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CN119604267A - Compositions with improved SPF and UVA photoprotection - Google Patents

Compositions with improved SPF and UVA photoprotection Download PDF

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Publication number
CN119604267A
CN119604267A CN202380054705.9A CN202380054705A CN119604267A CN 119604267 A CN119604267 A CN 119604267A CN 202380054705 A CN202380054705 A CN 202380054705A CN 119604267 A CN119604267 A CN 119604267A
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China
Prior art keywords
substituted
unsubstituted
methyl
alkyl
group
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CN202380054705.9A
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Chinese (zh)
Inventor
约根·克劳斯
埃夫·聚斯
伊姆克·迈耶
尼古拉斯·布格丹
萨比娜·兰格
卡罗琳·海因
丹尼尔·贝恩特
卢卡斯·沙夫
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Symrise AG
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Symrise AG
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Priority claimed from PCT/EP2022/072097 external-priority patent/WO2024027928A1/en
Priority claimed from PCT/EP2023/071719 external-priority patent/WO2025031562A1/en
Application filed by Symrise AG filed Critical Symrise AG
Publication of CN119604267A publication Critical patent/CN119604267A/en
Pending legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02Preparations containing skin colorants, e.g. pigments

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)

Abstract

The present invention relates to a sunscreen product, cosmetic or pharmaceutical formulation or home care product with UVA and/or UVB protection comprising an inorganic UV filter and certain retinoid amino acid compounds. The products and formulations provide improved SPF performance and UVA photoprotection. Furthermore, the products and formulations according to the invention provide broad spectrum photoprotection against UV radiation. Furthermore, the present invention relates to the use of such a retinoid amino acid compound for promoting SPF and/or UVA photoprotection of a sunscreen product, a cosmetic or pharmaceutical formulation or a home care product comprising an inorganic UV filter. Furthermore, the present invention relates to a method for enhancing the SPF and/or UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising an inorganic UV filter by adding a certain class of bacteriocin amino acid compounds. Finally, the present invention relates to a method for providing anti-aging benefits to skin, whitening skin or preventing skin darkening, improving skin appearance, reducing visible signs of skin aging and improving the shine and firmness of skin by topically applying a sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention to skin.

Description

Compositions with improved SPF and UVA photoprotection
Technical Field
The present invention relates to a sunscreen product, cosmetic or pharmaceutical formulation or home care product with UVA and/or UVB protection comprising an inorganic UV filter and certain retinoid amino acid compounds. The products and formulations provide improved SPF performance and UVA photoprotection. Furthermore, the products and formulations according to the invention provide broad spectrum photoprotection against UV radiation. In addition, the present invention relates to the use of such a retinoid amino acid compound for promoting SPF and UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising an inorganic UV filter. Furthermore, the present invention relates to a method for enhancing the SPF and UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising an inorganic UV filter by adding a certain class of bacteriocin amino acid compounds. Finally, the present invention relates to a method for providing anti-aging benefits to skin, whitening skin or preventing skin darkening, improving skin appearance, reducing visible signs of skin aging and improving the shine and firmness of skin by topically applying a sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention to skin.
Background
The negative effects of exposure to UV light are well known. Prolonged exposure to sunlight can cause damage such as sunburn to the skin and cause the hair to dry out and become brittle. When skin is exposed to UV rays having a wavelength of 290nm to 400nm, long-term damage may lead to serious conditions, such as skin cancer, the type of damage being dependent on the wavelength of the radiation.
Sunlight includes two types of UV radiation, long-wave ultraviolet a (UVA: wavelength 320nm to 400 nm) and short-wave ultraviolet B (UVB: wavelength 280nm to 320 nm). UVA is further divided into two wavelength ranges, UVA1 (340 nm to 400 nm) and UVA2 (320 nm to 340 nm).
UVA rays account for the majority (95%) of UV radiation. They have longer wavelengths than UVB and UVC rays, which means that they have less energy (shorter wavelengths have more energy than longer wavelengths). Because of their longer wavelength, they can penetrate into the dermis, which is composed mainly of collagen. When UVA rays are absorbed by the skin, they generate free radicals that can damage cells and DNA and break down collagen. This is why UVA radiation is highly associated with premature ageing. Skin damage caused by UVA radiation accelerates the appearance of aging, such as loss of skin elasticity and appearance of wrinkles. This process is commonly referred to as photoaging. As the skin ages, the outer skin layer (epidermis) becomes thinner, even though the number of cells remains largely unchanged. However, the number of pigment-containing cells (melanocytes) is reduced. Thus, the skin looks pale and translucent. Large pigment spots (age spots, liver spots or freckles) may occur in areas exposed to the sun. The change in connective tissue reduces the strength and elasticity of the skin, which becomes more pronounced in areas exposed to the sun (solar elastosis). Elastosis creates a leather-like, saturated wind cream appearance common to farmers and water craft who spend a significant amount of time outdoors. Furthermore, UVA radiation can trigger phototoxic or photosensitizing skin reactions.
UVB rays account for less than 5% of UV radiation and, due to their shorter wavelength, only penetrate the epidermis. Here, they are taken up directly by DNA and melamine and can cause genetic mutations that, if not corrected by the natural defenses of the cell, can lead to rapid proliferation of the mutated cells and ultimately to skin cancer. The damage caused by UVB radiation can be seen almost immediately in the form of sunburn, which is an inflammatory response to skin damage.
So far, UVC radiation is the most damaging of the three types of UV radiation. However, due to their short wavelength they are fully absorbed by the atmosphere and therefore cannot reach our skin.
In order to attenuate these negative effects of UV radiation, i.e. for the purpose of protecting the skin and keratin materials from UV radiation, anti-sun/sunscreen compositions comprising a screening agent active in the UVA range and in the UVB range (i.e. in the whole range from 280nm to 400 nm) are generally used.
UV filters are compounds that have a significant absorption capacity for ultraviolet radiation. They are used in particular in sunscreen products, cosmetics, dermatological and pharmacological preparations or sunscreen products, but also for improving the light resistance of industrial products, such as paints, varnishes, plastics, textiles, polymers, such as, for example, polymers and copolymers of mono-and diolefins, polystyrene, polyurethane, polyamide, polyester, polyurea and polycarbonate, packaging materials and rubber.
UV filters are classified into UVA filters and UVB filters according to the location of their maximum absorption, and if they absorb both UVA and UVB, they are referred to as UVA/UVB broadband absorbers or UVA/UVB broadband filters.
To obtain the desired maximum protection against UV radiation, sunscreen products or cosmetic, in particular dermatological and pharmacological preparations, are formulated to contain mixtures with different concentrations of UV filters, and the choice of UV filter used is determined by regulations in the national or economic sector. For example, UV filters useful for skin protection are managed in the united states by the FDA via its OTC monograph system and in the european union by cosmetic regulations. Other countries and regions also have regulations regarding the use of UV filters. These regulations not only define the filters that can be used, but also determine the maximum usage level of each UV filter.
To achieve broad spectrum UV protection, sunscreen formulations typically comprise a combination of several organic UV filters, which may be supplemented with inorganic UV filters in order to increase efficacy.
However, the use of organic UV filters is of increasing interest as they are suspected to be a possible cause of skin irritation and allergy to sensitive people and their potentially harmful effects on the environment. Furthermore, some organic UV filters suffer from photo-instability.
In contrast, inorganic UV filters are photostable and give broader spectral protection over UVA and UVB. Inorganic UV filters are also known to cause less skin irritation. However, one of the major drawbacks of inorganic UV filters is that they may lead to a "whitening" effect on the skin, which is less appreciated by consumers from an aesthetic point of view. Another problem with inorganic UV filters is that they are typically used in the form of nano-sized pigments in order to provide an effective light shielding capability in the UV region while maintaining a high transparency in the visible region. The smaller size of these mineral particles increases the user's acceptability with their cosmetics because they are less visible after application. On the other hand, such nanoscale pigments tend to be less effective in UV shielding.
The number of known UVA filters and particularly approved UVA filters is small and thus the product is limited in the way that UVA filters can be used to provide broad spectrum protection.
Thus, there remains a continuing need to provide additional materials that improve the SPF performance and UVA photoprotection of sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters.
It is therefore an object of the present invention to provide inorganic UV filters comprising sunscreen products, cosmetic or pharmaceutical formulations or home care products with UVA and/or UVB protection, which exhibit improved SPF performance as well as improved UVA photoprotection. It is desirable that a sunscreen product, cosmetic or pharmaceutical formulation or home care product provide improved UV filter performance, in particular UVA photoprotection, and thus may allow for a reduction in the amount of inorganic UV filter without affecting the envisaged SPF.
It is another object of the present invention to provide the use of a substance to promote SPF performance and UVA photoprotection in a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising an inorganic UV filter.
It is a further object of the present invention to provide a method of enhancing or promoting SPF performance and UVA photoprotection in a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising an inorganic UV filter.
It is a further object of the present invention to provide a method of providing anti-aging benefits to skin, whitening or preventing skin darkening, improving skin appearance, reducing visible signs of skin aging, and improving the shine and firmness of skin by a sunscreen product or cosmetic or pharmaceutical formulation comprising an inorganic UV filter.
Surprisingly, it has been found that SPF performance and UVA photoprotection in sunscreen products, cosmetic or pharmaceutical formulations or home care products having UVA and/or UVB protection can be significantly improved by the addition of certain classes of mycosporine amino acid compounds.
This problem is solved by the subject matter of the independent claims. Further aspects of the invention are, however, apparent from the wording of the dependent claims, in the following detailed description in connection with the accompanying examples and figures.
Disclosure of Invention
To accomplish the above problems, the present invention provides in a first aspect a sunscreen product or cosmetic or pharmaceutical formulation comprising or consisting of:
(a) At least one inorganic UV filter, and
(B) At least one mycosporine-like amino acid compound,
The at least one mycosporine-like amino acid compound is represented by the general formula (V)
As defined herein, or a tautomer or stereoisomer or salt thereof;
Or (b)
Represented by the general formula (VI)
As defined herein, or a tautomer or stereoisomer or salt thereof;
or any mixture of the above compounds.
In a second aspect, the present invention provides the use of at least one retinoid amino acid compound as defined herein or a mixture thereof (b) for promoting SPF performance and UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising at least one inorganic UV filter.
In a further aspect, the present invention relates to a method of enhancing or promoting SPF performance and UVA photoprotection of a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising at least one inorganic UV filter, the method comprising adding to the sunscreen product, cosmetic or pharmaceutical formulation or home care product an effective amount of a retinoid amino acid compound (b) as defined herein or a mixture thereof.
Finally, the present invention relates to a method of providing anti-aging benefits to skin, whitening or preventing skin darkening, improving skin appearance, reducing visible signs of skin aging and improving the shine and firmness of skin by topically applying a sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention to the skin.
The invention is specified in the appended claims. The invention itself, however, as well as a preferred variant, further objects and advantages thereof, will be apparent from the following detailed description when read in conjunction with the accompanying examples.
Detailed Description
In the context of the present invention, the following general meanings apply:
The terms "comprising" and "including" are to be construed as open-ended terms and mean that named components following the term are necessary, but are not "limited to" these named components, and that other components may be added and still be encompassed by the present invention.
The term "consisting of" as used in accordance with the present invention means that the total amount of components (a) and (b) adds up to 100 wt% based on the total weight of the sunscreen product, cosmetic or pharmaceutical formulation, or home care product, and means that the subject matter is closed and may include only the limitations explicitly set forth.
Whenever "comprising" is mentioned, it is intended to cover two meanings as alternatives, i.e. unless the context clearly indicates otherwise, the meaning may be "comprising" or "consisting of.
The term "optionally" means that the subsequently described compound may be present but need not be present in the composition, and that the description includes variants comprising the compound or variants in which the compound is not present.
The term "or" and/or "is used as a functional word to indicate that two words or phrases are to be taken together or separately.
The endpoints of all ranges directed to the same component or property are inclusive and combinable individually.
The term "compound" or "compound of the invention" refers to all compounds encompassed by structural formula (V) and/or formula (VI) and/or formula (VII) and/or formula (XIII) and/or formula (IX) and/or formula (X) and/or formula (a) and their subformulae disclosed herein, and includes each subgenera and all specific compounds within the formulae of which the structure is disclosed herein.
Compounds may be identified by their chemical structure and/or chemical name. When chemical structures and chemical names conflict, the chemical structures determine the identity of the compounds.
The term "at least one..the..a. Compound" means a food or cosmetic or pharmaceutical formulation according to the invention, in particular a sunscreen product or a home care product, may comprise any one of the individual compounds described subsequently or a mixture of two, three, four, five, six or even more different of the subsequent compounds.
The term "cosmetic or pharmaceutical formulation" in the context of the present invention is a composition for cosmetic or pharmaceutical purposes, which contains a UV filter to protect the skin, hair or nails from UV radiation. In addition to providing photoprotection, the cosmetic or pharmaceutical formulations according to the present invention may also be used to provide anti-aging benefits to the skin, whiten or prevent skin darkening, improve skin appearance, reduce visible signs of skin aging, and improve skin shine and firmness.
The term "sunscreen composition" or "sunscreen agent" or "skin care product" (also referred to as "sun oil", "sunscreen cream" or "sun wash") refers to any topical product that reflects and/or absorbs certain portions of UV radiation, thereby helping to prevent sunburn and, most importantly, skin cancer. Thus, the term "sunscreen composition" is to be understood to include not only 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 modifiers, stabilizers, preservatives, or fragrances). Sunscreens are lotions, sprays, gels, foams (such as expanding foam lotions or whipped emulsions), sticks, powders and other topical products. The UV absorbing compounds are used not only in sunscreens but also in other personal care products such as lipsticks, shampoos, hair gels, body washes, hand soaps and insect repellents.
In the context of the present invention, the term "home care product" is a necessity for home daily care and cleaning. They are used to maintain hygiene and good home atmosphere. Home care products typically include laundry detergents (powders, liquids and tablets), fabric conditioners, dishwashing detergents (liquids and tablets), hard floor and surface cleaners, glass cleaners, carpet cleaners, oven cleaners, air fresheners, disinfectants, soil release agents, and car wash products. These products are typically manufactured in the form of liquids, powders, sprays, granules, and the like. Such sunscreen-containing formulations prevent premature photodamage and photobleaching to the surface and to the home care formulation itself.
The sunscreen products, cosmetic or pharmaceutical formulations or home care products of the present invention provide enhanced SPF performance and UVA photoprotection, as well as broad spectrum photoprotection from UV radiation.
As used herein, the term "photostabilizer" is a compound suitable for protecting body care and household cleaners and treatments from photodegradation.
The term "photostability" refers to the ability of a UV filter or any other molecule to remain stable under radiation when exposed to sunlight. In particular, this means that the compound does not undergo degradation processes under UV radiation.
The Sun Protection Factor (SPF) indicates the ability of a sunscreen, cosmetic or pharmaceutical formulation, or home care product to prevent UVB radiation, but does not adequately specify the extent, if any, of protection of the sunscreen composition from UVA radiation. SPF is a measure of the amount of solar energy (UV radiation) required to produce sunburn on protected skin (i.e., in the presence of a sunscreen) relative to the amount of solar energy required to produce sunburn on unprotected skin. As the SPF value increases, the protection against sunburn increases. The skin was irradiated with an artificial UV source with and without sunscreens until erythema was present (minimum erythema dose-MED). The SPF is then calculated by dividing the MED of the protected skin by the MED of the unprotected skin, i.e. how long it takes for the skin to sun burn with and without the sunscreen. Theoretically, this means that a sunscreen with an SPF of 50 means that it can be exposed to UV radiation for a 50-fold longer period before sunburn.
UVA photoprotection is expressed as UVA protection factor (UVA-PF). UVA-PF is similar to SPF in that it is a measure of how much a sunscreen protects the skin from UVA radiation. This is done in a similar way by irradiating the skin with UVA. This can be done in vivo with human skin or in vitro by applying the sunscreen to an acrylic or plastic slide and measuring how much UVA passes through the slide with or without the sunscreen. To characterize protection against UVA radiation, a PPD (persistent pigment darkening) method was used, which measures the skin color observed 2 to 4 hours after skin exposure to UVA radiation. The PPD method appears to correlate well with in vitro UVA-PF testing.
The sustained pigment blackout (PPD) based UVA protection factor is designated "UVA PPD PF" and is expressed mathematically by the ratio of the dose of UVA radiation (MPPDp) necessary to reach the pigmentation threshold using a UV screening agent to the dose of UVA radiation (MPPDnp) necessary to reach the pigmentation threshold without using a UV screening agent, as follows:
UVA PPD PF for a sunscreen product, cosmetic or pharmaceutical formulation or home care product is typically at least 4. Properly treated skin with a cosmetic composition having UVA PPD PF of 4 means that it takes about 4 times longer for the skin to darken (i.e., to reach a threshold level of pigment darkening) compared to skin that has not been treated with a sunscreen product, cosmetic or pharmaceutical formulation, or home care product.
The term "broad spectrum photoprotection" means photoprotection against UVA and UVB radiation. The broad spectrum is based on the breadth of protection provided by sunscreens in the UVA and UVB spectra. In order for a sunscreen to be considered broad spectrum, it must reach a critical wavelength of at least 370 nm. The critical wavelength of >370nm is the strict minimum that the sunscreen product should reach that is marked as "broad spectrum".
The term "critical wavelength" is defined as the wavelength at which the area under the UV protection curve (% protection versus wavelength) accounts for 90% of the total area under the curve in the UV region (280 nm-400 nm). For example, a critical wavelength of 370nm indicates that the protection of the sunscreen composition is not limited to the wavelength of UV-B (i.e. a wavelength of 280nm-320 nm), but extends to 370nm such that 90% of the total area under the protection curve in the UV region is reached at 370 nm. The higher the critical wavelength, the better the protection against UV radiation.
To calculate the critical wavelengthThe measured spectral absorption from 290nm to 400nm was mathematically integrated to calculate the area under the absorbance curve. The critical wavelength value is based on the intrinsic shape and width of the absorbance curve, rather than its amplitude. The critical wavelength is the wavelength below which 90% of the area under the absorbance curve lies. The critical wavelength of UVB sunscreens is less than the critical wavelength of sunscreens that prevent both UVB and UVA. Higher critical wavelengths ensure more UV protection, in particular protection from longer wavelength UVA rays. For example, a sunscreen having a critical wavelength of 370nm provides more protection against UVA radiation than a sunscreen having a critical wavelength of 350 nm.
The combination of in vivo SPF rating and critical wavelength provides a complete description of the photoprotective properties of the product.
