sesameoil (Sesamum indicum), carrot root (Daucuscarota sativa), raspberry seed oil (Rubus idaeus), traditional medicinal plants from Sri Lanka (Aporosa lindleyana (Euphorbiaceae), Atalantia ceylanica (Rutaceae), Hibiscus furcatus (Malvaceae), Olaxzeylanica (Olacaceae), Ophiorrhiza mungos (Rubiaceae), Argyreia populifolia (Convolvulaceae), Ipomoea mauritiana (Convolvulaceae), Lasia spinosa (Araceae), Leucas zeylanica (Lamiaceae), Plectranthus zeylanicus (Lamiaceae) and Brazil (D. gardneriana seeds, L. microphylla leafs, Amburana cearensis, Aspidosperma cuspa, Aspidosperma pyrifolium, Croton sonderianus, Curatella americana, Dimophandra gardneriana, Lippia microphylla, Luehea paniculata, Sida galheirensis and any mixture thereof.
[0209] Preferably, the plant extracts with UV protection properties are selected from the group consisting of Lignin / Cellulose, Lignin, Lignin Hydrolyzed, Galanga Extract, Porphyra, red algae (Porphyra Umbilicalis), Green Microalgae (e.g. Interfilum and Klebsormidium), Seaweed (e.g. Padina australis, Euchema, cottonii), Pongamia Glabra Seed Oil, Karanja oil (Millettia pinnata), Rhatania Extrakt (Krameria lappacea), Soybean, Bamboo, Buriti Oil (Mauritia flexuosa), Cyanobacteria, Fernblock (Polypodium leucotomos), Green Tee, Black Tea (Camellia sinensis), Evening primrose oil, Cashew nut shell, Pomegranate (Punica granatu), and any mixture thereof.
[0210] Advantageously, the amount of secondary sun protection substances in the cosmetic or pharmaceutical preparation or homecare product according to the present230135 invention is advantageously from 0.005 to 5.0 % by weight, preferably from 0.01 to 4.0 % by weight, most preferred from 0.05 to 3.0 % by weight, based on the total weight of the ready-to-use formulation.
[0211] Within the context of the present invention, it is also possible and in some cases advantageous to combine the food, cosmetic or pharmaceutical preparation or homecare product according to the first aspect of the present invention with other customary active substances, adjuvants or additives, customarily used for food, cosmetic or pharmaceutical compositions or homecare products, as further described below, in order to obtain a ready-for-use preparation or formulation.
[0212] The other active agents and / or adjuvants and / or additives or auxiliaries are for example abrasives, anti-acne agents, agents against ageing of the skin, anti-cellulitis agents, anti-dandruff agents, anti-inflammatory agents, irritation-preventing agents, irritation-inhibiting agents, antioxidants, alkanediols, astringents, odour absorbers, perspiration-inhibiting agents, antiseptic agents, anti-statics, antimicrobial agents, binders, buffers, carrier materials, oil components, chelating agents, cell stimulants, cleansing agents, depilatory agents, surface-active substances, deodorizing agents, antiperspirants, softeners, emulsifiers, enzymes, enzyme inhibitors, essential oils, fibres, film-forming agents, water resistance improving agents fixatives, foam-forming agents, foam stabilizers, substances for preventing foaming, foam boosters, gelling agents, gel- forming agents, hair care agents, hair-setting agents, hair-straightening agents, moisture- donating agents, moisturizing substances, moisture-retaining substances, bleaching agents, strengthening agents, stain-removing agents, optically brightening agents, impregnating agents, dirt-repellent agents, dyes, friction-reducing agents, lubricants, moisturizing creams, ointments, opacifying agents, plasticizing agents, covering agents, polish, preservatives, gloss agents, green and synthetic polymers, powders, proteins, re- oiling agents, abrading agents, silicones, skin-soothing agents, skin-cleansing agents, skin care agents, skin-healing agents, skin-lightening agents, skin-protecting agents, skin-softening agents, hair promotion agents, cooling agents, skin-cooling agents, warming agents, skin-warming agents, stabilizers, surfactants, antimicrobial agents, detergents / surfactants, fabric conditioning agents, suspending agents, skin-tanning230135 agents, actives modulating skin or hair pigmentation, matrix-metalloproteinase inhibitors, skin moisturizing agents, glycosaminoglycan stimulators, TRPV1 antagonists, desquamating agents, anti-cellulite agents or fat enhancing agents, hair growth activators or inhibitors, thickeners, rheology additives, vitamins, oils, waxes, pearlizing waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, α-hydroxy acids, polyhydroxy fatty acids, liquefiers, dyestuffs, colour-protecting agents, pigments, anti-corrosives, fragrances or perfume oils, aromas, flavouring substances, odoriferous substances, polyols, electrolytes, organic solvents, and mixtures of two or more of the aforementioned substances, as further described below.
[0213] Carriers: The compositions according to the present invention may comprise a carrier or a mixture of different carriers. Most common acceptable carrier is water. Acceptable carries other than water include glycerin, C1-4 alcohols, organic solvents, fatty alcohols, fatty ethers, fatty esters, polyols, glycols, vegetable oils, mineral oils, liposomes, laminar lipid materials, water, or a mixture thereof. Non-limiting examples of organic solvents include mono alcohols and polyols such as ethyl alcohol, isopropyl alcohol, propyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or ethers thereof such as, for example, monomethyl ether of propylene glycol, butylene glycol, hexylene glycol, dipropylene glycol as well as alkyl ethers of diethylene glycol, for example monoethyl ether or monobutyl ether of diethylene glycol. Other suitable examples of organic solvents are ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, propane diol, and glycerin. The organic solvents can be volatile or non-volatile compounds. The total amount of carrier in the compositions can vary but is typically 40 to 90 % by weight, based on the total weight of the composition.
[0214] The products or preparations of the present invention may include at least one water-soluble or organic solvent. Non-limiting examples of organic solvents include monoalcohols and polyols such as ethyl alcohol, isopropyl alcohol, propyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or ethers thereof such as, for example, monomethyl ether of propylene glycol, butylene230135 glycol, hexylene glycol, dipropylene glycol as well as alkyl ethers of diethylene glycol, for example monoethyl ether or monobutyl ether of diethylene glycol. Other suitable examples of organic solvents are ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, propane diol, and glycerin. The organic solvents can be volatile or non- volatile compounds.
[0215] Further non-limiting examples of water-soluble solvents include alkanols (polyhydric alcohols such as glycols and polyols) such as glycerin, 1 ,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, hexylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 1 ,3-butanediol, 2,3-butanediol, 1 ,4-butanediol, 3-methyl-1 ,3- butanediol, 1 ,5- pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2,4- pentanediol, polyethylene glycol, 1 ,2,4-butanetriol, 1 ,2,6-hexanetriol, 2-butene-1 ,4- diol, 2-ethyl-1 ,3- hexanediol, 2-methyl-2,4-pentanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-decanediol, and 4-methyl-1,2-pentanediol; alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t- butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-iso-propyl ether; 2-pyrrolidone, N-methyl-2- pyrrolidone, 1,3-dimethyl-2- imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbit, sorbitan, acetine, diacetine, triacetine, sulfolane, and any mixture thereof. The total amount water-soluble or organic solvent(s) in the composition according to the present invention may vary but is typically 0.1 to 50 % by weight, based on the total weight of the composition.230135
[0216] Solubilizing agents: The products or preparations of the present invention may include at least one solubilizing agent. Solubilizing agents are compounds that help solubilize the components in the compositions. A particularly useful but non limiting example of a solubilizing agent is a hydrotrope. Hydrotropes (or hydrotropic agents) are a diverse class of typically water-soluble compounds that may be characterized by an amphiphilic molecular structure and an ability to dramatically increase the solubility of poorly soluble organic molecules in water. Non-limiting examples of hydrotopes include sodium 1,3-benzenedisulfonate, sodium benzoate, sodium 4-pyridinecarboxylate, sodium salicylate, sodium benzene sulfonate, caffeine, sodium p-toluene sulfonate, sodium butyl monoglycolsulfate, 4- aminobenzoic acid HCI, sodium cumene sulfonate, N,N-diethylnicotinamide, N-picolylnicotinamide, N-allylnicotinamide, 2- methacryloyloxyethyl phosphorylcholine, resorcinol, butylurea, pyrogallol, N- picolylacetamide 3.5, procaine HCI, proline HCI, nicotinamide, pyridine, 3-picolylamine, sodium ibuprofen, sodium xylenesulfonate, ethyl carbamate, pyridoxal hydrochloride, sodium benzoate, 2-pyrrolidone, ethylurea, N,N-dimethylacetamide, N-methylacetamide, and isoniazid and any mixture thereof. In some cases, particularly useful hydrotropes include nicotinamide (niacinamide), caffeine, sodium PCA, sodium salicylate, urea, and dhydroxyethyl urea, in particular, nicotinamide (niacinamide) and / or caffeine. A combination of two or more, three or more, or four or more hydrotopes may also be used in the compositions according to the present invention. The total amount of solubilizing agent(s) in the compositions of the present invention may vary but are typically in an amount of 0.01 to 20 % by weight, based on the total weight of the composition.
[0217] In addition, hydrotropes, for example ethanol, isopropyl alcohol or polyols, may be used to improve flow behaviour. Suitable polyols preferably contain 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, more especially amino groups, or may be modified with nitrogen. Typical examples are - glycerol; - alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1000 Dalton; - technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10, such230135 as for example technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight; - methylol compounds such as, in particular, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol and dipentaerythritol; - lower alkyl glucosides, particularly those containing 1 to 8 carbon atoms in the alkyl group, for example methyl and butyl glucoside; - sugar alcohols containing 5 to 12 carbon atoms, for example sorbitol or mannitol, - sugars containing 5 to 12 carbon atoms, for example glucose or sucrose; - amino sugars, for example glucamine; and - dialcoholamines, such as diethanolamine or 2-aminopropane-1,3-diol.
[0218] Oil components: The products or preparations according to the present invention may include at least one oil phase or at least one oil component, waxes, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, talc and zinc oxide or any mixture thereof. Powders include carriers such as lactose, talc, silica, aluminium hydroxide, calcium silicate and polyamide powder or any mixture thereof. Solutions and emulsions include carriers such as solvents such as water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, propylene glycol, etc. or any mixture thereof. However, preparations solely based on water are also possible. Oils, oil- in-water and water-in-oil emulsions, etc. are preferred.
[0219] The oil phase or the oil component in the products or preparations according to the present invention which may be suitable are for example plant oils, hydrocarbons, fatty alcohols, fatty acid esters, or mixtures of two or more of the aforesaid oil components.
[0220] The oil phase or oil component in the products or preparations according to the present invention is preferably a plant oil and even more preferably a liquid plant oil. It can also advantageously be a mixture of two or more plant oils components, especially liquid plant oil mixtures.
[0221] Plant oils or vegetable oils are oils extracted from seeds, or less often, from other parts of fruits. Like animal fats, plant oils are mixtures of triglycerides. Soybean oil,230135 rapeseed oil and cocoa butter are examples of plant oils from seeds. Olive oil, palm oil and rice bran oil are examples of oils from other parts of fruits. In common usage, plant oil or vegetable oil may refer exclusively to vegetable fats which are liquid at room temperature or at 35 to 37 °C skin temperature. Vegetable oils are usually edible.
[0222] The term “plant oils” also includes unsaturated plant oils. Unsaturated oils or vegetable oils can be transformed through partial or complete “hydrogenation” into oils of higher melting point. The hydrogenation process involves “sparging” the oil at high temperature and pressure with hydrogen in the presence of a catalyst, typically a powdered nickel compound. As each carbon-carbon double-bond is chemically reduced to a single bond, two hydrogen atoms each form single bonds with the two carbon atoms. The elimination of double bonds by adding hydrogen atoms is called saturation; as the degree of saturation increases, the oil progresses toward being fully hydrogenated. An oil may be hydrogenated to increase resistance to rancidity (oxidation) or to change its physical characteristics. As the degree of saturation increases, the oil's viscosity and melting point increase.
[0223] In a preferred variant, the plant oil is selected from the group consisting of Persea Gratissima (Avocado Oil), Abies Alba Seed Oil, Acacia Victoriae Seed Oil, Actinidia Chinensis (Kiwi) Seed Oil, Amaranthus Hypochondriacus Seed Oil, Arachis Hypogaea (Peanut) Oil, Astrocaryum Murumuru Seed Butter, Astrocaryum Tucuma Seed Butter, Astrocaryum Tucuma Seed Oil, Astrocaryum Vulgare Fruit Oil, Astrocaryum Vulgare Kernel Oil, Avena Sativa (Oat) Kernel Oil, Brassica Alba Seed Oil, Brassica Campestris (Rapeseed) Seed Oil, Butyrospermum Parkii (Shea) Butter, Butyrospermum Parkii (Shea) Oil, Calendula Officinalis Seed Oil, Calophyllum Inophyllum Seed Oil, Calophyllum Tacamahaca Seed Oil, Camellia Oleifera Seed Oil, Camellia Reticulata Seed Oil, Camellia Sinensis Seed Oil, Cannabis Sativa Seed Oil, Cannabis Sativa Seed / Stem Oil, Canola Oil, Carthamus Tinctorius (Safflower) Seed Oil, Chlorella Vulgaris Oil, Citrullus Lanatus (Watermelon) Seed Oil, Citrus Aurantifolia (Lime) Seed Oil, Citrus Aurantium Dulcis (Orange) Seed Oil, Citrus Grandis (Grapefruit) Seed Oil, Cocos Nucifera (Coconut) Oil, Cocos Nucifera (Coconut) Seed Butter, Coffea Arabica (Coffee) Seed Oil, Chlorella Oil (biotech), Corylus Americana (Hazelnut) Seed Oil, Corylus230135 Avellana (Hazelnut) Seed Oil, Cucumis Melo (Melon) Seed Oil, Cucumis Sativus (Cucumber) Seed Oil, Cucurbita Pepo (Pumpkin) Seed Oil, Elaeis Guineensis (Palm) Oil, Elaeis (Palm) Fruit Oil, Glycine Soja (Soybean) Oil, GosSY-pium Herbaceum (Cotton) Seed Oil, GosSY-pium Hirsutum (Cotton) Seed Oil, Helianthus Annuus (Sunflower) Seed Oil, Macadamia Integrifolia Seed Oil, Macadamia Ternifolia Seed Oil, Mangifera Indica (Mango) Seed Butter, Mangifera Indica (Mango) Seed Oil, Melissa Officinalis Seed Oil, Microalgae Oil, Moringa Oleifera Seed Oil, Moringa Peregrina Seed Oil, Oenothera Biennis (Evening Primrose) Oil, Olea Europaea (Olive) Fruit Oil, Olus Oil, Orbignya Oleifera Seed Oil, Orbignya Speciosa Kernel Oil, Oryza Sativa (Rice) Bran / Germ Oil, Oryza Sativa (Rice) Bran Oil, Oryza Sativa (Rice) Germ Oil, Oryza Sativa (Rice) Lipids, Oryza Sativa (Rice) Seed Oil, Papaver Somniferum Seed Oil, Passiflora Edulis Seed Oil, Persea Gratissima (Avocado) Butter, Persea Gratissima (Avocado) Oil, Prunus Amygdalus Dulcis (Sweet Almond) Oil, Prunus Armeniaca (Apricot) Kernel Oil, Prunus Persica (Peach) Kernel Oil, Punica Granatum Seed Oil, Pyrus Malus (Apple) Seed Oil, Ricinoleic / Caproic / Caprylic / Capric Triglyceride(s), Ricinus Communis (Castor) Seed Oil, Rosa Canina Fruit Oil, Rosa Moschata Seed Oil, Rubus Idaeus (Raspberry) Seed Oil, Sesamum Indicum (Sesame) Seed Butter, Soybean Glycerides, Theobroma Cacao (Cocoa) Seed Butter, Theobroma Grandiflorum Seed Butter, Triticum Vulgare (Wheat) Bran Lipids, Triticum Vulgare (Wheat) Germ Oil, Vitis Vinifera (Grape) Seed Oil, Zea Mays (Corn) Germ Oil, and Zea Mays (Corn) Oil.
[0224] The above specified plant oils are the most common natural lipid components used as basic substances for the manufacture of cosmetics or pharmaceutical formulations.
[0225] Hydrocarbons (mineral oils) are in general organic compounds consisting entirely of hydrogen and carbon. As defined by IUPAC nomenclature or organic chemistry, the classifications for hydrocarbons are: 2. Saturated hydrocarbons are the simplest of the hydrocarbon species. They are composed entirely of single bonds and are saturated with hydrogen. The formula for acyclic saturated hydrocarbons (i.e., alkanes) is CnH2n+2.The most general form of saturated hydrocarbons is CnH2n+2(1-r), where r is the number of rings. Those with230135 exactly one ring are the cycloalkanes. Saturated hydrocarbons are the basis of petroleum fuels and are found as either linear or branched species. 3. Unsaturated hydrocarbons have one or more double or triple bonds between carbon atoms. Those with double bond are called alkenes. Those with one double bond have the formula CnH2n (assuming non-cyclic structures). Those containing triple bonds are called alkynes. Those with one triple bond have the formula CnH2n−2. 4. Aromatic hydrocarbons, also known as arenes, are hydrocarbons that have at least one aromatic ring.
[0226] Hydrocarbons can be inter alia liquids (e.g. hexane and benzene), waxes or low melting solids (e.g. paraffin wax and naphthalene). The term 'aliphatic' refers to non- aromatic hydrocarbons. Saturated aliphatic hydrocarbons are sometimes referred to as “paraffins”. Mineral oils and waxes are mixtures of predominantly saturated hydrocarbons consisting of straight‐chain, branched and ring structures with carbon chain lengths greater than C14. Mineral oils and waxes are chemical substances prepared from naturally occurring crude petroleum oil. They mainly consist of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). Hydrocarbons have been used for many decades in skin and lip care cosmetic products due to their excellent skin tolerance as well as their high protecting and cleansing performance and broad viscosity options. In contrast to vegetable oils, mineral oils are non‐allergenic since they are highly stable and not susceptible to oxidation or rancidity.
[0227] A fatty alcohol (or long-chain alcohol) is usually a high-molecular-weight, straight- chain primary alcohol, but can also range from as few as 4 to 6 carbons to as many as 22 to 26, derived from natural fats and oils. The precise chain length varies with the source. Some commercially important fatty alcohols are lauryl, stearyl and oleyl alcohols. They are colourless oily liquids (for smaller carbon numbers) or waxy solids, although impure samples may appear yellow. Fatty alcohols usually have an even number of carbon atoms and a single alcohol group (–OH) attached to the terminal carbon. Some are unsaturated and some are branched. Most fatty alcohols in nature are found as waxes which are esters with fatty acids and fatty alcohols. The traditional sources of fatty alcohols have largely been various vegetable oils and these remain a large-scale230135 feedstock. The alcohols are obtained from the triglycerides (fatty acid triesters), which form the bulk of the oil. The process involves the transesterification of the triglycerides to give methyl esters which are then hydrogenated to give the fatty alcohols. Fatty alcohols are also prepared from petrochemical sources. In the Ziegler process, ethylene is oligomerized using triethylaluminium followed by air oxidation. Alternatively, ethylene can be oligomerized to give mixtures of alkenes, which are subjected to hydroformylation, this process affording odd-numbered aldehyde, which is subsequently hydrogenated. Fatty alcohols are mainly used in the production of detergents and surfactants. They are components also of cosmetic solvents. They find use as co-emulsifiers, emollients and thickeners in cosmetics.
[0228] In a preferred variant, the fatty alcohol is selected from the group consisting of phenyl propanol, dimethyl phenylbutanol, hexyldecanol, octyldodecanol, octyldecanol, tridecylalcohol, isostearyl alcohol, phenylisohexanol, phenylpropanol, trimethylbenzenepropanol, isoamylalcohol, isostearyl alcohol, and isotridecyl alcohol. In a more preferred variant, the fatty alcohol is selected from the group consisting of hexyldecanol, octyldodecanol, phenylpropanol, isoamylalcohol, and mixtures of two or more of the aforesaid fatty alcohols. The fatty alcohol can be used either as a single component or in a mixture with one or more further different fatty alcohol(s) as specified above.
[0229] A fatty acid ester is a type of ester that results from the combination of a fatty acid with an alcohol. When the alcohol component is glycerol, the fatty acid esters produced can be monoglycerides, diglycerides or triglycerides. Fatty acid esters have a conditioning effect of softening the skin to create a smoothing sensation. They are also added to cosmetics to dissolve high-polarity active ingredients and UV absorbers. Esters of straight-chain fatty acids and lower alcohols are effective for dissolving slightly soluble ingredients for oils with a light touch during application. Isostearic acids and other liquid oils with branched fatty acids and unsaturated fatty acids are commonly used as emollients. Higher fatty acid esters and esters of higher alcohols with relatively high melting points are added to skin creams to adjust the application touch.230135
[0230] Oil bodies or emollients: In addition to the oil phase or oil component as defined above, the products or preparations according to the present invention preferably includes one or more oil bodies or emollients. An emollient is an oleaginous or oily substance which helps to smooth and soften the skin, and may also reduce its roughness, cracking or irritation. Especially, in sunscreen products emollients counteract the known stickiness of some UV-filters and keep the crystalline and oil-soluble organic and inorganic UV-filters solubilized and prevent them from recrystallisation. In addition, emollients serve as wetting agents for inorganic UV-filters for a homogeneous dispersion in the formulations. Suitable oil bodies, which form constituents of the O / W emulsions, are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C5 – C22 fatty acids with linear or branched C5 - C22 fatty alcohols or esters of branched C1 – C13 carboxylic acids with linear or branched C6 – C22 fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C6 – C22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C18 – C38 alkylhydroxy carboxylic acids with linear or branched C6 – C22 fatty alcohols, in particular Dioctyl Malate, esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and / or Guerbet alcohols, triglycerides based on C6 – C10 fatty acids, liquid mono- / di- / triglyceride mixtures based on C6 – C18 fatty acids, esters of C6 – C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2 – C12 dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted230135 cyclohexanes, linear and branched CC – C22 fatty alcohol carbonates, such as, for example, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and / or branched C6-C22-alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.) and / or aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes, and any mixture thereof.
[0231] Powders: The compositions as defined herein may optionally include powders. The optional powders provide formulas that are smoother and softer on the skin. Representative powders include talc, mica, magnesium carbonate, calcium carbonate, magnesium silicate, aluminium magnesium silicate, silica, titanium dioxide, zinc oxide, red iron oxide, yellow iron oxide, black iron oxide, polyethylene powder, methacrylate powder, polystyrene powder, silk powder, Preferred solid powder materials, which may be a component of the composition according to the invention are hydrocolloids, such as starches, degraded starches, chemically or physically modified starches, dextrins, (powdery) maltodextrins (preferably with a dextrose equivalent value of 5 to 25, preferably of 10 – 20), lactose, silicon dioxide, glucose, modified celluloses, gum arabic, ghatti gum, traganth, karaya, carrageenan, pullulan, curdlan, xanthan gum, gellan gum, guar flour, carob bean flour, alginates, agar, pectin, inulin, and mixtures of two or more of these solids, in particular maltodextrins (preferably with a dextrose equivalent value of 15 – 20), lactose, silicon dioxide and / or glucose.
[0232] Film formers: The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention may advantageously include one or more film formers or film forming agent. A film forming agent is a hydrophobic material that imparts water resistance and film forming characteristics to the sunscreen products, cosmetic or pharmaceutical preparations or homecare products. Standard film formers are preferably chitosan, microcrystalline chitosan, quaternized chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, polymers of the acrylic acid230135 series, quaternary cellulose derivatives, collagen, hyaluronic acid and salts thereof and similar compounds. Preferred film formers for improving water resistance of the composition are selected from the group consisting of Polyamide-8 (such as Oleocraft LP 20 PA (MV)), Polyamide-3 (such as Oleocraft MP 32 PA (MV)), Trimethylpentanediol / Adipic Acid / Glycerin Crosspolymer (such as WetFilm), Octyldodecyl Citrate Crosspolymer (such as CosmoSurf CE 100), Polyglyceryl-3 Methyl Glucose Distearate (such as TegoCare 450), C28-52 Olefin / Undecylenic Acid Copolymer (such as Performa V6112), Hydrolyzed Jojoba esters, Jojoba Esters, Aqua (such as Floraester Jojoba K100), Cyclopentasiloxane Acrylates / Dimethicone copolymer (such as KP545), Acrylates / Beheneth-25 Methacylate Copolymer (such as Volarest), Styrene / Acrylates Copolymer (such as Dermacryl E Polymer), Polyurethane (such as Baycusan C1001), Polyurethane-2 and Polymethyl Methacrylate (such as Hybridur 875 Polymer), Acrylates / Octylacrylamide Copolymer (such as Dermacryl 2.0 Polymer), Beeswax (Cera Alba) (and) Sodium Stearoyl Lactylate (such as SymEffect Sun), Pullulan, Xanthan Gum, Hydrogenated Palm Oil, Saccharum Officinarum Extract (SymEffect™UV), Microcrystalline cellulose (and) Sphingomonas ferment extract (and) Cellulose gum (such as PemuPur™ START Polymer), Acacia Senegal Gum and Xanthan Gum (such as SOLAGUM™ AX), Microcrystalline Cellulose (and) Cellulose Gum (such as Natpure Cellgum Plus), Sodium Stearoyl Glutamate (such as AMISOFT® HS-11P), Hydrogenated Polycyclopentadiene (and) Caprylic / Capric Triglyceride (such as Koboguard® 5400 CCT), Glyceryl Hydrogenated Rosinate (and) Caprylic / Capric Triglyceride (and) Tocopherol (such as KOBOGUARD® NATURAL 2063-CCT), Galactoarabinan (such as LaraCare® A 200), C26-28 Alkyl Dimethicone (such as Wacker BELSIL® CDM 3526 VP), Caprylyl Methicone (such as Silsoft 034), Stearyl Dimethicone (and) Octadecene (such as Dowsil 2503 Cosmetic Wax), VP / Hexadecene Copolymer (such as Antaron™ V 216), Triacontanyl PVP (such as Antaron™ WP-660), Capryloyl Glycerin / Sebacic Acid Copolymer (such as LexFilm™ Sun Natural MB), Poly C10-30 Alkyl Acrylate (such as Tego SP 13 Sun Up), Microcrystalline Cellulose (such as Sunspheres™ BIO SPF Booster), and any mixture thereof. The aforesaid film forming agents are used in the sunscreen, cosmetic or pharmaceutical preparation or homecare product either as a single component or preferably in a mixture with two or more further of said film forming agents as specified above. The film forming agents are used in230135 amounts effective to allow the final formulation to remain on the skin or surface after exposure to circulating water for at least 40 minutes, preferably 80 minutes. The film forming agent is present in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.01 to 10.0 % by weight, preferably 0.05 to 8.0 % by weight, based on the total weight of the final formulation.