According to the invention, the main object of the invention is solved by a sunscreen product, a cosmetic, in particular a dermatological or pharmaceutical formulation or a home care product comprising or consisting of:
(a) At least one inorganic UV filter, and
(B) At least one mycosporine-like amino acid compound,
The at least one mycosporine-like amino acid compound is represented by the general formula (V)
Wherein the method comprises the steps of
-Z is selected from the group consisting of O-R2 'or amide';
-R1' is selected from the group consisting of CH 2, unsubstituted or substituted CH (alkyl), unsubstituted or substituted C (alkyl) 2, unsubstituted or substituted CH (cycloalkyl), unsubstituted or substituted CH (aryl), unsubstituted or substituted CH (heterocycloalkyl), unsubstituted or substituted CH (heteroaryl), CR7' R8', c=o, halogen, O, S, SO, SO 2, NH, unsubstituted or substituted N (alkyl), unsubstituted or substituted N (alkenyl), unsubstituted or substituted N (alkynyl), unsubstituted or substituted N (alkoxy), unsubstituted or substituted N (alkylthio), unsubstituted or substituted N (cycloalkyl), unsubstituted or substituted N (aryl), unsubstituted or substituted N (heterocycloalkyl), and unsubstituted or substituted C-spiro;
-R2' is selected from the group consisting of H, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl;
-amide ' is selected from the group consisting of NH 2, unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (alkenyl), unsubstituted or substituted NH (alkynyl), unsubstituted or substituted NH (alkoxy), unsubstituted or substituted NH (alkylthio), unsubstituted or substituted NH (cycloalkyl), unsubstituted or substituted NH (aryl), unsubstituted or substituted NH (heterocycloalkyl), unsubstituted or substituted NH (heteroaryl) and unsubstituted or substituted NR9' R10', unsubstituted or substituted-N (O-alkyl) (Weinreb amide), -N (OH) (H) (hydroxamic acid) and unsubstituted or substituted-N (OH) (alkyl) (alkylated hydroxamic acid);
-R3 'is selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C (=o) -, -CH 2-OH、-R-CH2 -OH, -C (=o) -O-Y, -R-C (=o) -O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO 2、NH2, unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (cycloalkyl), unsubstituted or substituted NH (aryl), unsubstituted or substituted NH (heterocycloalkyl), unsubstituted or substituted NH (heteroaryl), unsubstituted or substituted NR9' and unsubstituted spiro ring of R10;
-substituents R4', R5' and R6', which can be identical or different, are independently of each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C (=o) -, -CH 2-OH、-R-CH2 -OH, -C (=o) -O-Y, -R-C (=o) -O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO 2、-S(=O)2 OH, sulfonyl, NH 2, unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (alkenyl), unsubstituted or substituted NH (alkynyl), unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (alkoxy), unsubstituted or substituted cycloalkyl, unsubstituted or substituted heteroaryl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl
-A substituted or substituted NR9'R10' and an unsubstituted or substituted C-spiro ring, -R7 'and R8', which can be the same or different, are independently selected from the group consisting of:
H. OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted NH (alkynyl), unsubstituted or substituted alkanoyl/acyl R-C (=o) -, -CH 2-OH、-R-CH2 -OH, -C (=o) -O-Y, -R-C (=o) -O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO 2、NH2, unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (alkenyl), unsubstituted or substituted NH (alkylthio), unsubstituted or substituted NH (cycloalkyl), unsubstituted or substituted NH (aryl), unsubstituted or substituted heterocycle (R) and unsubstituted or substituted heterocycle (R10';
-R9 'and R10', which can be the same or different, are independently from each other selected from the group consisting of H, OH, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C (=o) -, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heteroaryl;
y is selected from the group consisting of H and unsubstituted or substituted alkyl, and
-R is unsubstituted or substituted alkyl;
or a tautomer or stereoisomer or salt of the above compound;
Or by the general formula (VI)
Wherein the method comprises the steps of
-R1 "is selected from the group consisting of CH 2, unsubstituted or substituted CH (alkyl), unsubstituted or substituted C (alkyl) 2, unsubstituted or substituted CH (cycloalkyl), unsubstituted or substituted CH (aryl), unsubstituted or substituted CH (heterocycloalkyl), unsubstituted or substituted CH (heteroaryl), -CR7" R8", c=o, halogen, O, S, SO, SO 2, NH, unsubstituted or substituted N (alkyl), unsubstituted or substituted N (alkenyl), unsubstituted or substituted N (alkynyl), unsubstituted or substituted N (alkoxy), unsubstituted or substituted N (alkylthio), unsubstituted or substituted N (cycloalkyl), unsubstituted or substituted N (aryl), unsubstituted or substituted N (heterocycloalkyl), unsubstituted or substituted N (heteroaryl) and unsubstituted or substituted C-spiro;
-R2 "is selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C (=o) -, -CH 2-OH、-R-CH2 -OH-C (=o) -O-Y, -C (=o) -amide", unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO 2、NH2, unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (alkenyl), unsubstituted or substituted NH (alkynyl), unsubstituted or substituted NH (alkylthio), unsubstituted or substituted NH (NH) C (=o) -Y, -C (=o) -amide ", unsubstituted or substituted cycloalkyl, unsubstituted or substituted heteroaryl, unsubstituted or substituted NH (NH) or substituted cycloalkyl, unsubstituted or substituted NH (NH) or substituted heteroaryl, unsubstituted or substituted NH (NH) 10;
-X is selected from the group consisting of CH 2, unsubstituted or substituted CH (alkyl), unsubstituted or substituted CH (alkenyl), unsubstituted or substituted CH (alkynyl), unsubstituted or substituted CH (alkoxy), unsubstituted or substituted CH (alkylthio), unsubstituted or substituted CH (cycloalkyl), unsubstituted or substituted CH (aryl), unsubstituted or substituted CH (heterocycloalkyl), unsubstituted or substituted CH (heteroaryl), -CR7"R8", c= O, O, S, SO, SO 2, NH, unsubstituted or substituted N (alkyl), unsubstituted or substituted N (alkenyl), unsubstituted or substituted N (alkylthio), unsubstituted or substituted N (cycloalkyl), unsubstituted or substituted N (aryl), unsubstituted or substituted N (heterocycloalkyl), unsubstituted or substituted heterocycle, unsubstituted or substituted N (heteroaryl), and unsubstituted or substituted spiro;
-substituents R4", R5" and R6", which can be the same or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C (=o) -, -CH 2-OH、-R-CH2 -OH, -C (=o) -O-Y, -R-C (=o) -O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (alkenyl), unsubstituted or substituted NH (alkynyl), unsubstituted or substituted alkanoyl/acyl R-C (=o) -, -CH 2-OH、-R-CH2 -OH, -C (=o) -O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, SO 2、-S(=O)2 OH, sulfonyl, NH 2, unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (alkenyl), unsubstituted or substituted NH (alkynyl), unsubstituted or substituted NH (alkoxy), unsubstituted or substituted NH (alkyl), unsubstituted or substituted cycloalkyl (NH) and unsubstituted or substituted cycloalkyl (NH) or unsubstituted or substituted NH (NH) 10";
-R7 "and R8", which can be the same or different, are independently from each other selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C (=o) -, -CH 2-OH、-R-CH2 -OH, -C (=o) -O-Y, -R-C (=o) -O-Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO 2、NH2, unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (alkenyl), unsubstituted or substituted NH (alkynyl), unsubstituted or substituted NH (alkoxy), unsubstituted or substituted alkanoyl/acyl R-C (=o) -, -CH 2-OH、-R-CH2 -OH, -C (=o) -O-Y, -R-C (=o) -Y, unsubstituted or substituted cycloalkyl, unsubstituted or substituted heteroaryl, unsubstituted or substituted NH (NH) and unsubstituted or substituted heteroaryl;
The amide "is selected from the group consisting of NH 2, unsubstituted or substituted NH (alkyl), unsubstituted or substituted NH (alkenyl), unsubstituted or substituted NH (alkynyl), unsubstituted or substituted NH (alkoxy), unsubstituted or substituted NH (alkylthio), unsubstituted or substituted NH (cycloalkyl), unsubstituted or substituted NH (aryl), unsubstituted or substituted NH (heterocycloalkyl), unsubstituted or substituted NH (heteroaryl), unsubstituted or substituted NR9" R10", unsubstituted or substituted-N (O-alkyl) (Weinreb amide), -N (OH) (H) (hydroxamic acid) and unsubstituted or substituted-N (OH) (alkyl) (alkylated hydroxamic acid);
-R9 "and R10", which can be the same or different, are independently from each other selected from the group consisting of H, OH, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C (=o) -, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heteroaryl;
y is selected from the group consisting of H and unsubstituted or substituted alkyl, and
-R is unsubstituted or substituted alkyl;
or a tautomer or stereoisomer or salt of the above compound;
or any mixture of the above compounds.
The sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention comprises at least one inorganic UV filter (a) which provides protection against UVA and/or UVB radiation.
UV filters are compounds or mixtures of compounds that block or absorb Ultraviolet (UV) light. UV classification includes UVA (320 nm to 400 nm), UVB (290 nm to 320 nm) and UVC (200 nm to 280 nm). The UV absorbing compounds are used not only in sunscreens but also in other personal care products such as lipsticks, shampoos, hair gels, body washes, hand soaps and insect repellents. Chemical filters prevent UV radiation by absorbing, reflecting or scattering. Reflection and scattering are achieved by inorganic physical UV filters such as titanium dioxide (TiO 2) and zinc oxide (ZnO). Absorption (mainly of UVB) is accomplished by organic UV filters, which are called chemical UV filters. The sunscreen product or cosmetic or pharmaceutical formulation according to the present invention provides broad spectrum photoprotection, i.e. protection against UVA and UVB.
According to the invention, the at least one inorganic UV filter (a) is selected from the group of pigments consisting of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form), zinc oxide (ZnO), iron oxide (Fe 2O3), zirconium oxide (ZrO 2), silicon dioxide (SiO 2), manganese oxide (e.g. MnO), aluminum oxide (Al 2O3), cerium oxide (Ce 2O3), barium carbonate (BaCO 3), calcium carbonate (CaCO 3) and mixtures thereof.
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 dioxide 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 TiO 2 provides better UVB protection.
According to another variant, the at least one inorganic UV filter is in the form of particles having a weight average particle diameter d 50 of 1nm to 1000nm, preferably 3nm to 800nm, more preferably 5nm to 600nm and most preferably 10nm to 400nm.
Inorganic UV filters also encompass nanopigments of untreated or treated metal oxides (average size of primary particles: typically 1nm to 100nm, preferably 3nm to 90nm, more preferably 5nm to 80nm and most preferably 10nm to 70 nm), such as, for example, nanopigments of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase forms), zinc oxide (ZnO), iron oxide (Fe 2O3), zirconium oxide (ZrO 2), silicon dioxide (SiO 2), manganese oxide (e.g., mnO), aluminum oxide (Al 2O3), cerium oxide (Ce 2O3), barium carbonate (BaCO 3), calcium carbonate (CaCO 3) or mixtures thereof.
The treated nanopigments and non-nanopigments are pigments that have been surface treated with one or more of chemical, electronic, mechanochemical and/or mechanical properties with compounds such as amino acids, beeswax, fatty acids, fatty acid esters, fatty alcohols, anionic surfactants, lecithin, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal (titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen or elastin), alkanolamines, silica, metal oxides, sodium hexametaphosphate, alumina or glycerol, hydrated silica, stearic acid, jojoba esters or glutamic acid derivatives.
The treated nanopigments and non-nanopigments may more particularly be titanium oxide treated with silica and alumina, alumina and aluminum stearate, alumina and aluminum laurate, aluminum hydroxide, iron oxide and iron stearate, silica, alumina and silicone, sodium hexametaphosphate, octyltrimethoxysilane, alumina and stearic acid, alumina and glycerol, or alumina and silicone or polyhydroxystearic acid, hydrated silica, jojoba esters, stearoyl glutamic acid, glutamic acid and derivatives, trioxyoctanoyl silane, glycerol, dimethicone hydrodimethicone, dimethicone, or combinations thereof. The other titanium dioxide nanopigments treated with silicone are preferably TiO 2 treated with octyltrimethylsilane, preferably with an average size of the primary particles of 25nm to 40nm, tiO 2 treated with polydimethylsiloxane, preferably with an average size of the primary particles of 21nm, or TiO 2 treated with polydimethylsiloxane, preferably with an average size of the primary particles of 25nm.
The zinc oxide nanopigments and zinc oxide non-nanopigments coated are, for example, znO coated with polymethylhydrosiloxane; A dispersion of ZnO in cyclomethicone/oxyethylenated polydimethylsiloxane comprises 30% or 80% of nano-or non-nano-zinc oxide coated with silicon dioxide and polymethylhydrosiloxane, znO coated with a copolymer of perfluoroalkyl phosphate and based on perfluoroalkyl ethyl as dispersion in cyclopentasiloxane, znO coated with a cross-linked polymer of dimethoxydiphenyl silane triethoxy octyl silane, znO coated with glutamic acid, znO coated with octyl triethoxysilane, znO coated with a silicone grafted acrylic polymer dispersed in cyclomethicone, znO coated with triethoxy octyl silane, znO coated with polyhydroxystearic acid, znO treated with aluminum oxide dispersed in a mixture of ethylhexyl methoxycinnamate/PVP-hexadecene/polymethylsiloxane copolymer, znO coated with silicon dioxide and polymethylsilsesquioxane, znO dispersed in a polycondensate of hydroxystearic acid, or ZnO coated with a mixture of stearoyl, jojoba ester, polyhydroxy polysiloxane, isopropyl titanate, hydrogenated titanium, sodium stearyl silicate, and a cross-linked lactic acid.
Also preferred are particulate UV filters or inorganic pigments, such as oxides of iron (Fe 2O3), zirconium (ZrO 2), silicon (SiO 2), manganese oxide (e.g., mnO), aluminum oxide (Al 2O3), cerium (e.g., ce 2O3), barium carbonate (BaCO 3), calcium carbonate (CaCO 3) or mixtures thereof, which may optionally be hydrophobized.
The previously specified inorganic UV filters are used in sunscreen products, cosmetic or pharmaceutical preparations or home care products as a single component or as a mixture with two, three, four or more of the inorganic UV filters.
Component (b) in the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the first aspect of the invention is at least one mycosporine amino acid compound represented by the general formula (V)
As defined herein;
Or (b)
Represented by the general formula (VI)
As defined herein.
A mycosporine-like amino acid (MAA) is a small secondary metabolite produced by organisms living in a high-insolation environment (usually a marine environment). MAA is an imine derivative of a cephalosporin and comprises an amino-cyclohexene-imine ring linked to an amino acid, an amino alcohol or an amino group. The compound is capable of achieving electron delocalization. In addition, the compounds demonstrate antioxidant qualities.
Unless otherwise indicated, in the context of the present invention, especially for the definition of a retinoid amino acid compound represented by any one of the formulae, the following general meanings apply:
according to the present invention, the term "halogen" residue/moiety or group alone or as part of another substituent means F, cl, br or I.
According to the invention, the term "alkyl" alone or as part of another substituent means a saturated or monounsaturated or polyunsaturated, linear or branched monovalent hydrocarbon radical obtained by removing a hydrogen atom from a single carbon atom of the corresponding parent alkane.
In preferred variants, the term "alkyl" also includes any alkyl moiety in the group derived therefrom, such as an alkoxy, alkylthio, alkylsulfonyl saturated straight chain or branched hydrocarbon group having 1 to 10, 1 to 8, 1 to 6 or 1 to 4 carbon atoms.
If the alkyl group is further bonded to another atom, the group becomes an alkylene or alkylidene group. In other words, the term "alkylene" also refers to a divalent straight or branched chain alkyl group. For example, -CH 2CH3 is ethyl and-CH 2CH2 -is ethylene.
The term "alkylene" alone or as part of another substituent refers to a saturated straight or branched chain divalent hydrocarbon radical obtained by removing two hydrogen atoms from a single carbon atom or two different carbon atoms of the starting alkane.
In a preferred variant according to the 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 from 1 to 6 carbon atoms.
More preferred according to the invention are saturated straight-chain or branched C1 to C6 alkyl groups or saturated straight-chain or branched C1 to C6 alkylene groups.
Most preferred are straight or branched alkyl or alkylene groups having 1 to 4 carbon atoms.
Preferred alkyl radicals/moieties or alkyl groups include, but are not limited to: a C1-C6-alkyl group, including methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, and 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl.
In a preferred variant, the alkyl radicals/moieties are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferably from the group consisting of methyl and ethyl.
The alkyl or alkylene groups as defined above may be further substituted.
The term "alkyl" or "alkylene" also includes groups having any degree of saturation, i.e., groups having only carbon-carbon single bonds ("alkyl" or "alkylene"), groups having one or more carbon-carbon double bonds ("alkenyl"), groups having one or more carbon-carbon triple bonds ("alkynyl"), and groups having mixtures of carbon-carbon single, double, and/or triple bonds.
According to the present invention, the term "alkenyl" alone or as part of another substituent refers to an unsaturated, straight or branched monovalent hydrocarbon radical having at least one carbon-carbon double bond (c=c double bond). The group may be in cis or trans configuration with respect to the double bond. Such that the term "alkenyl" also includes the corresponding cis/trans isomer.
In a preferred variant according to the 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.
In still further preferred variants, the linear or branched alkenyl group comprises 2 to 4 carbon atoms.
According to the invention, preference is given to monounsaturated or di-unsaturated, linear or branched C1 to C6 alkenyl groups.
Typical alkenyl or alkenyl groups include, but are not limited to, ethenyl, propenyl, such as prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl (allyl), prop-2-en-2-yl, cyclopropan-1-en-1-yl, cyclopropan-2-en-1-yl, butenyl, such as but-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-2-yl, but-1, 3-dien-1-yl, but-1, 3-dien-2-yl, and the like.
Alkenyl groups as defined above may be further substituted.
According to the invention, the term "alkynyl" alone or as part of another substituent refers to an unsaturated, straight-chain or branched monovalent hydrocarbon radical having at least one carbon-carbon triple bond (c≡c triple bond).
In a preferred variant according to the invention, the straight-chain or branched alkynyl group comprises 2 to 10 carbon atoms. In other preferred variants, the alkynyl group has 2 to 6 carbon atoms. In still other preferred variants, the alkynyl group includes 2 to 4 carbon atoms.
According to the invention, most preferred are monounsaturated or di-unsaturated straight or branched C1 to C6 alkynyl groups.
Typical alkynyl/moiety or alkynyl groups include, but are not limited to, ethynyl, propynyl, such as prop-1-yn-1-yl, prop-2-en-1-yl and the like, butynyl, such as but-1-yl, but-1-but-3-yl, but-3-but-1-yl and the like.
Alkynyl groups as defined above may be further substituted. The alkyl or alkylene groups as defined above may be further substituted.
According to the present invention, the term "alkoxy" alone or as part of another substituent refers to a linear or branched group of the formula-O-R, wherein R is alkyl or a net substituted alkyl, as defined herein.
In a preferred variant according to the 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.
According to the invention, most preferred are straight or branched C1 to C6 alkoxy groups.
Typical alkoxy/moiety or alkoxy groups include C1 to C6 alkoxy groups, including C1 to C4 alkoxy groups such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy; and pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy, 3-methylbutyloxy, 1-dimethylpropyloxy, 1, 2-dimethylpropyloxy, 2-dimethylpropyloxy, 1-ethylpropyloxy, hexyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1-dimethylbutyloxy 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2-dimethylbutoxy, 2, 3-dimethylbutoxy, 3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 2-trimethylpropoxy, 1, 2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.
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 preferably from the group consisting of methoxy (-O-methyl) and ethoxy (-O-ethyl).
The alkoxy group or alkylene group as defined above may be further substituted.
According to the present invention, the term "alkylthio" or "thioalkoxy" alone or as part of another substituent refers to a group of formula-S-R, wherein R is alkyl or substituted alkyl, as defined herein.
According to the present invention, the term "alkyl" or "alkylene" also includes heteroalkyl or heteroalkyl groups. The term "heteroalkyl" by itself or as part of another substituent means an alkyl group in which one or more of the carbon atoms are independently replaced with the same heteroatom or another heteroatom or with the same heteroatom group or another heteroatom group. Typical heteroatoms or heteroatom groups that may be substituted for carbon atoms include, but are not limited to, -O-, -S-, -N-, -Si-, -NH-, -S (O) 2-、-S(O)NH-、-S(O)2 NH-, and the like, and combinations thereof. The heteroatom or heteroatom group may be located at any internal position of the alkyl group.
Typical heteroatom 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, aralkyl, substituted aralkyl, cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted cycloheteroalkyl, heteroalkyl, substituted heteroalkyl, heteroaryl, substituted heteroaryl, heteroarylalkyl, or substituted heteroarylalkyl, as defined herein.
The alkyl or alkylene groups as defined above may be further substituted.
According to the present invention, the term "acyl" or "alkanoyl" alone or as part of another substituent refers to the group R-C (=o) -, wherein R is hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, arylalkyl, unsubstituted or substituted heteroalkyl, unsubstituted or substituted heteroarylalkyl, as defined herein.
Representative examples include, but are not limited to, formyl, acetyl, propionyl, butyryl, pentanoyl, benzoyl, cyclohexylcarbonyl, cyclohexylmethylcarbonyl, benzylcarbonyl, and the like.
According to the invention, the term "cycloalkyl", alone or as part of another substituent, refers to a saturated or monounsaturated or polyunsaturated, non-aromatic, cyclic monovalent hydrocarbon radical in which the carbon atoms are ring-linked and are free of heteroatoms.
Carbocycles may occur as single ring compounds with only a single ring, or as multicyclic compounds having two or more rings.
In a preferred variant, the term "cycloalkyl" includes a three to ten membered monocyclic cycloalkyl or cycloalkyl group or a nine to twelve membered polycyclic cycloalkyl or cycloalkyl group. In other still more preferred variants, the cycloalkyl moiety comprises a five-, six-, or seven-membered monocyclic cycloalkyl moiety or a nine-to twelve-membered bicyclic cycloalkyl moiety.
In a preferred embodiment according to the invention, the cycloalkyl group or group contains 3 to 20 carbon atoms. In an even more preferred embodiment, cycloalkyl groups comprise 6 to 15 carbon atoms. In a most preferred embodiment, cycloalkyl groups comprise 6 to 10 carbon atoms. Most preferred are monocyclic C3 to C7 cycloalkyl groups.
Typical cycloalkyl or cycloalkyl groups include, but are not limited to, saturated carbocyclyl groups having 3 to 20 carbon atoms, such as C3 to C12 carbocyclyl groups including cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl-methyl, cyclobutyl-ethyl, cyclopentyl-methyl, cyclopentyl-ethyl, cyclohexyl-methyl, or C3-C7 carbocyclyl groups including cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl-methyl, cyclopentyl-ethyl, cyclohexyl-methyl, cyclobutbut-1-en-1-yl, cyclobutbut-1-en-3-yl, 3-dien-1-yl and the like.
Preferred polycyclic cycloalkyl groups or cycloalkyl groups according to the present invention include, but are not limited to, naphthyl, indenyl, and the like.
According to the present invention, the term "cycloalkyl" also includes cycloalkenyl groups, i.e. unsaturated cyclic hydrocarbon groups containing a c=c double bond between two carbon atoms of the ring molecule. In a broader sense cycloalkenyl is a compound having one, two or more double bonds, wherein the number of possible, mostly conjugated double bonds in the molecule depends on the ring size.
Typical cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, and the like.
According to the invention, the term "cycloalkyl" also includes cycloalkynyl groups, i.e. unsaturated-C.ident.C-triple bonds, comprising a cyclic hydrocarbon group between two carbon atoms of a ring molecule, which triple bonds depend on the ring size due to ring tension.
Typical cycloalkynyl groups include cyclosporins.
Cycloalkyl, cycloalkenyl or cycloalkynyl moieties or groups as defined above may be further substituted.
According to the present invention, the term "aryl" alone or as part of another substituent refers to a monovalent aromatic hydrocarbon radical derived by the removal of a hydrogen atom from a single carbon atom of an aromatic ring system.
In a preferred variant, the term "aryl" includes three to ten membered monocyclic aryl or aryl groups or nine to twelve membered polycyclic aryl or aryl groups. In other still more preferred variants, the carboaryl group includes five-, six-, or seven-membered monocyclic carboaryl groups or nine-to twelve-membered bicyclic carboaryl groups.
In a preferred embodiment according to the invention, the aryl group comprises 3 to 20 carbon atoms. In a preferred variant, the aryl moiety comprises from 6 to 15 ring atoms. In an even more preferred embodiment, the aryl group comprises 6 to 10 carbon atoms.
According to the invention, most preferred are monocyclic C3 to C10 aryl groups. Most preferred are monocyclic C3 to C7 aryl groups.
Typical aryl groups include, but are not limited to, benzene, phenyl, biphenyl, naphthyl (such as 1-or 2-naphthyl, tetrahydronaphthyl), fluorenyl, indenyl, and phenanthryl. Typical carboaryl moieties also include, but are not limited to, groups derived from, acetate (ACEANTHRYLENE), acenaphthylene (ACENAPHTHYLENE), acetenaphthalene (acetenyl), anthracene, azulene, benzene, chrysene (chrysene), hexabenzone, fluoranthene (fluoranthene), fluorene, hexabenzene, hexylene (hexaphene), hexylene glycol (hexalene), asymmetric benzobisindene (as-indacene), symmetric benzobisindene (S-indacene), indane, indene, naphthalene, octabenzene, octafin (octaphene), octacene (ocene), egg benzene (ovalene), penta-2, 4-diene, pentacene, pentalene (pentaphene), perylene (perylene), propylene naphthalene (phenalene), phenanthrene (PHENANTHRENE), picene (picene), pleidene (pleiadiene), pyrene (pyranthrene), pyranthrone (rubicene), benzotris (TRIPHENYLENE), and the like.
Aromatic polycyclic aryl or aryl groups preferred according to the present invention include, but are not limited to, naphthalene, biphenyl, and the like.
The aryl moiety or group as defined above may be further substituted.
According to the present invention, the term "arylalkyl" alone or as part of another substituent refers to a non-cyclic alkyl group in which one of the hydrogen atoms attached to a carbon atom (typically a terminal or sp carbon atom) is replaced by an aryl group as defined herein. In other words, arylalkyl can also be considered to be alkyl substituted with aryl. Typical arylalkyl groups include, but are not limited to, benzyl, 2-phenylethan-1-yl, naphthylmethyl, 2-naphthylethan-1-yl, naphthyridinyl, 2-naphthylethan-1-yl and the like.
The term "heteroarylalkyl" alone or as part of another substituent refers to a cyclic alkyl group in which one of the hydrogen atoms attached to a carbon atom is replaced with a heteroaryl group. In a preferred embodiment according to the invention, the heteroarylalkyl group is a 6-to 20-membered heteroarylalkyl group, e.g. the alkyl, alkenyl or alkynyl group of the heteroarylalkyl group is a C1 to C6 alkyl group and the heteroaryl group is a 5-to 15-membered heteroaryl group. In other embodiments, the heteroarylalkyl is a 6-to 13-membered heteroarylalkyl, e.g., the alkyl, alkenyl, or alkynyl group is a C1 to C3 alkyl, and the heteroaryl group is a 5-to 10-membered heteroaryl.
According to the present invention, the term "heterocycloalkyl" alone or as part of another substituent means a saturated or monounsaturated or polyunsaturated, non-aromatic, cyclic monovalent hydrocarbon radical in which one or more carbon atoms are individually replaced by the same or different heteroatoms. Typical heteroatoms replacing carbon atoms include, but are not limited to N, P, O, S, si and the like. Typical heterocycloalkyl groups include, but are not limited to, groups derived from epoxides, azine rings, thiirane rings, imidazolidines, morpholines, piperazines, piperidines, pyrazolidines, pyrrolidinones, quinuclidines, and the like.
In a preferred embodiment according to the invention, the heterocycloalkyl moiety or group comprises 3 to 20 ring atoms. In a preferred variant, the heterocycloalkyl moiety includes from 6 to 15 ring atoms. In an even more preferred embodiment, the heterocycloalkyl moiety includes from 6 to 10 carbon atoms.
The heterocycloalkyl moiety may occur as a single ring compound having only a single ring, or as a polycyclic compound having two or more rings, such as a bicyclic, tricyclic, or spiro ring.
Preferably, the term "heterocycloalkyl" includes three to seven membered saturated or monounsaturated or polyunsaturated heterocycloalkyl moieties, including one, two, three or four heteroatoms selected from the group consisting of O, N and S. One or more heteroatoms may occupy any position in the heterocycloalkyl ring.
In a preferred variant, the term "heterocycloalkyl" includes three to ten membered monocyclic heterocycloalkyl or nine to twelve membered polycyclic heterocycloalkyl. In other still more preferred variants, the heterocycloalkyl moiety comprises a five-, six-, or seven-membered monocyclic heterocycloalkyl moiety or a nine-to twelve-membered bicyclic heterocycloalkyl moiety.
According to the present invention, most preferred is a monocyclic heterocycloalkyl group comprising 3 to 12 carbon atoms. Most preferred are monocyclic heterocycloalkyl groups having 5 to 7 ring atoms.
Typical heterocycloalkyl moieties include, but are not limited to: five-or six-membered saturated or monounsaturated heterocycloalkyl containing one or two nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms as ring members, including 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidone, 4-imidazolidone, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1, 3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyrimidinyl, and hexahydropyrimidinyl, 2-piperazinyl, and the like.
The heterocycloalkyl moiety or group as defined above may be further substituted.
According to the invention, the term "heteroaryl" by itself or as part of another substituent means a monovalent heteroaromatic radical obtained by removal of a hydrogen atom from a single atom of a heteroaromatic ring system. Typical heteroaryl or heteroaryl groups include, but are not limited to, groups derived from acridine, β -carboline, chroman, chromium, cinnoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromium, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, naphthyridine, phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, thiazole, thiophene, triazole, xanthene, and the like.
The heteroaryl moiety may occur as a single ring compound having only a single ring, or as a polycyclic compound having two or more rings.
In a preferred variant, the term "heteroaryl" includes three to ten membered monocyclic heteroaryl or nine to twelve membered polycyclic heteroaryl. In other still more preferred variants, the heteroaryl moiety comprises a five-, six-, or seven-membered monocyclic heteroaryl moiety or a nine-to twelve-membered bicyclic heteroaryl moiety.
Preferably, the term "heteroaryl" includes three to seven membered monocyclic heteroaryl groups including one, two, three or four heteroatoms selected from the group consisting of O, N and S. One or more heteroatoms may occupy any position in the heteroaryl ring.
In a preferred embodiment according to the invention, the heteroaryl moiety or group comprises 3 to 20 ring atoms. In even more preferred variants, the heteroaryl moiety comprises from 6 to 15 ring atoms. In a most preferred embodiment, the heteroaryl group comprises 6 to 10 ring atoms. According to the invention, most preferred are monocyclic C3 to C7 heteroaryl groups.
Particularly preferred heteroaryl moieties or heteroaryl groups include, but are not limited to, groups derived from furan, thiophene, pyrrole, benzothiophene, benzofuran, benzimidazole, indole, pyridine, pyrazole, quinoline, imidazole, oxazole, isoxazole, and pyrazine.
Five-membered aromatic heteroaryl radicals which contain one, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring atoms in addition to carbon atoms include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl and 1,3, 4-triazolyl-2-yl.
Five-membered aromatic heteroaryl groups containing one, two, three or four nitrogen atoms as ring atoms include 1-, 2-or 3-pyrrolyl, 1-, 3-or 4-pyrazolyl, 1-, 2-or 4-imidazolyl, 1,2,3- [1H ] -triazol-1-yl, 1,2,3- [2H ] -triazol-2-yl, 1,2,3- [1H ] -triazol-4-yl, 1,2,3- [1H ] -triazol-5-yl, 1,2,3- [2H ] -triazol-4-yl, 1,2,4- [1H ] -triazol-1-yl, 1,2,4- [1H ] -triazol-3-yl, 1,2,4- [1H ] -triazol-5-yl, 1,2,4- [4H ] -triazol-4-yl, 1,2,4- [4H ] -triazol-3-yl, [1H ] -tetrazol-1-yl, [1H ] -tetrazol-5-yl, [2H ] -tetrazol-5-yl, and the like.
Five-membered aromatic heteroaryl groups containing heteroatoms selected from oxygen or sulfur and optionally one, two or three nitrogen atoms as ring atoms include 2-furyl, 3-furyl, 2-thienyl, 3-or 4-isoxazolyl, 3-or 4-isothiazolyl, 2-, 4-or 5-oxazolyl, 2-, 4-or 5-thiazolyl, 1,2, 4-thiadiazol-3-yl, 1,2, 4-thiadiazol-5-yl, 1,3, 4-thiadiazol-2-yl, 1,2, 4-oxadiazol-3-yl, 1,2, 4-oxadiazol-5-yl and 1,3, 4-oxadiazol-2-yl.
Six membered heteroaryl groups containing one or two or one, two or three nitrogen atoms as ring atoms in addition to carbon atoms and include, for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,2, 4-triazin-3-yl, 1,2, 4-triazin-5-yl, 1,2, 4-triazin-6-yl and 1,3, 5-triazin-2-yl.
Heteroaryl moieties or groups as defined above may be further substituted.
The term "C-spiro" in the context of the present application means a compound having at least two molecular rings having only one common atom. The simplest spiro compounds are bicyclic (only two rings) or have a bicyclic moiety as part of a larger ring system, in either case both rings being linked by a defined single common atom. One common atom joining the participating rings distinguishes the spiro compound from other bicyclic structures such as isolated ring compounds having no linking atoms, e.g., biphenyl, fused ring compounds having two rings joined by two adjacent atoms, e.g., decalin, and bridged ring compounds having two rings joined by two non-adjacent atoms, e.g., norbornane. The spiro compound may be an all-carbocyclic (all-carbon) or heterocyclic (having one or more non-carbon atoms, such as N, O and S). The common atom connecting the two (or sometimes three) rings is referred to as a spiro atom. Preferably, the spiro atom is a carbon atom. More preferably, a C-spiro compound means a fully carbocyclic (full carbon) compound.
In the context of the present invention, the term "substituted" means that one or more hydrogen atoms of the indicated group(s) are independently replaced by identical or different substituents. In addition, the term "substituted" specifically provides one or more, i.e., two, three, four, five, six or more substituents commonly used in the art. However, it is well known that substituents should be selected such that they do not adversely affect the useful properties of the compound or its function.
Suitable substituents in the context of the present invention preferably include halogen, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl groups or heteroaryl groups, aryloxy groups or heteroaryloxy groups, arylalkyl groups or heteroarylalkyl groups, arylalkoxy groups or heteroarylalkoxy groups, amino groups, alkyl groups and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, carboxyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, arylsulfonyl groups, cycloalkyl groups, cyano groups, C1 to C6 alkylthio groups, arylthio groups, nitro groups, ketone groups, acyl groups, boric acid groups or boric acid groups, phosphoric groups or phosphonic groups, sulfonyl groups, sulfinyl groups, and combinations thereof.
Substituents or substituent groups that may be used to replace a saturated carbon atom in the indicated group more preferably include, but are not limited to, halogen, hydroxy, alkyl, alkenyl, alkynyl, alkoxy, -NH 2, amino (primary, secondary or tertiary), nitro, thiol, thioether, imine, cyano, amido, phosphonic acid group, phosphine, carboxyl, thiocarbonyl, sulfonyl, sulfonamide, ketone, aldehyde, ester, acetyl, acetoxy, carbamoyl, oxygen (O); haloalkyl (e.g., trifluoromethyl), aminoacyl and aminoalkyl, carbocyclcycloalkyl (which may be monocyclic or fused or unfused polycyclic (e.g., cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl)), or heterocycloalkyl (which may be monocyclic or fused or unfused polycyclic (e.g., pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl or thiazinyl)), carbocycle or heterocycle, monocyclic or fused or unfused polycyclic aryl (e.g., phenyl, naphthyl, pyrrolyl, indolyl, furanyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, benzimidazolyl, benzothienyl or benzofuranyl) )、-CO2CH3、-CONH2、-OCH2CONH2;-SO2NH2、-OCHF2、-CF3、-OCF3.
According to the present invention, the substituents used to replace a particular group or groups may in turn be further substituted, typically by one or more of the same or different groups selected from the various groups indicated above and defined in detail above. In the case of substituted combinations such as substituted arylalkyl groups, the aryl or alkyl groups may be substituted, or both the aryl and alkyl groups may be substituted with one or more substituents.
In a preferred variant, Z in the general formula (V) is-O-R2 'or an amide'.
In another preferred variant, R1' in formula (V) is CH 2.
In another preferred variant, R1' in formula (V) is C (alkyl) 2.
In another preferred variant, R1' in formula (V) is O.
In another preferred variant, R1' in formula (V) is S.
In another preferred variant, R1' in formula (V) is SO.
In another preferred variant, R1' in formula (V) is SO 2.
In another preferred variant, R1' in the general formula (V) is NH.
In yet another preferred variant, R1' in formula (V) is N (alkyl).
Most preferably, R1' in formula (V) is CH 2 or C (alkyl) 2.
In a preferred variant, R2' in formula (V) is H.
In another preferred variant, R2' in formula (V) is methyl.
In another preferred variant, R2' in formula (V) is ethyl.
In another preferred variant, R2' in formula (V) is propyl.
In another preferred variant, R2' in formula (V) is isopropyl.
In another preferred variant, R2' in formula (V) is butyl.
In another preferred variant, R2' in formula (V) is isobutyl.
In another preferred variant, R2' in formula (V) is tert-butyl.
In another preferred variant, R2' in formula (V) is
In another preferred variant, R2' in formula (V) is
In a preferred variant, R2' in formula (V) is(2-Ethyl-hexyl).
In yet another preferred variant, R2' in formula (V) is phenyl.
Most preferably, R2' in formula (V) is H or ethyl or isopropyl or 2-ethylhexyl or phenyl.
In a preferred variant, the amide' in the general formula (V) is NH 2.
In a further preferred variant, the amide' in formula (V) is NH (alkyl), wherein alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In another preferred variant, the amide' in formula (V) is N (alkyl) 2, wherein the alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In another preferred variant, the amide' in formula (V) is-N (O-alkyl) (Weinreb amide), wherein the alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In yet another preferred variant, the amide' in formula (V) is-N (OH) (H) (hydroxamic acid).
Most preferably, the amide' in formula (V) is NH 2, N (methyl) 2 or N (ethyl) 2 or-N (O-alkyl) (Weinreb amide), wherein alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl or-N (OH) (H) (hydroxamic acid).
In a preferred variant, R3' in formula (V) is H.
In another preferred variant, R3' in formula (V) is methyl.
In another preferred variant, R3' in formula (V) is ethyl.
In another preferred variant, R3' in formula (V) is-O-methyl.
In another preferred variant, R3' in formula (V) is-C (=o) -OH.
In another preferred variant, R3' in formula (V) is-C (=o) -CH 3.
In another preferred variant, R3' in formula (V) is-C (=o) -C 3H7.
In yet another preferred variant, R3' in formula (V) is-C (=o) -O-methyl.
Most preferably, R3' in formula (V) is H or methyl or-O-methyl.
In a preferred variant according to the first aspect of the present invention, the retinoid amino acid compound (b) of the general formula (V) is an acid compound or an ester compound represented by the general formula (VII)
Wherein R1', R2', R3', R4', R5 'and R6' have the same meaning as defined herein for formula (V).
In a preferred variant according to the first aspect of the invention, the retinoid amino acid compound (b) of formula (V) is an acid compound represented by formula (VII-acid)
Wherein R1', R3', R4', R5' and R6' have the same meaning as defined herein for formula (V).
The retinoid amino acid compounds according to the general formula (VII-acid) are particularly light-and temperature-stable compounds and show stability and no degradation in pH solutions or in different emulsion types.
In particular, the retinoid amino acid compounds as defined herein have better pH stability over a wider pH range, in contrast to their respective ester compounds which hydrolyze and are therefore unstable in alkaline solutions having a pH above 9.
In addition, the retinoid amino acid compounds also have better solubility in water than their corresponding ester compounds. Due to their better solubility in water, the retinoid amino acid compounds may be incorporated into the aqueous phase of the formulation at higher concentrations, resulting in improved SPF performance enhancing effects and improved UVA photoprotection in sunscreen products, cosmetic or pharmaceutical formulations or home care products.
In a preferred variant according to the first aspect of the invention, the retinoid amino acid compound (b) of formula (V) is an ester compound represented by formula (VII-ester)
Wherein R1', R3', R4', R5' and R6' have the same meaning as defined herein for formula (V).
Preferably, the alkyl residue in the formula (VII-ester) is methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl. Most preferably, the alkyl residue in the general formula (VII-ester) is methyl. The ester compounds are particularly stable.
In an alternative preferred variant according to the first aspect of the invention, the retinoid amino acid compound (b) of formula (V) is an amide compound represented by formula (VIII)
Wherein R1', amide', R3', R4', R5 'and R6' have the same meaning as defined herein for formula (V).
In a more preferred variant according to the first aspect of the invention, the retinoid amino acid compound (b) of formula (V) is an amide compound represented by formula (VIII-amide)
Wherein R1', R3', R4', R5' and R6' have the same meaning as defined herein for formula (V), and R11' and R12' are independently selected from the group consisting of H, OH and alkyl.
In a preferred variant according to the first aspect of the invention, in the general formula (VIII-amide), R11 'and/or R12' are H.
In another preferred variant, the R11 'alkyl and R12' alkyl in the general formula (VIII-amide) are independently of each other selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
Preferably, R11 'and/or R12' in the general formula (VIII-amide) are each H or are each methyl.
In still more preferred variants, the retinoid amino acid compound (b) of formula (V) is a Weinreb amide compound represented by formula (VIII-Weinreb amide)
Wherein R1', R3', R4', R5' and R6' have the same meanings as defined for formula (V) herein.
In a preferred variant, the alkyl residue in the general formula (VIII-Weinreb amide) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferably the alkyl residue is methyl.
Alternatively, in still more preferred variants, the retinoid amino acid compound (b) of formula (V) is a hydroxamic acid compound represented by formula (VIII-hydroxamic acid derivative)
Wherein R1', R3', R4', R5' and R6' have the same meaning as defined herein for formula (V).
Alternatively, in a still further preferred variant, the retinoid amino acid compound (b) of formula (V) is an alkylated hydroxamic acid compound represented by formula (VIII-alkylated hydroxamic acid derivative)
Wherein R1', R3', R4', R5' and R6' have the same meaning as defined herein for formula (V).
In a preferred variant, the alkyl residue in the general formula (VIII-alkylated hydroxamic acid derivative) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferably the alkyl group is methyl.
In a preferred alternative variant, the retinoid amino acid compound (b) is represented by the general formula (A)
Wherein R1', R3', R4', R5' and R6' have the same meaning as defined herein for formula (V).
In the present invention, the same preferred variants as defined herein for the retinoid amino acid compound according to formula (V) apply similarly to the retinoid amino acid compounds according to formula (VII) or (VIII) and their variants or formula (a).
In another preferred variant, R1' in the general formula (VI) is CH 2.
In another preferred variant, R1' in formula (VI) is C (alkyl) 2.
In another preferred variant, R1' in the general formula (VI) is O.
In another preferred variant, R1' in the general formula (VI) is S.
In another preferred variant, R1' in formula (VI) is SO.
In another preferred variant, R1' in formula (VI) is SO 2.
In another preferred variant, R1' in the general formula (VI) is NH.
In yet another preferred variant, R1' in formula (VI) is N (alkyl).
Most preferably, R1' in formula (VI) is CH 2 or C (alkyl) 2.
In a preferred variant, R2' in the general formula (VI) is-CH 2 -OH.
In another preferred variant, R2 "in the general formula (VI) is-C (=o) -O-Y.
In another preferred variant, R2 "in formula (VI) is-C (=o) -amide.
Most preferably, R2 "in formula (VI) is-C (=o) -O-Y or-C (=o) -amide.
In another preferred variant, X in formula (VI) is CH 2.
In another preferred variant, X in formula (VI) is c=o.
In another preferred variant, X in the general formula (VI) is O.
In another preferred variant, X in formula (VI) is S.
In another preferred variant, X in formula (VI) is SO.
In another preferred variant, X in formula (VI) is SO 2.
In another preferred variant, X in the general formula (VI) is NH.
In yet another preferred variant, X in formula (VI) is N (alkyl), wherein alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.
Most preferably, X in formula (VI) is S, SO or SO 2.
In a preferred variant, Y in the general formula (VI) is H.
In another preferred variant, Y in the general formula (VI) is methyl.
In another preferred variant, Y in the formula (VI) is ethyl.
In another preferred variant, Y in formula (VI) is propyl.
In another preferred variant, Y in formula (VI) is isopropyl.
In another preferred variant, Y in the formula (VI) is butyl.
In another preferred variant, Y in the formula (VI) is isobutyl.
In another preferred variant, Y in the formula (VI) is tert-butyl.
In another preferred variant, Y in the formula (VI) is
In another preferred variant, Y in the formula (VI) is
In a preferred variant, Y in the formula (VI) is(2-Ethyl-hexyl).
In yet another preferred variant, Y in formula (VI) is phenyl.
Most preferably, Y in formula (VI) is H or ethyl or isopropyl or 2-ethylhexyl or phenyl.
In a preferred variant, the amide "in the general formula (VI) is NH 2.
In a further preferred variant, the amide "in the general formula (VI) is NH (alkyl), wherein the alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In another preferred variant, the amide "in formula (VI) is an N (alkyl) 2 wherein the alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In another preferred variant, the amide "in formula (VI) is-N (O-alkyl) (Weinreb amide), wherein the alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In yet another preferred variant, the amide "in formula (V) is-N (OH) (H) (hydroxamic acid).
Most preferably, the amide in formula (V) is NH 2, N (methyl) 2 or N (ethyl) 2 or-N (O-alkyl) (Weinreb amide), wherein alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl or-N (OH) (H) (hydroxamic acid).
In a more preferred variant according to the first aspect of the invention, the retinoid amino acid compound (b) is an alcohol compound represented by the general formula (IX-alcohol)
Wherein R1", X, R", R5 "and R6" have the same meaning as defined herein for formula (VI).
Alternatively, in a more preferred variant according to the first aspect of the present invention, the retinoid amino acid compound (b) of formula (VI) is an acid compound represented by formula (IX-acid)
Wherein R1", X, R", R5 "and R6" have the same meaning as defined herein for formula (VI).
Alternatively, in a more preferred variant according to the first aspect of the present invention, the retinoid amino acid compound (b) of formula (VI) is an ester compound represented by formula (VII-ester)
Wherein R1", X, R", R5 "and R6" have the same meaning as defined herein for formula (VI).
Preferably, the alkyl residue in the general formula (VII-ester) is methyl or ethyl or propyl or isobutyl or butyl or isobutyl or tert-butyl, more preferably the alkyl residue is methyl.
In an alternative more preferred variant according to the first aspect of the invention, the retinoid amino acid compound (b) of formula (VI) is an amide compound represented by formula (X)
Wherein R1", amide", X, R, R5 "and R6" have the same meaning as defined herein for formula (VI).
In a more preferred alternative variant according to the first aspect of the invention, the retinoid amino acid compound (b) of formula (VI) is an amide compound represented by formula (X-amide),
Wherein R1", X, R", R5 "and R6" have the same meaning as defined herein for formula (VI) and R11 "and R12" are independently of each other selected from the group consisting of H, OH and alkyl.
In a preferred variant according to the first aspect of the invention, in the general formula (X-amide), R11 'and/or R12' are H.
Preferably, R11 "alkyl and R12" alkyl in formula (X-amide) are methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl.
Preferably, R11 "and/or R12" in the general formula (X-amide) are each H or are each methyl.
In still more preferred variants, the retinoid amino acid compound (b) of formula (VI) is a Weinreb amide compound represented by formula (X-Weinreb amide)
Wherein R1", X, R", R5 "and R6" have the same meaning as defined herein for formula (VI).
In a preferred variant, the alkyl residue in the general formula (X-Weinreb amide) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferably the alkyl residue is methyl.
Alternatively, in still more preferred variants, the retinoid amino acid compound (b) of formula (VI) is a hydroxamic acid compound represented by formula (X-hydroxamic acid derivative)
Wherein R1", X, R", R5 "and R6" have the same meanings as defined above for formula (VI).
Alternatively, in yet another preferred variant, the retinoid amino acid compound (b) of formula (VI) is an alkylated hydroxamic acid compound represented by formula (VIII-alkylated hydroxamic acid derivative)
Wherein R1", X, R", R5 "and R6" have the same meanings as defined herein for formula (VI).
In a preferred variant, the alkyl residue in the general formula (X-alkylated hydroxamic acid derivative) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, more preferably the alkyl residue is methyl.
In the present invention, the same preferred variants as defined herein for the retinoid amino acid compounds according to formula (VI) apply similarly to the retinoid amino acid compounds according to formula (IX) or (X) and their variants.
In the following and throughout the specification, the term "according to the general formula YZ and variants thereof" includes any sub-formula (e) of said general formula as disclosed herein. Thus, variants of formulae (V) and (VI) as defined herein include formula (VII), formula (VIII), formula (IX) and formula (X) as defined herein. Variants of formulae (VII) and (VIII) as defined herein include the sub-formulae (VII-acid), sub-formulae (VII-ester), sub-formulae (VIII-amide), sub-formulae (VIII-Weinreb amide), sub-formulae (VIII-hydroxamic acid derivatives) and sub-formulae (VIII-alkylated hydroxamic acid derivatives) as defined herein. Variants of the general formulae (IX) and (X) as defined herein include the formula (IX-acid), the formula (IX-ester), the formula (X-amide), the formula (X-Weinreb amide), the formula (X-hydroxamic acid derivatives) and the formula (X-alkylated hydroxamic acid derivatives) as defined herein.