[0233] Water resistance improving agents: The sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention may advantageously include one or more agents for improving water resistance. An agent for improving water resistance is a hydrophobic material that imparts film forming and water resistance characteristics to an emulsion. Typical suitable water resistance improving agents include copolymers derived from polymerization of octadecene-1 and maleic anhydride. A preferred water resistance improving agent is a polyanhydride resin. Another preferred water resistance improving agent is a copolymer of vinyl pyrrolidone and eicosene monomers. The water resistance improving agent(s) is / are used in amounts effective to allow the final formulation to remain on the skin or surface after exposure to circulating water for at least 40 minutes, preferably 80 minutes. One or more water resistance improving agents can optionally be included in the final formulation in an amount ranging from 0.01 to 10.0 % by weight, preferably 0.05 to 8.0 % by weight, more preferably 0.1 to 5.0 % by weight, based on the total weight of the final formulation.
[0234] Silicones: In order to impart a silky, spreadable, and luxurious texture and to make skin look and feel smoother, and additionally to improve processability (antifoaming) the sunscreen product, cosmetic or pharmaceutical preparation or homecare product according to the present invention preferably includes one or more silicones or silicone derivatives. The total amount of silicone compound(s) in the compositions according to the present invention can vary but is typically 0.1 to 35.0 % by weight, based on the total weight of the composition.
[0235] Dry-feel modifiers: The sunscreen product or cosmetic or pharmaceutical preparation according to the present invention is preferably combined with dry-feel modifiers. A dry-feel modifier is an agent which, when incorporated in an emulsion,230135 imparts a "dry feel" to the skin when the emulsion dries. Dry-feel modifiers may also reduce sunscreen migration on the skin. Dry feel modifiers can include starches, talc, kaolin, chalk, zinc oxide, 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 Aerosil® available from the Degussa Inc. of New York, N.Y. U.S.A. or mixtures thereof; dimethicone, a mixture of mixture of methylated linear siloxane polymers, available as DC200 fluid, tradename of Dow Corning, Midland, Mich. U.S.A. One or more dry-feel modifiers can optionally be included in the sunscreen in amounts ranging from 0.01 to 20 % by weight, more preferably from 0.1 to 10.0 % by weight.
[0236] Lenitive substances: The composition according to the present invention can also contain advantageously one or more lenitive substances, wherein any lenitive substances can be used which are suitable or customary in cosmetic or pharmaceutical applications such as alpha-bisabolol, azulene, guaiazulene, 18-beta-glycyrrhetinic acid, allantoin, Aloe vera juice or gel, extracts of Hamamelis virginiana (witch hazel), Echinacea species, Centella asiatica, chamomile, Arnica monatana, Glycyrrhiza species, algae, seaweed and Calendula officinalis, and vegetable oils such as sweet almond oil, baobab oil, olive oil and panthenol, Laureth-9, Trideceth-9 and 4-t-butylcyclohexanol.
[0237] Physiological cooling agents: The compositions according to the present invention can be particularly advantageously combined with one or more physiological cooling agent(s). The use of cooling agents can alleviate itching. Preferred individual cooling agents for use within the framework of the present invention are listed below. The person skilled in the art can add many other cooling agents to this list; the cooling agents listed can also be used in combination with one another: which are preferably selected here from the following list: menthol and menthol derivatives (for example L-menthol, D- menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol) menthylethers (for example (I-menthoxy)-1,2-propanediol, (l-menthoxy)-2-methyl-1,2-propanediol, l- menthyl-methylether), menthone glyceryl acetal, menthone glyceryl ketal or mixtures of both, menthylesters (for example menthylformiate, menthylacetate, menthylisobutyrate, menthyhydroxyisobutyrat, menthyllactates, L-menthyl-L-lactate, L-menthyl-D-lactate,230135 menthyl-(2-methoxy)acetate, menthyl-(2-methoxyethoxy)acetate, menthylpyroglutamate), menthylcarbonates (for example menthylpropyleneglycolcarbonate, menthylethyleneglycolcarbonate, menthylglycerolcarbonate or mixtures thereof), the semi-esters of menthols with a dicarboxylic acid or derivatives thereof (for example mono-menthylsuccinate, mono- menthylglutarate, mono-menthylmalonate, O-menthyl succinic acid ester-N,N- (dimethyl)amide, O-menthyl succinic acid ester amide), menthanecarboxylic acid amides (in this case preferably menthanecarboxylic acid-N-ethylamide [WS3] or Nα- (menthanecarbonyl)glycinethylester [WS5], menthanecarboxylic acid-N-(4- cyanophenyl)amide or menthanecarboxylic acid-N-(4-cyanomethylphenyl)amide, menthanecarboxylic acid-N-(alkoxyalkyl)amides), menthone and menthone derivatives (for example L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butyric acid derivatives (for example 2,3-dimethyl-2-(2-propyl)-butyric acid-N-methylamide [WS23]), isopulegol or its esters (I-(-)-isopulegol, I-(-)-isopulegolacetate), menthane derivatives (for example p-menthane-3,8-diol), cubebol or synthetic or natural mixtures, containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (for example 3-methyl-2(1- pyrrolidinyl)-2-cyclopentene-1-one) or tetrahydropyrimidine-2-one (for example iciline or related compounds, as described in WO 2004 / 026840), further carboxamides (for example N-(2-(pyridin-2-yl)ethyl)-3-p-menthanecarboxamide or related compounds), (1R,2S,5R)-N-(4-Methoxyphenyl)-5-methyl-2-(1-isopropyl)cyclohexane-carboxamide [WS12], oxamates and [(1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl] 2-(ethylamino)-2- oxo-acetate (X Cool). Cooling agents which are preferred due to their particular synergistic effect are l-menthol, d-menthol, racemic menthol, menthone glycerol acetal (trade name: Frescolat®MGA), menthyl lactate (preferably l-menthyl lactate, in particular l-menthyl l-lactate (trade name: Frescolat®ML)), substituted menthyl-3-carboxamides (such as menthyl-3-carboxylic acid N-ethyl amide), 2-isopropyl-N-2,3-trimethyl butanamide, substituted cyclohexane carboxamides, 3-menthoxypropane-1,2-diol, 2- hydroxyethyl menthyl carbonate, 2-hydroxypropyl menthyl carbonate and isopulegol. Particularly preferred cooling agents are l-menthol, racemic menthol, menthone glycerol acetal (trade name: Frescolat®MGA), menthyl lactate (preferably l-menthyl lactate, in particular l-menthyl l-lactate (trade name: Frescolat®ML)), 3-menthoxypropane-1,2-diol, 2-hydroxyethyl menthyl carbonate and 2-hydroxypropyl menthyl carbonate. Very230135 particularly preferred cooling agents are l-menthol, menthone glycerol acetal (trade name: Frescolat®MGA) and menthyl lactate (preferably l-menthyl lactate, in particular l-menthyl l-lactate (trade name: Frescolat®ML).
[0238] Alkanediols: In a further preferred variant, the food, cosmetic or pharmaceutical preparation, in particular sunscreen product, or homecare product according to the invention comprises one or more linear alkanediol(s) having a carbon chain of 5 to 12 carbon atoms. Preferably, said one or more linear alkanediol(s) is / are selected from the group consisting of 1,2-alkanediols, 2,3-alkanediols, 3,4-alkanediols and 1,3-alkanediols, more preferably of 2,3-alkanediols and 1,3-alkanediols. Most preferably, said linear alkanediol(s) is / are 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.
[0239] Initial observations of the inventors surprisingly indicated that compositions according to the invention comprising one or more linear alkanediol(s) having a carbon chain of 5 to 12 carbon atoms, preferably as defined herein, display particularly advantageous emulsifying properties. In particular, it was surprisingly found that the one or more of said linear alkanediol(s) (if not emulsions themselves) support(s) the formation of water or oil droplets with a particularly small average size in emulsions or (if emulsions themselves) contain water or oil droplets with a particularly small average size.
[0240] Additionally, it was found that the presence of an alkanediol, in particular a 1,2- alkanediol or 2,3-alkanediol, improves the solubility of oil components, such as one or more oil body / bodies or wax(es), in food, cosmetic or pharmaceutical preparation or homecare product according to the present invention. Preferably the oil body / bodies or wax(es) are selected from the group consisting of natural fats and oils, fatty alcohols and alcohols, glyceryl esters and derivatives thereof, esters, ethers, siloxanes and silanes, waxes, and naphthenic hydrocarbons, preferably selected from the group consisting of squalene, dialkylcyclohexanes, tetradecane, isohexadecane, dodecane, docosane, paraffin, and mineral oils, and further described below.230135
[0241] A combination of one or more of said alkanediol(s) with 4-hydroxyacetophenon, typically in amounts from 0.1 to 2 % by weight, more preferably from 0.1 to 1 % by weight, improves the solubility of the oil components even in a synergistic manner.
[0242] 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(s) having a carbon chain of 5 to 12 carbon atoms and defined herein, based on the total weight of the composition.
[0243] Antioxidants: The food, cosmetic or pharmaceutical preparation or homecare product according to the present invention may contain at least one antioxidant.
[0244] The term “antioxidant” as used in the present application refers to a substance or composition which significantly delays, prevents or even inhibits oxidation. Antioxidants react with free radicals, reducing them to stable, unreactive products. Oxidation is a chemical reaction that produces free radicals chain reactions which generate highly reactive peroxides and hydroperoxides. In turn, these peroxides and hydroperoxides react with substrates present in a cosmetic composition or in food which result in decomposition products such as carboxylic acids, aldehydes and ketones, among other, which alter the sensory properties of the productions and lead to degradation of the composition.
[0245] Antioxidants play an important physiological role as radical scavenger. In the organism antioxidants inactivate biologically important reactive free radicals or other reactive oxygen species (ROS) which excessively occurrence leads to oxidative stress. In a biological context, reactive oxygen species (ROS) are formed as a natural by-product of the normal metabolism of oxygen and have important roles in cell signalling and homeostasis. However, at times of environmental stress (for example UV or heat exposure), ROS levels can increase dramatically.
[0246] With the use of an antioxidant, the above-described oxidation processes in the formulations according to the present invention or the above described biochemically230135 reactions caused by oxidative stress and excess reactive oxygen species (ROS) can be down regulated.
[0247] The food, cosmetic or pharmaceutical composition or homecare product according to the first aspect of the present invention encompasses at least one antioxidant selected from the group consisting of dimethylmethoxy chromanol, arbutin, amino acids (for example arginine, lysine, glycine, histidine, tyrosine, tryptophan) and their derivatives (for example acetylcysteine), tert-butylhydroquinone, caffeic acid, chlorogenic acid, imidazoles (for example urocanic acid) and their derivatives, cannabinoids, cannabidiol and its extracts (cannabis sativa seed oil, cannabis sativa extract), cannabinol, kojic acid, peptides such as D,L-carnosine, D-carnosine, L- carnosine and their derivatives (for example anserine), hydroxyphenyl propamidobenzoic acid (dihydroavenanthramide D), diethylhexyl syringylidene malonate, phenylethyl resorcinol, gallic acid and their derivatives, quercetin, hydroxyacetophenone, rosmarinic acid, carotenoids, carotenes (for example α-carotene, β-carotene, lycopene), phytoene, phytofluene and their derivatives, lipoic acid and its derivatives (for example dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (for example thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulphoximine compounds (for example buthionine sulphoximines, lactobacillus (ferment, filtrate, lysate), homocysteine sulphoximines, buthionine sulphones, penta-, hexa-, hepta- thionine sulphoximine) in very low tolerated doses, and also (metal) chelating agents (for example α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin, α-hydroxy acids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, hinokitiol, EDTA, EGTA, Trisodium Dicarboxymethyl Alaninate, MGDA (methylglycinic diacetic acid), GLDA (Glutamic acid diacetic acid )) and their derivatives, unsaturated fatty acids and their derivatives (for example γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, triethyl citrate, Vitamin C and its derivatives (for example ascorbyl palmitate, magnesium230135 ascorbyl phosphate, ascorbyl acetate), tocopherols and their derivatives (for example α- tocopherol, ß-tocopherol, γ-tocopherol, δ-tocopherol, tocopheryl acetate), dexpanthenol, Vitamin A and its derivatives (for example Vitamin A palmitate, Hydroxypinacolone Retinoate) and also coniferyl benzoate of benzoin resin, rutinic acid and its derivatives, ferrulic acid and its derivatives, butylhydroxytoluene, butylhydroxyanisole, hydroxymethoxyphenyl decanone, nordihydroguaiacic acid, nordihydroguaiaretic acid, allantoin, tropolone, trihydroxybutyrophenone, uric acid and its derivatives, urea, mannose and its derivatives, hydroxy acetophenone (ortho / para), zinc and its derivatives (for example ZnO, ZnSO4), beta-aspartyl arginine, selenium and its derivatives (such as selenium methionine), Vitis Vinifera (Grape) seed extract, oat extract, Cichorium intubybus (chicory) leaf extract, Leon-topodium Alpinum extract, green tea extract, Curcumin, Zingiber Officinalis (Ginger) Root) Extract, Silymarin, stilbenes and their derivatives (such as stilbene oxide, trans-stilbene oxide) as well as the derivatives of said antioxidants, such as salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids, and mixtures of two or more of said antioxidants.
[0248] In a preferred variant, the antioxidant of the cosmetic or pharmaceutical composition or homecare product of the present invention is selected from the group consisting of dimethylmethoxy chromanol, hydroxyacetophenone, acorbic acid and its salts, hydroxymethoxyphenyl decanone, beta-aspartyl arginine, uric acid, urea, hydroxypinacolone retinoate, vitamin A and vitamin A derivatives, butylhydroxytoluol (BHT), butylhydroxyanisol (BHA), hydroxyphenyl propamidobenzoic acid, ascorbyl palmitate, ascorbyl phosphate and salts thereof, carnosine, rutin, tocopherol, tocopheryl acetate, ubiquinone-10, dilauryl thiodipropionate, pentaerythrityl tetra-di-t-butyl hydroxyhydrocinnamate, triethyl citrate, diethylhexyl syringylidene malonate, lactobacillus (ferment, filtrate, lysate), cannabinoids, cannabidiol and its extracts (cannabis sativa seed oil, cannabis sativa extract), cannabinol, hydroxyphenyl propamidobenzoic acid (dihydroavenanthramide D), green tea extract, Zingiber Officinalis (Ginger) root extract, tropolone, allantoin, and mixtures of two or more of said antioxidants.230135
[0249] In a particularly preferred variant, the antioxidant of the cosmetic or pharmaceutical composition of the present invention is tocopherol or tocopheryl acetate. Also preferred is dimethylmethoxy chromanol.
[0250] Still more preferred from the above antioxidants are antioxidants selected from the group consisting of cannabinoids, cannabidiol and its extracts (cannabis sativa seed oil, cannabis sativa extract), hydroxyacetophenone, cannabinol, hydroxymethoxyphenyl decanone hydroxyphenyl propamidobenzoic acid (dihydroavenanthramide D).
[0251] The aforesaid antioxidants can be used either as a single component or in admixture with one or more further antioxidants as specified above.
[0252] The at least one antioxidant according to the present invention is present in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.0001 to 10.0 % by weight, based on the total weight of the final formulation. In a preferred variant, the food, cosmetic or pharmaceutical preparation or homecare product comprises the antioxidant in an amount of 0.0005 to 8.0 % by weight, based on the total weight of the final formulation. In a most preferred variant, the antioxidant is advantageously used in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.001 to 6.0 % by weight, based on the total weight of the final formulation.
[0253] For a mixture of antioxidants the above amounts relate to the total content of the antioxidants in the mixture, i.e. the amount is the sum of the content of all antioxidants (c) in the mixture.
[0254] Emulsifiers: In addition, the food, cosmetic or pharmaceutical preparation or homecare product according to the present invention can also advantageously contain one or more emulsifiers in order to keep the food, product, cosmetic or pharmaceutical preparation or homecare product stable. Emulsifiers include amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsifiers are chosen in an230135 appropriate manner according to the emulsion to be obtained. Preferred examples include: - products of the addition of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide onto linear C8-22 fatty alcohols, onto C12-22 fatty acids and onto alkyl phenols containing 8 to 15 carbon atoms in the alkyl group; - C12 / 18 fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol; - glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and ethylene oxide addition products thereof; - addition products of 15 to 60 mol ethylene oxide onto castor oil and / or hydrogenated castor oil; - polyol esters and in particular, polyglycerol esters such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate isostearate. Mixtures of compounds from several of these classes are also suitable; - addition products of 2 to 15 mol ethylene oxide onto castor oil and / or hydrogenated castor oil; - partial esters based on linear, branched, unsaturated or saturated C6 / 22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose); - mono-, di and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and salts thereof, such as Potassium Cetyl Phosphate and Hydrogenated Palm Glycerides; - wool wax alcohols; - polysiloxane / polyalkyl polyether copolymers and corresponding derivatives; - mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of C6-22 fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol, - polyalkylene glycols and - glycerol carbonate.230135
[0255] The addition products of ethylene oxide and / or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or onto castor oil are known commercially available products. They are homologue mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C12 / 18 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as lipid layer enhancers for cosmetic formulations. The preferred emulsifiers are described in more detail as follows:
[0256] Partial glycerides: Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quantities of triglyceride from the production process. Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto the partial glycerides mentioned are also suitable.
[0257] Sorbitan esters: Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Addition products of 1 to230135 30 and preferably 5 to 10 mol ethylene oxide onto the sorbitan esters mentioned are also suitable.
[0258] Polyglycerol esters: Typical examples of suitable polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls®PGPH), Polyglycerin-3-Diisostearate (Lameform®TGI), Polyglyceryl-4 Isostearate (Isolan®GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care®450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane®NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul®WOL 1403), Polyglyceryl Dimerate Isostearate, and mixtures thereof. Examples of other suitable polyolesters are the mono-, di- and triesters of trimethylol propane or pentaerythritol with lauric acid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like optionally reacted with 1 to 30 mol ethylene oxide.
[0259] Anionic emulsifiers: Typical anionic emulsifiers are aliphatic C12 to C 22 fatty acids, such as palmitic acid, stearic acid or behenic acid for example, and C12 to C22 dicarboxylic acids, such as azelaic acid or sebacic acid for example, potassium cetyl phosphate, and hydrogenated palm glycerides (Emulsiphos / Emulsiphos F).
[0260] Amphoteric emulsifiers: Other suitable emulsifiers are amphoteric or zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3- carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a C8 / 18 alkyl or acyl group,230135 contain at least one free amino group and at least one ^COOH- or -SO3H- group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N- alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C12 / 18 acyl sarcosine.
[0261] Anti-ageing actives: A composition according to the present invention is preferably combined with one or more anti-ageing actives. In the context of the invention, anti-ageing or biogenic agents are, for example antioxidants, matrix-metalloproteinase inhibitors (MMPI), skin moisturizing agents, glycosaminglycan stimulators, anti- inflammatory agents, TRPV1 antagonists and plant extracts.
[0262] Matrix-Metalloproteinase inhibitors (MMPI): The compositions according to the present invention are preferably combined with one or more matrix-metalloproteinase inhibitors, especially those inhibiting matrix-metalloproteinases enzymatically cleaving collagen, 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-dihydro- 6-hydroxy-7-methoxy-2,2-dimethyl-1(2H)-benzopyran, benzamidine hydrochloride, the cysteine proteinase inhibitors N-ethylmalemide and epsilon-amino-n-caproic acid of the serinprotease inhibitors: phenylmethylsufonylfluoride, collhibin (company Pentapharm; INCI: hydrolysed rice protein), oenotherol (company Soliance; INCI: propylene glycol, aqua, Oenothera biennis root extract, ellagic acid and ellagitannins, for example from pomegranate), phosphoramidone hinokitiol, EDTA, MGDA (Trisodiumdicarboxymethyl alaninante), galardin, EquiStat (company Collaborative Group; apple fruit extract, soya seed extract, ursolic acid, soya isoflavones and soya proteins), sage extracts, MDI (company Atrium; INCI: glycosaminoglycans), fermiskin (company Silab / Mawi; INCI: water and lentinus edodes extract), actimp 1.9.3 (company Expanscience / Rahn; INCI: hydrolysed lupine protein), lipobelle soyaglycone (company Mibelle; INCI: alcohol, polysorbate 80, lecithin and soy isoflavones), extracts from green and black tea and230135 further plant extracts, proteins or glycoproteins from soya, hydrolysed proteins from rice, pea or lupine, plant extracts which inhibit MMPs, preferably extracts from shitake mushrooms, extracts from the leaves of the Rosaceae family, sub-family Rosoideae, quite particularly extracts of blackberry leaf, as e.g. SymMatrix (company Symrise, INCI: Maltodextrin, Rubus Fruticosus (Blackberry) Leaf Extract). Preferred actives of are selected from the group consisting of retinyl palmitate, ursolic acid, extracts from the leaves of the Rosaceae family, sub-family Rosoideae, genistein and daidzein.
[0263] Skin moisturizing and / or moisture-retaining substances: The compositions according to the present invention advantageously comprise one or more skin- moisturizing and / or moisture-retaining substances. Preferred skin moisturizing and / or moisture-retaining substances are selected from the group consisting of alkane diols or alkane triols comprising 3 to 12 carbon atoms, preferably C3-C10-alkane diols and C3-C10- alkane triols. More preferably the skin moisturizing agents are selected from the group consisting of glycerol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,2- pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol and 1,2-decanediol. Further skin moisturizing and / or moisture-retaining substances include sodium lactate, urea, urea derivatives, alcohols, glycerol, diols such as propylene glycol, hexylene glycol, collagen, elastin or hyaluronic acid, diacyl adipates, petrolatum, urocanic acid, lecithin, panthenol, phytantriol, lycopene, (pseudo-)ceramides, glycosphingolipids, cholesterol, phytosterols, chitosan, chondroitin sulphate, lanolin, lanolin esters, amino acids, alpha-hydroxy acids (such as citric acid, lactic acid, malic acid) and their derivatives, mono-, di- and oligosaccharides such as glucose, galactose, fructose, mannose, fructose and lactose, polysugars such as R-glucans, in particular 1,3-1,4-β-glucan from oats, alpha-hydroxy fatty acids, triterpene acids such as betulinic acid or ursolic acid, and algae extracts.
[0264] Glycosaminoglycan stimulators: Preferred compositions according to the present invention comprise one or more substances stimulating the synthesis of glycosaminoglycans which are 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 galanga leaf extract, Xanthan Gum, Caprylic / Capric Triglyceride), Stimulhyal230135 (Soliance, INCI: Calcium ketogluconate), Syn-Glycan (DSM, INCI: Tetradecyl Aminobutyroylvalylaminobutyric Urea Trifluoroacetate, Glycerin, Magnesium chloride), Kalpariane (Biotech Marine), DC Upregulex (Distinctive Cosmetic Ingredients, INCI: Water, Butylene Glycol, Phospholipids, Hydrolyzed Sericin), glucosamine, N-acetyl glucosamine, retinoids, preferably retinol and vitamin A, Arctium lappa fruit extract, Eriobotrya japonica extract, Genkwanin, N-Methyl-L-serine, (-)-alpha-bisabolol or synthetic alpha-bisabolol such as e.g. Dragosantol and Dragosantol 100 from Symrise, oat glucan, Echinacea purpurea extract and soy protein hydrolysate. Preferred actives are selected from the group consisting of hyaluronic acid and derivatives or salts, retinol and derivatives, (-)-alpha-bisabolol or synthetic alpha-bisabolol such as e.g. Dragosantol and Dragosantol 100 from Symrise, oat glucan, Echinacea purpurea extract, Sinorhizobium Meliloti Ferment Filtrate, Calcium ketogluconate, Alpinia galanga leaf extract and tetradecyl aminobutyroylvalylaminobutyric urea trifluoroacetate.
[0265] Anti-inflammatory agents: The compositions according to the present invention are preferably combined with anti-inflammatory and / or redness and / or itch ameliorating ingredients, in particular steroidal substances of the corticosteroid type selected from the group consisting of hydrocortisone, dexamethasone, dexamethasone phosphate, methyl prednisolone or cortisone, are advantageously used as anti-inflammatory active ingredients or active ingredients to relieve reddening and itching, the list of which can be extended by the addition of other steroidal anti-inflammatories. Non-steroidal anti- inflammatories can also be used. More particularly: (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, (ii) non-steroidal anti-inflammatory substances, in particular oxicams such as piroxicam or tenoxicam, salicylates such as aspirin, disalcid, solprin or fendosal, acetic acid derivatives such as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or clindanac, fenamates such as mefenamic, meclofenamic, flufenamic or niflumic, propionic acid derivatives such as ibuprofen, naproxen or benoxaprofen, pyrazoles such as phenylbutazone, oxyphenylbutazone, febrazone or azapropazone,230135 (iii) natural or naturally occurring anti-inflammatory substances or substances that alleviate reddening and / or itching, in particular extracts or fractions from camomile, Aloe vera, Commiphora species, Rubia species, willow, willow-herb, oats, calendula, arnica, St John's wort, honeysuckle, rosemary, Passiflora incarnata, witch hazel, ginger or Echinacea, or single active compounds thereof, (iv) histamine receptor antagonists, serine protease inhibitors (e.g. of Soy extracts), TRPV1 antagonists (e.g.4-t-Butylcyclohexanol), NK1 antagonists (e.g. Aprepitant, Hydroxyphenyl Propamidobenzoic Acid), cannabinoid receptor agonists (e.g. Palmitoyl Ethanolamine) and TRPV3 antagonists.
[0266] Examples which can be cited here are oxicams such as piroxicam or tenoxicam; salicylates such as aspirin, disalcid, solprin or fendosal; acetic acid derivatives such as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or clindanac; fenamates such as mefenamic, meclofenamic, flufenamic or niflumic; propionic acid derivatives such as ibuprofen, naproxen, benoxaprofen or pyrazoles such as phenylbutazone, oxyphenylbutazone, febrazone or azapropazone. Anthranilic acid derivatives are preferred anti-itch ingredients in a composition according to the present invention.
[0267] Also useful are natural or naturally occurring anti-inflammatory mixtures of substances or mixtures of substances that alleviate reddening and / or itching, in particular extracts or fractions from camomile, Aloe vera, Commiphora species, Rubia species, willow, willow-herb, oats, calendula, arnica, St John’s wort, honeysuckle, rosemary, Passiflora incarnata, witch hazel, ginger or Echinacea; preferably selected from the group consisting of extracts or fractions from camomile, Aloe vera, oats, calendula, arnica, honeysuckle, rosemary, witch hazel, ginger or Echinacea, and / or pure substances, preferably alpha-bisabolol, apigenin, apigenin-7-glucoside, gingerols, shogaols, gingerdiols, dehydrogingerdiones, paradols, natural or naturally occurring avenanthramides, preferably tranilast, avenanthramide A, avenanthramide B, avenanthramide C, non-natural or non-naturally occuring avenanthramides, preferably dihydroavenanthramide D, dihydroavenanthramide E, avenanthramide D, avenanthramide E, avenanthramide F, boswellic acid, phytosterols, glycyrrhizin, glabridin and licochalcone A; preferably selected from the group consisting of alpha-bisabolol,230135 natural avenanthramides, non-natural avenanthramides, preferably dihydroavenanthramide D (as described in WO 2004 047833 A1), boswellic acid, phytosterols, glycyrrhizin, and licochalcone A, and / or allantoin, panthenol, lanolin, (pseudo-)ceramides [preferably Ceramide 2, hydroxypropyl bispalmitamide MEA, cetyloxypropyl glyceryl methoxypropyl myristamide, N-(1-hexadecanoyl)-4-hydroxy-L- proline (1-hexadecyl) ester, hydroxyethyl palmityl oxyhydroxypropyl palmitamide], glycosphingolipids, phytosterols, chitosan, mannose, lactose and ß-glucans, in particular 1,3->1,4-ß-glucan from oats.