In another preferred variant, in formulae (VI), (IX), (X) and variants thereof, X is selected from the group consisting of CH 2, unsubstituted or substituted CH (alkyl), unsubstituted or substituted C (alkyl) 2, unsubstituted or substituted CH (alkenyl), unsubstituted or substituted CH (alkynyl), unsubstituted or substituted CH (alkoxy), unsubstituted or substituted CH (alkylthio), unsubstituted or substituted CH (cycloalkyl), unsubstituted or substituted CH (aryl), unsubstituted or substituted CH (heterocycloalkyl), unsubstituted or substituted CH (heteroaryl), -CR7"R8", C= O, S, SO, SO 2, NH, unsubstituted or substituted N (alkyl), unsubstituted or substituted N (alkenyl), unsubstituted or substituted N (alkynyl), unsubstituted or substituted N (alkoxy), unsubstituted or substituted N (alkylthio), unsubstituted or substituted cycloalkyl), unsubstituted or substituted spirocyclic ring (C) and unsubstituted or substituted cycloalkyl.
In another preferred variant according to the first aspect of the invention, the class of mycosporine amino acid compounds are compounds according to the general formula (V), wherein
Z is-O-R2 'or an amide' -, and/or
R1' is selected from the group consisting of CH 2, C (alkyl) 2、O、S、SO、SO2, NH and N (alkyl), and/or
R2' is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-Ethyl-hexyl) and phenyl, or
The amide' is selected from the group consisting of NH 2, NH (alkyl), N (alkyl) 2, -N (O-alkyl) (Weinreb amide) and-N (OH) (H) (hydroxamic acid), and/or
-R3' is selected from the group consisting of H, methyl, ethyl, -O-methyl, -C (=O) -OH, -C (=O) -CH 3、-C(=O)-C3H7, and-C (=O) -O-methyl, and/or
-Said substituents R4', R5' and R6' have the same meaning as defined for formula (V);
-wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In a further preferred variant according to the first aspect of the invention, the mycosporine amino acid compound is a compound according to formula (VII) or (VIII), wherein
R1' is selected from the group consisting of CH 2, C (alkyl) 2、O、S、SO、SO2, NH and N (alkyl), and/or
R2' is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-Ethyl-hexyl) and phenyl, or
The amide' is selected from the group consisting of NH 2, NH (alkyl), N (alkyl) 2, -N (O-alkyl) (Weinreb amide) and-N (OH) (H) (hydroxamic acid), and/or
-R3' is selected from the group consisting of H, methyl, ethyl, -O-methyl, -C (=O) -OH, -C (=O) -CH 3、-C(=O)-C3H7, and-C (=O) -O-methyl, and/or
-Said substituents R4', R5' and R6' have the same meaning as defined for formula (V);
-wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In another preferred variant according to the first aspect of the invention, the class of mycosporine amino acid compounds are compounds according to the general formula (VI), wherein
R1' is selected from the group consisting of CH 2, C (alkyl) 2、O、S、SO、SO2, NH and N (alkyl), and/or
-R2 'is selected from the group consisting of-CH 2 -OH, -C (=O) -O-Y and-C (=O) -amide', and/or
X is selected from the group consisting of CH 2、C=O、O、S、SO、SO2, NH and N (alkyl) and/or
Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,(2-Ethyl-hexyl) and phenyl, and/or
The amide "is selected from the group consisting of NH 2, NH (alkyl), N (alkyl) 2, -N (O-alkyl) (Weinreb amide), and-N (OH) (H) (hydroxamic acid), and/or
-Said substituents R4", R5" and R6 "have the same meaning as defined for formula (VI);
-wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In another preferred variant according to the first aspect of the invention, the class of mycosporine amino acid compounds are compounds according to the general formula (V), wherein
Z is-O-R2 'or an amide' -, and/or
R1' is selected from the group consisting of CH 2 and C (methyl) 2, and/or
R2' is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-Ethyl-hexyl) and phenyl, or
The amide' is selected from the group consisting of NH 2, NH (alkyl), N (alkyl) 2, -N (O-alkyl) (Weinreb amide) and-N (OH) (H) (hydroxamic acid), and/or
-R3' is selected from the group consisting of H, methyl, ethyl, -O-methyl, -C (=O) -OH, -C (=O) -CH 3、-C(=O)-C3H7, and-C (=O) -O-methyl, and/or
-Said substituents R4', R5' and R6' have the same meaning as defined for formula (V);
-wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In a further preferred variant according to the first aspect of the invention, the mycosporine amino acid compound is a compound according to formula (VII) or (VIII), wherein
R1' is selected from the group consisting of CH 2 and C (methyl) 2, and/or
R2' is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-Ethyl-hexyl) and phenyl, or
The amide' is selected from the group consisting of NH 2, NH (alkyl), N (alkyl) 2, -N (O-alkyl) (Weinreb amide) and-N (OH) (H) (hydroxamic acid), and/or
-R3' is selected from the group consisting of H, methyl, ethyl, -O-methyl, -C (=O) -OH, -C (=O) -CH 3、-C(=O)-C3H7, and-C (=O) -O-methyl, and/or
-Said substituents R4', R5' and R6' have the same meaning as defined for formula (V);
-wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In another preferred variant according to the first aspect of the invention, the class of mycosporine amino acid compounds are compounds according to the general formula (VI), wherein
R1' is selected from the group consisting of CH 2 and C (methyl) 2, and/or
-R2 'is selected from the group consisting of-CH 2 -OH, -C (=O) -O-Y and-C (=O) -amide', and/or
X is selected from the group consisting of CH 2、C=O、O、S、SO、SO2, NH and N (alkyl) and/or
Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-Ethyl-hexyl) and phenyl, and/or
The amide "is selected from the group consisting of NH 2, NH (alkyl), N (alkyl) 2, -N (O-alkyl) (Weinreb amide), and-N (OH) (H) (hydroxamic acid), and/or
-Said substituents R4", R5" and R6 "have the same meaning as defined for formula (VI);
-wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In a still more preferred variant according to the invention, the sunscreen product, the cosmetic or pharmaceutical preparation or the home care product comprises at least one mycosporine amino acid compound selected from the group consisting of the following compounds I-1 to I-128 according to the general formula (V) and II-1 to II-192 according to the general formula (VI):
table 1:
Or a tautomer or stereoisomer or salt of the above compounds or any mixture of the above compounds.
In the retinoid amino acid compounds of table 1, the benzene ring may be unsubstituted or substituted. The substituents R4', R5', R6', R4", R5", R6", amide', Y, amide" and alkyl have the same meaning as defined previously for the retinoid amino acid compounds according to formula (V) or (VI).
Particularly preferred are those retinoid amino acid compounds, wherein in formula (V) R1' is CH 2 or C (methyl) 2, or wherein in formula (VI) R1 "is CH 2 or C (methyl) 2:
table 2:
Or a tautomer or stereoisomer or salt of the above compounds or any mixture of the above compounds.
In the retinoid amino acid compounds of table 2, the benzene ring may be unsubstituted or substituted. The substituents R4', R5', R6', R4", R5", R6", amide', Y, amide" and alkyl have the same meaning as defined previously for the retinoid amino acid compounds according to formula (V) or (VI).
Preferably, in the retinoid amino acid compounds according to the general formulae (V) and (VI) specified in tables 1 and 2
R2' is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-Ethylhexyl) and phenyl;
-amide' is selected from the group consisting of NH 2, NH (alkyl), N (alkyl) 2, -N (O-alkyl) (Weinreb amide), and-N (OH) (H) (hydroxamic acid);
Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-Ethylhexyl) and phenyl;
the amide "is selected from the group consisting of NH 2, NH (alkyl), N (alkyl) 2, -N (O-alkyl) (Weinreb amide), and-N (OH) (H) (hydroxamic acid), and
The alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In a most preferred variant according to the first aspect of the invention, the class of mycosporine amino acid compounds is compounds according to formula (V) and variants thereof or compounds of formula (VI) and variants thereof, wherein R1' or R1 "is CH 2. This class of mycosporine amino acid compounds has particularly good water solubility.
In yet another preferred variant according to the first aspect of the invention, the class of mycosporine amino acid compounds are compounds according to the general formulae (VI), (IX), (X) and variants thereof, wherein X is selected from the group consisting of S, SO and SO 2.
Such an amino acid compound of the class of bacteriocins alters the UV absorption profile of the sunscreen product or cosmetic or pharmaceutical formulation and widens the UV absorption spectrum of the formulation over the entire UV radiation spectrum.
In still more preferred variants according to the first aspect of the invention, the class of mycosporine amino acid compounds are compounds according to the general formulae (VI), (IX), (X) and variants thereof, wherein X is S. However. The S atom in the compound is susceptible to oxidation.
In a more preferred variant according to the first aspect of the invention, the class of mycosporine amino acid compounds are compounds according to the general formulae (VI), (IX), (X) and variants thereof, wherein X is SO or SO 2. Such class of mycosporine amino acid compounds are particularly stable due to their oxidation state.
In a still further preferred variant according to the invention, in the formulae (V) to (X) and variants thereof, n is 1.
In a still more preferred variant according to the first aspect of the invention, the retinoid amino acid compound is a compound according to formula (V), wherein
Z is-O-R2 'or an amide' -, and/or
R1' is CH 2 or C (methyl) 2, and/or
R2' is H or ethyl or isopropyl or 2-ethylhexyl or phenyl, or
-Amide' is NH 2 or N (methyl) 2 or N (ethyl) 2 or-N (O-alkyl) (Weinreb amide) or-N (OH) (H) (hydroxamic acid), and/or
-R3' is H or-O-methyl or-C (=O) -OH or-C (=O) -CH 3 or-C (=O) -O-methyl, and/or
-Said substituents R4', R5' and R6' have the same meaning as defined for formula (V);
-wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In a more preferred variant according to the first aspect of the invention, the class of mycosporine amino acid compounds are compounds according to formula (VII) or (VIII), wherein
R1' is CH 2 or C (methyl) 2, and/or
R2' is H or ethyl or isopropyl or 2-ethylhexyl or phenyl, or
-Amide' is NH 2 or N (methyl) 2 or N (ethyl) 2 or-N (O-alkyl) (Weinreb amide) or-N (OH) (H) (hydroxamic acid), and/or
-R3' is H or-O-methyl or-C (=O) -OH or-C (=O) -CH 3 or-C (=O) -O-methyl, and/or
-Said substituents R4', R5' and R6' have the same meaning as defined for formula (V);
-wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.
In a more preferred variant according to the first aspect of the invention, the class of mycosporine amino acid compounds are compounds according to the general formula (VI), wherein
R1' is CH 2 or C (methyl) 2, and/or
-R2 'is-C (=O) -O-Y or-C (=O) -amide', and/or
-X is S, SO or SO 2, and/or
Y is H or ethyl or isopropyl or 2-ethylhexyl or phenyl, or
The amide "is NH 2 or N (methyl) 2 or N (ethyl) 2 or-N (O-alkyl) (Weinreb amide) or-N (OH) (H) (hydroxamic acid), and/or
-Said substituents R4", R5" and R6 "have the same meaning as defined for formula (VI);
-wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and butyl.
The benzene ring in the retinoid amino acid compounds according to formulae (V) to (X) and their variants may be unsubstituted or substituted.
In a preferred variant, the benzene ring in the retinoid amino acid compounds according to formulae (V) to (X) is unsubstituted, i.e. the substituents R4', R5' and R6 'on the benzene ring in formula (V) are H, or the substituents R4', R5 'and R6' on the benzene ring in formula (VI) are H.
In another preferred variant, the benzene ring in the retinoid amino acid compounds according to formulae (V) to (X) and their variants is substituted.
Most preferably, the benzene ring in the cephalosporin amino acid compounds according to formula (V), (VII), (VIII) and variants thereof is unsubstituted, i.e. the substituents R4', R5' and R6' are each H. Alternatively, most preferably, the benzene ring in the retinoid amino acid compounds according to formulae (VI), (IX), (X) and variants thereof is unsubstituted, i.e. the substituents R4", R5" and R6 "are each H. The compounds have improved water solubility.
Preferably, the benzene ring in the retinoid amino acid compounds according to formulae (V) to (X) and their variants is mono-, di-or tri-substituted.
In a still more preferred variant according to the first aspect of the invention, the retinoid amino acid compounds are compounds according to formulae (V), (VII) and (VIII) and variants thereof, wherein the substituents R4', R5' and R6', which may be identical or different, are independently of each other selected from the group consisting of H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S (=o) 2 OH and sulfonyl.
Still more preferably, the substituents R4', R5' and R6', which may be the same or different, in the general formulae (V), (VII), (VIII) and variants thereof are independently selected from the group consisting of H, OH, methyl, O-methyl, -S (=o) 2 OH and sulfonyl.
Alternatively, the retinoid compounds are retinoid compounds according to the general formulae (VI), (IX) and (X) and variants thereof, wherein the substituents R4", R5" and R6", which may be identical or different, are independently of each other selected from the group consisting of H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S (=o) 2 OH and sulfonyl.
Still more preferably, the substituents R4", R5" and R6", which may be identical or different, in the general formulae (VI), (IX), (X) and variants thereof are independently of each other selected from the group consisting of H, OH, methyl, O-methyl, -S (=o) 2 OH and sulfonyl.
Among the formulae (V) to (X) and their variants, the following substitution patterns are particularly preferred:
R4' =h and R5' =h and R6' =h, or
R4' =h and R5' =h and R6' =oh, or
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) 2 OH, 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) 2 OH, 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) 2 OH, 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) 2 OH, or
R4' =h and R5' =o-methyl and R6' =sulfonyl, or
R4' =h and R5' = -S (=o) 2 OH and R6' =h, or
R4' =h and R5' = -S (=o) 2 OH and R6' =oh, or
R4' =h and R5' = -S (=o) 2 OH and R6' =methyl, or
R4' =h and R5' = -S (=o) 2 OH and R6' =o-methyl, or
R4' =h and R5' = -S (=o) 2 OH and R6' = -S (=o) 2 OH, or
R4' =h and R5' = -S (=o) 2 OH and R6' =sulfonyl, or
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) 2 OH, 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) 2 OH, 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) 2 OH, 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) 2 OH, 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, or
R4' =oh and R5' =o-methyl and R6' =o-methyl, or
R4' =oh and R5' =o-methyl and R6' = -S (=o) 2 OH, or
R4' =oh and R5' =o-methyl and R6' =sulfonyl, or
R4' =oh and R5' = -S (=o) 2 OH and R6' =h, or
R4' =oh and R5' = -S (=o) 2 OH 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) 2 OH and R6' = -S (=o) 2 OH, or
R4' =oh and R5' = -S (=o) 2 OH 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) 2 OH, 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) 2 OH, 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) 2 OH, or
R4' =methyl and R5' =oh and R6' =sulfonyl, or
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) 2 OH, 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) 2 OH, or
R4' =methyl and R5' =o-methyl and R6' =sulfonyl, or
R4' =methyl and R5' = -S (=o) 2 OH and R6' =h, or
R4' =methyl and R5' = -S (=o) 2 OH 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) 2 OH and R6' = -S (=o) 2 OH, or
R4' =methyl and R5' = -S (=o) 2 OH 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) 2 OH, 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, or
R4' =o-methyl and R5' =h and R6' = -S (=o) 2 OH, 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) 2 OH, 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) 2 OH, 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) 2 OH, or
R4' =o-methyl and R5' =o-methyl and R6' =sulfonyl, or
R4' =o-methyl and R5' = -S (=o) 2 OH and R6' =h, or
R4' =o-methyl and R5' = -S (=o) 2 OH 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) 2 OH and R6' = -S (=o) 2 OH, or
R4' =o-methyl and R5' = -S (=o) 2 OH and R6' =sulfonyl, or
R4' =o-methyl and R5' =sulfonyl and R6' =h, or
R4' =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) 2 OH, or
R4' =o-methyl and R5' =sulfonyl and R6' =sulfonyl, or
R4' = -S (=o) 2 OH and R5' =h and R6' =h, or
R4' = -S (=o) 2 OH and R5' =h and R6' =oh, or
R4' = -S (=o) 2 OH and R5' =h and R6' =methyl, or
R4' = -S (=o) 2 OH and R5' =h and R6' =o-methyl, or
R4' = -S (=o) 2 OH and R5' = H and R6' = -S (=o) 2 OH, or
R4' = -S (=o) 2 OH and R5' =h and R6' =sulfonyl, or
R4' = -S (=o) 2 OH and R5' =oh and R6' =h, or
R4' = -S (=o) 2 OH and R5' =oh and R6' =oh, or
R4' = -S (=o) 2 OH and R5' =oh and R6' =methyl, or
R4' = -S (=o) 2 OH and R5' =oh and R6' =o-methyl, or
R4' = -S (=o) 2 OH and R5' = -OH and R6' = -S (=o) 2 OH, or
R4' = -S (=o) 2 OH and R5' =oh and R6' =sulfonyl, or
R4' = -S (=o) 2 OH and R5' =methyl and R6' =h, or
R4' = -S (=o) 2 OH and R5' =methyl and R6' =oh, or
R4' = -S (=o) 2 OH and R5' =methyl and R6' =methyl, or
R4' = -S (=o) 2 OH and R5' =methyl and R6' =o-methyl, or
R4' = -S (=o) 2 OH and R5' = -methyl and R6' = -S (=o) 2 OH, or
R4' = -S (=o) 2 OH and R5' =methyl and R6' =sulfonyl, or
R4' = -S (=o) 2 OH and R5' =o-methyl and R6' =h, or
R4' = -S (=o) 2 OH and R5' =o-methyl and R6' =oh, or
R4' = -S (=o) 2 OH and R5' =o-methyl and R6' =methyl, or
R4' = -S (=o) 2 OH and R5' =o-methyl and R6' =o-methyl, or
R4' = -S (=o) 2 OH and R5' = O-methyl and R6' = -S (=o) 2 OH, or
R4' = -S (=o) 2 OH and R5' =o-methyl and R6' =sulfonyl, or
R4' = -S (=o) 2 OH and R5' = -S (=o) 2 oh=and R6' =h, or
R4' = -S (=o) 2 OH and R5' = -S (=o) 2 OH and R6' =oh, or
R4' = -S (=o) 2 OH and R5' = -S (=o) 2 OH and R6' =methyl, or
R4' = -S (=o) 2 OH and R5' = -S (=o) 2 OH and R6' =o-methyl, or
R4' = -S (=o) 2 OH and R5' =sulfonyl and R6' =h, or
R4' = -S (=o) 2 OH and R5' =sulfonyl and R6' =oh, or
R4' = -S (=o) 2 OH and R5' =sulfonyl and R6' =methyl, or
R4' = -S (=o) 2 OH 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) 2 OH, 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) 2 OH, 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) 2 OH, or
R4' =sulfonyl and R5' =methyl and R6' =sulfonyl, or
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) 2 OH, or
R4' =sulfonyl and R5' =o-methyl and R6' =sulfonyl, or
R4' =sulfonyl and R5' = -S (=o) 2 OH and R6' =h, or
R4' =sulfonyl and R5' = -S (=o) 2 OH and R6' =oh, or
R4' =sulfonyl and R5' = -S (=o) 2 OH and R6' =methyl, or
R4' =sulfonyl and R5' = -S (=o) 2 OH 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
R4 "=h and R5" =h and R6 "=h, or
R4 "=h and R5" =h and R6 "=oh, or
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) 2 OH, 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) 2 OH, 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) 2 OH, 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) 2 OH, or
R4 "=h and R5" =o-methyl and R6 "=sulfonyl; or
R4 "=h and R5" = -S (=o) 2 OH and R6 "=h, or
R4 "=h and R5" = -S (=o) 2 OH and R6 "=oh, or
R4 "=h and R5" = -S (=o) 2 OH and R6 "=methyl, or
R4 "=h and R5" = -S (=o) 2 OH and R6 "=o-methyl, or
R4 "= H and R5" = -S (=o) 2 OH and R6 "= -S (=o) 2 OH, or
R4 "=h and R5" = -S (=o) 2 OH and R6 "=sulfonyl; or
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) 2 OH, 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) 2 OH, 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) 2 OH, 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) 2 OH, 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, or
R4 "=oh and R5" =o-methyl and R6 "=o-methyl, or
R4 "=oh and R5" =o-methyl and R6 "= -S (=o) 2 OH, or
R4 "=oh and R5" =o-methyl and R6 "=sulfonyl; or
R4 "=oh and R5" = -S (=o) 2 OH and R6 "=h, or
R4 "=oh and R5" = -S (=o) 2 OH and R6 "=oh, or
R4 "=oh and R5" = -S (=o) 2 OH and R6 "=methyl, or
R4 "=oh and R5" = -S (=o) 2 OH and R6 "=o-methyl, or
R4 "= OH and R5" = -S (=o) 2 OH and R6 "= -S (=o) 2 OH, or
R4 "=oh and R5" = -S (=o) 2 OH 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) 2 OH, 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) 2 OH, 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) 2 OH, or
R4 "=methyl and R5" =oh and R6 "=sulfonyl, or
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) 2 OH, 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) 2 OH, or
R4 "=methyl and R5" =o-methyl and R6 "=sulfonyl; or
R4 "= methyl and R5" = -S (=o) 2 OH and R6 "= H, or
R4 "= methyl and R5" = -S (=o) 2 OH and R6 "= OH, or
R4 "= methyl and R5" = -S (=o) 2 OH and R6 "= methyl, or
R4 "= methyl and R5" = -S (=o) 2 OH and R6 "= O-methyl, or
R4 "= methyl and R5" = -S (=o) 2 OH and R6 "= -S (=o) 2 OH, or
R4 "= methyl and R5" = -S (=o) 2 OH 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) 2 OH, 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, or
R4 "=o-methyl and R5" =h and R6 "= -S (=o) 2 OH, 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) 2 OH, 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) 2 OH, 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) 2 OH, or
R4 "=o-methyl and R5" =o-methyl and R6 "=sulfonyl; or
R4 "=o-methyl and R5" = -S (=o) 2 OH and R6 "=h, or
R4 "=o-methyl and R5" = -S (=o) 2 OH and R6 "=oh, or
R4 "=o-methyl and R5" = -S (=o) 2 OH and R6 "=methyl, or
R4 "=o-methyl and R5" = -S (=o) 2 OH and R6 "=o-methyl, or
R4 "= O-methyl and R5" = -S (=o) 2 OH and R6 "= -S (=o) 2 OH, or
R4 "=o-methyl and R5" = -S (=o) 2 OH and R6 "=sulfonyl; or
R4 "=o-methyl and R5" =sulfonyl and R6 "=h, or
R4 "=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) 2 OH, or
R4 "=o-methyl and R5" =sulfonyl and R6 "=sulfonyl, or
R4 "= -S (=o) 2 OH and R5" =h and R6 "=h, or
R4 "= -S (=o) 2 OH and R5" =h and R6 "=oh, or
R4 "= -S (=o) 2 OH and R5" =h and R6 "=methyl, or
R4 "= -S (=o) 2 OH and R5" =h and R6 "=o-methyl, or
R4 "= -S (=o) 2 OH and R5" = H and R6 "= -S (=o) 2 OH, or
R4 "= -S (=o) 2 OH and R5" =h and R6 "=sulfonyl; or
R4 "= -S (=o) 2 OH and R5" =oh and R6 "=h, or
R4 "= -S (=o) 2 OH and R5" =oh and R6 "=oh, or
R4 "= -S (=o) 2 OH and R5" = OH and R6 "= methyl, or
R4 "= -S (=o) 2 OH and R5" = OH and R6 "= O-methyl; or
R4 "= -S (=o) 2 OH and R5" = OH and R6 "= -S (=o) 2 OH, or
R4 "= -S (=o) 2 OH and R5" = OH and R6 "= sulfonyl; or
R4 "= -S (=o) 2 OH and R5" = methyl and R6 "= H, or
R4 "= -S (=o) 2 OH and R5" = methyl and R6 "= OH, or
R4 "= -S (=o) 2 OH and R5" = methyl and R6 "= methyl, or
R4 "= -S (=o) 2 OH and R5" = methyl and R6 "= O-methyl, or
R4 "= -S (=o) 2 OH and R5" = methyl and R6 "= -S (=o) 2 OH, or
R4 "= -S (=o) 2 OH and R5" = methyl and R6 "= sulfonyl; or
R4 "= -S (=o) 2 OH and R5" = O-methyl and R6 "= H, or
R4 "= -S (=o) 2 OH and R5" = O-methyl and R6 "= OH, or
R4 "= -S (=o) 2 OH and R5" = O-methyl and R6 "= methyl, or
R4 "= -S (=o) 2 OH and R5" = O-methyl and R6 "= O-methyl, or
R4 "= -S (=o) 2 OH and R5" = O-methyl and R6 "= -S (=o) 2 OH, or
R4 "= -S (=o) 2 OH and R5" = O-methyl and R6 "= sulfonyl; or
R4 "= -S (=o) 2 OH and R5" = -S (=o) 2 oh=and R6 "= H, or
R4 "= -S (=o) 2 OH and R5" = -S (=o) 2 OH and R6 "= OH, or
R4 "= -S (=o) 2 OH and R5" = -S (=o) 2 OH and R6 "= methyl, or
R4 "= -S (=o) 2 OH and R5" = -S (=o) 2 OH and R6 "= O-methyl, or
R4 "= -S (=o) 2 OH and R5" = sulfonyl = and R6 "= H, or
R4 "= -S (=o) 2 OH and R5" = sulfonyl and R6 "= OH, or
R4 "= -S (=o) 2 OH and R5" = sulfonyl and R6 "= methyl, or
R4 "= -S (=o) 2 OH 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) 2 OH, 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) 2 OH, 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) 2 OH, or
R4 "=sulfonyl and R5" =methyl and R6 "=sulfonyl, or
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) 2 OH, or
R4 "=sulfonyl and R5" =o-methyl and R6 "=sulfonyl, or
R4 "=sulfonyl and R5" = -S (=o) 2 OH and R6 "=h, or
R4 "=sulfonyl and R5" = -S (=o) 2 OH and R6 "=oh, or
R4 "=sulfonyl and R5" = -S (=o) 2 OH and R6 "=methyl, or
R4 "=sulfonyl and R5" = -S (=o) 2 OH 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.
In the general formulae (V), (VI), (VII), (VIII), (IX), (X) and variants thereof, the substituted benzene ring bonded to the imino functionality is preferably selected from the group consisting of:
wherein the dotted line indicates the binding site to the cyclohexenimine ring.
In a still more preferred variant according to the first aspect of the invention, in the general formulae (V), (VII), (VIII) and variants thereof, the substituents R4', R5' and R6', which may be identical or different, are independently of one another selected from the group consisting of H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S (=O) 2 OH, and sulfonyl, provided that if the substituted benzene ring is monosubstituted, the substituents are located ortho or meta to the imino functionality of the general formulae (V), (VI) and (VIII) and not para to the imino functionality.
In still more preferred variants according to the first aspect of the invention, in the general formulae (VI), (IX), (X) and variants thereof, the substituents R4 ', R5 ' and R6 ', which may be identical or different, are independently of one another selected from the group consisting of H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S (=O) 2 OH and sulfonyl, provided that if the substituted benzene ring is monosubstituted, the substituents are located ortho or meta to the imino functionality of the general formulae (VI), (IX), (X) and not para to the imino functionality.
According to a first aspect of the invention, still more preferably, the sunscreen product, cosmetic or pharmaceutical formulation or home care product comprises at least one mycosporine amino acid compound selected from the group consisting of:
Table 3:
Or a tautomer or stereoisomer or salt of the above compounds or any mixture of the above compounds.
Of the above-specified retinoid amino acid compounds, the compounds MAA-1 and MAA-13 are particularly preferred because they have remarkable SPF properties and UVA photoprotection improving effects. Most preferred are acid compounds MAA-20, MAA-21, MAA-22, MAA-23, MAA-24, MAA-26, MAA-27, MAA-28, MAA-29, MAA-30, MAA-31 and amide compounds MAA-32, MAA-33, MAA-34, MAA-35, MAA-36, MAA-37, MAA-38 and MAA-39. The compounds having acid or amide functionality are photo-stable and temperature stable and exhibit stability in pH solutions or in oil-in-water emulsions and do not degrade compared to the corresponding ester analogues. Particularly preferred are the acid compounds MAA-20, MAA-21, MAA-22, MAA-23, MAA-24, MAA-26, MAA-27, MAA-28, MAA-29, MAA-30 and MAA-31 due to their stability and their increased solubility in water.
In particular, the retinoid amino acid compounds MAA-20, MAA-21, MAA-22, MAA-23, MAA-24, MAA-26, MAA-27, MAA-28, MAA-29, MAA-30 and MAA-31 have better stability over a wider pH range, in contrast to their respective ester compounds which hydrolyze and are therefore unstable in alkaline solutions/formulations having a pH above 9.
Due to their better solubility in water, the retinoid amino acid compounds may be incorporated into the aqueous phase of the emulsion at higher concentrations, resulting in improved SPF performance enhancing effects and improved UVA photoprotection in sunscreen products, cosmetic or pharmaceutical formulations or home care products.
According to a first aspect of the invention, still more preferably, the sunscreen product, cosmetic or pharmaceutical formulation or home care product comprises at least one mycosporine amino acid compound selected from the group consisting of:
MAA-A:
MAA-B:
And
MAA-C:
Or a tautomer or stereoisomer or salt thereof, or any mixture of the foregoing, wherein alkyl is preferably methyl or ethyl or propyl or isopropyl or butyl or isobutyl or tert-butyl, most preferably methyl.
The retinoid amino acid compounds according to the invention and as defined herein are used as a single substance or in admixture with one, two or more different retinoid amino acid compounds as defined herein.
Particularly preferred are mixtures of two retinoid amino acid compounds according to the invention and as defined herein. As demonstrated in the examples below, this mixture exhibits particularly excellent SPF performance and UVA photoprotection promoting effects.
The sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the first aspect of the present invention is further characterized in that it does not contain one or more of the following bacteriocin-like amino acid compounds:
Compound 1:
Compound 2:
compound 3:
compound 4:
compound 5:
compound 6:
compound 7:
compound 8:
compound 9:
And
Compound 10:
The various mycosporine amino acid compounds (b) as described herein comprise one or more chiral centers and may thus exist as racemic mixtures of enantiomers, mixtures of diastereomers or as enantiomerically or optically pure compounds. It should also be noted that the compounds of the present invention include the E and Z isomers or mixtures thereof, as well as the cis and trans isomers or mixtures thereof.
Thus, the chemical structures of the formulae (V) to (X) and variants and compounds thereof explicitly disclosed herein include all possible enantiomers and diastereomers or stereoisomers.
In certain embodiments, the retinoid amino acid compound (b) used according to the invention is isolated as E or Z isomer. In other embodiments, the compounds of the invention are mixtures of E and Z isomers.
Alternatively, the stereoisomerically pure compounds are used in sunscreen products, cosmetic or pharmaceutical preparations or home care products according to the invention. As used herein and unless otherwise indicated, the term "stereoisomerically pure" means that one stereoisomer of a compound is substantially free of other stereoisomers of the compound, or that one geometric isomer (e.g., about one double bond) is substantially free of other geometric isomers. For example, a stereoisomerically pure compound of the invention having one chiral centre will be substantially free of the opposite enantiomer of the compound. The stereoisomerically pure compound of the invention or a composition thereof having two chiral centers will be substantially free of other diastereomers of the compound. The stereoisomerically pure compounds of the invention or compositions thereof having a double bond capable of E/Z isomerisation will be substantially free of one of the E/Z isomers.
Typical stereoisomerically pure compounds include more than about 80% by weight of one stereoisomer or E/Z isomer and less than about 20% by weight of the other stereoisomers or E/Z isomers, more preferably more than about 90% by weight of the compound and less than about 10% by weight of the other stereoisomers or E/Z isomers, even more preferably more than about 95% by weight of the compound and less than about 5% by weight of the other stereoisomers or E/Z isomers, and most preferably more than about 97% by weight of the compound and less than about 3% by weight of the other stereoisomers or E/Z isomers.
As used herein and unless otherwise indicated, the term "stereoisomer-enriched" means a compound of the invention or a composition thereof that comprises greater than about 60% of one stereoisomer or E/Z isomer by weight of the compound of the invention, preferably greater than about 70% by weight, more preferably greater than about 80% of one stereoisomer or E/Z isomer by weight of the compound of the invention.
It should therefore be noted that the term "retinoid amino acid compound" according to formulae (V) to (X) and variants thereof, as well as the individual retinoid amino acid compounds specified herein, shall be construed as encompassing racemic mixtures of enantiomers, mixtures of diastereomers or enantiomerically or optically pure compounds, unless otherwise specified.
Due to their amino-cyclohexene-imine structure and their electron delocalization ability, the retinoid amino acid compounds according to formulae (V) to (X) and variants thereof are in equilibrium with their tautomeric structures, wherein the hydrogen of the amino group changes its position with the double bond of the cyclohexene ring.
Tautomerism is defined as each of two or more isomers of a compound that coexist in an equilibrium state and are readily interchanged by migration of an atom or group within the molecule. Over time, tautomeric pure or enriched systems will readily interchange into equilibrium.
The tautomer of formula (V) is represented by formula (V- τ):
The tautomer of formula (VI) is represented by formula (VI- τ):
The above principle of tautomerism and redeposition, which is explained based on the retinoid amino acid compounds according to formulae (V) and (VI), is equally applicable to any of the retinoid amino acid compounds defined by formulae (VII), (VIII), (IX), (X) and variants thereof, or to any of the individual retinoid amino acid compounds specified herein.
Thus, in the following and throughout the specification, references to a retinoid amino acid compound represented by any one of formulae (V) to (X) and variants thereof, or to individual retinoid amino acid compounds specified herein, are likewise intended to encompass tautomeric isomers thereof.
According to a first aspect of the invention, the retinoid amino acid compounds according to formulae (V) to (X) and their variants, as well as the individual retinoid amino acid compounds specified herein, are used in neutral (i.e. uncharged form) or in the form of their salts, such as acid addition salts with inorganic or organic acids.
The term "salt" in the context of the present invention refers to a salt of a compound having the desired effect or pharmacological activity of the parent compound. Such salts include:
(1) An acid addition salt with an inorganic acid, or with an organic acid, preferably a monovalent or polyvalent carboxylic acid, or
(2) Salts formed when acidic protons present in the starting compounds are replaced by metal ions (e.g., alkali metal ions, alkaline earth metal ions, or aluminum ions), or salts formed when coordinated with organic bases.
Among these salts, acid addition salts are also particularly preferred, since the retinoid amino acid compounds according to formulae (V) to (X) and their variants or the retinoid amino acid compounds specified herein comprise a protonizable N atom.
The inorganic acid forming an acid addition salt with the retinoid amino acid compound is preferably selected from the group consisting of hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and the like. Particularly preferred are hydrochloride or sulfate or phosphate salts.
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 the group consisting of saturated or mono-or polyunsaturated C1 to C30 mono-carboxylic acids, saturated or mono-or polyunsaturated C3 to 10 di-or tricarboxylic acids. The carboxylic acid may be mono-or polysubstituted with hydroxyl groups, preferably alpha-hydroxycarboxylic acids, wherein the hydroxyl groups are located on the carbon atoms adjacent to the carboxyl groups. Many representatives are naturally occurring in the form of so-called fruit acids. Preferred alpha-hydroxycarboxylic acids are malic acid, citric acid, 2-hydroxy-4-methyl mercaptobutyric acid, glycolic acid, isocitric acid, mandelic acid, lactic acid, tartronic acid or tartaric acid.
The organic acid forming an acid addition salt with the retinoid amino acid compound is preferably selected from the group consisting of amino acids, acetic acid, trifluoroacetic acid, propionic acid, caproic acid, cyclopentanepropionic acid, glycolic acid, pyruvic acid, lactic acid, malonic acid, oxalic acid, succinic acid, malic acid, maleic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, 3- (4-hydroxybenzoyl) benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, 1, 2-ethanedisulfonic acid, 2-hydroxyethanesulfonic acid, benzenesulfonic acid, 4-chlorobenzenesulfonic acid, 2-naphthalenesulfonic acid, 4-toluenesulfonic acid, camphorsulfonic acid, 4-methylbicyclo [2.2.2] -oct-2-ene-1-carboxylic acid, glucoheptonic acid, 3-phenylpropionic acid, trimethylacetic acid, t-butylacetic acid, lauryl sulfuric acid, gluconic acid, glutamic acid, hydroxynaphthoic acid, salicylic acid, stearic acid, muconic acid, 4-hydroxybutyric acid, and the like.
Suitable anionic counterions are in particular chloride, bromide, hydrogen sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and anions of C1 to C4-alkanoic acids, preferably formate, acetate, trifluoroacetate, propionate and butyrate, furthermore lactate, gluconate, and anions of polybasic acids such as succinate, oxalate, maleate, fumarate, malate, tartrate and citrate, furthermore sulfonate anions such as benzenesulfonate (benzenesulfonate), toluenesulfonate (p-toluenesulfonate), naphthalenesulfonate (naphthalene-2-sulfonate), methanesulfonate (methanesulfonate), ethanesulfonate (ethanesulfonate) and ethanedisulfonate. They can be formed by reacting the compounds according to the invention having basic functional groups with acids of the corresponding anions. Preferred salts of the compounds of formulae (I) to (III) and the individual retinoid amino acid compounds specified herein are chloride salts.
The metal ion for salt formation that replaces the acidic proton present in the starting compound is selected from the group consisting of: alkali metal ions (preferably Na+, K+ or Li+), alkaline earth metal ions (preferably Ca++ or Mg++) aluminum+++ or nh4+.
The coordinating organic base used for salification is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, N-methylglucamine, triethylamine, and the like.
In the following description and claims, unless otherwise indicated, the term "retinoid amino acid compound" includes compounds/molecules in neutral, uncharged form, as well as salt forms of the compounds.
The salt form of the retinoid amino acid compound results in lower log p OW and thus makes the compound more hydrophilic, which results in better water solubility. In particular, the cationic salts of the retinoid amino acid compounds support the emulsification process in the emulsion due to their surface activity (i.e., co-emulsifying properties). In addition, the cationic salt forms of the cephalosporin compounds exhibit excellent substantivity behaviour on skin and hair, most conditioning actives are cationic, conditioning effects result in softer skin feel which makes the final product more acceptable to consumers. In addition, the cationic salt forms of the retinoid amino acid compounds exhibit antimicrobial activity.
In a particularly advantageous variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the first aspect of the invention comprises one of the following combinations of components (a) and (b):
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), a combination of all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, with at least one compound according to the general formula (V) as defined herein, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, in combination with at least one compound according to the general formula (VI) as defined herein.
Such combinations of inorganic UV filters and retinoid amino acid compounds exhibit synergistic SPF performance and UVA photoprotection improving effects for sunscreen products, cosmetic or pharmaceutical formulations or home care products.
In a sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the first aspect of the invention, a more preferred combination of components (a) and (b) is:
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-1, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-2, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-3, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-4, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-5, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-6, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-7, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-8, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-9, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-11, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-12, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-13, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-14, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-16, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-17, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-20, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-21, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-22, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-23, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-24, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-25, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-26, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-27, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, in combination with MAA-28, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-29, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, in combination with MAA-30, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-31, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-32, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, in combination with MAA-, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-34, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, combined with MAA-35, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, in combination with MAA-36, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, in combination with MAA-37, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, in combination with MAA-38, or
■ At least one inorganic UV filter of titanium dioxide (TiO 2) (amorphous or crystalline, rutile and/or anatase form) and/or zinc oxide (ZnO) and/or iron oxide (Fe 2O3) and/or zirconium oxide (ZrO 2) and/or silicon dioxide (SiO 2) and/or manganese oxide (e.g., mnO), aluminum oxide (Al 2O3) and/or cerium oxide (Ce 2O3) and/or barium carbonate (BaCO 3) and/or calcium carbonate (CaCO 3), all of the above inorganic UV filters in the form of non-nanopigments, treated non-nanopigments and treated nanopigments, in combination with MAA-39;
In particular, the combination with the retinoid amino acid compound and the inorganic UV filter shows synergistic SPF performance and UVA photoprotection improving effect. This SPF performance and UVA photoprotection improving effect is especially observed when the retinoid amino acid is in its acid form or in its salt form, i.e. in its cationic form. Synergistic SPF performance and UVA photoprotection improvement effects are particularly pronounced for the retinoid amino acid compounds MAA-1 or MAA-13 and MAA-20 to MAA-39 when combined with any of the inorganic UV filters.
In the preparation of a sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention, the compounds defined herein may be used in combination with a further UV absorber different from the at least one inorganic UV filter (a) in order to further optimize the SPF, i.e. to obtain a high SPF in the range of 6 to 100, preferably in the range of 6 to 70, and to cover a broad UVA and UVB range.
Thus, at least an inorganic UV filter (a) in a sunscreen product, cosmetic or pharmaceutical formulation or home care product as defined herein is advantageously combined with at least one primary organic UV filter and/or with at least one secondary sun protection ingredient or secondary sun protection UV filter.
The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention therefore advantageously contains at least one additional primary organic UVA filter and/or UVB filter and/or broadband filter for their use in blocking UV radiation.
Non-limiting examples of such primary organic UV filters include:
(i) Slightly soluble UV filters (not significantly soluble in water or oil), such as methylenebis-benzotriazole-tetramethylbutylphenol, tris-biphenyltriazines, methanones, 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 solvents) such as bis-ethylhexyloxyphenol methoxyphenyl triazine, butyl methoxydibenzoyl methane (BMBM), oxybenzone, sulfoisophenone, diethylhexyl Butyrylamiyltriazinone (DBT), cresyl trisiloxane, ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate (EHS), ethylhexyl triazinone (EHT), homosalate, isopentyl p-methoxycinnamate, 4-methylbenzylidene camphor, octyl cyanobiphenyl acrylate (OCR), polysiloxane-15, and hexyl Diethylaminohydroxybenzoate (DHHB), and
(Iii) Water soluble UV filters such as phenylbenzimidazole sulfonic acid (PBSA), sulfoisophenone-sodium salt, bendienecarbosylic acid, camphorbenzalkonium methylsulfate, cinnabar, disodium phenyldibenzylimidazoletetrasulfonate, terephthalylene dicamphsylic acid, PABA and PEG-25PAB, and any mixtures thereof.
According to the invention, a number of different organic compounds can be used as UV filters. They fall into several structural categories:
(1) Benzophenone compounds
A. benzophenone-3 (BP 3)
B. Benzophenone-4 (BP 4)
(3) Salicylate salts
A. Homosalate (HMS)
2-Ethylhexyl salicylate (EHS)
(4) Para aminobenzoic acid and derivatives
A. dimethyl PABA ethylhexyl ester (OD-PABA)
B.4-para-aminobenzoic acid (PABA)
(5) Benzimidazole derivatives
A. Phenylbenzimidazole sulfonic acid (PMDSA)
B. phenyl bis-benzimidazole tetrasulfonate disodium salt (disodium bis-cercis-diene)
(6) Triazines
A. ethylhexyl triazone (OT)
B. Diethylhexyl Butyrylamide Triazinone (DBT)
C. Bis-ethylhexyl oxyphenol methoxyphenyl triazine (EMT)
(7) Benzotriazole compounds
A. cresol trazotrisiloxane (DRT)
B. Methylene bis-benzotriazolyl tetramethylbutylphenol (MBP, biscotrizole)
(8) Dibenzoylmethane derivatives
4-Tert-butyl-4' -methoxydibenzoylmethane (BM-DBM, avobenzone)
(9) Cinnamic acid esters
A. Ethylhexyl methoxycinnamate (OMC)
B. Iso-amyl p-methoxy cinnamate (IMC, A Mi Shazhi)
(10) Camphor derivative
A. Terephthalylene dicamphor sulfonic acid (PDSA)
3-Methylbenzylidene camphor (3 BC)
C. Benzylidene camphorsulfonic acid (BCSA)
D.4-Methylbenzylidene camphor (4-MBC)
E. Polyacrylamide methyl benzylidene camphor (PBC)
(11) Camphorbenzalkonium methyl sulfate (CBM)
In some cases, the UV filter is one or more of a para-aminobenzoic acid derivative, a salicylic acid derivative, a cinnamic acid derivative, a benzophenone or aminobenzophenone, an anthranilic acid derivative, b-diphenylacrylate derivative, a benzylidene camphor derivative, a phenylbenzimidazole derivative, a benzotriazole derivative, a triazine derivative, a bisresorcinol triazine, an imidazoline derivative, a benzylidene malonate derivative, a 4, 4-diarylbutadiene derivative, a benzoxazole derivative, a merocyanine, a malononitrile or malonate diphenylbutadiene derivative, a chalcone, and any mixture thereof.