[0268] TRPV1 antagonists: Preferred compositions according to the present invention comprise one or more TRPV1 antagonists. Suitable compounds which reduce the hypersensitivity of skin nerves based on their action as TRPV1 antagonists, encompass e.g., trans-4-tert-butyl cyclohexanol, or indirect modulators of TRPV1 by an activation of the µ-receptor, e.g., acetyl tetrapeptide-15, are preferred.
[0269] Antimicrobial agents: The food, cosmetic or pharmaceutical preparation or homecare product according to the present invention can advantageously combined with an antimicrobial agent which act primarily against microorganisms, in particular bacteria, yeast and / or fungi and includes one or more antimicrobial agents such as Caprylhydroxamic Acid, o-Cymen-5-ol, Isopropylparaben, Capryloyl Glycine, Phenylpropanol, Tropolone, PCA Ethyl Cocoyl Arginate, 2-Methyl 5-Cyclohexylpentanol, Phenoxyethanol, Disodium EDTA, Methylparaben and its salts, Sodium Benzoate, Benzyl Alcohol, Potassium Sorbate, Benzyl Salicylate, Propylparaben, Sodium Methylparaben, Methylchloroisothiazolinone, Methylisothiazolinone, Ethylhexylglycerin, Butylparaben, Ethylparaben, Sodium Propylparaben, DMDM Hydantoin, Dehydroacetic Acid, Salicylic Acid, Chlorphenesin, Isobutylparaben, Sodium Ethylparaben, Diazolidinyl Urea, Diazolidinyl Urea, Farnesol, Bisabolol, Glyceryl Caprylate, Sodium Phytate or Phytic Acid, Sodium Levulinate or Levulinic Acid and esters and / or ketals thereof, Chlorhexidine, Glyceryl Laurate, Anisic Acid and its salts, Chlorhexidine Digluconate, TEA-salicylate, Phenethyl Alcohol, Glyceryl Caprate, Sorbitan Caprylate, Tetrasodium Glutamate Diacetate, Trisodium Ethylenediamine Disuccinate, Hydroxyethoxyphenyl Butanone, Hydroxyethoxyphenyl Butanol, Itaconic Acid, Octopirox, Propanediol Caprylate,230135 Climbazole, Undecylenoyl Glycine, Thymol, 4-Hydroxyacetophenone, Lactic Acid, Sodium Lactate, Trisodium Dicarboxymethyl Alaninate, Frambinon, Xylityl caprylate, Benzoic acid 3-hyroxypropylester, Anisic acid 3-hydroxypropylester, 3-Hydroxypropyl 2- hydroxybenzoate,1,3-propanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2- octanediol, 1,2-nonanediol, 1,2-decanediol, 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.
[0270] Preferably, the food, cosmetic or pharmaceutical preparation or homecare product according to the present invention comprises one or more antimicrobial agent 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-cyclohexylpentanol, 3-hydroxypropyl 2- hydroxybenzoate, 4-hydroxyacetophenone, and any mixture thereof. More preferably, the food, cosmetic or pharmaceutical preparation or homecare product according to the present invention comprises one or more antimicrobial agent 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.
[0271] In order to further enhance antimicrobial efficacy, the food, cosmetic or pharmaceutical preparation or homecare product as defined herein, is advantageously combined with at least one further antimicrobial agent which is different from the anti- microbial agents specified above. The combination with a further antimicrobial agent provides reliable protection against microbial degradation and deterioration of the preparation, in particular during storage. Additionally, the further different antimicrobial agent provides reliable protection against other microorganisms as described above, for example Corynebacterium, Anaerococcus, Finegoldia, Moraxella, Porphyromonas, Fusobacterium, Malassezia, Peptoniphilus, Streptococcus, Lactobacillus, Gardnerella, Fannyhessea, Epidermophyton, Trichophyton, Cutibacterium. Hence, the combination230135 with a further different antimicrobial agent allows antimicrobial protection against different groups of microorganisms, and, thus, a broader spectrum of microorganism. The further different antimicrobial agent in the context of the present invention is preferably selected from the group consisting of 2-benzylheptanol, alkyl (C 12-22) trimethyl ammonium bromide and chloride, ascorbic acid and salts thereof, benzalkonium bromide, benzalkonium chloride, benzalkonium saccharinate, benzethonium chloride, Benzoic Acid, camphor, cetylpyridinium chloride, chlorhexidine diacetate, chlorhexidine dihydrochloride, chlorocresol, chloroxylenol, Cyclohexylglycerin, Dimethyl phenylbutanol, Dimethyl phenylpropanol, ethanol, ethyl lauroyl arginate HCl, Ethyl Lauroyl Arginate Laurate, eucalyptol, gluconic acid and salts thereof, glycerin, hexamidine, hexamidine diisethionate, Hexylglycerin, Iodopropynyl Butylcarbamate, jasmol, lauryl alcohol, Levulinic Acid and esters and / or ketals thereof, mannitol, menthol, methyl salicylate, Octenidine HCl, polyarginine, Polyglyceryl-10 Laurate, polyglyceryl-2 caprate, Polyglyceryl-3 caprylate, polylysine, Salvia Officinalis (Sage) Oil, silver chloride, silver citrate, sodium caproyl lactylate, Sodium Caproyl / Lauroyl Lactylate, sodium lauroyl lactylate, Sorbic Acid, sorbitol, Tetraselmis extract, triclocarban, triclosan, Triethyl citrate, Xylityl Sesquicaprylate, zinc citrate, zinc pyrithione, Zinc ricinoleate, and any mixture thereof.
[0272] The aforesaid antimicrobial agents are used in the food, cosmetic or pharmaceutical preparation or homecare product either as a single component or preferably in a mixture with two or more further of said antimicrobial agents as specified above.
[0273] The antimicrobial agent is present in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.01 to 25.0 % by weight, preferably 0.02 to 15.0 % by weight, most preferred in an amount of 0.05 to 6.0 % by weight, based on the total weight of the final formulation.
[0274] Advantageously, the at least one antimicrobial alkanediol is present in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.1 to 5 % by weight, based on the total weight of the final formulation and / or the 4-230135 hydroxyacetophenone in an amount of 0.01 to 2 % by weight, based on the total weight of the final formulation.
[0275] Preservatives: For preservative purposes, the compositions according to the present invention preferably comprise one or more preservatives. Suitable and advantageously preservatives are, for example, benzoic acid, sodium benzoate, ammonium benzoate, butyl benzoate, calcium benzoate, ethyl benzoate, isobutyl benzoate, isopropyl benzoate, magnesium benzoate, mea-benzoate, methyl benzoate, phenyl benzoate, potassium benzoate, propyl benzoate, propionic acid, ammonium propionate, calcium propionate, magnesium propionate, potassium propionate, sodium propionate, salicylic acid, calcium salicylate, magnesium salicylate, measalicylate, sodium salicylate, potassium salicylate, teasalicylate, sorbic acid, calcium sorbate, sodium sorbate, potassium sorbate, o-phenylphenol, sodium sulfite, ammonium bisulfite, ammonium sulfite, potassium sulfite, potassium hydrogen sulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, chlorobutanol, 4-hydroxybenzoic acid, methylparaben, potassium ethylparaben, potassium paraben. sodium methylparaben, sodium ethylparaben, ethylparaben, sodium paraben, potassium methylparaben, calcium paraben, butylparaben, propylparaben, sodium propoylparaben, sodium butylparaben, potassium butylparaben, potassium propylparaben, dehydroacetic acid, sodium dehydroacetate, formic acid, sodium formate, dibromohexamidine isethionate, thimerosal, phenyl mercuric acetate, phenyl mercuric benzoate, undecylenic acid, potassium undecylenate, sodium undecylenate, calcium undecylenate, mea- undecylenate, tea-undecylenate, hexetidine, 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2- nitropropane-1,3-diol, dichlorobenzyl alcohol, triclocarban, p-chloro-m-cresol, triclosan, chloroxylenol, imidazolidinyl urea, polyaminopropyl; biguanide, phenoxyethanol, methenamine, climbazole, DMDM hydantoin, benzyl alcohol, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl)-2 pyridon, piroctone olamine, bromochlorophene, o-cymen-5-ol, methylchloroisothiazolinone and methylisothiazolinone, chlorhexidine, chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidine dihydrochloride, phenoxyisopropanol, behentrimonium chloride(1), cetrimonium bromide, cetrimonium chloride(2), laurtrimoniumbromide, laurtrimonium chloride, steartrimonium bromide, steartrimonium chloride (2), dimethyl oxazolidine, diazolidinyl urea, hexamidine, hexamidine230135 diisethionate, hexamidine diparaben, hexamidine paraben, glutaral, 7- ethylbicyclooxazolidine, chlorphenesin, sodium hydroxymethylglycinate, silver chloride, benzethonium chloride, benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate, benzylhemiformal, iodopropynyl butylcarbamate, methylisothiazolinone, citric acid, silver citrate, hydroxyethoxy-phenyl butanone (HEPB) and any mixture thereof.
[0276] Antibacterial or antimycotic active substances: In addition to the antimicrobials as described therein, antibacterial or antimycotic active substances can also particularly advantageously be used in the compositions according to the present invention, wherein any antibacterial or antimycotic active substances can be used which are suitable or customary in cosmetic or pharmaceutical, in particular dermatological applications. In addition to the large group of conventional antibiotics, other products which are advantageous here include those relevant to cosmetics such as in particular triclosan, climbazole, octoxyglycerin, Octopirox®(1-hydroxy-4-methyl-6-(2,4,4- trimethylpentyl)-2(1H)-pyridone 2-aminoethanol salt), chitosan, farnesol, glycerol monolaurate or combinations of said substances.
[0277] (Metal) chelating agents: A combination with one or more (metal) chelating agents can also be advantageous used in the compositions according to the present invention, wherein any metal chelating agents can be used which are suitable or customary in cosmetic or pharmaceutical applications. Preferred (metal) chelating agents include α-hydroxy fatty acids, phytic acid, lactoferrin, α-hydroxy acids, such as inter alia gluconic acid, glyceric acid, glycolic acid, isocitric acid, citric acid, lactic acid, malic acid, mandelic acid, tartaric acid, as well as humic acids, bile acids, bile extracts, bilirubin, biliverdin or EDTA, EGTA, MGDA (Trisodiumdicarboxymethyl alaninante), and their derivatives. The use of one or more chelating agent(s) improves the stability of the composition according to the present invention.
[0278] Surfactants: The compositions according to the present invention preferably include one or more anionic and / or amphoteric or zwitterionic surfactants. Typical examples encompass: Almondamidopropylamine Oxide, Almondamidopropyl Betaine, Aminopropyl Laurylglutamine, Ammonium C12-15 Alkyl Sulfate, Ammonium C12-16 Alkyl230135 Sulfate, Ammonium Capryleth Sulfate, Ammonium Cocomonoglyceride Sulfate, Ammonium Coco-Sulfate, Ammonium Cocoyl Isethionate, Ammonium Cocoyl Sarcosinate, Ammonium C12-15 Pareth Sulfate, Ammonium C9-10 Perfluoroalkylsulfonate, Ammonium Dinonyl Sulfosuccinate, Ammonium Dodecylbenzenesulfonate, Ammonium Isostearate, Ammonium Laureth-6 Carboxylate, Ammonium Laureth-8 Carboxylate, Ammonium Laureth Sulfate, Ammonium Laureth-5 Sulfate, Ammonium Laureth-7 Sulfate, Ammonium Laureth-9 Sulfate, Ammonium Laureth-12 Sulfate, Ammonium Lauroyl Sarcosinate, Ammonium Lauryl Sulfate, Ammonium Lauryl Sulfosuccinate, Ammonium Myreth Sulfate, Ammonium Myristyl Sulfate, Ammonium Nonoxynol-4 Sulfate, Ammonium Nonoxynol-30 Sulfate, Ammonium Oleate, Ammonium Palm Kernel Sulfate, Ammonium Stearate, Ammonium Tallate, AMPD-lsostearoyl Hydrolyzed Collagen, AMPD-Rosin Hydrolyzed Collagen, AMP- lsostearoyl Hydrolyzed Collagen, AMP-lsostearoyl Hydrolyzed Keratin, AMP-lsostearoyl Hydrolyzed Soy Protein, AMP-lsostearoyl Hydrolyzed Wheat Protein, Apricotamidopropyl Betaine, Arachidic Acid, Arginine Hexyldecyl Phosphate, Avocadamidopropyl Betaine, Avocado Oil Glycereth-8 Esters, Babassu Acid, Babassuamidopropylamine Oxide, Babassuamidopropyl Betaine, Beeswax Acid, Behenamidopropyl Betaine, Behenamine Oxide, Beheneth-25, Beheneth-30, Behenic Acid, Behenyl Betaine, Bis- Butyldimethicone Polyglyceryl-3, Butoxynol-5 Carboxylic Acid, Butoxynol-19 Carboxylic Acid, Butyldimoniumhydroxypropyl Butylglucosides Chloride, Butyldimoniumhydroxypropyl Laurylglucosides Chloride, Butyl Glucoside, Butylglucoside Caprate, Butylglucosides Hydroxypropyltrimonium Chloride, Butyloctanoic Acid, C18-36 Acid, C20-40 Acid, C30-50 Acid, C16-22 Acid Amide MEA, Calcium Dodecylbenzenesulfonate, Calcium Lauroyl Taurate, C9-16 Alkane / Cycloalkane, C10-14 Alkyl Benzenesulfonic Acid, C12-14 Alkyl Diaminoethylglycine HCL, C9-15 Alkyl Phosphate, Candida Bombicola / Glucose / Methyl Rapeseedate Ferment, Canolamidopropyl Betaine, Capric Acid, Caproic Acid, Caproyl Ethyl Glucoside, Capryl / Capramidopropyl Betaine, Capryleth-4 Carboxylic Acid, Capryleth-6 Carboxylic Acid, Capryleth-9 Carboxylic Acid, Caprylic Acid, Capryloyl Collagen Amino Acids, Capryloyl Glycine, Capryloyl Hydrolyzed Collagen, Capryloyl Hydrolyzed Keratin, Capryloyl Keratin Amino Acids, Capryloyl Silk Amino Acids, Caprylyl / Capryl Glucoside, Caprylyl / Capryl Wheat Bran / Straw Glycosides, Caprylyl Glucoside, Caprylyl Glyceryl230135 Ether, Caprylyl Pyrrolidone, Carnitine, Ceteareth-20, Ceteareth-23, Ceteareth-24, Ceteareth-25, Ceteareth-27, Ceteareth-28, Ceteareth-29, Ceteareth-30, Ceteareth-33, Ceteareth-34, Ceteareth-40, Ceteareth-50, Ceteareth-55, Ceteareth-60, Ceteareth-80, Ceteareth-100, Ceteareth-25 Carboxylic Acid, Ceteareth-2 Phosphate, Ceteareth-4 Phosphate, Ceteareth-5 Phosphate, Ceteareth-10 Phosphate, Ceteth-20, Ceteth-23, Ceteth-24, Ceteth-25, Ceteth-30, Ceteth-40, Ceteth-45, Ceteth-150, Ceteth-8 Phosphate, Ceteth-10 Phosphate, Ceteth-20 Phosphate, Cetoleth-22, Cetoleth-24, Cetoleth-25, Cetoleth-30, Cetyl Betaine, Chrysanthemum Sinense Flower Extract, C12-14 Hydroxyalkyl Hydroxyethyl Beta-Alanine, C12-14 Hydroxyalkyl Hydroxyethyl Sarcosine, Cocamidoethyl Betaine, Cocamidopropylamine Oxide, Cocamidopropyl Betainamide MEA Chloride, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Cocamine Oxide, Cocaminobutyric Acid, Cocaminopropionic Acid, Coceth-7 Carboxylic Acid, Coceth-4 Glucoside, Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, Coco-Betaine, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Coco-Glucoside, Cocoglucosides Hydroxypropyltrimonium Chloride, Coco- Hydroxysultaine, Coco-Morpholine Oxide, Coconut Acid, Coconut Oil Glycereth-8 Esters, Coco / Oleamidopropyl Betaine, Coco-Sultaine, Coco / Sunfloweramidopropyl Betaine, Cocoylcholine Methosulfate, Cocoyl Glutamic Acid, Cocoyl Hydrolyzed Collagen, Cocoyl Hydrolyzed Keratin, Cocoyl Hydrolyzed Oat Protein, Cocoyl Hydrolyzed Rice Protein, Cocoyl Hydrolyzed Silk, Cocoyl Hydrolyzed Soy Protein, Cocoyl Hydrolyzed Wheat Protein, Cocoyl Sarcosine, Corn Acid, Cottonseed Acid, Cottonseed Oil Glycereth-8 Esters, C10-16 Pareth-1, C10-16 Pareth-2, C11-13 Pareth-6, C11-13 Pareth-9, C11-13 Pareth-10, C11-15 Pareth-30, C11-15 Pareth-40, C12-13 Pareth-1, C12-13 Pareth- 23, C12-14 Pareth-5, C12-14 Pareth-9, C13-15 Pareth-21, C14-15 Pareth-8, C20-22 Pareth- 30, C20- 40 Pareth-40, C20-40 Pareth-95, C22-24 Pareth-33, C30-50 Pareth-40, C9-11 Pareth-6 Carboxylic Acid, C9-11 Pareth-8 Carboxylic Acid, C11-15 Pareth-7 Carboxylic Acid, C12-13 Pareth-5 Carboxylic Acid, C12-13 Pareth-7 Carboxylic Acid, C12-13 Pareth- 8 Carboxylic Acid, C12-13 Pareth-12 Carboxylic Acid, C12-15 Pareth-7 Carboxylic Acid, C12-15 Pareth-8 Carboxylic Acid, C12-15 Pareth- 12 Carboxylic Acid, C14-15 Pareth-8 Carboxylic Acid, C6-10 Pareth-4 Phosphate, C12-13 Pareth-2 Phosphate, C12-13 Pareth-10 Phosphate, C12-15 Pareth-6 Phosphate, C12-15 Pareth-8 Phosphate, C12-15230135 Pareth-10 Phosphate, C12-16 Pareth-6 Phosphate, C4-18 Perfluoroalkylethyl Thiohydroxypropyltrimonium Chloride, Cupuassuamidopropyl Betaine, DEA-C12-13 Alkyl Sulfate, DEA-C12-15 Alkyl Sulfate, DEA-Ceteareth-2 Phosphate, DEA-Cetyl Sulfate, DEA- Cocoamphodipropionate, DEA-C12-13 Pareth-3 Sulfate, DEA- Cyclocarboxypropyloleate, DEA- Dodecylbenzenesulfonate, DEA-lsostearate, DEA- Laureth Sulfate, DEA-Lauryl Sulfate, DEA- Linoleate, DEA-Methyl Myristate Sulfonate, DEA-Myreth Sulfate, DEA-Myristate, DEA-Myristyl Sulfate, DEA-Oleth-5 Phosphate, DEA-Oleth-20 Phosphate, DEA PG-Oleate, Deceth-7 Carboxylic Acid, Deceth-7 Glucoside, Deceth-9 Phosphate, Decylamine Oxide, Decyl Betaine, Decyl Glucoside, Decyltetradeceth-30, Decyltetradecylamine Oxide, Diammonium Lauramido-MEA Sulfosuccinate, Diammonium Lauryl Sulfosuccinate, Diammonium Oleamido PEG-2 Sulfosuccinate, Dibutoxymethane, Di-CI 2-15 Pareth-2 Phosphate, Di-CI 2-15 Pareth-4 Phosphate, Di-CI 2-15 Pareth-6 Phosphate, Di- C12-15 Pareth-8 Phosphate, Di-CI 2-15 Pareth-10 Phosphate, Didodecyl Butanetetracarboxylate, Diethylamine Laureth Sulfate, Diethylhexyl Sodium Sulfosuccinate, Dihydroxyethyl C8-10 Alkoxypropylamine Oxide, Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Dimethicone PEG-7 Phosphate, Dimethicone PEG-10 Phosphate, Dimethicone PEG / PPG-7 / 4 Phosphate, Dimethicone PEG / PPG-12 / 4 Phosphate, Dimethicone / Polyglycerin-3 Crosspolymer, Dimethicone Propyl PG- Betaine, Dimyristyl Phosphate, Dioleoylamidoethyl Hydroxyethylmonium Methosulfate, DIPA- Hydrogenated Cocoate, DIPA-Lanolate, DIPA-Myristate, Dipotassium Capryloyl Glutamate, Dipotassium Lauryl Sulfosuccinate, Dipotassium Undecylenoyl Glutamate, Disodium Babassuamido MEA-Sulfosuccinate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Capryloyl Glutamate, Disodium Cetearyl Sulfosuccinate, Disodium Cetyl Phenyl Ether Disulfonate, Disodium Cetyl Sulfosuccinate, Disodium Cocamido MEA-Sulfosuccinate, Disodium Cocamido MIPA PEG-4 Sulfosuccinate, Disodium Cocamido MIPA-Sulfosuccinate, Disodium Cocamido PEG-3 Sulfosuccinate, Disodium Coceth-3 Sulfosuccinate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate,230135 Disodium Cocoamphodipropionate, Disodium Coco-Glucoside Sulfosuccinate, Disodium Coco-Sulfosuccinate, Disodium Cocoyl Butyl Gluceth-10 Sulfosuccinate, Disodium Cocoyl Glutamate, Disodium C12-14 Pareth-1 Sulfosuccinate, Disodium C12-14 Pareth- 2 Sulfosuccinate, Disodium C12-15 Pareth Sulfosuccinate, Disodium C12-14 Sec-Pareth- 3 Sulfosuccinate, Disodium C12-14 Sec-Pareth-5 Sulfosuccinate, Disodium C12-14 Sec- Pareth-7 Sulfosuccinate, Disodium C12-14 Sec-Pareth-9 Sulfosuccinate, Disodium C12- 14 Sec-Pareth-12 Sulfosuccinate, Disodium Deceth-5 Sulfosuccinate, Disodium Deceth- 6 Sulfosuccinate, Disodium Decyl Phenyl Ether Disulfonate, Disodium Dihydroxyethyl Sulfosuccinylundecylenate, Disodium Ethylene Dicocamide PEG-15 Disulfate, Disodium Hydrogenated Cottonseed Glyceride Sulfosuccinate, Disodium Hydrogenated Tallow Glutamate, Disodium Hydroxydecyl Sorbitol Citrate, Disodium lsodecyl Sulfosuccinate, Disodium lsostearamido MEA-Sulfosuccinate, Disodium lsostearamido MIPA- Sulfosuccinate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium lsostearyl Sulfosuccinate, Disodium Laneth-5 Sulfosuccinate, Disodium Lauramido MEA-Sulfosuccinate, Disodium Lauramido MIPA Glycol Sulfosuccinate, Disodium Lauramido PEG-2 Sulfosuccinate, Disodium Lauramido PEG-5 Sulfosuccinate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Laureth- 7 Citrate, Disodium Laureth Sulfosuccinate, Disodium Laureth-6 Sulfosuccinate, Disodium Laureth-9 Sulfosuccinate, Disodium Laureth-12 Sulfosuccinate, Disodium Lauriminobishydroxypropylsulfonate, Disodium Lauriminodiacetate, Disodium Lauriminodipropionate, Disodium Lauriminodipropionate Tocopheryl Phosphates, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium N- Lauroyl Aspartate, Disodium Lauroyl Glutamate, Disodium Lauryl Phenyl Ether Disulfonate, Disodium Lauryl Sulfosuccinate, Disodium Myristamido MEA- Sulfosuccinate, Disodium Nonoxynol-10 Sulfosuccinate, Disodium Oleamido MEA- Sulfosuccinate, Disodium Oleamido MIPA-Sulfosuccinate, Disodium Oleamido PEG-2 Sulfosuccinate, Disodium Oleoamphodipropionate, Disodium Oleth-3 Sulfosuccinate, Disodium Oleyl Phosphate, Disodium Oleyl Sulfosuccinate, Disodium Palmitamido PEG- 2 Sulfosuccinate, Disodium Palmitoleamido PEG-2 Sulfosuccinate, Disodium PEG-4 Cocamido MIPA-Sulfosuccinate, Disodium PEG-12 Dimethicone Sulfosuccinate, Disodium PEG-8 Palm Glycerides Sulfosuccinate, Disodium PPG-2-lsodeceth-7 Carboxyamphodiacetate, Disodium Ricinoleamido MEA-Sulfosuccinate, Disodium230135 Sitostereth-14 Sulfosuccinate, Disodium Soyamphodiacetate, Disodium Stearamido MEA-Sulfosuccinate, Disodium Steariminodipropionate, Disodium Stearoamphodiacetate, Disodium Stearoyl Glutamate, Disodium Stearyl Sulfosuccinamate, Disodium Stearyl Sulfosuccinate, Disodium 2-Sulfolaurate, Disodium 2-Sulfopalmitate, Disodium Tallamido MEA-Sulfosuccinate, Disodium Tallowamido MEA- Sulfosuccinate, Disodium Tallowamphodiacetate, Disodium Tallowiminodipropionate, Disodium Tallow Sulfosuccinamate, Disodium Tridecylsulfosuccinate, Disodium Undecylenamido MEA-Sulfosuccinate, Disodium Undecylenamido PEG-2 Sulfosuccinate, Disodium Undecylenoyl Glutamate, Disodium Wheat Germamido MEA- Sulfosuccinate, Disodium Wheat Germamido PEG-2 Sulfosuccinate, Disodium Wheatgermamphodiacetate, Di-TEA-Cocamide Diacetate, Di-TEA-Oleamido PEG-2 Sulfosuccinate, Di-TEA-Palmitoyl Aspartate, Ditridecyl Sodium Sulfosuccinate, Dodecylbenzene Sulfonic Acid, Erucamidopropyl Hydroxysultaine, Ethylhexeth-3 Carboxylic Acid, Ethyl PEG-15 Cocamine Sulfate, Glyceryl Capryl Ether, Hexyldecanoic Acid, Hydrogenated Coconut Acid, Hydrogenated Laneth-25, Hydrogenated Menhaden Acid, Hydrogenated Palm Acid, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallow Acid, Hydrogenated Tallowamine Oxide, Hydrogenated Tallow Betaine, Hydrogenated Talloweth-25, Hydrogenated Tallowoyl Glutamic Acid, Hydrolyzed Candida Bombicola Extract, Hydroxyceteth-60, Hydroxyethyl Acetomonium PG- Dimethicone, Hydroxyethylbutylamine Laureth Sulfate, Hydroxyethyl Carboxymethyl Cocamidopropylamine, Hydroxyethyl Hydroxypropyl C12-15 Alkoxypropylamine Oxide, Hydroxylauryl / Hydroxymyristyl Betaine, Hydroxystearic Acid, Hydroxysuccinimidyl C10- 40 lsoalkyl Acidate, Hydroxysuccinimidyl C21-22 lsoalkyl Acidate, Hydroxysultaines, IPDI / PEG-15 Soyamine Oxide Copolymer, IPDI / PEG-15 Soyethonium Ethosulfate Copolymer, IPDI / PEG-15 Soy Glycinate Copolymer, lsoceteth-30, lsolaureth-4 Phosphate, lsopolyglyceryl-3 Dimethicone, lsopolyglyceryl-3 Dimethiconol, lsopropanolamine Lanolate, lsopropylamine Dodecylbenzenesulfonate, lsostearamidopropylamine Oxide, lsostearamidopropyl Betaine, lsostearamidopropyl Morpholine Oxide, lsosteareth-8, lsosteareth-16, lsosteareth-22, lsosteareth-25, lsosteareth-50, lsostearic Acid, lsostearoyl Hydrolyzed Collagen, Jojoba Oil PEG-150 Esters, Jojoba Wax PEG-80 Esters, Jojoba Wax PEG-120 Esters, Laneth-20, Laneth-25, Laneth-40, Laneth-50, Laneth-60, Laneth-75, Lanolin Acid, Lauramidopropylamine230135 Oxide, Lauramidopropyl Betaine, Lauramidopropyl Hydroxysultaine, Lauramine Oxide, Lauraminopropionic Acid, Laurdimoniumhydroxypropyl Decylglucosides