The at least one primary organic UV filter is preferably selected from the group consisting of camphorbenzalkonium methyl sulfate, homosalate, benzophenone-3, phenylbenzimidazole sulfonic acid, terephthalylene dicarbamate sulfonic acid, butylmethoxydibenzoylmethane, benzylidene camphorsulfonic acid, octyl cyanobiphenyl acrylate, polyacrylamide methylbenzylidene camphor, ethylhexyl methoxycinnamate, PEG-25PABA, isopentyl p-methoxycinnamate, ethylhexyl triazone, cresol trazotrisiloxane, diethylhexyl butyrylamiyltriazone, 4-methylbenzylidene camphor, ethylhexyl salicylate, dimethyl PABA ethylhexyl ester, benzophenone-4, benzophenone-5, methylenebis-benzotriazole tetramethylbutylphenol (nanometers), disodium phenyldibenzoyltetrasulfonate, bis-ethylhexyloxyphenol methoxyphenyltriazine, polysiloxane-15, diethylaminohydroxy benzoyl benzoate, tris-biphenyl triazine (nanometers), phenylenediphenyl bis-diphenyltriazine, methoxypropylaminocyclohexenyl ethoxyethyl cyanoacetate, bis- (hydroxy benzoyl) piperazine, teaba, and any of the following, and mixtures thereof.
More preferably, the at least one primary organic UV filter is selected from the group consisting of camphorbenzalkonium methyl sulfate, benzophenone-3, terephthalenedicamphsylic acid, benzylenecamphorsulfonic acid, polyacrylamide methylbenzylenecamphor, PEG-25PABA, cresol trisiloxane, dimethyl PABA ethylhexyl ester, benzophenone-4, benzophenone-5, methylenebis-benzotriazole tetramethylbutylphenol, polysiloxane-15, titanium dioxide (nanometers), tris-biphenyltriazine (nanometers), phenylenediphenyl triazine, methoxypropylaminocyclohexenylethylenecyanoacetate, bis- (diethylaminohydroxybenzoyl) piperazine, benzophenone-8, dimethyl PAB A ethylhexyl ester, homosalate, phenylbenzimidazole sulfonic acid, butyl methoxydibenzoylmethane, octocrylic acid, ethylhexyl methoxycinnamate, isopentyl p-methoxycinnamate, ethylhexyl triazone, diethylhexyl triadimefriazinone, 4-methylbenzylenecamphor, ethylhexyl salicylate, phenylsodium tetramethoxybenzene sulfonate, bis-phenylhexanesulfonate, bis-phenylhexanyl benzoate, and mixtures of any of these.
Most preferably, the at least one primary organic UV filter is selected from the group consisting of homosalate, phenylbenzimidazole sulfonic acid, butyl methoxydibenzoylmethane, octyl cyanobiphenyl acrylate, ethylhexyl methoxycinnamate, isoamyl p-methoxycinnamate, ethylhexyl triazone, diethylhexyl butyrylaminotriazone, 4-methylbenzylidene camphor, ethylhexyl salicylate, disodium phenylbisbenzimidazole tetrasulfonate, bis-ethylhexyl oxyphenol methoxyphenyl triazine, diethylaminohydroxy benzoyl benzoate, menthyl anthranilate, and any mixture thereof.
Advantageously, the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention comprises at least one UVA filter and at least one UVB filter. Such sunscreen products, cosmetic or pharmaceutical formulations or home care products according to the present invention provide broad spectrum protection against light protection, i.e. protection against both UVA and UVB.
In a further preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention comprises a combination with one or more broadband filters selected from the group consisting of 2-ethylhexyl-2-cyano-3, 3-diphenylacrylate, ethyl-2-cyano-3, 3 '-diphenylacrylate, dihydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, tetrahydroxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-4' -methylbenzophenone, Sodium hydroxymoxybenzophenone sulfonate, disodium-2, 2 '-dihydroxy-4, 4' -dimethoxy-5, 5 '-disulfobenzophenone, phenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3 (1, 3-tetramethyl-1- (trimethylsilyl) oxy) disiloxy) propyl), 2' -methylene-bis- (6- (2H-benzotriazol-2-yl) -4-1, 3-tetramethylbutyl) phenol (methylene-bis-benzotriazol-tetramethylbutylphenol), 2, 4-bis- [4- (2-ethylhexyloxy) -2-hydroxyphenyl ] -1,3, 5-triazine, 2, 4-bis- [ { (4- (2-ethylhexyl oxy) -2-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine (INCI: anisoyltriazine), 2, 4-bis- [ { (4- (3-sulfonate) -2-hydroxypropoxy) -2-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine sodium salt, 2, 4-bis- [ { (3- (2-propoxy) -2-hydroxypropoxy) -2-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis- [ {4- (2-ethylhexyl oxy) -2-hydroxy } phenyl ] -6- [4- (2-methoxyethylcarbonyl) phenylamino ] -1,3, 5-triazine, 2, 4-bis- [ {4- (3- (2-propoxy) -2-hydroxypropoxy) -2-hydroxy } phenyl ] -6- [4- (2-ethylcarboxy) phenylamino ] -1,3, 5-triazine, 2, 4-bis- [ {4- (2-ethylhexyloxy) -2-hydroxy } phenyl ] -6- (1-methylpyrrolidin-2-yl) -1,3, 5-triazine, 2, 4-bis- [ { 4-tris- (trimethylsiloxysiloxy) -2-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis- [ {4- (2 "-methacryloxy) -2-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis- [ {4- (1 ',1',1',3',5',5',5 '-heptamethylsiloxy-2 "-methylpropyloxy) -2-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine, dioctyl-butylamide triazone (INCI: dioctyl-butylamide triazone), 2, 4-bis- [5-1 (dimethylpropyl) benzooxazol-2-yl- (4-phenyl) -imino ] -6- (2-ethylhexyl) -imino-1, 3, 5-triazine, 4',4" - (1, 3, 5-triazine-2, 4, 6-triamino) tris-benzoic acid-tris (2-ethyl-hexyl) (also: 2,4, 6-tris [ anilino (p-carbon-2 '-ethyl-1' -hexyloxy) ] -1,3, 5-triazine (INCI: octyl triazone), tris (2-ethyl-hexyl) tris (2-ethylhexyl) phenyl) tris (2-ethylhexyl) tria-carboxylate, 2,4, 6-terphenyl-4-yl-1, 3, 5-triazine, 2-ethylhexyl 4-methoxycinnamate (ethylhexyl methoxycinnamate), benzoic acid, 2-hydroxy-, 3, 5-trimethylcyclohexyl (homosalate), 2-ethylhexyl salicylate (ethylhexyl salicylate), 2-ethylhexyl 4- (dimethylamino) benzoate (dimethyl PABA ethylhexyl), N, N, N-trimethyl-4- (2-oxo-boron-3-ylmethylene), aniline methyl sulfate (camphorbenzammonium methyl sulfate), dimethyl diethyl benzalmalonate (polysiloxane-15), and any mixtures thereof.
The aforementioned primary organic UV filters that can be used in the context of the present invention are preferred, but naturally not limiting.
The primary organic UV filters described above are used as a single component in sunscreens or cosmetic or pharmaceutical preparations or comprise at least two, more preferably at least three, most preferably at least four or even more different UV filters.
The combination of different classes of effective sun-protecting UV filters, such as UVA filters, UVB, broadband filters, inorganic pigments, etc., provides reliable protection against different UV rays in the wavelength range 290nm to 400 nm.
In a further preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention comprises a primary organic and/or inorganic UV filter in such a way that the product or preparation according to the invention has a total sun protection factor SPF of from 6 to 100, preferably from 6 to 70. Such compositions according to the invention are particularly suitable for protecting skin, hair and nails.
In addition to the above-described set of primary inorganic and organic sun-protecting UV filters, secondary sun-protecting ingredients of the antioxidant type can also be advantageously used in the sun-protecting agent products, cosmetic or pharmaceutical preparations or home care products according to the invention to further optimize UV protection.
The secondary sunscreen ingredients of the antioxidant type interrupt the photochemical reaction chain that is initiated when UV rays penetrate the skin.
Typical examples of secondary sunscreen ingredients are very low compatible doses of amino acids (e.g. arginine, lysine, glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides such as D, L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotenoids, carotenes (e.g. alpha-carotene, beta-carotene, lycopene) and derivatives thereof, chlorogenic acids and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), thiosugars, propylthiopyrimidines and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cysteamine and glycosyl, N-acetyl, methyl, ethyl, propyl, pentyl, butyl and lauryl, palmitoyl, oleyl, alpha-linoleyl, cholesterol and glycerides thereof) and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionate and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoxylamine compounds (e.g. thioflavin sulfoxylamine, homocysteine sulfoxylamine, sulfoxylamine sulfone, penta-, hexa-and hepta-thionin sulfoxylamine), and (metal) chelators (e.g. alpha-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), alpha-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acids, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives thereof (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives thereof (e.g. vitamin E acetate), vitamin a and derivatives thereof (vitamin a palmitate) and coniferyl benzoate of benzoin resins, rutin and derivatives thereof, glycosylrutin, ferulic acid, furfurylglucol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyric acid, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, sinapic acid malate, sinapic acid ester derivatives, selenium and derivatives thereof (e.g. selenomethionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and derivatives of these active substances suitable for the purposes of the present invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids).
The group of secondary sunscreen ingredients also encompasses plant-based extracts. The plant-based extract has antioxidant and general photoprotective properties, and interrupts a photochemical reaction chain induced when UV rays penetrate into the skin, thus effectively preventing skin aging. the plant extract with UV protecting effect is selected from lignin/cellulose, lignin, hydrolyzed lignin, propolis and green propolis, rhizoma Alpiniae Officinarum extract, macroalgae and microalgae (thallus Porphyrae, red algae (umbilical thallus Porphyrae (Porphyra Umbilicalis), palladium (PALMARIA PALMATA), herba Zosterae marinae (SACCHARINA LATISSIMA), chlorella (Corallina pilulifera), phaeophyllinin (Eckloina cava), sargassum (Sargassum sagamianum), sargassum, herba Porphyrae, and radix Glycyrrhizae, Porphyra rosengurttii, sargassum thunbergii (Sargassum siliquastrum), sargassum horneri (Thalassiosira weissflogii)), green microalgae (e.g., neisseria (Interfilum) and Cladonia (Klebsormidium)), seaweeds (e.g., padina japonica (Padina australis), eucheuma cottonii), wampee (Pongamia Glabra) seed oil, Kalanjia (Karanja) oil (wampee (MILLETTIA PINNATA)), rhatania Extrakt (burdock thorn cone (KRAMERIA LAPPACEA)), lichen, soybean, caper (Capparis spinosa), bamboo, green coffee oil, briqi (Buriti) oil (Coprinus comatus (Mauritia flexuosa)), black sea cucumber (Holothuria atra), cyanobacteria, white velvet water dragon (Polypodium leucotomos), and combinations thereof, Green tea, black tea (CAMELLIA SINENSIS), aloe, walnut, borage oil, evening primrose oil, avocado oil, tea tree oil, red clover (Trifolium pratense l.), soybean (Glycine max l.), cape jasmine (Capparis spinosa), almond, flammulina tree (Spathodea campanulata), silybum marianum (Silybum marianum l.), cashew shell, grape, blood orange, pomegranate (punica granatum (Punica granatu)) bilberry (Vaccinium myrtillus l.), vaccinium uliginosum (Vaccinium uliginosum l.), strawberry (FRAGARIA ANANASSA), polygonum multiflorum (Polygonum multiflorum Thunb), turmeric (Curcuma longa l.), ginseng (Panax ginseng), hedera helix (Hedera helix), broccoli (Brassica oleracea VAR ITALICA), and a combination of the above, Tamarind (Tamarindus indica), opuntia ficus, coffee, basil (Ocimum basicum, linn.), pomegranate seed oil (Punica granatum) wheat germ oil (Triticum vulgare), blackcurrant seed oil (Ribes nigrum), sesame oil (Sesamum indicum), carrot (Daucuscarota sativa), raspberry (Rubus idaeus), traditional medicinal plants from Styrax (Aporosa lindleyana (Euphorbiaceae), a plant oil (Euphorbiaceae), ATALANTIA CEYLANICA (Rutaceae), hibiscus furcatus (Malvaceae), olaxzeylanica (Cymosaceae), herba Hedyotidis Diffusae (Ophiorrhiza mungos) (Rubiaceae), argyreia populifolia (Convolvulaceae), radix Ardisiae Crispae (Ipomoea mauritiana) (Convolvulaceae), rhizoma Dioscoreae (Lasia spinosa) (Araceae), herba Hedyotidis Diffusae (Leucas zeylanica) (Labiatae), and, Plectranthus zeylanicus (Labiatae)) from Brazil (D.gardneriana seeds, L.microphyllla leaves, oryctolagus gracilis (Amburana cearensis), quebracho (Aspidosperma cuspa), quebracho (Aspidosperma pyrifolium), croton sonderianus, tin tree (Curatella americana)、Dimophandra gardneriana、Lippia microphylla、Luehea paniculata、Sida galheirensis),, and any mixtures thereof.
Preferably, the plant extract having UV protective properties is selected from the group consisting of lignin/cellulose, lignin, hydrolyzed lignin, galangal extract, laver, rhodophyta (Porphyra), green microalgae (e.g., neurospora and Clariana), seaweed (e.g., padina japonica, eucheuma cottonii), water yellow skin seed oil, kalannja oil (Yu She Citong oil), dragon blood tree extract (Lapatience madder extract), soybean, bamboo, buLi's oil (Murisa palm oil), cyanobacteria, phenol-Boke (white velvet-foot fern), green tea, black tea (tea tree), aloe, evening primrose oil, cashew shell, pomegranate (Granati) and any mixtures thereof.
Advantageously, the amount of secondary sunscreen material in the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention is advantageously from 0.005 to 5.0 wt%, preferably from 0.01 to 4.0 wt%, and most preferably from 0.05 to 3.0 wt%, based on the total weight of the ready-to-use formulation.
UV filters are incorporated into the aqueous or lipophilic parts of sunscreen products, cosmetic or pharmaceutical preparations or home care products, depending on whether they are water or oil (fat) soluble/miscible UV filters, or may even be added to the final product by standard methods known to the person skilled in the art.
The at least one inorganic UV filter (a) according to the first aspect of the invention is present in the sunscreen product, cosmetic or pharmaceutical formulation or home care product in an amount of from 0.5 to 60.0 wt%, based on the total weight of the final formulation. In a preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product comprises the inorganic UV filter (a) in an amount of from 0.3 to 55.0% by weight, based on the total weight of the final formulation. In a more preferred variant, the inorganic UV filter (a) is advantageously used in an amount of 0.1% to 50.0% by weight, based on the total weight of the final formulation, in a sunscreen product, a cosmetic or pharmaceutical formulation or a home care product. In a most preferred variant, the inorganic UV filter is advantageously used in a sunscreen product, a cosmetic or pharmaceutical formulation or a home care product in an amount of from 1.0 to 45.0% by weight, based on the total weight of the final formulation.
For a mixture of inorganic UV filters, the above amounts relate to the total content of inorganic UV filters in the mixture, i.e. the amount is the sum of the contents of all inorganic UV filters in the mixture.
The inorganic UV filter (a) and additional UV protective components such as primary organic UV filters and secondary sun protection ingredients (i.e. the total of all UV filters) as defined herein are present in the sunscreen product, cosmetic or pharmaceutical formulation or home care product of the present invention in an amount of 0.1 to 85.0 wt% based on the total weight of the final formulation. In a preferred variant, the sunscreen product, cosmetic or pharmaceutical formulation or home care product comprises the inorganic UV filter (a) as defined herein and further primary and secondary UV protecting components in an amount of 0.3 to 80.0 wt%, based on the total weight of the final formulation. In a more preferred variant, the inorganic UV filter (a) as defined herein and the further primary and secondary UV protective components are advantageously used in a sunscreen product, a cosmetic or pharmaceutical formulation or a home care product in an amount of from 0.5 to 75.0 wt.%, based on the total weight of the final formulation. Thus, the above amounts relate to the sum of the contents of all UV filter/UV protection components present in the sunscreen or cosmetic, pharmaceutical or home care formulation.
The at least one mycosporine amino acid compound (b) according to the first aspect of the invention is present in a sunscreen product, a cosmetic or pharmaceutical formulation or a home care product in an amount of from 0.001 to 15.0 wt%, based on the total weight of the final formulation. In a preferred variant, the sunscreen product, cosmetic or pharmaceutical preparation or home care product comprises at least one mycosporine amino acid compound (b) in an amount of from 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 amino acid compound (b) is advantageously used in an amount of 0.05 to 7.5% by weight, based on the total weight of the final formulation, in a sunscreen product, a cosmetic or pharmaceutical formulation or a home care product. In a most preferred variant, the at least one mycosporine amino acid compound (b) is advantageously used in an amount of 0.1 to 5.0% by weight, based on the total weight of the final formulation, in a sunscreen product, a cosmetic or pharmaceutical formulation or a home care product.
For a mixture of the retinoid amino acid compounds (b), the above amounts relate to the total content of the retinoid amino acid compounds in the mixture, i.e. the amount is the sum of the contents of all the retinoid amino acid compounds (b) in the mixture.
Advantageously, the sunscreen product according to the first aspect of the invention comprises
(I) 0.5 to 60.0% by weight of at least one inorganic UV filter, and
(Ii) 0.001 to 15.0 wt% of at least one mycosporine-like amino acid compound as defined herein;
Based on the total weight of the final formulation.
In a preferred variant, the cosmetic or pharmaceutical preparation according to the first aspect of the invention comprises
(Iii) 1.0 to 45.0% by weight of at least one inorganic UV filter, and
(Iv) 0.1 to 5.0% by weight of at least one retinoid amino acid compound as defined herein;
Based on the total weight of the final formulation.
The sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention provides broad spectrum photoprotection to the skin and thus protection against both UVA and UVB radiation. The Sun Protection Factor (SPF) is a measure of UVB protection, as described above. Typically, the compositions of the present invention have an SPF of at least 6. However, the SPF may be varied as desired. The type and amount of UVA and UVB filters can be varied to achieve the desired level of SPF.
Preferably, the SPF (UVB) of the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention is at least 6, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or even higher.
Furthermore, the SPF (UVA) or UVA SP of the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention is from 1 to 50, preferably at least 10, and most preferably greater than 2.
In the context of the present invention, it is also possible and in some cases advantageous to combine the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the first aspect of the present invention with other conventional active substances, adjuvants or additives conventionally used in sunscreen products, cosmetic or pharmaceutical compositions or home care products as described further below in order to obtain a ready-to-use formulation or formulation.
Other active agents and/or adjuvants and/or additives or adjuvants are, for example, abrasives, anti-acne agents, anti-skin aging agents, anti-cellulite agents, anti-dandruff agents, anti-inflammatory agents, anti-irritants, irritation inhibitors, antioxidants, alkanediols, astringents, odor absorbers, antiperspirants, preservatives, antistatics, antibacterials, adhesives, buffers, carrier materials, oil components, chelating agents, cell irritants, cleaning agents, depilatory, surfactant, deodorant, antiperspirant, softener, emulsifier, enzyme inhibitor, essential oil, fiber, film-forming agent, water resistance improver, fixative, foaming agent, foam stabilizer, and water resistance improver an anti-foaming agent, a foam booster, a gelling agent, a gel forming agent, a hair care agent, a hair styling agent, a hair straightening agent, a moisture supplying agent, a moisture retaining agent, a bleaching agent, an enhancing agent, a hair styling agent, a hair straightening agent, a hair styling agent detergents, optical brighteners, impregnating agents, anti-soiling agents, dyes, friction reducers, lubricants, moisturizing creams, ointments, opacifiers, plasticizers, spreaders, polishing agents, preservatives, gloss agents, green and synthetic polymers, powders, proteins, recoating agents, abrasives, silicones, skin soothing agents, skin cleansers, skin care agents, skin healing agents, skin lightening agents, skin protectants, skin softeners, hair promoters, cooling agents, skin coolants, warming agents, skin warming agents, stabilizers, surfactants, antibacterial agents, detergents/surfactants, fabric conditioning agents, suspending agents, skin tanning agents, actives that regulate skin or hair pigmentation, matrix metalloproteinase inhibitors, skin moisturizers, glycosaminoglycan stimulators, TRPV1 antagonists, desquamation agents, anti-cellulite agents or fat enhancers, hair growth activators or inhibitors, thickeners, rheology additives, vitamins, oils, waxes, pearlescent waxes, fats, phospholipids, saturated fatty acids, mono-or polyunsaturated fatty acids, alpha-hydroxy acids, polyhydroxy fatty acids, liquefying agents, dyes, color fixatives, pigments, preservatives, fragrances or perfume oils, perfumes, flavoring substances, odoriferous substances, polyols, electrolytes, organic solvents, and mixtures of two or more of the foregoing as further described below.
The above-mentioned cosmetic or pharmaceutical excipients and/or active substances and/or additives and/or auxiliary carriers, oil components, rheology additives, hydrotropes, solubilizers, powders, film formers, water resistance improvers, skin moisturizing and/or water retention substances, soothing substances, physiological cooling agents, alkanediols, antioxidants, anti-skin aging agents, matrix metalloproteinase inhibitors (MMPI), anti-inflammatory agents, TRPV1 antagonists, emulsifiers, antimicrobial agents, preservatives, antibacterial or antifungal active substances, chelating agents, surfactants, fragrance/perfume oils or perfume oils, and any mixtures of two or more of the above-mentioned substances are particularly preferred in the preparation of sunscreen products, cosmetic and pharmaceutical preparations or household care products.
Carrier-sunscreen products, cosmetics or pharmaceuticals, in particular dermatological preparations or home care products, in the form of ointments, pastes, creams and gels etc. as defined herein are preferably based on a carrier. The most commonly acceptable carrier is water. Acceptable carriers other than water include glycerin, C1-4 alcohols, organic solvents, fatty alcohols, fatty ethers, fatty esters, polyols, glycols, vegetable oils, mineral oils, liposomes, lamellar lipid materials, water, or mixtures thereof. Non-limiting examples of organic solvents include monohydric and polyhydric alcohols such as ethanol, isopropanol, propanol, benzyl alcohol and phenethyl alcohol, or ethylene glycol or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or their ethers such as, for example, propylene glycol, butylene glycol, hexylene glycol, monomethyl ether of dipropylene glycol and alkyl ethers of diethylene glycol, for example, monoethyl or monobutyl ethers of diethylene glycol. Examples of other suitable organic solvents are ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, propylene glycol and glycerol. The organic solvent may be a volatile or non-volatile compound. The total amount of carrier in the composition may vary, but is typically 40 to 90 weight percent, based on the total weight of the composition.
The compositions of the present invention may include at least one water-soluble or organic solvent. Non-limiting examples of organic solvents include monohydric and polyhydric alcohols such as ethanol, isopropanol, propanol, benzyl alcohol and phenethyl alcohol, or ethylene glycol or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or their ethers such as, for example, propylene glycol, butylene glycol, hexylene glycol, monomethyl ether of dipropylene glycol and alkyl ethers of diethylene glycol, for example, monoethyl or monobutyl ethers of diethylene glycol. Examples of other suitable organic solvents are ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, propylene glycol and glycerol. The organic solvent may be a volatile or non-volatile compound.
Further non-limiting examples of water-soluble solvents include alkanols (polyols such as ethylene glycol and polyols) such as glycerol, 1,2, 6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, hexylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 1, 3-butylene glycol, 2, 3-butylene glycol, 1, 4-butylene glycol, 3-methyl-1, 3-butylene glycol, 1, 5-pentylene glycol, tetraethylene glycol, 1, 6-hexylene glycol, 2-methyl-2, 4-pentylene glycol, polyethylene glycol, 1,2, 4-butanetriol, 1,2, 6-hexanetriol, 2-butene-1, 4-diol, 2-ethyl-1, 3-hexylene glycol, 2-methyl-2, 4-pentylene glycol, 1, 2-hexylene glycol, 1, 2-heptylene glycol, 1, 2-octylene glycol, 1, 2-decylene glycol and 4-methyl-1, 2-pentylene glycol; 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 monoisopropyl ether, diethylene glycol monoisopropyl 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 monoisopropyl ether, dipropylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono N-propyl ether and dipropylene glycol mono isopropyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbitol, sorbitan, acetin, diacetin, triacetin, sulfolane, and any mixtures thereof. The total amount of water-soluble solvent or organic solvent in the composition according to the invention may vary, but is typically from 0.1 to 50% by weight, based on the total weight of the composition.
Solubilizer the compositions of the present invention may comprise at least one solubilizer. Solubilizers are compounds that help to solubilize UV filters and/or other components in the composition. A particularly useful but non-limiting example of a solubilizing agent is a hydrotrope. Hydrotropes (or hydrotropes) are a diverse, typical class of water-soluble compounds that can be characterized by amphiphilic molecular structures and the ability to significantly increase the solubility of poorly soluble organic molecules in water. Non-limiting examples of hydrotropes include sodium 1, 3-benzenedisulfonate, sodium benzoate, sodium 4-pyridinecarboxylate, sodium salicylate, sodium benzenesulfonate, caffeine, sodium p-toluenesulfonate, sodium butyldiglycol sulfate, 4-aminobenzoic acid HCl, sodium cumene sulfonate, N-diethyl nicotinamide, N-pyridine methyl nicotinamide, N-allyl nicotinamide, 2-methacryloyloxyethyl phosphorylcholine, resorcinol, butylurea, pyrogallol, N-methylpyridine acetamide 3.5, procaine HCl, proline HCl, nicotinamide, pyridine, 3-methylpyridine amine, sodium ibuprofen, sodium xylenesulfonate, ethyl carbamate, pyridoxal hydrochloride, sodium benzoate, 2-pyrrolidone, ethylurea, N-dimethylacetamide, N-methylacetamide, and isoniazid, and any mixtures thereof. In some cases, particularly useful hydrotropes include nicotinamide (niacinamide), caffeine, sodium PCA, sodium salicylate, urea, and hydroxyethyl urea, particularly nicotinamide (niacinamide) and/or caffeine. Combinations of two or more, three or more or four or more hydrotropes may also be used in the compositions according to the invention. The total amount of solubilizer in the compositions of the present invention may vary, but is typically in an amount of from 0.01% to 20% by weight, based on the total weight of the composition.
The oil component of the sunscreen product, cosmetic or pharmaceutical formulation or home care product may comprise at least one oil phase or at least one oil component, wax, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, talc and zinc oxide or any mixtures thereof. The powder includes a carrier such as lactose, talc, silica, aluminum 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, and the like, or any mixtures thereof. However, formulations based on water alone are also possible. Oil, oil-in-water, water-in-oil emulsions, and the like are preferred.
An oily phase or oil component which may be suitable in a sunscreen product, cosmetic, pharmaceutical formulation or home care product according to the invention is, for example, a vegetable oil, hydrocarbon, fatty alcohol, fatty acid ester or a mixture of two or more of the foregoing oil components.
The oily phase or oil component in the sunscreen product, cosmetic, pharmaceutical formulation is preferably a vegetable oil, and even more preferably a liquid vegetable oil. It may also advantageously be a mixture of two or more vegetable oil components, in particular a liquid vegetable oil mixture.
Vegetable or vegetable oils are oils extracted from seeds or less from other parts of fruits. Like animal fats, vegetable oils are mixtures of triglycerides. Soybean oil, canola oil and cocoa butter are examples of vegetable oils from seeds. Olive oil, palm oil and rice bran oil are examples of oils from other parts of fruit. In common usage, vegetable or vegetable oil may refer exclusively to vegetable fat that is liquid at room temperature or skin temperature of 35 ℃ to 37 ℃. Vegetable oils are generally edible.
The term "vegetable oil" also includes unsaturated vegetable oils. Unsaturated oils or vegetable oils may be converted to oils of higher melting point by partial or complete "hydrogenation". The hydrogenation process involves "sparging" the oil with hydrogen in the presence of a catalyst (typically a powdered nickel compound) at high temperature and pressure. When each carbon-carbon double bond is chemically reduced to a single bond, two hydrogen atoms each form a single bond with two carbon atoms. The process of eliminating double bonds by adding hydrogen atoms is called saturation, and as saturation increases, the oil is gradually completely hydrogenated. The oil may be hydrogenated to increase resistance to rancidity (oxidation) or to alter its physical properties. As the saturation increases, the viscosity and melting point of the oil increases.
In a preferred variant, the vegetable oil is selected from the group consisting of: avocado (avocado oil), white fir seed oil, victoria farnesiana seed oil, kiwi (kiwi fruit) seed oil, amaranth seed oil, peanut (peanut) oil, mu Lumu Lu Zi butter, gallery Ma Zi butter, gallery Ma Ziyou, common star vine fruit oil, common star vine seed oil, oat bran powder (oat) kernel oil, white mustard seed oil, canola (rapeseed) seed oil, shea butter, shea (shea) oil, calendula seed oil, jatropha seed oil, taka Ma Haka seed oil, camellia seed oil, nettle tea seed oil, hemp seed/stem oil, rapeseed oil, safflower (safflower dye) seed oil Chlorella oil, watermelon (watermelon) seed oil, citrus aurantium (lime) seed oil, citrus sinensis (orange) seed oil, grapefruit (grapefruit) seed oil, cocoa (coconut) oil, coconut (coconut) seed butter of Palmaceae, coffee (coffee) seed oil of Rubiaceae, chlorella oil (biotechnology), hazelnut (hazelnut) seed oil, melon (melon) seed oil, cucumber (cucumber) seed oil, pumpkin (pumpkin) seed oil, oil palm (palm) seed oil, soybean (soybean) oil, cotton seed oil of Malvaceae plant, the oil is selected from the group consisting of compositae (sunflower) seed oil, macadamia nut seed oil, mangosteen (mango) seed oil, balm seed oil, microalgae oil, moringa seed oil, evening primrose (evening primrose) oil, olea (olive) seed oil, rice (rice) bran/germ oil, rice (rice) bran oil, rice (rice) germ oil, rice (rice) lipid, rice (rice) seed oil, poppy seed oil, passion fruit seed oil, avocado (avocado) butter, avocado (avocado) oil, almond (sweet almond) oil, apricot (apricot) kernel oil, peach (peach) oil, pomegranate seed oil, apple (apple) seed oil, castor oil/caproic acid/capric triglyceride, castor (castor) oil, dog rose fruit oil, musk rose seed oil, raspberry (raspberry) seed oil, sesame (sesame seed oil, soybean glyceride, cocoa butter, wheat (grape (maize) germ oil, wheat (maize germ oil), wheat (maize germ (maize) oil, maize germ (maize germ oil).
The vegetable oils specified above are the most common natural lipid ingredients used as the basic substance for the manufacture of cosmetic or pharmaceutical formulations.
Hydrocarbons (mineral oils) are generally organic compounds composed entirely of hydrogen and carbon. As defined according to IUPAC nomenclature or organic chemistry, the classification of hydrocarbons is as follows:
1. Saturated hydrocarbons are the simplest hydrocarbon species. They consist entirely of single bonds and are saturated with hydrogen. The formula of the acyclic saturated hydrocarbon (i.e., alkane) is C nH2n+2. The most common form of saturated hydrocarbon is C nH2n+2(1-r), where r is the number of rings. The hydrocarbon having just one ring is a cycloalkane. Saturated hydrocarbons are the basis for petroleum fuels and have been found to be linear or branched.
2. Unsaturated hydrocarbons have one or more double or triple bonds between carbon atoms. Hydrocarbons having double bonds are known as olefins. The hydrocarbon having one double bond has the formula C nH2n (assumed to be a non-cyclic structure). Hydrocarbons containing triple bonds are known as alkynes. The hydrocarbon having one triple bond has the formula C nH2n-2.
3. Aromatic hydrocarbons (also referred to as aromatic hydrocarbons) are hydrocarbons having at least one aromatic ring.
The hydrocarbon may be, inter alia, a liquid (e.g., hexane and benzene), a wax, or a low melting point solid (e.g., paraffin 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, branched and cyclic structures with carbon chain lengths greater than C14. Mineral oils and waxes are other chemicals from naturally occurring crude oils. They consist essentially of Mineral Oil Saturated Hydrocarbons (MOSH) and Mineral Oil Aromatic Hydrocarbons (MOAH). Hydrocarbons have been used in skin and lip care cosmetic products for decades for their excellent skin tolerance as well as high protection and cleaning properties and a wide range of viscosity options. Unlike vegetable oils, mineral oils do not cause allergies because they are highly stable and are not prone to oxidation or rancidity.
Fatty alcohols (or long chain alcohols) are typically high molecular weight linear primary alcohols derived from natural fats and oils, but may also range from as few as 4 to 6 carbons up to 22 to 26 carbons. The exact chain length will vary from source to source. Some commercially important fatty alcohols are lauryl alcohol, stearyl alcohol and oleyl alcohol. They are colorless oily liquids (for smaller carbon numbers) or waxy solids, but impure samples may appear yellow. Fatty alcohols typically have an even number of carbon atoms and a single alcohol group (-OH) attached to the terminal carbon. Some fatty alcohols are unsaturated and some are branched. It has been found that in nature most fatty alcohols are waxes, which are esters of fatty acids and fatty alcohols. The traditional sources of fatty alcohols are mostly various vegetable oils, and these are still large-scale raw materials. The alcohol is obtained from triglycerides (fatty acid triesters), which are the main components of the oil. The process involves transesterification of triglycerides to yield methyl esters, which are then hydrogenated to yield fatty alcohols. Fatty alcohols may also be prepared from petrochemical sources. In the Ziegler process, triethylaluminum oligomer is used, followed by air oxidation. Alternatively, ethylene may be oligomerized to a mixture of olefins, the mixture hydroformylated to an odd numbered aldehyde, and the aldehyde subsequently hydrogenated. Fatty alcohols are mainly used in the production of detergents and surfactants. They are also components of cosmetic solvents. They are used in cosmetics as co-emulsifiers, emollients and thickeners.
In a preferred variant, the fatty alcohol is selected from the group consisting of phenylpropanol, dimethylphenylbutanol, hexyldecanol, octyldodecanol, octyldecanol, tridecanol, isostearyl alcohol, phenylisohexanol, phenylpropanol, trimethylphenylpropanol, isoamyl alcohol, isostearyl alcohol and isotridecanol. In a more preferred variant, the fatty alcohol is selected from the group consisting of hexyldecanol, octyldodecanol, phenylpropanol, isoamyl alcohol, and mixtures of two or more of the foregoing fatty alcohols. The fatty alcohols may be used as a single component or in admixture with one or more additional different fatty alcohols as specified above.
Fatty acid esters are a type of ester produced from a combination of fatty acids and alcohols. When the alcohol component is glycerol, the fatty acid ester produced may be a monoglyceride, diglyceride or triglyceride. The fatty acid ester has conditioning effect of softening skin to generate smooth feeling. They are also added to cosmetics to dissolve highly polar active ingredients and UV absorbers. Esters of linear fatty acids and lower alcohols are effective for dissolving sparingly soluble components in oils, by gentle impingement during application. Isostearic acid and other liquid oils having branched and unsaturated fatty acids are commonly used as emollients. Esters of higher fatty acid esters and higher alcohols having relatively high melting points are added to skin creams to regulate the application Tu Chugan.
Oil bodies and emollients the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention advantageously comprises one or more oil bodies or emollients. Emollients are oily or oily substances that help smooth and soften the skin and may also reduce skin roughness, cracking or irritation. In particular, in sunscreen products, emollients keep crystalline and oil-soluble organic and inorganic UV filters in solution and prevent them from recrystallizing. In addition, emollients act as wetting agents for inorganic UV filters to disperse uniformly in the formulation. Suitable oils are, for example, guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of straight-chain C 6-C22 -fatty acids with straight-chain or branched-chain C 6-C22 -fatty alcohols, or esters of branched C 6-C13 -carboxylic acids with linear or branched C 6-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, myristyl stearate, stearyl palmitate, stearic stearate, isostearic stearate, oleic stearate, behenic stearate, erucic stearate, myristic isostearate, palmitic isostearate, isostearic stearate, stearic isostearate, isostearic isostearate, oleic isostearate, isostearic acid isostearate, behenic isostearate, Oleic acid isostearate, myristic acid oleate, palmitic acid oleate, stearic acid oleate, isostearic acid oleate, oleic acid oleate, behenic acid oleate, erucic acid oleate, myristic acid behenic acid ester, palmitic acid behenic acid ester, stearic acid behenic acid ester isostearic acid behenate, oleic acid behenate, behenate erucic acid ester, erucic acid ester sinapine palmitate, sinapine stearate, sinapine isostearate sinapine oleate, sinapine behenate and sinapine erucate. Also suitable are esters of linear C 6-C22 -fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C 18-C38 -alkyl hydroxycarboxylic acids with linear or branched C 6-C22 -fatty alcohols, in particular dioctyl malate, linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, Dimer or trimer alcohols) and/or esters of Guerbet alcohols, triglycerides based on C 6-C10 fatty acids, liquid mono-/di-/triglyceride mixtures based on C 6-C18 fatty acids, esters of C 6-C22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C 2-C12 dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C 6-C22 fatty alcohol carbonates such as, for example, dioctyl carbonateCC), based on guerbet carbonates of fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, benzoates with linear and/or branched C 6-C22 -alcohols (e.gTN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dioctyl etherOE), ring-opened products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicone, silicone methicone grades, etc.) and/or aliphatic or cycloalkanes such as, for example, squalane, squalene or dialkylcyclohexane, and any mixtures thereof.
Powder the composition as defined herein may optionally comprise a powder. The optional powder provides a formulation that makes the skin smoother and softer. Representative powders include talc, mica, magnesium carbonate, calcium carbonate, magnesium silicate, magnesium aluminum silicate, silica, titanium dioxide, zinc oxide, red iron oxide, yellow iron oxide, black iron oxide, polyethylene powder, methacrylate powder, polystyrene powder, silk powder, solid powder materials which may be preferred components of the composition according to the invention are hydrocolloids such as starch, degraded starch, chemically or physically modified starch, dextrins, (powdered) maltodextrins (preferably having a dextrose equivalent value of 5 to 25, preferably 10-20), lactose, silica, dextrose, modified cellulose, gum arabic, gum ghatti, tragacanth, karaya gum, carrageenan, pullulan, curdlan, xanthan gum, gellan gum, guar flour, carob flour, alginate, agar, pectin, inulin, and mixtures of two or more of these solids (preferably having a dextrose equivalent value of 15-20), lactose, silica, and/or dextrose.
Rheology modifier the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention advantageously comprises one or more thickeners and/or rheology modifiers. The rheology modifier is present in an amount that prevents the composition from significantly dripping or pooling after application to the skin or surface. Preferably, the rheology modifier is a carbomer. In some embodiments, the rheology modifier is selected from stearic acid, palmitic acid, stearyl alcohol, cetyl alcohol, behenyl alcohol, stearic acid, palmitic acid, a polyethylene glycol ether of stearyl alcohol having an average of about 1 to about 21 ethylene oxide units, a polyethylene glycol ether of cetyl alcohol having an average of about 1 to about 5 ethylene oxide units, and mixtures thereof.
Further examples of rheology modifiers include thickeners or gelling agents, including substances that can increase the viscosity of the composition. Thickeners include those that can increase the viscosity of the composition without substantially altering the efficacy of the active ingredient in the formulation. Thickeners may also increase the stability of the formulations of the present application. In certain aspects of the application, the thickener comprises hydrogenated polyisobutene or trihydroxystearin, or a mixture of both. Further non-limiting examples of additional thickeners that may be used in the context of the present application include carboxylic acid polymers, crosslinked polyacrylate polymers, polyacrylamide polymers, polysaccharides, and gums. Examples of carboxylic acid polymers include crosslinked compounds containing one or more monomers derived from acrylic acid, substituted acrylic acid, and salts and esters of these acrylic acid and substituted acrylic acid, wherein the crosslinking agent contains two or more carbon-carbon double bonds, and is derived from a polyol (see CTFA international cosmetic ingredient dictionary (CTFA International Cosmetic Ingredient Dictionary), fourth edition, 1991, pages 12 and 80). Examples of commercially available carboxylic acid polymers include carbomers, which are homopolymers of acrylic acid crosslinked with allyl ethers of sucrose or pentaerythritol (e.g., carbopol TM series 900 from b.f. goodrich). Non-limiting examples of crosslinked polyacrylate polymers include cationic and nonionic polymers.
Non-limiting examples of polyacrylamide polymers (including nonionic polyacrylamide polymers, including substituted branched or unbranched polymers) include polyacrylamide, isoparaffin and laureth-7, acrylamide and multiblock copolymers of substituted acrylamide with acrylic acid and substituted acrylic acid.
Non-limiting examples of polysaccharides include cellulose, carboxymethyl hydroxyethyl cellulose, cellulose acetate propionate carboxylate, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, methyl hydroxyethyl cellulose, microcrystalline cellulose, sodium cellulose sulfate, and mixtures thereof. Another example is alkyl substituted cellulose wherein the hydroxyl groups of the cellulose polymer are hydroxyalkylated (preferably hydroxyethylated or hydroxypropylated) to form hydroxyalkylated cellulose, which is then further modified with C10-C30 linear or branched alkyl groups via ether linkages. Typically, these polymers are ethers of C10-C30 straight or branched chain alcohols with hydroxyalkyl celluloses. Other useful polysaccharides include scleroglucan, which comprises a linear chain of (1 to 3) linked glucose units, one (1 to 6) linked glucose per three units.
Non-limiting examples of gums that may be used with the compositions of the present invention include acacia, agar, alginate, alginic acid, ammonium alginate, pullulan, calcium alginate, calcium carrageenan, carnitine, carrageenan, dextrin, gelatin, gellan gum, guar hydroxypropyl trimethyl ammonium chloride, hectorite, hyaluronic acid, hydrated silica, hydroxypropyl chitosan, hydroxypropyl guar gum, karaya gum, kelp, locust bean gum, natto gum, potassium alginate, potassium carrageenan, propylene glycol alginate, sclerotium gum, sodium carboxymethyl dextran, sodium carrageenan, tragacanth gum, xanthan gum, and mixtures thereof. In one embodiment, the thickener is carrageenan (carrageenan) extract.
Film-forming agent the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention may advantageously comprise one or more film-forming agents or film-forming agents. Film formers are hydrophobic materials that impart water resistance and film forming properties to sunscreen products, cosmetic or pharmaceutical formulations, or household care products. The standard film forming agents are preferably chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of the acrylic series, quaternary cellulose derivatives, collagen, hyaluronic acid and salts and similar compounds thereof. Preferred film formers for improving the water repellency of the composition are selected from the group consisting of: polyamide-8 (such as Oleocraft LP PA (MV)), polyamide-3 (such as Oleocraft MP PA (MV)), trimethylpentanediol/adipic acid/glycerol cross-linked polymer (such as WetFilm), octyldodecyl citrate cross-linked polymer (such as CosmoSurf CE), polyglycerol-3 methyl glucose distearate (such as TegoCare 450), C28-52 olefin/undecylenic acid copolymer (such as Performa V6112), hydrolyzed jojoba ester, aqueous agent (such as Floraester Jojoba K), cyclopentasiloxane acrylate/polydimethylsiloxane copolymer (such as KP 545), acrylate/behenyl polyether-25 methacrylate copolymer (such as Volarest), styrene/acrylate copolymer (such as DERMACRYL E polymer), polyurethane (such as Baycusan C1001), polyurethane-2 and polymethyl methacrylate (such as hybrid 875 polymer), acrylate/octylacrylamide copolymer (such as Dermacryl 2.0 polymer), white beeswax (and sodium stearoyl lactylate (such as SYMEFFECT SUN), pullulan, palm polysaccharide, palm oil, hydrogenated cellulose (such as 2,15, crystalline cellulose, and polysaccharide (such as table gum) and polysaccharide (such as table gum) may be added to the aqueous solution of the cellulose, the aqueous solution of the cellulose (such as water) may be added to the aqueous solution of the cellulose (such as water) and the aqueous solution of the cellulose solution (such as water) may be mixed with the aqueous solution of the aqueous solution) Acacia and xanthan gum (such as SOLAGUATM AX), microcrystalline cellulose (and) cellulose gum (e.g., SOLAGUM TM AX), microcrystalline cellulose (and) cellulose gum (such as Natpure Cellgum Plus), sodium stearyl glutamate (such asHS-11P), hydrogenated polycyclopentadiene (and) caprylic/capric triglyceride (such as5400 CCT), hydrogenated glyceryl rosinate (and) caprylic/capric triglyceride (and) tocopherols (such asNATURAL 2063-CCT), galactaran (such asA200) C26-28 alkyl polydimethylsiloxanes (such as Wacker)CDM 3526 VP), octanoyl polymethylsiloxane (such as Silsoft 034), stearyl polydimethylsiloxane (and) octadecene (such as Dowsil 2503Cosmetic Wax), VP/hexadecene copolymer (such as Antaron TM V216), triacontyl PVP (such as Antaron TM WP-660), octanoyl glycerol/sebacic acid copolymer (such as LexFilm TM Sun Natural MB), poly C10-30 alkyl acrylate (such as Tego SP 13Sun Up), microcrystalline cellulose (such as suspheres TM BIO SPF boost), and any mixtures thereof. The aforementioned film forming agents are used as a single component in sunscreens, cosmetic or pharmaceutical preparations or household care products or preferably in combination with two or more of the film forming agents as specified above. The film forming agent is used in an effective amount 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 formulation or home care product in an amount of from 0.01 to 10.0 wt%, preferably from 0.05 to 8.0 wt%, based on the total weight of the final formulation.