Chloride, Laurdimoniumhydroxypropyl Laurylglucosides Chloride, Laureth-16, Laureth-20, Laureth-21, Laureth-23, Laureth-25, Laureth-30, Laureth-38, Laureth-40, Laureth-3 Carboxylic Acid, Laureth-4 Carboxylic Acid, Laureth-5 Carboxylic Acid, Laureth- 6 Carboxylic Acid, Laureth-8 Carboxylic Acid, Laureth-10 Carboxylic Acid, Laureth-11 Carboxylic Acid, Laureth-12 Carboxylic Acid, Laureth-13 Carboxylic Acid, Laureth-14 Carboxylic Acid, Laureth-17 Carboxylic Acid, Laureth-6 Citrate, Laureth-7 Citrate, Laureth-1 Phosphate, Laureth-2 Phosphate, Laureth-3 Phosphate, Laureth-4 Phosphate, Laureth-7 Phosphate, Laureth-8 Phosphate, Laureth-7 Tartrate, Laurie Acid, Laurimino Bispropanediol, Lauriminodipropionic Acid, Lauroamphodipropionic Acid, Lauroyl Beta- Alanine, Lauroyl Collagen Amino Acids, Lauroyl Ethyltrimonium Methosulfate, Lauroyl Hydrolyzed Collagen, Lauroyl Hydrolyzed Elastin, Lauroyl Methyl Glucamide, Lauroyl Sarcosine, Lauroyl Silk Amino Acids, Lauryl Betaine, Lauryl Dimethicone / Polyglycerin-3 Crosspolymer, Lauryldimoniumhydroxypropyl Cocoglucosides Chloride, Lauryl Glucoside, Laurylglucosides Hydroxypropyltrimonium Chloride, Lauryl Glycol Hydroxypropyl Ether, Lauryl Hydroxysultaine, Lauryl Malamide, Lauryl Methylglucamide, Lauryl / Myristyl Glycol Hydroxypropyl Ether, Lauryl / Myristyl Wheat Bran / Straw Glycosides, Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone, Lauryl Pyrrolidone, Lauryl Sultaine, Linoleic Acid, Linolenic Acid, Linseed Acid, Lysine Cocoate, Macadamia Seed Oil Glycereth-8 Esters, Magnesium Coceth Sulfate, Magnesium Coco- Sulfate, Magnesium Isododecylbenzenesulfonate, Magnesium Laureth-11 Carboxylate, Magnesium Laureth Sulfate, Magnesium Laureth-5 Sulfate, Magnesium Laureth-8 Sulfate, Magnesium Laureth-16 Sulfate, Magnesium Laureth-3 Sulfosuccinate, Magnesium Lauryl Hydroxypropyl Sulfonate, Magnesium Lauryl Sulfate, Magnesium Methyl Cocoyl Taurate, Magnesium Myreth Sulfate, Magnesium Oleth Sulfate, Magnesium / TEA-Coco-Sulfate, Manicouagan Clay, MEA-Cocoate, MEA-Laureth-6 Carboxylate, MEA- Laureth Sulfate, MEA-Lauryl Sulfate, MEA PPG-6 Laureth-7 Carboxylate, MEA-PPG-8-Steareth-7 Carboxylate, MEA-Undecylenate, Meroxapol 108, Meroxapol 174, Meroxapol 178, Meroxapol 254, Meroxapol 255, Meroxapol 258, Meroxapol 314, Methoxy PEG-450 Amidoglutaroyl Succinimide, Methoxy PEG-450 Amido Hydroxysuccinimidyl Succinamate, Methoxy PEG-450 Maleimide, Methyl230135 Morpholine Oxide, Milkamidopropyl Amine Oxide, Milkamidopropyl Betaine, Minkamidopropylamine Oxide, Minkamidopropyl Betaine, MIPA C12-15 Pareth Sulfate, MIPA-Dodecylbenzenesulfonate, MIPA-Laureth Sulfate, MIPA-Lauryl Sulfate, Mixed lsopropanolamines Lanolate, Mixed lsopropanolamines Lauryl Sulfate, Mixed lsopropanolamines Myristate, Morpholine Oleate, Morpholine Stearate, Myreth-3 Carboxylic Acid, Myreth-5 Carboxylic Acid, Myristalkonium Chloride, Myristamidopropylamine Oxide, Myristamidopropyl Betaine, Myristamidopropyl Dimethylamine Phosphate, Myristamidopropyl Hydroxysultaine, Myristamidopropyl PG- Dimonium Chloride Phosphate, Myristamine Oxide, Myristaminopropionic Acid, Myristic Acid, Myristoyl Ethyltrimonium Methosulfate, Myristoyl Glutamic Acid, Myristoyl Hydrolyzed Collagen, Myristoyl Sarcosine, Myristyl Betaine, Myristyl / Cetyl Amine Oxide, Myristyldimoniumhydroxypropyl Cocoglucosides Chloride, Myristyl Glucoside, Myristyl Phosphate, Nonoxynol-20, Nonoxynol-23, Nonoxynol-25, Nonoxynol-30, Nonoxynol-35, Nonoxynol-40, Nonoxynol-44, Nonoxynol-50, Nonoxynol-100, Nonoxynol-120, Nonoxynol-5 Carboxylic Acid, Nonoxynol-8 Carboxylic Acid, Nonoxynol-10 Carboxylic Acid, Nonoxynol-3 Phosphate, Nonoxynol-4 Phosphate, Nonoxynol-6 Phosphate, Nonoxynol-9 Phosphate, Nonoxynol-10 Phosphate, Nonyl Nonoxynol-30, Nonyl Nonoxynol-49, Nonyl Nonoxynol-100, Nonyl Nonoxynol-150, Nonyl Nonoxynol-7 Phosphate, Nonyl Nonoxynol-8 Phosphate, Nonyl Nonoxynol-9 Phosphate, Nonyl Nonoxynol-10 Phosphate, Nonyl Nonoxynol-11 Phosphate, Nonyl Nonoxynol-15 Phosphate, Nonyl Nonoxynol-24 Phosphate, Oatamidopropyl Betaine, Octoxynol-16, Octoxynol-25, Octoxynol-30, Octoxynol-33, Octoxynol-40, Octoxynol-70, Octoxynol-20 Carboxylic Acid, Octyldodeceth-20, Octyldodeceth-25, Octyldodeceth-30, Oleamidopropylamine Oxide, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysultaine, Oleamine Oxide, Oleic Acid, Oleoyl Hydrolyzed Collagen, Oleoyl Sarcosine, Oleth-20, Oleth-23, Oleth-24, Oleth-25, Oleth-30, Oleth-35, Oleth-40, Oleth-44, Oleth-50, Oleth-3 Carboxylic Acid, Oleth-6 Carboxylic Acid, Oleth-10 Carboxylic Acid, Oleyl Betaine, Olivamidopropylamine Oxide, Olivamidopropyl Betaine, Olive Acid, Olivoyl Hydrolyzed Wheat Protein, Ophiopogon Extract Stearate, Ozonized Oleth-10, Ozonized PEG-10 Oleate, Ozonized PEG-14 Oleate, Ozonized Polysorbate 80, Palm Acid, Palmamidopropyl Betaine, Palmeth-2 Phosphate, Palmitamidopropylamine Oxide, Palmitamidopropyl Betaine, Palmitamine Oxide, Palmitic Acid, Palmitoyl Collagen Amino230135 Acids, Palmitoyl Glycine, Palmitoyl Hydrolyzed Collagen, Palmitoyl Hydrolyzed Milk Protein, Palmitoyl Hydrolyzed Wheat Protein, Palmitoyl Keratin Amino Acids, Palmitoyl Oligopeptide, Palmitoyl Silk Amino Acids, Palm Kernel Acid, Palm Kernelamidopropyl Betaine, Peach Kernel Oil Glycereth-8 Esters, Peanut Acid, PEG-10 Castor Oil, PEG-40 Castor Oil, PEG-44 Castor Oil, PEG-50 Castor Oil, PEG-54 Castor Oil, PEG-55 Castor Oil, PEG-60 Castor Oil, PEG-80 Castor Oil, PEG-100 Castor Oil, PEG-200 Castor Oil, PEG-11 Cocamide, PEG-6 Cocamide Phosphate, PEG-4 Cocamine, PEG-8 Cocamine, PEG-12 Cocamine, PEG-150 Dibehenate, PEG-90 Diisostearate, PEG-75 Dilaurate, PEG-150 Dilaurate, PEG-75 Dioleate, PEG-150 Dioleate, PEG-75 Distearate, PEG-120 Distearate, PEG-150 Distearate, PEG-175 Distearate, PEG-190 Distearate, PEG-250 Distearate, PEG-30 Glyceryl Cocoate, PEG-40 Glyceryl Cocoate, PEG-78 Glyceryl Cocoate, PEG-80 Glyceryl Cocoate, PEG-30 Glyceryl Isostearate, PEG-40 Glyceryl Isostearate, PEG-50 Glyceryl Isostearate, PEG-60 Glyceryl Isostearate, PEG-90 Glyceryl Isostearate, PEG-23 Glyceryl Laurate, PEG-30 Glyceryl Laurate, PEG-25 Glyceryl Oleate, PEG-30 Glyceryl Oleate, PEG-30 Glyceryl Soyate, PEG-25 Glyceryl Stearate, PEG-30 Glyceryl Stearate, PEG-40 Glyceryl Stearate, PEG-120 Glyceryl Stearate, PEG- 200 Glyceryl Stearate, PEG-28 Glyceryl Tallowate, PEG-80 Glyceryl Tallowate, PEG-82 Glyceryl Tallowate, PEG-130 Glyceryl Tallowate, PEG-200 Glyceryl Tallowate, PEG-45 Hydrogenated Castor Oil, PEG-50 Hydrogenated Castor Oil, PEG-54 Hydrogenated Castor Oil, PEG-55 Hydrogenated Castor Oil, PEG-60 Hydrogenated Castor Oil, PEG-80 Hydrogenated Castor Oil, PEG-100 Hydrogenated Castor Oil, PEG-200 Hydrogenated Castor Oil, PEG-30 Hydrogenated Lanolin, PEG-70 Hydrogenated Lanolin, PEG-50 Hydrogenated Palmamide, PEG-2 Isostearate, PEG-3 Isostearate, PEG-4 Isostearate, PEG-6 Isostearate, PEG-8 Isostearate, PEG-10 Isostearate, PEG-12 Isostearate, PEG- 20 Isostearate, PEG-30 Isostearate, PEG-40 Isostearate, PEG- 26 Jojoba Acid, PEG-40 Jojoba Acid, PEG-15 Jojoba Alcohol, PEG-26 Jojoba Alcohol, PEG-40 Jojoba Alcohol, PEG-35 Lanolin, PEG-40 Lanolin, PEG-50 Lanolin, PEG-55 Lanolin, PEG-60 Lanolin, PEG- 70 Lanolin, PEG-75 Lanolin, PEG-85 Lanolin, PEG-100 Lanolin, PEG-150 Lanolin, PEG-75 Lanolin Oil, PEG-2 Lauramide, PEG-3 Lauramine Oxide, PEG-20 Laurate, PEG- 32 Laurate, PEG-75 Laurate, PEG-150 Laurate, PEG-70 Mango Glycerides, PEG-20 Mannitan Laurate, PEG-8 Methyl Ether Dimethicone, PEG-120 Methyl Glucose Dioleate, PEG-80 Methyl Glucose Laurate, PEG-120 Methyl Glucose Trioleate, PEG-4 Montanate,230135 PEG-30 Oleamine, PEG-20 Oleate, PEG-23 Oleate, PEG-32 Oleate, PEG-36 Oleate, PEG-75 Oleate, PEG-150 Oleate, PEG-20 Palmitate, PEG-150 Polyglyceryl-2 Tristearate, PEG / PPG-28 / 21 Acetate Dimethicone, PEG / PPG-24 / 18 Butyl Ether Dimethicone, PEG / PPG-3 / 17 Copolymer, PEG / PPG-5 / 35 Copolymer, PEG / PPG-8 / 55 Copolymer, PEG / PPG-10 / 30 Copolymer, PEG / PPG-10 / 65 Copolymer, PEG / PPG-12 / 35 Copolymer, PEG / PPG-16 / 17 Copolymer, PEG / PPG-20 / 9 Copolymer, PEG / PPG-20 / 20 Copolymer, PEG / PPG-20 / 60 Copolymer, PEG / PPG- 20 / 65 Copolymer, PEG / PPG-22 / 25 Copolymer, PEG / PPG-28 / 30 Copolymer, PEG / PPG-30-35 Copolymer, PEG / PPG-30 / 55 Copolymer, PEG / PPG-35 / 40 Copolymer, PEG / PPG-50 / 40 Copolymer, PEG / PPG-150 / 35 Copolymer, PEG / PPG-160 / 30 Copolymer, PEG / PPG-190 / 60 Copolymer, PEG / PPG- 200 / 40 Copolymer, PEG / PPG-300 / 55 Copolymer, PEG / PPG-20 / 22 Methyl Ether Dimethicone, PEG-26-PPG-30 Phosphate, PEG / PPG-4 / 2 Propylheptyl Ether, PEG / PPG- 6 / 2 Propylheptyl Ether, PEG-7 / PPG-2 Propylheptyl Ether, PEG / PPG-8 / 2 Propylheptyl Ether, PEG / PPG- 10 / 2 Propylheptyl Ether, PEG / PPG-14 / 2 Propylheptyl Ether, PEG / PPG-40 / 2 Propylheptyl Ether, PEG / PPG-10 / 2 Ricinoleate, PEG / PPG-32 / 3 Ricinoleate, PEG-55 Propylene Glycol Oleate, PEG-25 Propylene Glycol Stearate, PEG- 75 Propylene Glycol Stearate, PEG-120 Propylene Glycol Stearate, PEG-5 Rapeseed Sterol, PEG-10 Rapeseed Sterol, PEG-40 Ricinoleamide, PEG-75 Shea Butter Glycerides, PEG-75 Shorea Butter Glycerides, PEG-20 Sorbitan Cocoate, PEG-20 Sorbitan Isostearate, PEG-40 Sorbitan Lanolate, PEG-75 Sorbitan Lanolate, PEG-10 Sorbitan Laurate, PEG-40 Sorbitan Laurate, PEG-44 Sorbitan Laurate, PEG-75 Sorbitan Laurate, PEG-80 Sorbitan Laurate, PEG-20 Sorbitan Oleate, PEG-80 Sorbitan Palmitate, PEG-40 Sorbitan Stearate, PEG-60 Sorbitan Stearate, PEG-160 Sorbitan Triisostearate, PEG-40 Soy Sterol, PEG-2 Stearamide Carboxylic Acid, PEG-9 Stearamide Carboxylic Acid, PEG-20 Stearate, PEG-23 Stearate, PEG-25 Stearate, PEG-30 Stearate, PEG-32 Stearate, PEG-35 Stearate, PEG-36 Stearate, PEG-40 Stearate, PEG-45 Stearate, PEG- 50 Stearate, PEG-55 Stearate, PEG-75 Stearate, PEG-90 Stearate, PEG-100 Stearate, PEG- 120 Stearate, PEG-150 Stearate, PEG-45 Stearate Phosphate, PEG-20 Tallate, PEG-50 Tallow Amide, PEG-2 Tallowamide DEA, PEG-20 Tallowate, PEG-66 Trihydroxystearin, PEG-200 Trihydroxystearin, PEG-60 Tsubakiate Glycerides, Pelargonic Acid, Pentadoxynol-200, Pheneth-6 Phosphate, Poloxamer 105, Poloxamer 108, Poloxamer 182, Poloxamer 183, Poloxamer 184, Poloxamer 188, Poloxamer 217,230135 Poloxamer 234, Poloxamer 235, Poloxamer 237, Poloxamer 238, Poloxamer 288, Poloxamer 334, Poloxamer 335, Poloxamer 338, Poloxamine 908, Poloxamine 1508, Polydimethylsiloxy PEG / PPG-24 / 19 Butyl Ether Silsesquioxane, Polydimethylsiloxy PPG-13 Butyl Ether Silsesquioxane, Polyglyceryl-6 Caprate, Polyglyceryl-10 Dilaurate, Polyglyceryl-20 Heptacaprylate, Polyglyceryl-20 Hexacaprylate, Polyglyceryl-2 Lauryl Ether, Polyglyceryl-10 Lauryl Ether, Polyglyceryl-20 Octaisononanoate, Polyglyceryl-6 Pentacaprylate, Polyglyceryl-10 Pentacaprylate, Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone, Polyglyceryl-6 Tetracaprylate, Polyglyceryl-10 Tetralaurate, Polyglyceryl-6 Tricaprylate, Polyglyceryl-10 Trilaurate, Polyquaternium- 77, Polyquaternium-78, Polyquaternium-79, Polyquaternium-80, Polyquaternium-81, Polyquaternium- 82, Pomaderris Kumerahou Flower / Leaf Extract, Poria Cocos Extract, Potassium Abietoyl Hydrolyzed Collagen, Potassium Babassuate, Potassium Behenate, Potassium C9-15 Alkyl Phosphate, Potassium C11-15 Alkyl Phosphate, Potassium C12-13 Alkyl Phosphate, Potassium C12-14 Alkyl Phosphate, Potassium Caprate, Potassium Capryloyl Glutamate, Potassium Capryloyl Hydrolyzed Rice Protein, Potassium Castorate, Potassium Cocoate, Potassium Cocoyl Glutamate, Potassium Cocoyl Glycinate, Potassium Cocoyl Hydrolyzed Casein, Potassium Cocoyl Hydrolyzed Collagen, Potassium Cocoyl Hydrolyzed Corn Protein, Potassium Cocoyl Hydrolyzed Keratin, Potassium Cocoyl Hydrolyzed Oat Protein, Potassium Cocoyl Hydrolyzed Potato Protein, Potassium Cocoyl Hydrolyzed Rice Bran Protein, Potassium Cocoyl Hydrolyzed Rice Protein, Potassium Cocoyl Hydrolyzed Silk, Potassium Cocoyl Hydrolyzed Soy Protein, Potassium Cocoyl Hydrolyzed Wheat Protein, Potassium Cocoyl Hydrolyzed Yeast Protein, Potassium Cocoyl PCA, Potassium Cocoyl Sarcosinate, Potassium Cocoyl Taurate, Potassium Cornate, Potassium Cyclocarboxypropyloleate, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Dimethicone PEG-7 Phosphate, Potassium Dodecylbenzenesulfonate, Potassium Hempseedate, Potassium Hydrogenated Cocoate, Potassium Hydrogenated Palmate, Potassium Hydrogenated Tallowate, Potassium Hydroxystearate, Potassium Isostearate, Potassium Lanolate, Potassium Laurate, Potassium Laureth-3 Carboxylate, Potassium Laureth-4 Carboxylate, Potassium Laureth-5 Carboxylate, Potassium Laureth-6 Carboxylate, Potassium Laureth- 10 Carboxylate, Potassium Laureth Phosphate, Potassium Lauroyl Collagen Amino Acids, Potassium Lauroyl Glutamate, Potassium Lauroyl Hydrolyzed Collagen,230135 Potassium Lauroyl Hydrolyzed Pea Protein, Potassium Lauroyl Hydrolyzed Soy Protein, Potassium Lauroyl PCA, Potassium Lauroyl Pea Amino Acids, Potassium Lauroyl Sarcosinate, Potassium Lauroyl Silk Amino Acids, Potassium Lauroyl Wheat Amino Acids, Potassium Lauryl Phosphate, Potassium Lauryl Sulfate, Potassium Linoleate, Potassium Metaphosphate, Potassium Methyl Cocoyl Taurate, Potassium Myristate, Potassium Myristoyl Glutamate, Potassium Myristoyl Hydrolyzed Collagen, Potassium Octoxynol-12 Phosphate, Potassium Oleate, Potassium Oleoyl Hydrolyzed Collagen, Potassium Olivate, Potassium Olivoyl Hydrolyzed Oat Protein, Potassium Olivoyl Hydrolyzed Wheat Protein, Potassium Olivoyl / Lauroyl Wheat Amino Acids, Potassium Olivoyl PCA, Potassium Palmate, Potassium Palmitate, Potassium Palmitoyl Hydrolyzed Corn Protein, Potassium Palmitoyl Hydrolyzed Oat Protein, Potassium Palmitoyl Hydrolyzed Rice Protein, Potassium Palmitoyl Hydrolyzed Sweet Almond Protein, Potassium Palmitoyl Hydrolyzed Wheat Protein, Potassium Palm Kernelate, Potassium Peanutate, Potassium Rapeseedate, Potassium Ricinoleate, Potassium Safflowerate, Potassium Soyate, Potassium Stearate, Potassium Stearoyl Hydrolyzed Collagen, Potassium Tallate, Potassium Tallowate, Potassium Taurate, Potassium Taurine Laurate, Potassium Trideceth-3 Carboxylate, Potassium Trideceth-4 Carboxylate, Potassium Trideceth-7 Carboxylate, Potassium Trideceth-15 Carboxylate, Potassium Trideceth-19 Carboxylate, Potassium Trideceth-6 Phosphate, Potassium Trideceth-7 Phosphate, Potassium Tsubakiate, Potassium Undecylenate, Potassium Undecylenoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Rice Protein, PPG-30- Buteth-30, PPG- 36-Buteth-36, PPG-38-Buteth-37, PPG-30-Capryleth-4 Phosphate, PPG-10 Cetyl Ether Phosphate, PPG-2 C9-11 Pareth-8, PPG-1-Deceth-5, PPG-3-Deceth-2 Carboxylic Acid, PPG-30 Ethylhexeth-4 Phosphate, PPG-20-Glycereth-30, PPG-2 Hydroxyethyl Coco / lsostearamide, PPG-2- lsodeceth-8, PPG-2-lsodeceth-10, PPG-2-lsodeceth-18, PPG-2-lsodeceth-25, PPG-4-lsodeceth-10, Propyltrimonium Hydrolyzed Collagen, Quaternium-24, Quaternium-52, Quaternium-87, Rapeseed Acid, Rice Bran Acid, Rice Oil Glycereth-8 Esters, Ricinoleamidopropyl Betaine, Ricinoleic Acid, Ricinoleth-40, Safflower Acid, Sapindus Oahuensis Fruit Extract, Saponaria Officinalis Root Powder, Saponins, Sekken-K, Sekken-Na / K, Sekken Soji, Sekken Soji-K, Sesame Oil Glycereth- 8 Esters, Sesamidopropylamine Oxide, Sesamidopropyl Betaine, Shea Butteramidopropyl Betaine, Shea Butter Glycereth-8 Esters, Sodium Arachidate, Sodium230135 Arganampohoacetate, Sodium Astrocaryum Murumuruate, Sodium Avocadoate, Sodium Babassuamphoacetate, Sodium Babassuate, Sodium Babassu Sulfate, Sodium Behenate, Sodium Bisglycol Ricinosulfosuccinate, Sodium Bis- Hydroxyethylglycinate Coco-Glucosides Crosspolymer, Sodium Bis-Hydroxyethylglycinate Lauryl- Glucosides Crosspolymer, Sodium Borageamidopropyl PG-Dimonium Chloride Phosphate, Sodium Butoxynol-12 Sulfate, Sodium Butylglucosides Hydroxypropyl Phosphate, Sodium C13- 17 Alkane Sulfonate, Sodium C14-18 Alkane Sulfonate, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium C10-16 Alkyl Sulfate, Sodium C11-15 Alkyl Sulfate, Sodium C12-13 Alkyl Sulfate, Sodium C12-15 Alkyl Sulfate, Sodium C12-18 Alkyl Sulfate, Sodium C16-20 Alkyl Sulfate, Sodium C9-22 Alkyl Sec Sulfonate, Sodium C14-17 Alkyl Sec Sulfonate, Sodium Caprate, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Caproyl Methyltaurate, Sodium Caprylate, Sodium Capryleth-2 Carboxylate, Sodium Capryleth-9 Carboxylate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryloamphopropionate, Sodium Capryloyl Glutamate, Sodium Capryloyl Hydrolyzed Wheat Protein, Sodium Caprylyl PG- Sulfonate, Sodium Caprylyl Sulfonate, Sodium Castorate, Sodium Ceteareth-13 Carboxylate, Sodium Cetearyl Sulfate, Sodium Ceteth-13 Carboxylate, Sodium Cetyl Sulfate, Sodium Cocamidopropyl PG-Dimonium Chloride Phosphate, Sodium Cocaminopropionate, Sodium Coceth Sulfate, Sodium Coceth-30 Sulfate, Sodium Cocoabutteramphoacetate, Sodium Cocoa Butterate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cocoate, Sodium Coco / Babassu / Andiroba Sulfate, Sodium Coco / Babassu Sulfate, Sodium Cocoglucosides Hydroxypropyl Phosphate, Sodium Cocoglucosides Hydroxypropylsulfonate, Sodium Coco-Glucoside Tartrate, Sodium Cocoglyceryl Ether Sulfonate, Sodium Coco / Hydrogenated Tallow Sulfate, Sodium Cocoiminodiacetate, Sodium Cocomonoglyceride Sulfate, Sodium Cocomonoglyceride Sulfonate, Sodium Coco PG-Dimonium Chloride Phosphate, Sodium Coco-Sulfate, Sodium Coco Sulfoacetate, Sodium Cocoyl Alaninate, Sodium Cocoyl Amino Acids, Sodium Cocoyl Collagen Amino Acids, Sodium Cocoyl Glutamate, Sodium Cocoyl Glutaminate, Sodium Cocoyl Glycinate, Sodium Cocoyl / Hydrogenated Tallow Glutamate, Sodium Cocoyl Hydrolyzed Collagen, Sodium Cocoyl Hydrolyzed Keratin, Sodium Cocoyl Hydrolyzed230135 Rice Protein, Sodium Cocoyl Hydrolyzed Silk, Sodium Cocoyl Hydrolyzed Soy Protein, Sodium Cocoyl Hydrolyzed Sweet Almond Protein, Sodium Cocoyl Hydrolyzed Wheat Protein, Sodium Cocoyl Hydrolyzed Wheat Protein Glutamate, Sodium Cocoyl Isethionate, Sodium Cocoyl Methylaminopropionate, Sodium Cocoyl Oat Amino Acids, Sodium Cocoyl / Palmoyl / Sunfloweroyl Glutamate, Sodium Cocoyl Proline, Sodium Cocoyl Sarcosinate, Sodium Cocoyl Taurate, Sodium Cocoyl Threoninate, Sodium Cocoyl Wheat Amino Acids, Sodium C12-14 Olefin Sulfonate, Sodium C14-16 Olefin Sulfonate, Sodium C14- 18 Olefin Sulfonate, Sodium C16-18 Olefin Sulfonate, Sodium Cornamphopropionate, Sodium Cottonseedamphoacetate, Sodium C13-15 Pareth-8 Butyl Phosphate, Sodium C9-11 Pareth-6 Carboxylate, Sodium C11-15 Pareth-7 Carboxylate, Sodium C12-13 Pareth-5 Carboxylate, Sodium C12-13 Pareth-8 Carboxylate, Sodium C12-13 Pareth-12 Carboxylate, Sodium C12-15 Pareth-6 Carboxylate, Sodium C12-15 Pareth-7 Carboxylate, Sodium C12-15 Pareth-8 Carboxylate, Sodium C14-15 Pareth-8 Carboxylate, Sodium C12-14 Sec-Pareth-8 Carboxylate, Sodium C14-15 Pareth-PG Sulfonate, Sodium C12-13 Pareth-2 Phosphate, Sodium C13-15 Pareth-8 Phosphate, Sodium C9-15 Pareth-3 Sulfate, Sodium C10-15 Pareth Sulfate, Sodium C10-16 Pareth-2 Sulfate, Sodium C12-13 Pareth Sulfate, Sodium C12-15 Pareth Sulfate, Sodium C12-15 Pareth-3 Sulfate, Sodium C13-15 Pareth-3 Sulfate, Sodium C12-14 Sec-Pareth-3 Sulfate, Sodium C12-15 Pareth-3 Sulfonate, Sodium C12-15 Pareth-7 Sulfonate, Sodium C12-15 Pareth-15 Sulfonate, Sodium Deceth-2 Carboxylate, Sodium Deceth Sulfate, Sodium Decylbenzenesulfonate, Sodium Decylglucosides Hydroxypropyl Phosphate, Sodium Decylglucosides Hydroxypropylsulfonate, Sodium Dilaureth-7 Citrate, Sodium Dilaureth-10 Phosphate, Sodium Dilinoleamidopropyl PG-Dimonium Chloride Phosphate, Sodium Dilinoleate, Sodium Dioleth-8 Phosphate, Sodium Dodecylbenzenesulfonate, Sodium Ethyl 2- Sulfolaurate, Sodium Glyceryl Oleate Phosphate, Sodium Grapeseedamidopropyl PG- Dimonium Chloride Phosphate, Sodium Grapeseedamphoacetate, Sodium Grapeseedate, Sodium Hempseedamphoacetate, Sodium Hexeth-4 Carboxylate, Sodium Hydrogenated Cocoate, Sodium Hydrogenated Cocoyl Methyl Isethionate, Sodium Hydrogenated Palmate, Sodium Hydrogenated Tallowate, Sodium Hydrogenated Tallowoyl Glutamate, Sodium Hydroxylauryldimonium Ethyl Phosphate, Sodium Hydroxypropyl Palm Kernelate Sulfonate, Sodium Hydroxypropylphosphate230135 Decylglucoside Crosspolymer, Sodium Hydroxypropylphosphate Laurylglucoside Crosspolymer, Sodium Hydroxypropylsulfonate Cocoglucoside Crosspolymer, Sodium Hydroxypropylsulfonate Decylglucoside Crosspolymer, Sodium Hydroxypropylsulfonate Laurylglucoside Crosspolymer, Sodium Hydroxystearate, Sodium Isostearate, Sodium lsosteareth-6 Carboxylate, Sodium Isosteareth- 11 Carboxylate, Sodium Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium N-lsostearoyl Methyltaurate, Sodium Laneth Sulfate, Sodium Lanolate, Sodium Lardate, Sodium Lauramido Diacetate, Sodium Lauraminopropionate, Sodium Laurate, Sodium Laureth-3 Carboxylate, Sodium Laureth-4 Carboxylate, Sodium Laureth-5 Carboxylate, Sodium Laureth-6 Carboxylate, Sodium Laureth-8 Carboxylate, Sodium Laureth-11 Carboxylate, Sodium Laureth-12 Carboxylate, Sodium Laureth-13 Carboxylate, Sodium Laureth-14 Carboxylate, Sodium Laureth-16 Carboxylate, Sodium Laureth-17 Carboxylate, Sodium Laureth Sulfate, Sodium Laureth-5 Sulfate, Sodium Laureth-7 Sulfate, Sodium Laureth-8 Sulfate, Sodium Laureth-12 Sulfate, Sodium Laureth-40 Sulfate, Sodium Laureth-7 Tartrate, Sodium Lauriminodipropionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Lauroyl Aspartate, Sodium Lauroyl Collagen Amino Acids, Sodium Lauroyl Glycine Propionate, Sodium Lauroyl Hydrolyzed Collagen, Sodium Lauroyl Hydrolyzed Silk, Sodium Lauroyl Hydroxypropyl Sulfonate, Sodium Lauroyl Isethionate, Sodium Lauroyl Methylaminopropionate, Sodium Lauroyl Methyl Isethionate, Sodium Lauroyl Millet Amino Acids, Sodium Lauroyl / Myristoyl Aspartate, Sodium Lauroyl Oat Amino Acids, Sodium Lauroyl Sarcosinate, Sodium Lauroyl Silk Amino Acids, Sodium Lauroyl Taurate, Sodium Lauroyl Wheat Amino Acids, Sodium Lauryl Diethylenediaminoglycinate, Sodium Lauryl Glucose Carboxylate, Sodium Laurylglucosides Hydroxypropyl Phosphate, Sodium Laurylglucosides Hydroxypropylsulfonate, Sodium Lauryl Glycol Carboxylate, Sodium Lauryl Hydroxyacetamide Sulfate, Sodium Lauryl Phosphate, Sodium Lauryl Sulfate, Sodium Lauryl Sulfoacetate, Sodium Linoleate, Sodium Macadamiaseedate, Sodium Mangoamphoacetate, Sodium Mangoseedate, Sodium / MEA Laureth-2 Sulfosuccinate, Sodium Methoxy PPG-2 Acetate, Sodium Methyl Cocoyl Taurate, Sodium Methyl Lauroyl Taurate, Sodium Methyl Myristoyl Taurate, Sodium Methyl Oleoyl Taurate, Sodium Methyl Palmitoyl Taurate, Sodium Methyl Stearoyl Taurate, Sodium Methyl 2-230135 Sulfolaurate, Sodium Methyl 2- Sulfopalmitate, Sodium Methyltaurate Isopalmitamide, Sodium Methyltaurine Cocoyl Methyltaurate, Sodium Myreth Sulfate, Sodium Myristate, Sodium Myristoamphoacetate, Sodium Myristoyl Glutamate, Sodium Myristoyl Hydrolyzed Collagen, Sodium Myristoyl Isethionate, Sodium Myristoyl Sarcosinate, Sodium Myristyl Sulfate, Sodium Nonoxynol-6 Phosphate, Sodium Nonoxynol-9 Phosphate, Sodium Nonoxynol-1 Sulfate, Sodium Nonoxynol-3 Sulfate, Sodium Nonoxynol-4 Sulfate, Sodium Nonoxynol-6 Sulfate, Sodium Nonoxynol-8 Sulfate, Sodium Nonoxynol-10 Sulfate, Sodium Nonoxynol-25 Sulfate, Sodium Octoxynol-2 Ethane Sulfonate, Sodium Octoxynol-2 Sulfate, Sodium Octoxynol-6 Sulfate, Sodium Octoxynol- 9 Sulfate, Sodium Oleate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Oleoyl Hydrolyzed Collagen, Sodium Oleoyl Isethionate, Sodium Oleth Sulfate, Sodium Oleyl Methyl Isethionate, Sodium Oleyl Sulfate, Sodium Olivamphoacetate, Sodium Olivate, Sodium Olivoyl Glutamate, Sodium Palmamphoacetate, Sodium Palmate, Sodium Palm Glyceride Sulfonate, Sodium Palmitate, Sodium Palmitoyl Hydrolyzed Collagen, Sodium Palmitoyl Hydrolyzed Wheat Protein, Sodium Palmitoyl Sarcosinate, Sodium Palm Kernelate, Sodium Palm Kerneloyl Isethionate, Sodium Palmoyl Glutamate, Sodium Passiflora Edulis Seedate, Sodium Peanutamphoacetate, Sodium Peanutate, Sodium PEG-6 Cocamide Carboxylate, Sodium PEG-8 Cocamide Carboxylate, Sodium PEG-4 Cocamide Sulfate, Sodium PEG-3 Lauramide Carboxylate, Sodium PEG-4 Lauramide Carboxylate, Sodium PEG-8 Palm Glycerides Carboxylate, Sodium Pentaerythrityl Hydroxypropyl lminodiacetate Dendrimer, Sodium Propoxy PPG-2 Acetate, Sodium Rapeseedate, Sodium Ricebranamphoacetate, Sodium Ricinoleate, Sodium Ricinoleoamphoacetate, Sodium Rose Hipsamphoacetate, Sodium Rosinate, Sodium Safflowerate, Sodium Saffloweroyl Hydrolyzed Soy Protein, Sodium Sesameseedate, Sodium Sesamphoacetate, Sodium Sheabutteramphoacetate, Sodium Soyate, Sodium Soy Hydrolyzed Collagen, Sodium Stearate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Stearoyl Casein, Sodium Stearoyl Glutamate, Sodium Stearoyl Hyaluronate, Sodium Stearoyl Hydrolyzed Collagen, Sodium Stearoyl Hydrolyzed Corn Protein, Sodium Stearoyl Hydrolyzed Silk, Sodium Stearoyl Hydrolyzed Soy Protein, Sodium Stearoyl Hydrolyzed Wheat Protein, Sodium Stearoyl Lactalbumin,230135 Sodium Stearoyl Methyl Isethionate, Sodium Stearoyl Oat Protein, Sodium Stearoyl Pea Protein, Sodium Stearoyl Soy Protein, Sodium Stearyl Dimethyl Glycine, Sodium Stearyl Sulfate, Sodium Sunflowerseedamphoacetate, Sodium Surfactin, Sodium Sweetalmondamphoacetate, Sodium Sweet Almondate, Sodium Tallamphopropionate, Sodium Tallate, Sodium Tallowamphoacetate, Sodium Tallowate, Sodium Tallow Sulfate, Sodium Tamanuseedate, Sodium Taurate, Sodium Taurine Cocoyl Methyltaurate, Sodium Taurine Laurate, Sodium / TEA-Lauroyl Collagen Amino Acids, Sodium / TEA- Lauroyl Hydrolyzed Collagen, Sodium / TEA-Lauroyl Hydrolyzed Keratin, Sodium / TEA- Lauroyl Keratin Amino Acids, Sodium / TEA-Undecylenoyl Collagen Amino Acids, Sodium / TEA- Undecylenoyl Hydrolyzed Collagen, Sodium / TEA-Undecylenoyl Hydrolyzed Corn Protein, Sodium / TEA-Undecylenoyl Hydrolyzed Soy Protein, Sodium / TEA-Undecylenoyl Hydrolyzed Wheat Protein, Sodium Theobroma Grandiflorum Seedate, Sodium Trideceth-3 Carboxylate, Sodium Trideceth-4 Carboxylate, Sodium Trideceth-6 Carboxylate, Sodium Trideceth-7 Carboxylate, Sodium Trideceth-8 Carboxylate, Sodium Trideceth-12 Carboxylate, Sodium Trideceth-15 Carboxylate, Sodium Trideceth-19 Carboxylate, Sodium Trideceth Sulfate, Sodium Tridecylbenzenesulfonate, Sodium Tridecyl Sulfate, Sodium Trimethylolpropane Hydroxypropyl lminodiacetate Dendrimer, Sodium Undeceth-5 Carboxylate, Sodium Undecylenate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Undecylenoyl Glutamate, Sodium Wheat Germamphoacetate, Sorbeth-160 Tristearate, Soy Acid, Soyamidopropylamine Oxide, Soyamidopropyl Betaine, Soybean Oil Glycereth-8 Esters, Stearamidopropylamine Oxide, Stearamidopropyl Betaine, Stearamine Oxide, Steareth-15, Steareth-16, Steareth- 20, Steareth-21, Steareth-25, Steareth-27, Steareth-30, Steareth- 40, Steareth-50, Steareth-80, Steareth-100, Steareth-2 Phosphate, Steareth-3 Phosphate, Stearic Acid, Stearoxypropyltrimonium Chloride, Stearoyl Glutamic Acid, Stearoyl Sarcosine, Stearyl Betaine, Stearyldimoniumhydroxypropyl Butylglucosides Chloride, Stearyldimoniumhydroxypropyl Decylglucosides Chloride, Stearyldimoniumhydroxypropyl Laurylglucosides Chloride, Sulfated Castor Oil, Sulfated Coconut Oil, Sulfated Glyceryl Oleate, Sulfated Olive Oil, Sulfated Peanut Oil, Sunfloweramide MEA, Sunflower Seed Acid, Sunflowerseedamidopropyl Hydroxyethyldimonium Chloride, Sunflower Seed Oil Glycereth-8 Esters, Tall Oil Acid,230135 Tallow Acid, Tallowamidopropylamine Oxide, Tallowamidopropyl Betaine, Tallowamidopropyl Hydroxysultaine, Tallowamine Oxide, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Tallowoyl Ethyl Glucoside, TEA-Abietoyl Hydrolyzed Collagen, TEA-C12-14 Alkyl Phosphate, TEA-C10-15 Alkyl Sulfate, TEA-C11-15 Alkyl Sulfate, TEA- C12-13 Alkyl Sulfate, TEA-C12-14 Alkyl Sulfate, TEA-C12-15 Alkyl Sulfate, TEA C14-17 Alkyl Sec Sulfonate, TEA-Canolate, TEA-Cocamide Diacetate, TEA-Cocoate, TEA-Coco-Sulfate, TEA-Cocoyl Alaninate, TEA-Cocoyl Glutamate, TEA-Cocoyl Glutaminate, TEA-Cocoyl Glycinate, TEA-Cocoyl Hydrolyzed Collagen, TEA-Cocoyl Hydrolyzed Soy Protein, TEA-Cocoyl Sarcosinate, TEA- Dimethicone PEG-7 Phosphate, TEA-Dodecylbenzenesulfonate, TEA-Hydrogenated Cocoate, TEA- Hydrogenated Tallowoyl Glutamate, TEA-lsostearate, TEA-lsostearoyl Hydrolyzed Collagen, TEA- Lauraminopropionate, TEA-Laurate, TEA-Laurate / Myristate, TEA-Laureth Sulfate, TEA- Lauroyl Collagen Amino Acids, TEA-Lauroyl Glutamate, TEA-Lauroyl Hydrolyzed Collagen, TEA-Lauroyl Keratin Amino Acids, TEA-Lauroyl Methylaminopropionate, TEA- Lauroyl / Myristoyl Aspartate, TEA- Lauroyl Sarcosinate, TEA-Lauryl Phosphate, TEA- Lauryl Sulfate, TEA-Myristaminopropionate, TEA- Myristate, TEA-Myristoyl Hydrolyzed Collagen, TEA-Oleate, TEA-Oleoyl Hydrolyzed Collagen, TEA- Oleoyl Sarcosinate, TEA- Oleyl Sulfate, TEA-Palmitate, TEA-PaIm Kernel Sarcosinate, TEA-PEG-3 Cocamide Sulfate, TEA-Rosinate, TEA-Stearate, TEA-Tallate, TEA-T ridecylbenzenesulfonate, TEA- Undecylenate, TEA-Undecylenoyl Hydrolyzed Collagen, Tetramethyl Decynediol, Tetrasodium Dicarboxyethyl Stearyl Sulfosuccinamate, TIPA-Laureth Sulfate, TIPA- Lauryl Sulfate, TIPA-Myristate, TIPA-Stearate, Tocopheryl Phosphate, Trehalose Undecylenoate, TM-C12-15 Pareth-2 Phosphate, TM-C12-15 Pareth-6 Phosphate, TM- C12-15 Pareth-8 Phosphate, TM-C12-15 Pareth-10 Phosphate, Trideceth-20, Trideceth- 50, Trideceth-3 Carboxylic Acid, Trideceth-4 Carboxylic Acid, Trideceth-7 Carboxylic Acid, Trideceth-8 Carboxylic Acid, Trideceth-15 Carboxylic Acid, Trideceth-19 Carboxylic Acid, Trideceth-10 Phosphate, Tridecylbenzenesulfonic Acid, Trilaureth-9 Citrate, Trimethylolpropane Hydroxypropyl Bis-Hydroxyethylamine Dendrimer, Trisodium Lauroampho PG-Acetate Chloride Phosphate, Undecanoic Acid, Undeceth-5 Carboxylic Acid, Undecylenamidopropylamine Oxide, Undecylenamidopropyl Betaine, Undecylenic Acid, Undecylenoyl Collagen Amino Acids, Undecylenoyl Glycine, Undecylenoyl Hydrolyzed Collagen, Undecylenoyl Wheat Amino Acids, Undecyl Glucoside, Wheat230135 Germ Acid, Wheat Germamidopropylamine Oxide, Wheat Germamidopropyl Betaine, Yucca Schidigera Leaf / Root / Stem Extract, Yucca Schidigera Stem Extract, Zinc Coceth Sulfatea and Zinc Coco-Sulfate.
[0279] Fragrance / aroma: The food, cosmetic or pharmaceutical preparation or homecare product according to the present invention includes one or more fragrances and / or perfume oils.
[0280] The fragrance or aroma / flavouring compound can be chosen from synthetic flavouring liquid and / or oils derived from plants leaves, flowers, fruits and so forth, and combinations thereof. Representative fragrance or aroma / flavouring liquids include artificial, natural or synthetic fruit flavours such as eucalyptus, lemon, orange, banana, grape, lime, apricot and grapefruit oils and fruit essences including apple, strawberry, cherry, orange, pineapple and so forth; bean and nut derived flavours such as coffee, cocoa, cola, peanut, almond and so forth; and root derived flavours such as licorice or ginger.
[0281] Suitable perfume oils are mixtures of natural and / or synthetic perfumes. Natural perfumes include the extracts of blossoms (lily, lavender, rose, jasmine, neroli, ylang- ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom, costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and branches (spruce, fir, pine, dwarf pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, for example civet and beaver, may also be used. Typical synthetic perfume compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of perfume compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert. Butyl cyclohexylacetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether while aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial230135 and bourgeonal. Examples of suitable ketones are the ionones, betaisomethylionone and methyl cedryl ketone. Suitable alcohols are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include the terpenes and balsams.
[0282] However, it is preferred to use mixtures of different perfume compounds which, together, produce an agreeable perfume. Other suitable perfume oils are essential oils of relatively low volatility which are mostly used as aroma components. Examples are sage oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, and ladanum oil.
[0283] Fragrances (a) which are advantageously suitable are listed for example in S. Arctander, Perfume and Flavor Materials, volumes I and II, Montclair, N.J.1969, private publication, and / or in H. Surburg, J. Panten, Common Fragrance and Flavor Materials, 6thedition, Wiley-VCH, Weinheim 2016. The following list comprises examples of known odorant substances which are advantageously suitable in the present invention: - extracts of natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures such as for example: ambergris tincture; amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; tree moss absolute; bay oil; artemisia oil; benzoin resin; bergamot oil; dihydromyrcenol; lilial; lyral; citronellol; phenylethyl alcohol; hexylcinnamaldehyde; geraniol; benzyl acetone; cyclamen aldehyde; linalool; Boisambrene Forte; Ambroxan; indole; hedione; sandelice; citrus oil; mandarin oil; orange oil; allylamyl glycolate; cyclovertal; lavendin oil; clary oil; damascene; geranium oil bourbon; cyclohexyl salicylate; Vertofix Coeur; Iso-E-Super; Fixolide NP; evernyl; iraldein gamma; phenylacetic acid; geranyl acetate; benzyl acetate; rose oxide; romillat; irotyl, floramat; beeswax absolute; birch tar oil; bitter almond oil; savory oil; buchu leaf oil; cabreuva oil; cade oil; calamus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassie absolute; castoreum absolute cedar leaf oil; cedarwood oil; cistus oil; citronella oil; lemon oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill weed oil; dill seed oil; eau de brouts absolute; oak moss absolute; elemi oil; tarragon oil;230135 eucalyptus citriodora oil; eucalyptus oil; fennel oil; pine-needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calamus oil; blue camomile oil; Roman chamomile oil; carrot seed oil; cascarilla oil; pine-needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavandin absolute; lavandin oil; lavender absolute; lavender oil; lemongrass oil; lovage oil; distilled lime oil; pressed lime oil; linaloe oil; Litsea cubeba oil; bay leaf oil; mace oil; marjoram oil; mandarin oil; massoia bark oil; mimosa absolute; ambrette oil; musk tincture; muscatel sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove bud oil; neroli oil; olibanum absolute; olibanum oil; opopanax oil; orange blossom absolute; orange oil; origanum oil; palmarosa oil; patchouli oil; peri Ila oil; Peru balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; peppermint oil; pepper oil; pimento oil; pine oil; pennyroyal oil; rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; star anise oil; styrax oil; tagetes oil; fir needle oil; tea tree oil; turpentine oil; thyme oil; Tolu balsam; tonka absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; cognac oil; wormwood oil; Wintergreen oil; ylang ylang oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil, and fractions thereof or constituents isolated therefrom; individual fragrance substances from the group comprising hydrocarbons, such as for example: 3-carene; alpha- pinene; beta-pinene; alpha-terpinene; gamma-terpinene; p- cymene; bisabolene; camphene; caryophyllene; cedrene; famesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1 ,3,5-undecatriene; styrene; diphenylmethane; - aliphatic alcohols, such as for example: hexanol; octanol; 3-octanol; 2,6- dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixtures of 3,4,5,6,6-pentamethyl-3,4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7- methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; - aliphatic aldehydes and the acetals thereof, such as for example: hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2- methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-230135 undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10- trimethyl-5,9-undecadienal; heptanal diethylacetal; 1,1-dimethoxy-2,2,5- trimethyl- 4-hexene; citronellyloxyacetaldehyde; 1-(1-methoxypropoxy)-(E / Z)-3- hexene; - aliphatic ketones and the oximes thereof, such as for example: 2-heptanone; 2- octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one; - aliphatic sulphur-containing compounds, such as for example: 3-methylthio- hexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthen-8-thiol; - aliphatic nitriles, such as for example: 2-nonenoic acid nitrile; 2-undecenoic acid nitrile; 2-tridecenoic acid nitrile; 3,12-tridecadienoic acid nitrile; 3,7-dimethyl-2,6- octadienoic acid nitrile; 3,7-dimethyl-6-octenoic acid nitrile; - esters of aliphatic carboxylic acids, such as for example: (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl-isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl-2-methyl pentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl-(E,Z)-2,4- decadienoate; methyl-2-octinate; methyl-2-noninate; allyl-2-isoamyloxyacetate; methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl-crotonate; - acyclic terpene alcohols, such as for example: citronellol; geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl- 7- octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6- dimethyl- 5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6- octadien-3-ol; 3,7- dimethyl-1 ,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and the formates acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates thereof; - acyclic terpene aldehydes and ketones, such as for example: geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10- trimethyl-9-undecenal; geranyl acetone; and the dimethyl and diethyl acetals of geranial; neral; 7-hydroxy-3,7-dimethyloctanal;230135 - cyclic terpene alcohols, such as for example: menthol; isopulegol; alpha-terpineol; terpinenol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guaiol; and the formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates thereof; - cyclic terpene aldehydes and ketones, such as for example: menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; alpha- ionone; beta-ionone; alpha-n-methyl ionone; beta-n-methyl ionone; alpha-isomethyl ionone; beta-isomethyl ionone; alpha-irone; alpha-damascone; beta-damascone; beta-damascenone; delta-damascone; gamma-damascone; 1-(2,4,4-trimethyl-2- cyclohexen-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H- 2,4a-methanonaphthalen-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1- yl)-2-butenal; nootkatone; dihydronootkatone; 4,6,8-megastigmatrien-3-one; alpha- sinensal; beta-sinensal; acetylated cedarwood oil (methylcedryl ketone); - cyclic alcohols, such as for example: 4-tert-butylcyclohexanol; 3,3,5- trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9- cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; cycloaliphatic alcohols, such as for example: alpha-3, 3-trimethylcyclohexylmethanol; 1 –(4- isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butan- ol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1 -yl)-2-buten-1 -ol; 2-ethy l-4-(2 ,2 , 3-tri- methyl-3-cyclopent-1 -yl)-2-buten-1 -ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1 - yl)- pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3- dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6- trimethylcyclohexyl)pen- tan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; - cyclic and cycloaliphatic ethers, such as for example: cineole; cedryl methyl ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclo- dodecane; alpha-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1- b]furan; 3a-ethyl-6,6,9a-trimethyldodeca-hydronaphtho[2,1-b]furan; 1 ,5,9-trimethyl- 13-oxabicyclo[10.1,0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1- yl)-5-methyl-5-(1 -methylpropyl)-1,3-dioxane; - cyclic and macrocyclic ketones, such as for example: 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclo-230135 pentanone; 2-hydroxy-3-methyl-2-cyclopenten-1 -one; 3-methyl-cis-2-penten-1-yl- 2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4- cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3- methylcyclopentadecanone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7-dihydro-1,1,2,3,3- pentamethyl-4(5H)-indanone; 8-cyclohexadecen-1-one; 9- cycloheptadecen-1-one; cyclopentadecanone; cyclohexadecanone; - cycloaliphatic aldehydes such as for example: 2,4-dimethyl-3-cyclohexene carbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4- hydroxy-4- methylpentyl)-3-cyclohexene carbaldehyde; 4-(4-methyl-3-penten-1-yl)- 3-cyclo-hexene carbaldehyde; - cycloaliphatic ketones, such as for example: 1 –(3,3-dimethyl-cyclohexyl)-4-penten- 1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexene-1-yl)-1-propanone; 1-(5,5- dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8- octahydro-2-naphthalenyl methyl ketone; methyl-2,6,10-trimethyl-2,5,9- cyclododecatrienyl ketone; tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl)ketone; - esters of cyclic alcohols, such as for example: 2-tert-butylcyclohexyl acetate; 4-tert- butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2- cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a- hexahydro-5- or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6- indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl isobutyrate; 4,7-methanooctahydro-5- or 6-indenyl acetate; - esters of cycloaliphatic alcohols, such as for example: 1-cyclohexylethyl crotonate; - esters of cycloaliphatic carboxylic acids, such as for example: allyl-3-cyclohexyl propionate; allylcyclohexyl oxyacetate; cis- and trans-methyl dihydrojasmonate; cis and trans-methyl jasmonate; methyl-2-hexyl-3-oxocyclopentane carboxylate; ethyl- 2- ethyl-6,6-dimethyl-2-cyclohexene carboxylate; ethyl-2,3,6,6-tetramethyl-2- cyclohexene carboxylate; ethyl-2-methyl-1,3-dioxolane-2-acetate; - araliphatic alcohols, such as for example: benzyl alcohol; 1 -phenylethyl alcohol; 2- phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-230135 dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-di methyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3- phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl- 2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol; - esters of araliphatic alcohols and aliphatic carboxylic acids, such as for example: benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2- phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2- phenylethyl isovalerate; 1 -phenylethyl acetate; alpha-trichloromethylbenzyl acetate; alpha, alpha-dimethylphenylethyl acetate; alpha, alpha-dimethylphenyl- ethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; - araliphatic ethers, such as for example: 2-phenyl ethyl methyl ether; 2-phenyl ethyl isoamyl ether; 2-phenyl ethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal; hydratropaldehyde dimethylacetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3- dioxane; 4, 4a, 5,9b-tetrahydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4- dimethylindeno[1,2-d]-m-dioxin; - aromatic and araliphatic aldehydes, such as for example: benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropaldehyde; 4-methylbenz- aldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2- methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2- methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; alpha- butylcinnamaldehyde; alpha-amylcinnamaldehyde; alpha- hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4- hydroxy-3-methoxybenz-aldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4- methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4- methoxyphenyl)propanal; 2-methyl-3-(4- methylenedioxyphenyl)propanal; - aromatic and araliphatic ketones, such as for example: acetophenone; 4-methyl- acetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4- phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl230135 methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5- indenyl]ethanone; 5’,6’,7’,8’-tetrahydro-3’,5’,5’,6’,8’,8’-hexamethyl-2- acetonaphthone; - aromatic and araliphatic carboxylic acids and the esters thereof, such as for example: benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methylphenyl acetate; ethylphenyl acetate; geranylphenyl acetate; phenylethylphenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxy acetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl- 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl-3-phenyl glycidate; ethyl-3-methyl-3- phenyl glycidate; - nitrogenous aromatic compounds, such as for example: 2,4,6-trinitro-1,3-dimethyl- 5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butyl aceto-phenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenoic acid nitrile; 3-methyl-5- phenylpentanoic acid nitrile; methyl anthranilate; methyl-N-methyl anthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde 6- isopropyl quinoline; 6-isobutyl quinoline; 6-sec-butyl quinoline; 2-(3- phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3- methoxypyrazine; - phenols, phenyl ethers and phenyl esters, such as for example: estragole; anethole; eugenol; eugenyl methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy- 4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenyl acetate; - heterocyclic compounds, such as for example: 2,5-dimethyl-4-hydroxy-2H-furan-3- one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4- one; 2-ethyl-3-hydroxy-4H-pyran-4-one; - lactones, such as for example: 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4- nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecan- olide; 1,5-decanolide; 1,5-dodecanolide; 4-methyl-1,4-decanolide; 1,15-penta-230135 decanolide; cis- and trans-11-pentadecen-1,15-olide; cis- and trans-12-pentadecen- 1,15-olide; 1,16-hexadecanolide; 9-hexadecen-1,16-olide; 10-oxa-1,16- hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene 1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin; 2,3- dihydrocoumarin; octahydrocoumarin; and any mixture of the above fragrance substances.
[0284] Alternatively, the food, cosmetic or pharmaceutical preparation or homecare product according to the first aspect of the present invention encompasses at least on aroma / flavour compound selected from the group consisting of acetophenone, allyl caproate, alpha-ionone, beta-ionone, anisaldehyde, anisyl acetate, anisyl formate, anethole, benzaldehyde, Benzothiazole, benzyl acetate, benzyl alcohol, benzyl benzoate, beta-ionone, butyl butyrate, butyl caproate, butylidenphthalide, carvone, camphene, caryophyllene, cineole, cinnamyl acetate, Citral, Citronellol, Citronellal, citronellyl acetate, cyclohexyl acetate, cymene, damascone, decalactone, dihydrocoumarin, Dimethyl anthranilate, dimethyl anthranilate, dodecalactone, ethoxyethyl acetate, ethyl butyric acid, ethyl butyrate, ethyl caprate, ethyl caproate, ethyl crotonate, ethyl furaneol, ethyl guaiacol, ethyl isobutyrate, ethyl isovalerate, ethyl lactate, ethyl methyl butyrate, ethyl propionate, Eucalyptol, Eugenol, Ethyl heptylate, 4-(p-Hydroxyphenyl)-2-butanone, gamma- decalactone, Geraniol, geranyl acetate, geranyl acetate, grapefruit aldehyde, methyl dihydrojasmonate (e.g. hedione (R)), Heliotropin, 2-heptanone, 3-heptanone, 4- heptanone, trans-2-heptenal, cis-4-heptenal, trans-2-Hexenal, cis-3-Hexenol, trans-2- hexenoic acid, Trans-3-hexenoic acid, cis-2- hexenyl acetate, cis-3-hexenyl acetate, cis- 3-hexenyl caproate, trans-2-hexenyl caproate, cis-3-hexenyl formate, cis-2-hexyl acetate, cis-3-hexyl acetate, trans-2-hexyl acetate, cis-3- hexyl formate, para- hydroxybenzylacetone, isoamyl alcohol, isoamyl isovalerate, isobutyl butyrate, isobutyraldehyde, Isoeugenol methyl ether, isopropylmethylthiazole, lauric acid, leavulic acid, Linalool, linalool oxide, linalyl acetate, Menthol, Menthofuran, methyl anthranilate, methylbutanol, methylbutyric acid, 2-methylbutyl acetate, methyl caproate, methyl cinnamate, 5-methylfurfural, 3,2,2- methylcyclopentenolone, 6,5,2-methylheptenone, methyl dihydrojasmonate, methyl jasmonate, 2-methylmethylbutyrate, 2-Methyl-2- pentenoleic acid, methyl thiobutyrate, 3,1-methylthiohexanol, 3-methylthiohexyl acetate,230135 Nerol, neryl acetate, trans, trans-2,4-Nonadienal, 2,4-nonadienol, 2,6-nonadienol, 2,4- nonadienol, nootkatone, Delta-octactone, gamma-octactone, 2-Octanol, 3-Octanol, 1,3- Octenol, 1-octyl acetate, 3- octyl acetate, palmitic acid, paraldehyde, phellandrene, pentanedione, phenylethyl acetate, phenylethyl alcohol, phenylethyl alcohol, phenylethyl isovalerate, Piperonal, propionaldehyde, propyl butyrate, pulegone, Pulegol, Sinensal, Sulfurol, terpinene, Terpineol, terpinolene, 8,3-thiomenthanone, 4,4,2- thiomethylpentanone, Thymol, delta- undecalactone, gamma-undecalactone, valencene, valeric acid, Vanillin, Acetoin, ethylvanillin, ethylvanillin isobutyrate (= 3-Ethoxy-4- isobutyryloxybenzaldehyde), 2,5- Dimethyl-4-hydroxy-3(2 H)-furanone and the derivatives thereof (preferably Homofuraneol (= 2-Ethyl-4-hydroxy-5-methyl-3(2 H)- furanone), Homofuronol (= 2-ethyl-5-methyl-4-hydroxy-3(2 H)-furanone and 5-Ethyl-2- methyl-4-hydroxy-3(2 H)-furanone), Maltol and maltol derivatives (preferably ethylmaltol), Coumarin and coumarin derivatives, gamma-lactones (preferably gamma- undecalactone, gamma-nonalactone, gamma-decalactone), delta-lactones (preferably 4- methyl-delta-decalactone, massoilactone, delta-decalactone, tuberolactone), methyl sorbate, Divanillin, 4-Hydroxy-2(or 5)-ethyl-5(or 2)-methyl-3(2 H)-furanone, 2-Hydroxy- 3- methyl-2-cyclopentenone, 3-Hydroxy-4,5-dimethyl-2(5 H)-furanone, isoamyl acetate, ethyl butyrate, n-butyl butyrate, isoamyl butyrate, ethyl 3-methylbutyrate, ethyl n- hexanoate, allyl n-hexanoate, N-butyl n-hexanoate, ethyl n-octanoate, Ethyl 3- methyl-3- phenylglycidate, Ethyl 2-trans-4-cis-decadienoate, 4-(p-Hydroxyphenyl)-2- butanone, 1,1-Dimethoxy-2,2,5-trimethyl-4-hexane, 2,6-Dimethyl-5-hepten-1-al and phenylacetaldehyde, 2-Methyl-3-(methylthio)furan, 2-Methyl-3-furanthiol, Bis(2-methyl-3- furyl)disulfide, furfuryl mercaptan, Methional, 2-Acetyl-2-thiazoline, 3-Mercapto-2- pentanone, 2,5-Dimethyl-3-furanthiol, 2,4,5-trimethylthiazole, 2-acetylthiazole, 2,4- Dimethyl-5-ethylthiazole, 2-Acetyl-1-pyrroline, 2-Methyl-3-ethylpyrazine, 2-Ethyl-3,5- dimethylpyrazine, 2-Ethyl-3,6-dimethylpyrazine, 2,3-Diethyl-5-methylpyrazine, 3- Isopropyl-2-methoxypyrazine, 3-Isobutyl-2-methoxypyrazine, 2-acetylpyrazine, 2- pentylpyridine, (E,E)-2,4-Decadienal, (E,E)-2,4-Nonadienal, (E)-2-Octenal, (E)-2- Nonenal, 2-undecenal, 12-methyltridecanal, 1-Penten-3-one, 4-Hydroxy-2,5-dimethyl- 3(2H)-furanone, Guaiacol, 3-Hydroxy-4,5-dimethyl-2(5H)-furanone, 3-Hydroxy-4-methyl- 5-ethyl-2(5H)-furanone, cinnamaldehyde, cinnamyl alcohol, methyl salicylate, Isopulegol, sugar alcohols (e.g. Erythritol, Threitol, Arabitol, ribitol, Xylitol, Sorbitol, Mannitol, Dulcitol,230135 Lactitol); proteins (e.g. Miraculin, Monellin, Thaumatin, Curculin, Brazzein); sugar substitutes / bulk sweetener (e.g. Magap, sodium cyclamate, acesulfame K, neohesperidine dihydrochalcone, Saccharin sodium salt, aspartame, superaspartame, neotame, alitame, Sucralose, steviosides, rebaudiosides, Lugdarme, Carrelame, Sucrononate, Sucrooctate, Monatin, phenylodulcine); SUESS-TASTING amino acids (e.g. glycine, D-leucine, D-threonine, D-asparagine, D-phenylalanine, D-tryptophn, L- proline); SUESS-TASTING low molecular weight substances (e.g. Hernandulcin, dihydrochalcone glycosides, Glycyrrhizin, glycerrhetinic acid, derivatives and salts thereof, extracts of lacritz (Glycyrrhizza glabra ssp.), Lipia dulcis extracts, Momordica ssp. Extracts), plant extracts (e.g. Momordica grosvenori [Luo Han Guo] and the mogrosides obtained therefrom, Hydrangea dulcis or Stevia ssp. (for example Stevia rebaudiana) extracts or steviosides obtained therefrom, and any mixture of the above aroma / flavour substances.
[0285] According to the present invention, the food, cosmetic or pharmaceutical preparations or homecare products comprise at least one fragrance or aroma / flavour compound, preferably two, three, four, five, six, seven, eight or more fragrance or aroma / flavour compounds. Preferably, the fragrance or aroma / flavour is a fragrance composition comprising a mixture of multiple fragrance compounds or an aroma / flavour composition comprising a mixture of multiple aroma / flavour compounds.
[0286] In the context of the present invention, therefore the term “fragrance” encompasses similarly “fragrance composition” and the term “aroma / flavour” encompasses similarly “aroma / flavour composition”.
[0287] The above specified fragrances or aroma / flavour substances can also be used in encapsulated form. Suitable coating materials here are, for example, starches, including the degradation products thereof and chemically or physically produced derivatives (especially dextrins and maltodextrins), gelatin, gum 115rabic, Agar agar, Ghatti Gum, Gellan Gum, modified and unmodified celluloses, Pullulan, Curdlan, carrageenans, alginic acids, alginates, pectin, Inulin, Xanthan Gum and mixtures of two or more of these substances.230135
[0288] Due to their chemical structure and functionalities, the above specified fragrance or aroma / flavour substances are susceptible against oxidation, temperature, and / or light and degrade easily which results into odour change, i.e. malodour formation, and / or discoloration in the formulations according to the present invention.
[0289] The at least one fragrance or aroma / flavour compound is present in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.01 to 40.0 % by weight, based on the total weight of the food, cosmetic or pharmaceutical preparation or homecare product, preferably in an amount of 0.02 to 35.0 % by weight, more preferred in an amount of at 0.03 to 30.0 % by weight, and most preferred in an amount of at 0.04 to 25.0 % by weight.
[0290] For a mixture of fragrances, the above amounts relate to the total content of the fragrances in the mixture, i.e. the amount is the sum of the content of all fragrances in the mixture. Alternatively, for a mixture of aroma / flavours, the above amounts relate to the total content of the aroma in the mixture, i.e. the amount is the sum of the content of all aroma / flavours in the mixture.
[0291] In addition to the above-described substances, further ingredients commonly used in the food industry, cosmetic or pharmaceutical industry or for homecare products, which are suitable or customary in the compositions of the present invention, can be used.
[0292] The at least one mycosporine-like amino acid compound according to the present invention is present in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.001 to 15.0 % by weight, based on the total weight of the final formulation. In a preferred variant, the food, cosmetic or pharmaceutical preparation or homecare product comprises the at least one mycosporine-like amino acid compound in an amount of 0.01 to 10.0 % by weight, based on the total weight of the final formulation. In a more preferred variant, the at least one mycosporine-like amino acid compound is advantageously used in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of at 0.05 to 7.5 % by weight, based on the total weight of the final formulation. In a most preferred variant, the at least one mycosporine-like amino acid230135 compound is advantageously used in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of at 0.1 to 5.0 % by weight, based on the total weight of the final formulation.
[0293] For a mixture of mycosporine-like amino acid compounds, the above amounts relate to the total content of the mycosporine-like amino acid compounds in the mixture, i.e. the amount is the sum of the content of all mycosporine-like amino acid compounds in the mixture.
[0294] The cosmetic or pharmaceutical, in particular dermatological, preparations according to the present invention are intended for topical application. The term “topical” is understood to mean external applications on a mammal’s skin or mucosa, which are in particular for the protection, treatment, care and cleansing of the skin, scalp, eyelashes, eyebrows, nails, mucous membranes and hair. The mammal is preferably a human.
[0295] For topical application, the cosmetic or pharmaceutical preparation is either a rinse off or a leave on preparation.
[0296] The cosmetic or pharmaceutical or homecare products according to the present invention may be in the form of an aqueous solution, dispersions, a hydro alcoholic vehicle, a stick, an ointment, a gel, an aerosol (foams, sprays, propellant pump) and the like.
[0297] The cosmetic or pharmaceutical, in particular dermatological, preparation or homecare product according to the present invention can be present in different forms, e.g. in the form of a dispersion, in the form of a liquid surfactant formulation, in the form of a solid surfactant formulation, in the form of a water free formulation, or in the form of an aqueous, aqueous / alcoholic, in particular aqueous / ethanolic, aqueous / glycolic or alcoholic / glycolic, in particular ethanolic / glycolic, based solution.230135
[0298] In a preferred variant, the cosmetic or pharmaceutical preparation or homecare product according to the present invention is a dispersion. The term “dispersion” in the context of the present invention means, that the food, cosmetic or pharmaceutical preparation or homecare product is a disperse two-phase system consisting of colloidal particles (disperse phase) and a medium in which they are suspended (disperse medium). Both phases are not miscible with each other, only with an emulsifier. Such dispersions, for example emulsions, comprise the at least one oil component (without UV- filter(s)) preferably in an amount of ≥ 1 % by weight, more preferably in an amount of ≥ 3 % by weight.
[0299] Preferably, the food, cosmetic or pharmaceutical preparations or homecare products according to the present invention take various forms such as an emulsion, in particular a O / W emulsion, a W / O emulsion, a multiple emulsion, a hydrodispersion gel, a balm, a multiple emulsion of the water-in-oil type (W / O / WO) or of the oil-in-water type (O / W / O), PIT emulsion, Pickering emulsion, a micro-emulsion, a liquid, a lotion, a suspension, a milk, an ointment, a paste, a gel, a cream based, an oil based or a liposome-based formulation or a an aerosol such as foams and sprays, including all types of silicon based emulsions.
[0300] In a most preferred variant, the food, cosmetic or pharmaceutical preparations or homecare products according to the present invention are in the form of an emulsion as defined herein, advantageously in the form of an oil-in-water (O / W) emulsion comprising an oily phase dispersed in an aqueous phase in the presence of an O / W or polymeric emulsifier.
[0301] If the food, cosmetic or pharmaceutical preparation or homecare product according to the present invention is a dispersion, preferably an emulsion, the oil component (without UV-filter(s)) is present in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of 0.01 to 50.0 % by weight, based on the total weight of the composition. In a preferred variant, the food, cosmetic or pharmaceutical preparation or homecare product comprises the oil component in an amount of 0.1 to 45.0 % by weight, based on the total weight of the composition. In a230135 particular preferred variant, the oil component is advantageously used in the food, cosmetic or pharmaceutical preparation or homecare product in an amount of at 1.0 to 40 % by weight, based on the total weight of the composition.
[0302] In a further variant, the cosmetic or pharmaceutical, preferably dermatological, preparation or homecare product according to the first of the invention is a water free formulation, i.e. an oil formulation.
[0303] If the cosmetic or pharmaceutical preparation or homecare product according to the present invention is a water free formulation, i.e. an oil formulation, the oil component is present in the cosmetic or pharmaceutical preparation or homecare product in an amount of ≥ 60 % by weight, preferably in an amount of ≥ 75 % by weight, more preferably in an amount of ≥ 90 % by weight, based on the total weight of the composition.
[0304] Such water free formulations include e.g. oils, skin butters, powders, lip stick, antiperspirant / deo sticks, and decorative cosmetics.
[0305] In addition, further water free formulations are likewise formulations on the basis of ethanol / diols / triols / glycols such as sprays or gels.
[0306] In a further alternative, the cosmetic or pharmaceutical preparation or homecare product according to the present invention is a liquid surfactant formulation.
[0307] Such liquid surfactant formulations include form example shampoo, shower gel, micellar water, liquid soap, cleansing preparations.
[0308] In a further alternative, the cosmetic or pharmaceutical preparation or homecare product according to the present invention is a solid surfactant formulation.
[0309] Such solid surfactant formulations include for example solid shampoos, solid body wash, bar soaps.230135
[0310] If the cosmetic or pharmaceutical preparation or homecare product according to the present invention is a liquid or solid surfactant composition, the surfactant component is present in the cosmetic or pharmaceutical preparation or homecare product in an amount of 1.0 to 90 % by weight, preferably in an amount of 1.5 to 80.0 % by weight, more preferably in an amount of 2.0 to 70.0 % by weight, based on the total weight of the composition.
[0311] Alternatively, the cosmetic or pharmaceutical preparation or homecare product as disclosed herein is an aqueous or an aqueous / alcoholic, preferably aqueous / ethanolic, or an aqueous / glycolic, or an alcoholic / glycolic, preferably ethanolic / glycolic, based solution. Typically, this could be glycerin in water or alcohol compositions. Said solutions are homogeneous one phase system of water / alcohol / glycol and additional components. The aqueous / alcoholic or aqueous / glycolic or alcoholic / glycolic based solution comprises an aliphatic alcohol or a glycol in an amount of 0.1 to 70.0 % by weight, preferably in an amount of 0.5 to 60.0 % by weight, more preferably in an amount of 1.0 to 50.0 % by weight, based on the total weight of the solution. The aliphatic alcohol is preferably selected from the group consisting of ethanol, isopropanol, n-propanol. The glycol is preferably selected from the group consisting of glycerin, propylene glycol, 1,3- Propanediol, 1,2-Propanediol, 1,2–C5 to C10-alkanediols, butylene glycol or dipropylene glycol.
[0312] Preferably, the overall water content in the final aqueous based solutions can be ≥ 30 % by weight, more preferably ≥ 40 % by weight, most preferably ≥ 50 % by weight. New applications such as those including water wipes have high water content. In a particular variant, the inventive compositions can be used for such wet wipe applications. They may then most preferably contain ≥ 90 % water, or even ≥ 95 % water.
[0313] Such aqueous or aqueous / alcoholic or aqueous / glycolic or alcoholic / glycolic based solutions include for example deo / antiperspirant preparations, after shave, cleansing preparations, or anti-acne preparations, or wet wipe solutions.230135
[0314] In a further preferred variant, the inventive composition is an impregnation solution in the form of an emulsion spray, aqueous / alcoholic, aqueous / glycolic, alcoholic / glycolic or alcoholic / oil spray for wet wipes.
[0315] The above formulations or compositions are prepared according to usual and known methods.
[0316] The cosmetic preparation according to the present invention is a preparation for cosmetic and / or non-therapeutic use for personal care, skin protection, skin care, scalp protection, scalp care, hair care, nail care, in particular for the prevention and / or treatment of skin conditions, intolerant or sensitive skin, skin irritation, skin reddening, rosacea, wheals, pruritus (itching), skin aging, wrinkle formation, loss of skin volume, loss of skin elasticity, pigment spots, pigment abnormalities, skin dryness, flaking, greasiness, hypopigmentation and / or hyperpigmentation of the skin; or a preparation for animal care.
[0317] Examples of personal care are preferably anti-ageing preparations, skin care emulsions, body oils, body lotions, cleansing lotions, face or body balms, after shave balms, after sun balms, deo emulsions, cationic emulsions, body gels, treatment creams, skin protection ointments, moisturizing gels, face and / or body moisturizers, light protective preparations (sunscreens), micellar water, hair spray, colour protection hair care products, skin lightening product, anti-dark spot preparations, etc.
[0318] The cosmetic preparations include also make-ups, eye-care preparation, eye shadows, mascara, eyeliner, lip care preparation such as lip stick, lip gloss, nail care preparations, such as nail varnish, nail varnish removers,
[0319] The pharmaceutical, in particular dermatological, preparation according to the present invention is a preparation for the prevention and treatment of a condition of the skin or mucosa, hair or nails.
[0320] In order to be used, the cosmetic or pharmaceutical, in particular dermatological preparation according to the present invention is applied to the skin, hair, scalp and / or230135 nails in an adequate amount in such manner as is customary with cosmetics and dermatological products.
[0321] In addition, the products and preparations according to the present invention are pharmaceutical products for the prevention and damages to skin, in particular solar effects, including sunburn, pigmentation, anti-aging, sun-caused erythema, inflammation, melanoma, malignant melanoma, eye damages and local or systemic immune- suppression.
[0322] In addition, the products and preparations according to the present invention are homecare products. The homecare products are predominantly detergent formulations, usually liquids, powders, sprays, granules or tablets, used to remove dirt, including dust, stains, bad smells and clutter on surfaces or other types of housecleaning or laundry detergent that is added for cleaning laundry or liquid soap. Typical homecare products include all-purpose cleaners, dishwashing detergents, hard floor and surface cleaners, glass cleaners, carpet cleaners, oven cleaners, laundry detergents (powder, liquid and table), fabric softeners, laundry scent, scent lotions, air fresheners, disinfectants, stain removers, carwash products, rim block gel, all aforementioned goods also in encapsulated form, air fresheners or furniture polish, etc.
[0323] In a preferred variant according to the present invention, the formulation is a fragrance composition or an aroma / flavour composition.
[0324] Due to their distinguished ultraviolet radiation absorbing capacity that protect from damages caused by UV radiation as described above, the mycosporine-like amino acid compounds may be used to absorb UV radiations and, accordingly, qualify for different purposes.
[0325] Thus, in a further aspect, the present invention relates to the use of at least one mycosporine-like amino acid compound for the preparation of food, cosmetic or pharmaceutical preparations or homecare products, in particular for the preparation of sunscreen products.230135
[0326] In a further aspect, the present invention relates to the use of at least one mycosporine-like amino acid compound as defined herein or a formulation comprising at least one of said mycosporine-like amino acid compound for protecting skin, hair, nail of a human or an animal against the harmful effect of UV radiations.
[0327] In a further aspect, the present invention relates to the use of at least one mycosporine-like amino acid compound as defined herein for stabilizing of food, cosmetic or pharmaceutical preparations or homecare products against degradation of ingredients that are sensitive to UV light.
[0328] Surprisingly, it was found that the mycosporine-like amino acid compounds as defined herein have the property of being effective in stabilizing photo-unstable UV-filters, i.e. act as stabilizer when combined with a photo-unstable UV-filter, making them more effective for longer periods of time and to provide a constant protection during prolonged exposure to the sun. The compositions according to the present invention exhibits greater UV absorbance than a composition comprising the at least photo-unstable UV-filter material without the addition of at least one mycosporine-like amino acid compound.
[0329] With the admixture of a mycosporine-like amino acid compound according to the present invention to a sunscreen product or cosmetic or pharmaceutical preparation and stabilization effect against a photo-unstable UV-filter, the SPF of the sunscreen product, the cosmetic or pharmaceutical preparation or homecare product remains almost constant even during exposure to the sun, compared to products or preparations without the addition of the specified mycosporine-like amino acid compounds. The higher the SPF the more protective the sunscreen is.
[0330] Furthermore, the sunscreen product, cosmetic or pharmaceutical preparation or homecare product has an increase in pre-irradiation SPF as compared to a composition comprising the at least one photo-unstable UV-filter without any one of the mycosporine- like amino acid compound.230135
[0331] In addition, by stabilizing the UV-filter, its degradation upon exposure to UV- radiation can be reduced and the formation of phototoxic or photoallergic degradation products with a risk of adverse health effects when coming into direct contact with the skin can be reduced.
[0332] The above-described combinations of a photo-unstable UV-filter with any of a mycosporine-like amino acid compound defined herein result in distinguished stabilized sunscreen products or cosmetic or pharmaceutical products where degradation of the photo-unstable UV-filter is considerably reduced, as it is demonstrated by the following examples. Hence, a highly photostable sunscreen product is obtained with the addition of a mycosporine-like amino acid.
[0333] Thus, the present invention relates in a further aspect to the use of at least one mycosporine-like amino acid compound as defined herein for stabilizing an unstable UV filter in a food, cosmetic or pharmaceutical preparation or homecare product, preferably in a sunscreen product.
[0334] Surprisingly, it was found that the addition of a mycosporine-like amino acid compound as defined in the present application have the effect of improving SPF and boosting the UVA photoprotection. The higher the SPF or the UVA-PF the more protective the sunscreen is.
[0335] Furthermore, with the addition of a mycosporine-like amino acid compound or its salt, the critical wavelength of a sunscreen product, cosmetic or pharmaceutical preparation or homecare product can be increased to provide a broad-spectrum coverage having a critical wavelength greater than 370 nm.
[0336] These effects have the advantage that sunscreen products or cosmetic or pharmaceutical products can be provided having a broader spectrum protection covering UVA and UVB. In addition, an improved UV-filter performance, in particular UVA photoprotection, allows to reduce the amount of organic UV-filter agent without affecting the envisaged SPF.230135
[0337] As it is demonstrated by the following examples, the SPF and the UVA photoprotection is highly improved, i.e. increased by the addition of a mycosporine-like amino acid compound as defined therein. The control samples containing none mycosporine-like amino acid compound exhibited average or lower SPF.
[0338] With the addition of a mycosporine-like amino acid compound as defined herein, the SPF of a sunscreen product, a cosmetic or pharmaceutical preparation or homecare product comprising an organic UV-filter or a mixture of organic UV-filters can be increased by at least 5 %, preferably by at least 10 %, and more preferred by at least 10 % as it is demonstrated in the following examples.
[0339] Thus, the present invention relates in a further aspect to the use of at least one mycosporine-like amino acid compound as defined herein for increasing the SPF of a sunscreen product, a cosmetic or pharmaceutical preparation or homecare product comprising an organic UV-filter or a mixture of organic UV-filters or an inorganic UV-filter or a mixture of inorganic UV-filters.
[0340] Surprisingly, the addition of a mycosporine-like amino acid compound as defined herein to an antimicrobial component in food, a cosmetic or pharmaceutical preparation or homecare product has been found to synergistically enhance the antimicrobial effect thereof. The at least one antimicrobial compound and at least a mycosporine-like amino acid compound is characterized by a synergistically antimicrobial efficacy against a broad spectrum of microorganism, i.e. against bacteria, yeast and fungi / mould, when used in combination with an antimicrobial component, compared to their respective single antimicrobial substances as it is demonstrated in the following examples. Surprisingly, the synergistic antimicrobial effect can even be demonstrated for Candida, such as Candida albicans, and Aspergillus, such as Aspergillus brasiliensis, which both are known to be combated only with great difficulty.
[0341] Thus, in a further aspect, the present invention relates to the use of at least one mycosporine-like amino acid compound as defined herein for boosting the antimicrobial230135 efficacy of an antimicrobial agent in a food, a cosmetic or pharmaceutical preparations or homecare products. Accordingly, the activity or growth of microorganism in a cosmetic or pharmaceutical preparation or homecare product can be stronger suppressed or inhibited. Thereby the storage stability of such formulations can be considerably improved, and, thus, the shelf live can be prolonged.
[0342] Surprisingly, the addition of a mycosporine-like amino acid compound according to the present invention to a fragrance or aroma / flavour compound in food, a cosmetic or pharmaceutical preparation or homecare product leads to an improvement in fragrance or aroma / flavour stability. In the presence of a mycosporine-like amino acid compound the fragrance or aroma / flavour compound are protected from degradation by oxygen, temperature and / or light. Therefore, the use of mycosporine-like amino acid compounds prevents said formulations from degradation, odour change, i.e. malodour formation, and / or discoloration, as it is demonstrated in the following examples.
[0343] Due to the outstanding stabilizing effects as described above, the combined use of at least one fragrance or aroma / flavour compound and at least one mycosporine-like amino acid compound is suitable to improve storage stability and to prolonge shelf life of the food, cosmetic or pharmaceutical preparations or homecare products.
[0344] Thus, in a further aspect, the present invention relates to the use of at least one mycosporine-like amino acid compound as defined herein for stabilizing a fragrance or aroma / flavour compound or in a food, a cosmetic or pharmaceutical preparations or homecare products against degradation through oxidation, temperature or light. By stabilizing the fragrance or aroma / flavour compound the degradation and deterioration of the cosmetic or pharmaceutical preparation, in particular during storage, which goes along with impairment of the sensory quality of the products, can be prevented or at least minimized. The at least one mycosporine-like amino acid compound as defined herein is similary used for stabilizing a fragrance composition or aroma / flavour composition.
[0345] Surprisingly it turned out that with the addition of a mycosporine-like amino acid compound as defined herein to a food, cosmetic or pharmaceutical preparation or230135 homecare product according to the present invention comprising an antioxidant, the antioxidative efficacy of the antioxidant can significantly be improved. Preferably, the combination of a mycosporine-like amino acid compound and an antioxidant result in a synergistic stabilizing effect against oxidative degradation. The use of such a combination in food, a cosmetic or pharmaceutic preparation or homecare product in turn results in stable formulations with no or merely minor malodour and / or colour deviations. The improved antioxidative effect in turn results in formulations with improved storage stability and prolonged shelf life.
[0346] Thus, in a further aspect, the present invention relates to the use of at least one mycosporine-like amino acid compound as defined herein for boosting the antioxidative effect of an antioxidant, preferably in food, a cosmetic or pharmaceutical preparation or a homecare product for protecting them against oxidative degradation.
[0347] The present invention shall now be described in detail with reference to the following examples, which are merely illustrative of the present invention, such that the content of the present invention is not limited by or to the following examples.230135 Examples
[0348] Example 1 – Photostability Test
[0349] UV-filters are usually tested for photostability to ensure that no degradation of the UV-filter itself or in combination with other substances takes place.
[0350] The UV-filter stabilizing properties of mycosporine-like amino acid compounds were explored by comparing the behaviour of UV-filter alone relative to UV-filters in combination with a certain mycosporine-like amino acid compound.
[0351] In the present case single photo-unstable UV-filters as well as formulations of photo-unstable filters with certain mycosporine-like amino acid compounds were subjected to photostability testing, described in detail below, to determine the retention of absorption of UVA and UVB radiation (full spectrum analysis) after exposing the sample to 5 MED (minimal erythema) dose (1 MED = 250 J / m2). The minimum erythema dose (MED) (also erythema threshold dose) is a measure of the tolerance of human skin to solar radiation, especially to the short-wave ultraviolet portion of the spectrum around about 300 nm wavelength. Dermatologists determine MED by irradiating a test area, usually on the untanned back with gradually (so-called "light staircase") increased doses of a powerful UV lamp. 1 MED corresponds to the lowest irradiation dose that caused a sharply defined erythema (redness) of the skin when read after 24 hours.
[0352] Sample preparation: The substance or the formulation to be tested was dissolved in a suitable solvent. For this purpose, a certain amount of the substance or formulation was transferred by means of an analytical balance / pipette into a graduated flask and filled with the selected solvent. The filling up to the calibration mark of the230135 graduated flask was carried out only after complete dissolution of the substance and temperature control at 20 °C.
[0353] Preparation of solution E 1% / cm: 100 mg of the substance or formulation to be tested were weighed into a graduated flask and filled up to 100ml with the corresponding solvent. A clear solution was obtained. If necessary, an ultrasonic bath can be used to improve solubility. For further dilution the sample was adjusted to a temperature of 20 °C. 1 ml of the dissolved solution was added into a second graduated 100 ml flask, filled up to 100 ml at a temperature of 20 °C. The final concentration of the thus obtained solution was 0.001 %. (E1% / cm). This solution was used for absorbance measurement and irradiation. Said solution was transferred to a 10 mm quartz cuvette with closure.
[0354] Irradiation: Irradiation of the sample was performed for 32 min with 700W / m² emitted by an Atlas SUN Test CPS. This corresponds to an amount of energy of 5 MED (minimal erythema) dose (= 1,250 J / m2). At the same time, the temperature of the devise was adjusted to max 30 °C in order to avoid strong heating of the sample.
[0355] Measurement: The absorbance measurement of the sample in the quartz cuvette with closure (10 mm) was carried out in a wavelength range of 200 nm to 700 nm with a Lambda 25 UV spectrometer. A blank absorbance test was carried out with the corresponding solvent for preparing the samples as described above. The absorbance measurement of the samples was carried out before (pre-irradiation) and after irradiation emitted by a Atlas SUN Test CPS (see above).
[0356] The UV absorbance curves obtained demonstrates the amplitude and breadth of protection provided from 200 nm to 700 nm across the UV spectrum for each sample both before (pre-irradiation) and after irradiation as described above. The amplitude of the absorbance curve reflects the degree of protection. The higher the amplitude of the curve, the greater the absorbance and the more protection provided at that wavelength. Within the UVB portion of the spectrum (290 nm to 320 nm) this amplitude correlates with the230135 SPF. The greater the breadth of the curve, the more protection provided against longer wave UV ration. In other words, the greater the breadth of the curve, the broader the spectrum of sun protection provided.
[0357] The Tables show the changes in UV absorbance performance of either the individual components or the various combinations.
[0358] Samples with an absorbance loss < 20% after irradiation can be classified as photostable.
[0359] Tested samples: a) E1% / cm solution of pure substances: 1) MAA-20 (mycosporine-like amino acid compound) 2) MAA-28 (mycosporine-like amino acid compound) 3) Ethylhexyl Methoxycinnamate (UV-filter) 4) Butyl Methoxydibenzoylmethane (UV-filter) 5) Isoamyl p-Methoxycinnamate (UV-filter) b) E1% / cm solution of the following mixture: 1) MAA-20 plus Isoamyl p-Methoxycinnamate 2) MAA-20 plus Ethylhexyl Methoxycinnamate c) E1% / cm solution of the following mixture: 1) MAA-28 plus Isoamyl p-Methoxycinnamate 2) MAA-28 plus Ethylhexyl Methoxycinnamate
[0360] Results:230135 1) Photostability E1% / cm measurement of MAA-20 (mycosporine-like amino acid compound): Results: Absorbance loss 5,95 % at 324 nm. Very photostable molecule (see Figure 3 a). 2) Photostability E1% / cm measurement of MAA-28 (mycosporine-like amino acid compound): Results: Absorbance loss 15,03 % at 335 nm. A photostable molecule (see Figure 4 a). 3) Photostability E1% / cm measurement of Ethylhexyl Methoxycinnamate (UV- filter): Results: Absorbance loss 37.88 % at 310nm. Not photostable (see Figure 5). 4) Photostability E1% / cm measurement of Butyl Methoxydibenzoylmethane (UV- filter): Results: Absorbance loss 7.05 % at 358 nm. Butyl Methoxydibenzoylmethane is photostable in this kind of medium (see Figure 6). 5) Photostability E1% / cm measurement of Isoamyl p-Methoxycinnamate (UV- filter): Results: Absorbance loss 30.5 % at 310 nm. Not photostable (see Figure 7).230135 6) Photostability E1% / cm measurement of a mixture of MAA-20 and Isoamyl p- Methoxycinnamate: Results: Absorbance loss 16.41 % at 310 nm. In combination with MAA-20 it is possible to reduce the loss of Isoamyl p- Methoxycinnamate from 30.50 % to 14.41 % by approximately 52 %. The combination shows both UVB and UVA activity relative to Isoamyl p- Methoxycinnamate alone (see Figure 8). Additionally, the critical wavelength is shifted from 324 nm for Isoamyl p- Methoxycinnamate alone to 344 nm for the above mixture, which indicates that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e. wavelengths from 280 - 320 nm, but extends to 344 nm in such a way that 90 % of the total area under the protective curve in the UV region are reached at 344 nm. Product MAA-20 plus Isoamyl p- Isoamyl p- Methoxycinnamate Methoxycinnamate E max (nm) 318 310 Lost (%) after irradiation with 5 14.41 30.50 MED (1,250 J / m²) Critical Wavelength (nm) 344 324 Results photostable Placebo230135 7) Photostability E1% / cm measurement of a mixture of MAA-20 and Ethylhexyl Methoxycinnamate: Results: Absorbance loss 13.80 % at 318 nm. In combination with MAA-20 it is possible to reduce the loss Ethylhexyl Methoxycinnamate from 37.88 % to 13.80 % by approximately 64 %. The combination shows both UVB and UVA activity relative to Ethylhexyl Methoxycinnamate alone (see Figure 9). Additionally, the critical wavelength is shifted from 324 nm for Ethylhexyl Methoxycinnamate alone to 346 nm for the above mixture, which indicates that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e. wavelengths from 280 - 320 nm, but extends to 346 nm in such a way that 90 % of the total area under the protective curve in the UV region are reached at 346 nm. Product MAA-20 plus Ethylhexyl Ethylhexyl Methoxycinnamat Methoxycinnamate e E max (nm) 318 310 Lost (%) after irradiation with 5 13.80 37.88 MED (1,250 J / m²) Critical Wavelength (nm) 346 324 Results photostable Placebo230135 8) Photostability E1% / cm measurement of a mixture of MAA-28 and Isoamyl p- Methoxycinnamate: Results: Absorbance loss 16.41 % at 310 nm. In combination with MAA-28 it is possible to reduce the loss of Isoamyl p- Methoxycinnamate from 30.50 % to 19.80 % by approximately 35 %. The combination shows both UVB and UVA activity relative to Isoamyl p- Methoxycinnamate alone (see Figure 10). Additionally, the critical wavelength is shifted from 324 nm for Isoamyl p- Methoxycinnamate alone to 347 nm for the above mixture, which indicates that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e. wavelengths from 280 - 320 nm, but extends to 347 nm in such a way that 90 % of the total area under the protective curve in the UV region are reached at 347 nm. Product MAA-28 plus Isoamyl p- Isoamyl p-Methoxy- Methoxycinnamate cinnamate E max (nm) 315 310 Lost (%) after irradiation with 5 19,80 30.50 MED (1,250 J / m²) Critical Wavelength (nm) 347 324 Results photostable Placebo9) Photostability E1% / cm measurement of a mixture of MAA-28 and Ethylhexyl Methoxycinnamate: Results: Absorbance loss 13.80 % at 318 nm. In combination with MAA-28 it is possible to reduce the loss of Ethylhexyl Methoxycinnamate from 37.88 % to 19.54 % by approximately 48 %. The combination shows both UVB and UVA activity relative to Ethylhexyl Methoxycinnamate alone (see Figure 11). Additionally, the critical wavelength is shifted from 324 nm for Ethylhexyl Methoxycinnamate alone to 349 nm for the above mixture, which indicates that the protection of the sunscreen composition is not limited to the wavelengths of UV-B, i.e. wavelengths from 280 - 320 nm, but extends to 349 nm in such a way that 90 % of the total area under the protective curve in the UV region are reached at 349 nm. Product MAA-20 plus Ethylhexyl Ethylhexyl Methoxycinnamate Methoxycinnamate E max (nm) 317 310 Lost (%) after irradiation with 5 19.54 37.88 MED (1,250 J / m²) Critical Wavelength (nm) 349 324 Results photostable Placebo
[0361] Example 2 – Determination of the in-vitro SPFs and UVA-PF
[0362] The SPF boosting and UVA-PF boosting test is carried out as in-vitro determination of SPFs.
[0363] Principle: The formulation to be tested (emulsion, solution) is weighed on PMMA plates with the help of an analytical balance. The formulation if distributed and incorporated on the plate using a method corresponding to the formulation. The thus prepared plates are then measured on a Labsphere device and the results are calculated as SPF with a suitable software.
[0364] 1. Sample preparation:
[0365] PMMA plates (Polymethylmethacrylate), measuring 3 cm x 8.5 cm (WW5 plates based on ISOethA 24443:2012 “Determination of UVA photoprotection in vitro” with 5 µ roughness by Schönberg GmbH & Co. AG) are used to perform an SPF measurement.
[0366] 1.1 Preparation of reference samples:
[0367] A reference sample is obtained by distributing 25 to 28 mg glycerin (99.5 %) with the index finger on the roughened side of the PMMA plate. The glycerin film must be very thin and uniform. Subsequently, this plate is stored for at least 2 hours.
[0368] The reference plate is measured with the following transmission values: 290 nm > 60 % transmission; 300 nm > 69 % transmission; and 320 nm > 82 % transmission.
[0369] 1.2 Application of the sample to be measured:230135
[0370] The sample to be measured should be homogeneously mixed with a spatula before application.1.2 mg / cm2 of sample is evenly distributed in several rows of dots on the PMMA plate. In order to minimise the evaporation of the sample during weighing, this process must be carried out quickly. The sample is then evenly distributed by hand with a finger previously saturated with the sample material. The distribution takes place in two phases: Phase 1: Fast and uniform distribution with a slight pressure until the emulsion is broken. Phase 2: The sample is massaged into the rough surface with strong pressure and the process should last 30 seconds. In this context under strong pressure means that when massaged on a scale, this indicates at least 200 m.
[0371] Exceptions:
[0372] Sun oils: The product quantity is generally 1.3 mg / cm². For strongly spreading oils, less product is applied, as the amount of oil cannot be "absorbed" from the plate. Then the amount of application should be reduced to 1.0-0.75 mg / cm². Application method here is also the 30 s fast / light and 30 s strong method.
[0373] Sun sprays: The "30 / 30 method" applies here (especially for thicker sprays). For very liquid sprays (similar to water): Fast and uniform distribution with a slight pressure, until the emulsion "breaks". The process should take 45 s.
[0374] The finished sample plates are stored dust-free and measured at the earliest after 15 minutes.
[0375] 2. Measurement on the Labsphere:
[0376] The samples are measured using the UV-200S device, using the specified Colipa method. The Labsphere user manual also applies.230135
[0377] 2.1 Basic settings in the software:
[0378] A new "Study" is opened via File and then the "Colipa Guideline 2011" method is selected under the heading "Study". In the new window "Colipa Method Options" the number of plates (3 plates), the measuring points per plate (5 measuring points) and the in vivo SPF and, if necessary, the irradiance intensity of the external irradiance device (Solar Simulator Irradiance) entered.
[0379] The irradiance set on the external device is 765 W / m2 as standard. The complete naming of the sample is done via Study", "Study Information".
[0380] 2.2 Sample measurement:
[0381] At the beginning of the measurement, a blank value of the glycerin reference sample is measured ("scan blank plate"). In order to determine the SPF of a sample, a total of 15 measuring points (3 plates of 5 measuring points) are then created ("Scan Location"). The already scanned plates and measuring points are checked in the upper right window, while the absorbance of the currently measured plate is displayed in the middle window.
[0382] With irradiation:
[0383] After the first measurement run, the device calculates an irradiation dose (Irradiation Dose / J / cm2) and the duration (exposure time) for each plate. The plates are irradiated in the external irradiation device (irradiation duration = average value of the 3 plates).230135
[0384] The calculation of irradiation dose and exposure time is based on the irradiance (765 W / m2) set on the external device.
[0385] Without irradiation:
[0386] If no irradiation device is available or irradiation is not desired, the first plate is started again after completion of the 15 individual scans and the measurements are repeated (Background: Without the second measurement, no UVA / UVB balance calculation is performed by the software.)
[0387] After completion of the measurements, the "Study" is recorded and the data can be printed / exported as a "Report".
[0388] Example 2.1: Sunscreen product with modern organic UV-filter combination:
[0389] The formulation samples A and B as specified in the following Table 2 were prepared as follows:
[0390] Phase A: The ingredients of phase A without Keltrol® CG-BT were heated to 85 °C in order to dissolve the ingredients. After dissolution of the ingredients, Keltrol® CG- BT were added and the solutions was homogenized for a short time (Ultra Turrax® T25: 15,000rpm / 10 sec).
[0391] Phase B: The ingredients of phase B were mixed while stirring until the ingredients were dissolved. The water phase will be cloudy in combination with the sodium hydroxide solution. Afterwards, the water phase B was heated to 80 °C. Afterwards, the hot phase B was added to the hot phase A and homogenized (Ultra Turrax® T25: 13,000 rpm / 3 min). Finally, the mixture was cooled down to ambient temperature while stirring.230135
[0392] The results of the in vitro SPFs and UVA-PF determination are presented in Table 2.
[0393] Table 2: Pha-se Name INCI A B % w / w % w / w A Emulsiphos® F Potassium Cetyl Phosphate, 1.50 1.50 Hydrogenated Palm Glycerides Lanette® O Cetearyl Alcohol 2.00 2.00 Neo Heliopan® OS Ethylhexyl Salicylate 5.00 5.00 Neo Heliopan® 357 Butyl 3.00 3.00 Methoxydibenzoylmethane Neo Heliopan® EHT Ethylhexyl Triazone 3.00 3.00 Neo Heliopan® BMT Bis-Ethylhexyloxyphenol 3.00 3.00 Methoxyphenyl Triazine SymMollient® PDCC Propanediol 7.50 7.50 Dicaprylate / Caprate Isoadipate Disopropyl Adipate 7.50 7.50 Neutral oil Caprylic / Capric Triglyceride 10.0 10.0 Sodium Gluconate Sodium Gluconate 0.20 0.20 Keltrol® CG- V Xanthan GUM 0.50 0.50 Keltrol® CG-SFT Xanthan GUM 0.05 0.05 B Aqua / Water. Dem. Aqua 52.50 51.10 SymOcide® PH Phenoxyethanol, 1.50 1.50 Hydroxyacetophenone, Caprylyl glycol, aqua Glycerin 99,5% Glycerin 3.00 3.00 MAA-20 --- --- 1.00 NaOH, 10% aq Aqua, Sodium Hydroxide 0.05 0.15 Sum 100.0 100.0 pH value (23°C) 6.2 6.0 Viscosity: cp (Brookfield DVIII CP51 / 10RPM / 20°C 1041 1165 SPF in-vitro pre irradiation 52.4 57.1 Delta SPF in-vitro pre irradiation 4.7 UVA-PF post irradiation 20.90 24.70 Delta UVA-PF post irradiation 3.8 critical wavelength post irradiation (nm) 377.5 377.0230135
[0394] Results: As can be retrieved from Table 2, the in vitro SPF is highly improved, i.e. increased by the combination of the sunscreen formulation with the mycosporine-like amino acid compound MAA_20. The control example containing none mycosporine-like amino acid compound exhibited an SPF of 52.4. The addition of MAA-20 in an amount of 1.0 % by weight however results in an in vitro SPF of 57.1 which is 9 % higher than the in vitro SPF of the reference sample, i.e. the sample without the addition of the mycosporine-like amino acid compound MAA-20.
[0395] In addition, not only an improved SPF results from the addition of a certain mycosporine-like amino acid compound in the sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising a mixture of organic UV- filter, but also a boosted UVA-PF. In particular, the addition of MAA-20 in an amount of 1.0 % results in an improvement of the UVA-PF of 18.2 % compared to the control sample, i.e. containing none mycosporine-like amino acid compound.
[0396] Hence, as demonstrated by the above test samples, the addition of MAA-20 leads to a considerable improvement of the SPF and / or of the UVA-PF in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising a modern organic UV-filter composition.
[0397] Example 2.2: Sunscreen product with classic organic UV-filter combination:
[0398] The formulation samples A to D as specified in the following Table 3 were prepared as follows:
[0399] Phase A: The ingredients of phase A without Keltrol® CG-BT were heated to 85 °C in order to dissolve the ingredients. After dissolution of the ingredients, Keltrol® CG- BT were added and the solutions was homogenized for a short time (Ultra Turrax® T25: 15,000rpm / 10 sec).230135
[0400] Phase B: The ingredients of phase B were mixed while stirring until the ingredients were dissolved. The water phase will be cloudy in combination with the sodium hydroxide solution. Afterwards, the water phase B was heated to 80 °C. Afterwards, the hot phase B was added to the hot phase A and homogenized (Ultra Turrax® T25: 13,000 rpm / 3 min). Finally, the mixture was cooled down to ambient temperature while stirring.
[0401] The results of the in vitro SPFs and UVA-PF determination are presented in Table 3.
[0402] Table 3: Pha- Name INCI A B C D se % w / w % w / w % w / w % w / w A Emulsiphos® F Potassium Cetyl Phosphate, 1.50 1.50 1.50 1.50 Hydrogenated Palm Glycerides Lanette® O Cetearyl Alcohol2.00 2.00 2.00 2.00Neo Heliopan® OS Ethylhexyl Salicylate5.00 5.00 5.00 5.00Neo Heliopan® 357 Butyl Methoxydibenzoylmetha 5.00 3.00 5.00 3.00 ne Neo Heliopan® 303 Ethylhexyl Triazone10.00 10.00 10.00 10.00Neo Heliopan® HMS Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine10.0 10.0 10.0 10.0SymMollient® PDCC Propanediol Dicaprylate / Caprate2.00 4.00 2.00 4.00Sodium Gluconate Sodium Gluconate0.20 0.20 0.20 0.20Keltrol® CG-V Xanthan GUM0.50 0.50 0.50 0.50Keltrol® CG-SFT Xanthan GUM0.05 0.05 0.05 0.05BAqua / Water. Dem. Aqua59.25 59.25 58.15 58.15SymOcide® PH Phenoxyethanol, Hydroxyacetophenone, 1.50 1.50 1.50 1.50 Caprylyl glycol, Aqa Glycerin 99,5% Glycerin3.00 3.00 3.00 3.00MAA-20 ------ --- 1.00 1.00NaOH, 10% aq Aqua, Sodium Hydroxide--- --- 0.10 0.10230135 Sum 100.0 100.0 100.0 100.0 pH value (23°C)5.7 5.7 5.7 5.7Viscosity: cp (Brookfield DVIII1056CP51 / 10RPM / 20°C1087 1144 1196SPF in-vitro pre irradiation 51.454.5 53.5 55.0Delta SPF in-vitro pre irradiation ------ 2.1 0.5UVA-PF post irradiation 16.1011.40 18.40 13.60Delta UVA-PF post irradiation ------ 2.3 2.2critical wavelength post irradiation nm 380.0378.0 380.0 378.0
[0403] Results: As can be retrieved from Table 3, the sunscreen formulation C shows a SPF boosting and UVA boosting with the addition of the MAA-20 in an amount of 1.0 % by weight in comparison to the sunscreen formulation A without the addition of the mycosporine-like amino acid compound. The formulation D also shows UVA boosting with the addition of the MAA-20 in an amount of 1.0 % by weight in comparison to the sunscreen formulation B without the addition of the mycosporine-like amino acid compound.
[0404] Hence, as demonstrated by the above test samples, the addition of MAA-20 leads to an improvement of the SPF and / or of the UVA-PF in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising a classic organic UV-filter composition.
[0405] Example 3 – Determination of the in-vitro SPFs and UVA-PF
[0406] The SPF boosting and UVA-PF boosting test is carried out as in-vitro determination of SPFs.
[0407] Principle: The formulation to be tested (emulsion, solution) is weighed on PMMA plates with the help of an analytical balance. The formulation if distributed and incorporated on the plate using a method corresponding to the formulation. The thus230135 prepared plates are then measured on a Labsphere device and the results are calculated as SPF with a suitable software.
[0408] 1. Sample preparation:
[0409] PMMA plates (Polymethylmethacrylate), measuring 3 cm x 8.5 cm (WW5 plates based on ISOethA 24443:2012 “Determination of UVA photoprotection in vitro” with 5 µ roughness by Schönberg GmbH & Co. AG) are used to perform an SPF measurement.
[0410] 1.1 Preparation of reference samples:
[0411] A reference sample is obtained by distributing 25 to 28 mg glycerin (99.5 %) with the index finger on the roughened side of the PMMA plate. The glycerin film must be very thin and uniform. Subsequently, this plate is stored for at least 2 hours.
[0412] The reference plate is measured with the following transmission values: 290 nm > 60 % transmission; 300 nm > 69 % transmission; and 320 nm > 82 % transmission.
[0413] 1.2 Application of the sample to be measured:
[0414] The sample to be measured should be homogeneously mixed with a spatula before application.1.2 mg / cm2 of sample is evenly distributed in several rows of dots on the PMMA plate. In order to minimize the evaporation of the sample during weighing, this process must be carried out quickly. The sample is then evenly distributed by hand with a finger previously saturated with the sample material. The distribution takes place in two phases: Phase 1: Fast and uniform distribution with a slight pressure until the emulsion is broken.230135 Phase 2: The sample is massaged into the rough surface with strong pressure and the process should last 30 seconds. In this context under strong pressure means that when massaged on a scale, this indicates at least 200 m.
[0415] Exceptions:
[0416] Sun oils: The product quantity is generally 1.3 mg / cm². For strongly spreading oils, less product is applied, as the amount of oil cannot be "absorbed" from the plate. Then the amount of application should be reduced to 1.0-0.75 mg / cm². Application method here is also the 30 s fast / light and 30 s strong method".
[0417] Sun sprays: The "30 / 30 method" applies here (especially for thicker sprays). For very liquid sprays (similar to water): Fast and uniform distribution with a slight pressure, until the emulsion "breaks". The process should take 45 s.
[0418] The finished sample plates are stored dust-free and measured at the earliest after 15 minutes.
[0419] 2. Measurement on the Labsphere:
[0420] The samples are measured using the UV-200S device, using the specified Colipa method. The Labsphere user manual also applies.
[0421] 2.1 Basic settings in the software:
[0422] A new "Study" is opened via file and then the "Colipa Guideline 2011" method is selected under the heading "Study". In the new window "Colipa Method Options" the number of plates (3 plates), the measuring points per plate (5 measuring points) and the230135 in vivo SPF and, if necessary, the irradiance intensity of the external irradiance device (Solar Simulator Irradiance) entered.
[0423] The irradiance set on the external device is 765 W / m2 as standard. The complete naming of the sample is done via Study", "Study Information".
[0424] 2.2 Sample measurement:
[0425] At the beginning of the measurement, a blank value of the glycerin reference sample is measured ("scan blank plate"). In order to determine the SPF of a sample, a total of 15 measuring points (3 plates of 5 measuring points) are then created ("Scan Location"). The already scanned plates and measuring points are checked in the upper right window, while the absorbance of the currently measured plate is displayed in the middle window.
[0426] With irradiation: After the first measurement run, the device calculates an irradiation dose (Irradiation Dose / J / cm2) and the duration (exposure time) for each plate. The plates are irradiated in the external irradiation device (irradiation duration = average value of the 3 plates).
[0427] The calculation of irradiation dose and exposure time is based on the irradiance (765 W / m2) set on the external device.
[0428] Without irradiation: If no irradiation device is available or irradiation is not desired, the first plate is started again after completion of the 15 individual scans and the measurements are repeated (Background: Without the second measurement, no UVA / UVB balance calculation is performed by the software.)230135
[0429] After completion of the measurements, the "Study" is recorded and the data can be printed / exported as a "Report".
[0430] Example 3.1: O / W ZnO emulsion:
[0431] The formulation samples A and B as specified in the following Table 4 were prepared as follows:
[0432] Phase A: The ingredients of phase A were heated to 85 °C in order to dissolve the ingredients.
[0433] Phase A: The pigments were dissolved in the ingredients of phase B while stirring and homogenized (Ultra Turrax® T25: 10,000 rpm / 10 min). At the end of the homogenization the Keltrol® is added and dispersed.
[0434] Phase B: The ingredients of phase B were mixed and dissolved while stirring. The water phase will be cloudy in combination with the sodium hydroxide solution. Afterwards, the water phase B is heated to 80 °C. Afterwards, the hot phase B was added to the hot phase A and homogenized (Ultra Turrax® T25: 13,000 rpm / 3 min). Finally, the mixture was cooled down to ambient temperature while stirring. Subsequent, the mixture was homogenized for a short time (Ultra Turrax® T25: 13,000rpm / 1,5 min).
[0435] The results of the in vitro SPFs determination are presented in Table 4.230135
[0436] Table 4: Phase Ingredient INCI A B % w / w % w / w A Sisterna® PS750-C Sucrose Palmitate 3.50 3.50 Sisterna® SP10-C Sucrose Polystearate 1.00 1.00 Cutina® GMS V Glyceryl Stearate 1.25 1.25 Vitamin E Acetate Tococpheryl Acetate 0.50 0.50 Neutral Oil Caprylic / Capric Triglyceride 5.00 5.00 SymMollient® PDCC Propanediol / Dicaprylate / Caprate 7.00 7.00 PCL-Liquid® 100 Cetearyl Ethylhexanoate 8.00 8.00 Dispersum DSP- OL 100 Polyhydroxystearic Acid 1.00 1.00Neo Heliopan ZnO® 40 Zinc Oxide 23.68 23.68 Triethoxycaprylylsilane (nano) Neo Heliopan ZnO® 300 Zinc Oxide 2.55 2.55 Triethoxycaprylylsilane (non nano) Keltrol® CG - V Xanthan Gum 0.25 0.25B Water dem. Aqua 41.22 40.17 Glycerin 99,5% Glycerin 3.00 3.00 MAA-20--- 1.00Amisoft® HS-11P Sodium Steaoryl Glutamate 0.20 0.20 Sodium Gluconate Sodium Gluconate 0.20 0.20 PHENOXYETHANOL, SymOcide® PH HYDROXYACETOPHENONE, 1.50 1.50 CAPRYLYL GLYCOL, AQUA NaOH solution 10% aq. Aqua, Sodium Hydroxide 0.15 0.20Sum100.00 100.00colourwhite whitepH value (23°C)7.3 7.2Viscosity : cp Brookfield DVIII 2149 1113 CP51 / 10RPM / 20°C in vitro SPF pre 42.8 5.,0 irradiation UVA PF post 14.66 14.82 irradiation critical wavelengh 373 374
[0437] Results: As can be seen from Table 4, the in vitro SPF is highly improved by the combination of the formulation with the mycosporine-like amino acid compound MAA. The control example containing no mycosporine-like amino acid compound exhibited an SPF230135 of 42.8. The addition of MAA-20 in an amount of 1.0 % by weight however results in an in vitro SPF of 51.0 which is 19.2 % higher than the in vitro SPF of the reference sample, i.e. the control example without the addition of the mycosporine-like amino acid compound.
[0438] Furthermore, the addition of MAA-20 in an amount of 1.0 % result in an improvement of the UVA-PF of 0.16 compared to the control sample, i.e. containing none mycosporine-like amino acid compound.
[0439] The addition of MAA-20 also increases the broad-spectrum protection from a critical wavelength of 373 nm to 374 nm.
[0440] Hence, the addition of MAA-20 leads to an improvement of the SPF as well as of the UVA-PF in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an inorganic UV-filter in the form of an oil-in-water emulsion.
[0441] Example 3.2: W / O ZnO emulsion: The formulation samples A to E as specified in the following Table 6 and the formulation samples A and B as specified in the following Table 7 were prepared as follows:
[0442] Phase A: The ingredients of phase A were heated to 85 °C without pigment in order to dissolve the ingredients.
[0443] Phase A: The pigments in the oil phase were dissolved while stirring and homogenized (Ultra Turrax® T25: 10,000rpm / 10 min).
[0444] Phase B: The ingredients of phase B were mixed and dissolved while stirring. The water phase will be cloudy in combination with the sodium hydroxide solution. Afterwards, the water phase B is heated to 80 °C. Afterwards, the hot phase B was added230135 to the hot phase A and homogenized (Ultra Turrax® T25: 13,000rpm / 3 min). Finally, the mixture was cooled down to ambient temperature while stirring. Subsequent, the mixture was homogenized for a short time (Ultra Turrax® T25: 13,000rpm / 1,5 min).
[0445] The results of the in vitro SPFs determination are presented in Table 5.
[0446] Table 5:230135Phase Name INCI AB % w / w % w / w A Polyglyceryl-2 Dehymuls® PGPH Dipolyhydroxystearate 5.00 5.00 Monomuls® 90-O 18 Glyceryl Oleate 3.00 3.00 SymMollient® PDCC Propanediol Dicaprylate / Caprate 7.00 7.00 Neutral Oil Caprylic / Capric Triglyceride 5.00 5.00 PCL Liquid® 100 Cetearyl Ethylhexanoate 8.00 8.00 Tocopherol Acetate Tocopherol Acetate 0.50 0.50 Dispersum DSP OL 100 Polyhydroxystearic Acid 1.00 1.00 Thixcin R PC Trihydroxystearin 0.50 0.50 Neo Heliopan® ZnO Zinc Oxide , Triethoxycaprylylsilane 40 (nano) 23.68 23.68 Neo Heliopan® ZnO Zinc Oxide, Triethoxycaprylylsilane 300 (non nano) 2.55 2.55BWater dem Aqua 38.27 37.17 Glycerin 99,5% Glycerine 3.00 3.00 MAA-20 --- 1.00 Magnesium Sulphat Heptahydrat Magnesium Sulphat Heptahydrat 0.80 0.80 Sodium Gluconate Sodium Gluconate 0.10 0.10 PHENOXYETHANOL, SymOcide® PH HYDROXYACETOPHENONE, 1.50 1.50 CAPRYLYL GLYCOL, AQUA NaOH 10% aq.Aqua, Sodium Hydroxide 0.10 0.20Sum 100.00 100.00 pH value water phase (23°C) 7.2 7.2 Viscosity: cp (Brookfield DVIII CP51 / 10RPM / 20°C3997 2542SPF in-vitro pre irradiation24.6 29.5UVA-PF post irradiation14.39 14.21critical wavelength post irradiation nm372 372230135
[0447] Results: As can be seen from Table 5, the in vitro SPF is highly improved by the combination of the formulation with the mycosporine-like amino acid compound MAA-20. The control example containing no mycosporine-like amino acid compound exhibited an SPF of 24.6. The addition of MAA-20 in an amount of 1.0 % by weight however results in an in vitro SPF of 29.5 which is 19.9 % higher than the in vitro SPF of the reference sample, i.e. the control example without the addition of the mycosporine-like amino acid compound.
[0448] Hence, the addition of MAA-20 leads to an improvement of the SPF in a sunscreen product, cosmetic or pharmaceutical preparation or homecare product comprising an inorganic UV-filter in the form of a water-in-oil emulsion.
[0449] Example 4 – Antimicrobial boosting effect
[0450] The Minimum Inhibitory Concentration (MIC) test is a test on growth inhibition. The estimation of MICs is executed in 96 well plates. Through the comparison of bacterial growth with positive and negative controls via optical density (OD), different concentrations of given test substances are evaluated.
[0451] Bacteria were cultivated under adjusted conditions based on information of the German Collection of Microorganisms and Cell Cultures (DSMZ) and stored in 10 % or 50 % glycerol prior to use. Afterwards, the following method was applied: Growth medium (according to microorganism) was added to each well of the microplate. Then, test- substances solved in DMSO, and strain specific benchmarks were added. Additionally, positive controls (water controls only with medium) and solvent controls (DMSO controls only with medium) were performed. Finally, the microorganisms were added in a concentration of 1 to 6 x 106CFU / ml (CFU = colony forming units). The incubation of the microplates was carried out at appropriate conditions.
[0452] According to the resulting growth, substance concentrations are labelled either as inhibiting or not and MIC is defined as the lowest concentration where a complete growth inhibition is visible. Experiments at concentration limits (highest concentration230135 labelled as growth and lowest concentration labelled as inhibiting) are performed at least twice.
[0453] Tested concentrations were adjusted to performance of test substance, but in general: 5,000 ppm steps between 50,000 ppm and 10,000 ppm, and 2500 ppm steps below 10,000 ppm, finishing with 1000 ppm. To enhance resolution of the approach, additional intermediate steps were included in individual cases. For P. aeruginosa and A. brasiliensis, a maximum concentration of 25,000 ppm was applied as at this point the DMSO concentration itself showed inhibition. For ethylhexylglycerin and 1,2- pentanediol, pure substance without DMSO was tested.
[0454] To verify that the tested combinations act synergistically against microorganisms, corresponding experiments were conducted with Staphylococcus aureus, Candida albicans, Aspergillus brasiliensis, Pseudomonas aeruginosa and Escherichia coli. The synergistic activities of MAA-20 and different antimicrobial compounds in a mixture of 50 % and 50 % were determined by measuring the MIC of the mixture.
[0455] In order to calculate the synergy index with MIC values, the Kull equation was used as follows: SI = (MICmixture x PA) / MICA + (MICmixture x PB) / MICB wherein SI is the Synergy Index according to Kull MICA is the MIC value for Substance A MICB is the MIC value for Substance B MICmixture is the MIC value for the mixture of substances A and B PA is the proportion of the substance A in the mixture PB is the proportion of the substance B in the mixture A Synergy Index (SI) with a value lower than 1 indicates a synergistic effect of the mixture that has been tested. Values higher than 1 indicate the absence of a synergistic effect.230135 For mixtures for which no MIC value has been determined, the calculation of an SI is not applicable (marked as n.a. in the following tables).
[0456] Example 4.1: MIC values and synergy indices of MAA-20 in combination with either 4-hydroxyacetophenone, 1,2-pentanediol and ethylhexylglycerin against Staphylococcus aureus, Candida albicans, Aspergillus brasiliensis, Pseudomonas aeruginosa and Escherichia coli
[0457] The synergistic activity of MAA-20 in combination with different antimicrobial compounds was determined by measuring the Minimum Inhibitory Concentrations (MIC) according to the method as described above.
[0458] Table 6: MIC in ppm Staphylo- Pseudo- Escheri- Test substances Candida Aspergillus coccus monas chia albicans brasiliensis aureus aeruginosa coli MAA-20 > 25,000 > 25,000 > 30,000 > 30,000 15,000 4-Hydroxy- acetophenone5,000 6,000 2,500 4,000 2,500MAA-20 and 4-Hydroxy- 7,500 7,500 5,000 5,000 5,000 acetophenone (mixture 50 : 50) Synergy Index [SI=(MICmix X PA) / MICA + (MICmix X PB) / MICB] 0.90 0.78 1.08 0.71 1.10 Test substances MIC in ppm Staphylo- Escheri- Candida Aspergillus Pseudomonas coccus chia albicans brasiliensis aeruginosa aureus coli MAA-20 > 25,000 > 25,000 > 30,000 > 30,000 15,000 1,2-Pentanediol 35,000 12,500 17,500 30,000 15,000 MAA-20 and 1,2-pentanediol > 25,000 > 25,000 > 30,000 > 15,000 17,500 (mixture 50 : 50)230135 Synergy Index [SI=(MICmix X PA) / MICA + (MICmix X PB) / MICB] n.a. n.a. n.a. n.a. 0.93 Test substances MIC in ppm Staphylo...
Claims
230135 Claims 1. A compound, represented by the general formula (I)formula (I), wherein - Z is selected from the group consisting of O-R2’ and amide’; - R1’ is selected from the group consisting of CH2, unsubstituted or substituted CH(alkyl), and unsubstituted or substituted C(alkyl)2; - R2’ is H; - amide’ is NH2 or N(alkyl)2; - R3’ is selected from the group consisting of H, OH, halogen, and unsubstituted or substituted alkyl; - the substituents R4’, R5’ and R6’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, -S(=O)2OH, and sulfonyl; or a tautomer or a stereoisomer or a salt of the afore-mentioned compounds; or any mixture of the afore-mentioned compounds.
2. The compound according to claim 1, wherein the compound is represented by the general formula (II)230135formula (II), wherein R1’, R3’, R4’, R5’ and R6’ have the same meaning as defined for the general formula (I) in claim 1; or a tautomer or a stereoisomer or a salt of the afore-mentioned compounds; or wherein the compound is represented by the general formula (III)formula (III), wherein R1’, amide’, R3’, R4’, R5’ and R6’ have the same meaning as defined for the general formula (I) in claim 1; or a tautomer or a stereoisomer or a salt of the afore-mentioned compounds; or any mixture of the afore-mentioned compounds.
3. The compound according to claim 1 or claim 2, wherein in the general formula (I) - Z is -O-R2’ or amide’; and / or230135 - R1’ is selected from the group consisting of CH2 and C(methyl)2; and / or - R2’ is H; or - amide’ is NH2 or N(alkyl)2; and / or - R3’ is selected from the group consisting of H, OH, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl; and / or - the substituents R4’, R5’ and R6’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, -S(=O)2OH, and sulfonyl; wherein the alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl; or a tautomer or a stereoisomer or a salt of the afore-mentioned compounds; or any mixture of the afore-mentioned compounds. or wherein in the general formulae (II) or (III) - R1’ is selected from the group consisting of CH2 and C(methyl)2; and / or - R2’ H; or - amide’ is NH2 or N(alkyl)2; and / or - R3’ is selected from the group consisting of H, OH, halogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl; and / or - the substituents R4’, R5’ and R6’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, and unsubstituted or substituted alkoxy, -S(=O)2OH, and sulfonyl; wherein the alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl; or a tautomer or a stereoisomer or a salt of the afore-mentioned compounds; or any mixture of the afore-mentioned compounds.230135 4. The compound according to any one of claims 1 to 3, wherein in the general formulae (I) to (III) n is 1.
5. The compound according to any one of claims 1 to 4, wherein in the general formulae (I) to (III) the substituents R4’, R5’ and R6’ which may be identical or different, are independently from each other selected from the group consisting of H, OH, alkyl, preferably methyl, ethyl, propyl, iso-propyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl, or O-butyl, -S(=O)2OH, and sulfonyl.
6. The compound according to any one of claims 1 to 5, wherein in the general formulae (I) to (III) the substituted phenyl bonded to the imino functionality is selected from the group consisting of ,wherein the dotted line designates the binding site.
7. The compound according to any one of claims 1 to 6, wherein in the general formulae (I), (II) and (III), the substituents R4’, R5’, R6’, which may be identical or different, are independently from each other selected from the group consisting of H, OH, alkyl, preferably methyl, ethyl, propyl, iso-propyl, butyl, isobutyl or tert-butyl, and alkoxy, preferably O-methyl, O-ethyl or O-butyl; with the proviso, that if the substituted phenyl ring is monosubstituted, the substituent is either in the ortho or meta-position to the imino-functionality of the general formulae (I), (II) and (III).230135 8. The compound according to any one of claims 1 to 7, wherein the compound is selected from the group consisting of Com- Structure INCI / chemical name pound MAA-20 2-[(5,5-dimethyl-3-phenylimino- cyclohexen-1-yl)amino]acetic acid MAA-21 2-[(3-phenyliminocyclohexen-1- yl)amino]acetic acid MAA-22 2,5,5-trimethyl-3- (phenylimino)cyclohex-1-en-1-yl- glycine230135 MAA-23 2-[(2-methyl-3-phenylimino- cyclohexen-1-yl)amino]acetic acid MAA-24 3-((3,4-dimethoxyphenyl)imino)- 5,5-dimethylcyclohex-1-en-1-yl- glycine MAA-25 3-((3,4- dimethoxyphenyl)imino)cyclohex- 1-en-1-yl-glycine MAA-26 3-((3,4-dimethoxyphenyl)imino)- 2,5,5-trimethylcyclohex-1-en-1-yl- glycine230135 MAA-27 2-[(3-(3,4-dimethoxyphenyl)imino- 2-methyl-cyclohexen-1- yl)amino]acetic acid MAA-28 2-[(5,5-dimethyl-3-(4- sulfophenyl)imino-cyclohexen-1- yl)amino]acetic acid MAA-29 2-[(3-(4- sulfophenyl)iminocyclohexen-1- yl)amino]acetic acid MAA-30 2,5,5-trimethyl-3-((4- sulfophenyl)imino)cyclohex-1-en- 1-yl-glycine230135 MAA-31 2-methyl-3-((4- sulfophenyl)imino)cyclohex-1-en- 1-yl-glycine MAA-32 2-[(5,5-dimethyl-3-phenylimino- cyclohexen-1-yl)amino]acetamide MAA-33 2-[(3-phenyliminocyclohexen-1- yl)amino]acetamide MAA-34 2-((2,5,5-trimethyl-3- (phenylimino)cyclohex-1-en-1- yl)amino)acetamide230135 MAA-35 2-((2-methyl-3- (phenylimino)cyclohex-1-en-1- yl)amino)acetamide MAA-36 2-((3-((3,4- dimethoxyphenyl)imino)-5,5- dimethylcyclohex-1-en-1- yl)amino)acetamide MAA-37 2-[(3-(3,4- dimethoxyphenyl)iminocyclohexen -1-yl)amino]acetamide MAA-38 2-((3-((3,4- dimethoxyphenyl)imino)-2,5,5- trimethylcyclohex-1-en-1- yl)amino)acetamide230135 MAA-39 2-((3-((3,4- dimethoxyphenyl)imino)-2- methylcyclohex-1-en-1- yl)amino)acetamide or a tautomer or a stereoisomer or a salt of the afore-mentioned compounds; or any mixture of the afore-mentioned compounds.
9. A food, cosmetic or pharmaceutical preparation or homecare product, comprising or consisting of at least one mycosporine-like amino acid compound according to any one of claims 1 to 8.
10. The food, cosmetic or pharmaceutical preparation or homecare product according to claim 9, comprising the mycosporine-like amino acid compound or a mixture thereof in an amount of 0.001 to 15.0 % by weight, particularly 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 composition or product.
11. The food, cosmetic or pharmaceutical preparation or homecare product according to claim 9 or claim 10, further comprising at least one 1,2-alkanediol or one 2,3- alkanediol with 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-alkaediol 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.230135 12. The food, cosmetic or pharmaceutical preparation or homecare product according to any one of claims 9 to 11, 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-cyclohexylpentanol, 3-hydroxypropyl 2-hydroxybenzoate, 4- hydroxyacetophenone, and any mixture thereof.
13. The food, cosmetic or pharmaceutical preparation or homecare product according to any one of claims 9 to 12, further comprising at least one excipient and / or active substance selected from the group consisting of UV-filters, carriers, oil components, rheology additives, hydrotropes, solubilizing agents, powders, film formers, water resistance improving agents, skin moisturizing and / or moisture-retaining substances, lenitive substances, physiological cooling agents, antioxidants, agents against ageing of the skin, matrix-metalloproteinase inhibitors (MMPI), anti- inflammatory agents, TRPV1 antagonists, emulsifiers, antimicrobial agents, preservatives, antibacterial or antimycotic active substances, chelating agents, surfactants, fragrances / aroma or perfume oils, and any mixture of two or more of the afore-mentioned substances.
14. The food, cosmetic or pharmaceutical preparation or homecare product according to any one of claims 9 to 13 in the form of a (i) dispersion, preferably wherein the cosmetic or pharmaceutical preparation is in the form of an emulsion, in particular a O / W emulsion, a W / O emulsion, a multiple emulsion, a hydrodispersion gel, a balm, a multiple emulsion of the water-in-oil type (W / O / W) or of the oil-in-water type (O / W / O), a PIT emulsion, a Pickering emulsion, a micro-emulsion, a liquid, a lotion, a suspension, a milk, an ointment, a paste, a gel, a cream based, an oil based or a liposome-based formulation or an aerosol, in particular foams and sprays, including all types of silicon based emulsions;230135 (ii) a liquid surfactant formulation; (iii) a solid surfactant formulation; (iv) a water free formulation; or (v) an aqueous or an aqueous / alcoholic, in particular aqueous / ethanolic, or an aqueous / glycolic, or an alcoholic / glycolic, in particular ethanolic / glycolic, solution.
15. The food, cosmetic or pharmaceutical preparation or homecare product according to any one of claims 9 to 14 as a food, a cosmetic, for personal care, in particular for skin care, skin protection, sun care, scalp protection, scalp care, hair care, nail care, as a pharmaceutical, for animal care or for homecare.
16. The cosmetic or pharmaceutical preparation according to claim 15, wherein the cosmetic or pharmaceutical preparation is a sunscreen product.
17. Use of the mycosporine-like amino acid compound according to claims 1 to 8 or a mixture thereof or a formulation comprising at least one mycosporine-like amino acid compound according to claims 1 to 8 - for preparing of food, a cosmetic or pharmaceutical preparation or a homecare product, preferably for the preparation of a sunscreen product; or - for protecting skin, hair, or nail of a human or animal against harmful effect of UV radiations; or - for stabilizing food, a cosmetic or pharmaceutical preparation or a homecare product against degradation through UV radiation; or - for stabilizing a photo-unstable UV filter in a food, a cosmetic or pharmaceutical preparation or a homecare product, preferably in a sunscreen product; or - for improving the SPF and boosting the UVA photoprotection of a food, a cosmetic or pharmaceutical preparation or a homecare product, preferably in a sunscreen product, comprising an organic UV filter and / or an inorganic UV filter; or - for boosting the antimicrobial efficacy of an antimicrobial agent in a food, a cosmetic or pharmaceutical preparations or homecare products; or230135 - for stabilizing a fragrance or aroma / flavour compound, preferably a fragrance or aroma / flavour composition in a food, a cosmetic or pharmaceutical preparation or a homecare product; or - for boosting the antioxidative effect of an antioxidant in a food, a cosmetic or pharmaceutical preparation or a homecare product.