Water resistance improvers the sunscreen products, cosmetic or pharmaceutical preparations or household care products according to the invention may advantageously comprise one or more agents for improving water resistance. The agent for improving water resistance is a hydrophobic material imparting film-forming property and water resistance property to the emulsion. Typical suitable water resistance improvers include copolymers derived from the polymerization of octadecene-1 and maleic anhydride. The preferred water resistance improver is a polyanhydride resin. Another preferred water resistance improver is a copolymer of vinylpyrrolidone and an eicosane monomer. The water resistance improver is used in an amount effective to retain the final formulation on the skin or surface after exposure to circulating water for at least 40 minutes, preferably 80 minutes. The one or more water resistance modifiers may optionally be included in the final formulation in an amount ranging from 0.01 wt% to 10.0 wt%, preferably from 0.05 wt% to 8.0 wt%, more preferably from 0.1 wt% to 5.0 wt%, based on the total weight of the final formulation.
Silicones in order to impart a silky, spreadable and luxurious texture and to make the skin look and feel smoother, and in addition to improving the processability (antifoaming), the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention preferably comprises one or more silicones or silicone derivatives. The total amount of silicone compounds in the composition according to the invention may occur, but is typically from 0.1 to 35.0 wt% based on the total weight of the composition.
Dry feel modifier the sunscreen product or cosmetic or pharmaceutical formulation according to the invention is preferably combined with a dry feel modifier. The dryness modifying agent is an agent that when incorporated into an emulsion imparts a "dry feel" to the skin when the emulsion is dried. The dry feel modifier may also reduce migration of the sunscreen on the skin. The dry feel modifier may include starch, talc, kaolin, chalk, zinc oxide, hydroxyapatite (such as Tinomax CC), silicone fluids, inorganic salts (such as barium sulfate and sodium chloride), C6 to C12 alcohols (such as octanol), sulfonated oils, surface treated silica, precipitated silica, fumed silica, such as available from Degussa Inc. of New York, U.S. AOr mixtures thereof, dimethicone, a mixture of methylated linear siloxane polymers, available as a DC200 fluid under the trade name Dow Corning, midland, mich. U.S. A. One or more dry feel modifiers may optionally be included in the sunscreen in an amount ranging from 0.01% to 20% by weight, more preferably from 0.1% to 10.0% by weight.
Soothing substances the sunscreen product or cosmetic or pharmaceutical preparation according to the invention may advantageously also comprise one or more soothing substances, wherein any soothing substance suitable or usual in cosmetic or pharmaceutical application may be used, such as alpha-bisabolol, azulene, guaiac, 18-beta-glycyrrhetinic acid, allantoin, aloe vera juice or gel, witch hazel (Hamamelis), echinacea, centella asiatica, chamomile, arnica, glycyrrhiza, algae, seaweed and calendula extracts and vegetable oils such as sweet almond oil, monkey-tree oil, olive oil and panthenol, laureth-9, trideceth-9 and 4-t-butylcyclohexanol.
Physiological cooling agents the sunscreen products or cosmetic or pharmaceutical preparations according to the invention may be particularly advantageously combined with one or more physiological cooling agents. The use of a cooling agent can relieve itching. Preferred individual coolants for use within the scope of the present invention are listed below. The person skilled in the art can add many other coolants to this list, the listed coolants can also be used in combination with each other, which are here preferably selected from the list of menthol and menthol derivatives (e.g. L-menthol, D-menthol, racemic menthol, isophthol, neoisophthol), menthol ethers (e.g. (I-menthoxy) -1, 2-propanediol, (L-menthoxy) -2-methyl-1, 2-propanediol, L-menthyl-methyl ether), menthone glycerol acetals, menthone glycerol ketals or mixtures of both, menthyl esters (e.g. menthyl formate, menthyl acetate, menthyl isobutyrate, Menthyl hydroxyisobutyrate, menthyl lactate, L-menthyl-L-lactate, L-menthyl-D-lactate, menthyl- (2-methoxy-) acetate, menthyl- (2-methoxyethoxy) acetate, menthyl pyroglutamate), menthyl carbonate (e.g., menthyl propylene carbonate, menthyl ethylene carbonate, menthyl glycerol carbonate, or mixtures thereof), half esters of menthol with dicarboxylic acids or derivatives thereof (e.g., monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthylsuccinate-N, N- (dimethyl) amide, O-menthylsuccinate amide), and combinations thereof, menthane carboxylic acid amides (in this case preferably menthane carboxylic acid-N-acetamide [ WS3] or N α - (menthanecarbonyl) glycidyl ester [ WS5], menthane carboxylic acid-N- (4-cyanophenyl) amides or menthane carboxylic acid-N- (-4-cyanomethylphenyl) amides, menthane carboxylic acid-N- (alkoxyalkyl) amides), menthone and menthone derivatives (e.g. L-menthone glycerol ketal), 2, 3-dimethyl-2- (2-propyl) -butyric acid derivatives (e.g. 2, 3-dimethyl-2- (2-propyl) -butyric acid-N-methylamide [ WS23 ]), and menthone derivatives (e.g. 2, 3-dimethyl-2- (2-propyl) -butyric acid-N-methylamide [ WS23 ]), Isopulegol or an ester thereof (I- (-) -isopulegol, I- (-) -isopulegol acetate), menthane derivatives (e.g. p-menthane-3, 8-diol), piperlongum-l or synthetic or natural mixtures containing piper-cubol, pyrrolidone derivatives of cycloalkyl-dione derivatives (e.g. 3-methyl-2 (1-pyrrolidinyl) -2-cyclopenten-1-one) or tetrahydropyrimidin-2-one (e.g. iciline or related compounds as described in WO 2004/026840), further carboxamides (e.g. N- (2- (pyridin-2-yl) ethyl) -3-p-menthanecarboxamide or related compounds), (1R, 2S, 5R) -N- (4-methoxyphenyl) -5-methyl-2- (1-isopropyl) cyclohexanecarboxamide [ WS12], oxalate and [ (1R, 2S, 5R) -2-isopropyl-5-methylcyclohexyl ]2- (ethylamino) -2-oxo-acetate (Xcool). Preferred coolants for their particular synergistic effect are l-menthol, d-menthol, racemic menthol, menthone glycerol acetal (trade name: MGA), menthyl lactate (preferably l-menthyl lactate, in particular l-menthyl lactate (trade name: ML)), substituted menthyl-3-carboxamides (such as menthyl-3-carboxylic acid N-ethylamide), 2-isopropyl-N-2, 3-trimethylbutyramide, substituted cyclohexane carboxamides, 3-menthoxypropane-1, 2-diol, 2-hydroxyethyl menthyl carbonate, 2-hydroxypropyl menthyl carbonate, and isopulegol. Particularly preferred coolants are l-menthol, racemic menthol, menthone glycerol acetal (trade name: MGA), menthyl lactate (preferably l-menthyl lactate, in particular l-menthyl lactate (trade name: ML)), 3-menthoxypropane-1, 2-diol, 2-hydroxyethyl menthyl carbonate, and 2-hydroxypropyl menthyl carbonate. Very particularly preferred cooling agents are l-menthol, menthone glycerol acetal (trade name: MGA) and menthyl lactate (preferably menthyl l-lactate, in particular menthyl l-lactate (trade name: ML))。
Alkanediol in a further preferred variant, the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention comprises one or more linear alkanediols having a carbon chain of from 5 to 12 carbon atoms. Preferably, the one or more linear alkanediols are selected from the group consisting of 1, 2-alkanediol, 2, 3-alkanediol, 3, 4-alkanediol and 1, 3-alkanediol, more preferably 2, 3-alkanediol and 1, 3-alkanediol. Most preferably, the linear alkanediol is selected from the group consisting of 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-heptanediol, 1, 2-octanediol, 1, 2-nonanediol, 1, 2-decanediol, 1, 2-undecanediol, 1, 2-dodecanediol, 2, 3-pentanediol, 2, 3-hexanediol, 2, 3-heptanediol, 2, 3-octanediol, 2, 3-nonanediol, 2, 3-decanediol, 2, 3-undecanediol and 2, 3-dodecanediol.
Initial observations by the inventors surprisingly show that compositions according to the invention comprising one or more linear alkanediols having a carbon chain of 5 to 12 carbon atoms, preferably as defined herein, show particularly advantageous emulsifying properties. In particular, it has surprisingly been found that one or more of said linear alkanediols (in the case of not the emulsion itself) support the formation of water or oil droplets having a particularly small average size in the emulsion or (in the case of the emulsion itself) comprise water or oil droplets having a particularly small average size.
In addition, it has been found that the presence of an alkanediol, in particular a1, 2-alkanediol or a2, 3-alkanediol, increases the solubility of the oil component, such as one or more oil bodies or waxes, in the sunscreen product, the cosmetic or pharmaceutical preparation or the home care product according to the invention. Preferably, the oil bodies or waxes are selected from the group consisting of natural fats and oils, fatty alcohols and alcohols, glycerides and derivatives thereof, esters, ethers, siloxanes and silanes, waxes and cycloalkanes, preferably from the group consisting of squalene, dialkylcyclohexane, tetradecane, isohexadecane, dodecane, docosyl, paraffins and mineral oils, and are described further below.
The combination of one or more of said alkanediols with 4-hydroxyacetophenone generally increases the solubility of the oil component in an amount of from 0.1 to 2% by weight, more preferably from 0.1 to 1% by weight, even in a synergistic manner.
Preferably, the composition comprises 0.01 to 10 wt%, more preferably 0.1 to 5 wt%, still more preferably 0.3 to 3 wt%, most preferably 0.5 to 1 wt% of said linear alkanediol having a carbon chain of 5 to 12 carbon atoms and as defined herein, based on the total weight of the composition.
Antioxidants the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention advantageously comprises one or more antioxidants. Suitable antioxidants encompass very small tolerogenic doses (e.g. pmol to μmol/kg) of amino acids (preferably glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (preferably urocanic acid) and derivatives thereof, peptides (preferably D, L-carnosine, D-carnosine, L-carnosine) and derivatives thereof (preferably anserine), carnitine, creatine, matrikine peptides (preferably lysyl-threonyl-lysyl serine) and palmitoyl pentapeptides, carotenoids, carotenes (preferably alpha-carotene, beta-carotene, lycopene) and derivatives thereof, lipoic acid and derivatives thereof (preferably dihydrolipoic acid), gold thioglucose, propyl thiouracil and other thiols (preferably thioredoxin), Glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, pentyl, butyl and lauryl, palmitoyl, oleyl, gamma-linoleyl, cholesteryl, glyceryl and oligoglycerol esters thereof and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionate and derivatives thereof (preferably esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoxylamine compounds (preferably butylsulfanilamide, homocysteine sulfoxylamine, sulfolane, penta-, hexa-and heptathionamide), and (metal) chelators (preferably alpha-hydroxy fatty acids, palmitic acid, Phytic acid, lactoferrin, alpha-hydroxy acids (preferably citric acid, lactic acid, malic acid), humic acid, bile acids, bile extracts, tannins, bilirubins, biliverdin, EDTA, EGTA and derivatives thereof), unsaturated fatty acids and derivatives thereof (preferably gamma-linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and derivatives thereof, vitamin C and derivatives (preferably ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate, ascorbyl glucoside), tocopherols and derivatives (preferably vitamin E acetate), vitamin a and derivatives (vitamin a palmitate) and coniferyl benzoate of benzoin resins, rutinosic acid and derivatives thereof, flavonoids and glycosylated precursors thereof, in particular quercetin and derivatives thereof, preferably alpha-glucosyl rutin, Rosmarinic acid, carnosol, carnosic acid, resveratrol, caffeic acid and derivatives thereof, sinapic acid and derivatives thereof, ferulic acid and derivatives thereof, curcumin, chlorogenic acid and derivatives thereof, retinoids, preferably retinol palmitate, retinol or retinoic acid, ursolic acid, levulinic acid, butylhydroxytoluene, butylhydroxyanisole, dehydroguaiac acid, nordihydroguaiaretic acid, trihydroxybutyronic acid, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof (preferably ZnO, znSO 4), selenium and derivatives thereof (preferably selenomethionine), Superoxide dismutase, stilbenes and derivatives thereof (preferably stilbene oxide, stilbene trans oxide), as well as derivatives of these cited active ingredients (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) which are suitable according to the invention, or extracts or fractions of plants having antioxidant effects, preferably green tea, lewis, melaleuca tea, grape, rosemary, sage, melissa, thyme, lavender, olive, oat, cocoa, ginkgo, ginseng, licorice, honeysuckle, locust, kudzuvine root, pine, citrus, phyllanthus emblica or san johnsonii, grape seed, wheat germ, phyllanthus emblica, coenzymes, preferably coenzyme Q10, plastoquinone and menaquinone. Preferred antioxidants are selected from the group consisting of vitamin a and derivatives, vitamin C and derivatives, tocopherols and derivatives, preferably tocopheryl acetate and ubiquinone.
Emulsifying agent furthermore, the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention may advantageously comprise one or more emulsifying agents. Emulsifiers include amphoteric, anionic, cationic or nonionic emulsifiers, which may be used alone or in combination. The emulsifier is selected in a suitable manner according to the emulsion to be obtained. Preferred examples include:
-the product of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide to linear C 8-22 fatty alcohols, C 12-22 fatty acids and alkylphenols having 8 to 15 carbon atoms in the alkyl group;
c 12/18 fatty acid monoesters and diesters of products of addition of 1 to 30mol of ethylene oxide to glycerol;
-mono-and di-esters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms, sorbitol mono-and di-esters and their ethylene oxide addition products;
-products of addition of 15 to 60mol of 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 dimethyl isostearate. Mixtures of compounds from several of these classes are also suitable;
-products of addition of 2 to 15mol of ethylene oxide onto castor oil and/or hydrogenated castor oil;
Based on linear, branched, unsaturated or saturated C 6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
Mono-, di-and trialkyl-and mono-, di-and/or tri-PEG-alkyl phosphates and salts thereof;
-wool wax alcohol;
-polysiloxane/polyalkylpolyether copolymers and corresponding derivatives;
mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols and/or mixed esters of C 6-22 fatty acids, methyl glucose and polyols, preferably glycerol or polyglycerol,
Polyalkylene glycols and process for their preparation
Glycerol carbonate.
The addition of ethylene oxide and/or propylene oxide to fatty alcohols, fatty acids, alkylphenols, mono-and di-glycerides of fatty acids, and mono-and di-esters of sorbitan or to castor oil is a known commercially available product. They are mixtures of homologs whose average degree of alkoxylation corresponds to the ratio between the amounts of ethylene oxide and/or propylene oxide and the substrate undergoing the addition reaction. C 12/18 fatty acid monoesters and diesters of the addition products of ethylene oxide on glycerol are known as lipid layer enhancers for cosmetic formulations. Preferred emulsifiers are described in more detail below:
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 industrial mixtures thereof, possibly still containing small amounts of triglycerides from the production process. Products of the addition of 1 to 30 and preferably 5 to 10mol of ethylene oxide to the partial glycerides mentioned are also suitable.
Sorbitan esters: suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan fatty acid ester, and sorbitan fatty acid ester sorbitan monoerucate, sorbitan hemierucate, sorbitan glycerol digerucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan ditricinoleate, sorbitan triricinoleate, sorbitan monohydroxy stearate, sorbitan monoerucate, sorbitan hemierucate, sorbitan glycerol digerucate, sorbitan monoricinoleate sorbitan sesquiricinoleate, sorbitan ditricinoleate, sorbitan triricinoleate, sorbitan monohydroxy stearate. Products of addition of 1 to 30 and preferably 5 to 10mol of ethylene oxide to the sorbitan esters mentioned are also suitable.
Polyglycerol esters A typical example of a suitable polyglycerol ester is polyglycerol-2-dimer hydroxystearate @PGPH), polyglycerol-3 diisostearateTGI), polyglyceryl-4 isostearateGI 34), polyglycerol-3 oleate, polyglycerol diisostearate-3 diisostearatePDI), polyglycerol-3-methyl glucose distearate (Tego)450 Polyglycerol-3 beeswax (Cera)) Polyglyceryl-4 decanoate (polyglyceryl decanoate T2010/90), polyglyceryl-3 hexadecyl etherNL), polyglyceryl-3 distearateGS 32) and polyglyceryl polyricinoleateWOL 1403), polyglyceryl dimethyl ether isostearate and mixtures thereof. Examples of other suitable polyol esters are the monoesters, diesters and triesters of trimethylolpropane or pentaerythritol with lauric acid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid, and the like, optionally with 1 to 30 moles of ethylene oxide.
Anionic emulsifiers typical anionic emulsifiers are aliphatic C12-C22 fatty acids, such as palmitic acid, stearic acid or behenic acid, and C12-C22 dicarboxylic acids, such as azelaic acid or sebacic acid, for example potassium cetyl phosphate, and hydrogenated palmitoyl glyceride (Emulsiphos/Emulsiphos F).
Amphoteric emulsifiers other suitable emulsifiers are amphoteric or zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N, N-dimethylglycinates, for example cocoalkyl dimethyl ammonium glycinate, N-amidopropyl-N, N-dimethyl ammonium glycinate, for example cocoamidopropyl dimethyl ammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazoline and cocoaminoethyl hydroxyethyl carboxymethyl glycinate containing 8 to 18 carbon atoms in the alkyl or acyl group. Particularly preferred are the known fatty acid amide derivatives of CTFA name cocamidopropyl betaine. Amphoteric surfactants are also suitable emulsifiers. Amphoteric surfactants are surface-active compounds which, in addition to the C 8/18 alkyl or acyl groups, contain at least one free amino group and at least one-COOH-or-SO 3 H-group in the molecule and are capable of forming internal salts. Examples of suitable amphoteric surfactants are N-alkyl glycine, N-alkyl propionic acid, N-alkyl aminobutyric acid, N-alkyl iminodipropionic acid, N-hydroxyethyl-N-alkyl aminopropyl glycine, N-alkyl taurine, N-alkyl sarcosine, 2-alkyl aminopropionic acid and alkyl glycine, the alkyl groups of which contain from about 8 to 18 carbon atoms. Particularly preferred amphoteric surfactants are N-cocoalkyl aminopropionate, cocoyl amino ethyl aminopropionate and C12/18 acyl sarcosines.
Anti-aging actives the compositions according to the present invention are preferably combined with one or more anti-aging actives. In the context of the present invention, anti-aging agents or biogenic agents are, for example, antioxidants, matrix metalloproteinase inhibitors (MMPI), skin moisturizers, glycosaminoglycan stimulators, anti-inflammatory agents, TRPV1 antagonists and plant extracts.
Matrix metalloproteinase inhibitor (MMPI) the composition according to the invention is preferably combined with one or more matrix metalloproteinase inhibitors, especially those inhibiting the enzymatic cleavage of collagen by matrix metalloproteinases, selected from the group consisting of ursolic acid, retinyl palmitate, propyl gallate, prealkene, 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 protease inhibitor N-ethylmaleimide and the serine protease inhibitor epsilon-amino-N-caproic acid, phenylmethylsulfonyl fluoride, collhibin (Pentapharm Corp.; INCI: hydrolyzed rice protein), oenotherol (Soliance company; INCI: propylene glycol, water aqua, evening primrose root extract, ellagic acid and ellagitannin, e.g. from Granati), phosphoamidone hinokitiol, EDTA, MGDA (trisodium dicarboxylalaninate), galardin (galadin), equiStat (Collaborative Group company; apple fruit extract, soybean seed extract, ursolic acid, soybean isoflavone and soybean protein), sage extract, MDI (Atrium company; INCI: glycosaminoglycan), fermiskin (Silab/Mawi company; INCI: water and Lentinus edodes extract), actimp 1.9.3 (Expanscience/Rahn company; INCI: hydrolyzed lupin protein), soybean isoflavone (Mibelle company; INCI: ethanol, polysorbate 80), lecithin and soy isoflavones), green and black tea extracts and other plant extracts, proteins or glycoproteins from soybeans, hydrolyzed proteins from rice, peas or lupins, plant extracts inhibiting MMPs, preferably extracts from lentils, extracts from rosaceae rosaceous leaves, in particular blackberry leaves, such as SymMatrix (Symrise company, INCI: maltodextrin, blackberry (blackberry) leaf extracts, for example. Preferred active ingredients are selected from the group consisting of retinyl palmitate, ursolic acid, rosaceous leaf extract of rosaceous subfamily of rosaceous family, genistein and daidzein.
Skin moisturizing and/or moisturizing materials the sunscreen product or cosmetic or pharmaceutical formulation according to the present invention advantageously comprises one or more skin moisturizing and/or moisturizing materials. Preferred skin moisturizing and/or moisturizing materials are selected from the group consisting of alkanediols or triols comprising 3 to 12 carbon atoms, preferably C 3-C10 -alkanediols and C 3-C10 -alkanetriols. More preferably, the skin moisturizer is selected from the group consisting of glycerin, 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-heptanediol, 1, 2-octanediol, and 1, 2-decanediol. Other skin moisturizing and/or hydrating substances include sodium lactate, urea derivatives, alcohols, glycerol, glycols such as propylene glycol, hexylene glycol, collagen, elastin or hyaluronic acid, diacyl adipates, petrolatum, urocanic acid, lecithin, panthenol, phytantriol, lycopene, (pseudo) ceramides, glycosphingolipids, cholesterol, phytosterols, chitosan, chondroitin sulfate, lanolin esters, amino acids, alpha-hydroxy acids (such as citric acid, lactic acid, malic acid) and derivatives thereof, monosaccharides, disaccharides and oligosaccharides such as glucose, galactose, fructose, mannose, fructose and lactose, polysaccharides such as R-glucan, in particular 1,3-1, 4-beta-glucan from oat, alpha-hydroxy fatty acids, triterpenic acids such as betulinic acid or ursolic acid, and algae extracts.
Glycosaminoglycan stimulating agent preferred compositions according to the invention comprise one or more substances selected from the group consisting of hyaluronic acid and derivatives or salts thereof, subliskin (sederm: sinorhizobium fermentation filtrate, cetyl hydroxyethylcellulose, lecithin), hyalufix (BASF, INCI: water, butylene glycol, galangal leaf extract, xanthan gum, caprylic/capric triglyceride), stimulhyal (Soliance, INCI: calcium ketogluconate), syn-Glycan (DSM, INCI: tetradecylaminobutylamino-urea trifluoroacetate, glycerol, magnesium chloride), KALPARIANE (BIOTECH MARINE), DC Upregulex (feature cosmetic ingredient (DISTINCTIVE COSMETIC INGREDIENTS), INCI: water, butylene glycol, phospholipids, hydrolyzed serin), glucosamine, N-acetyl glucosamine, retinoids, preferably retinol and vitamin a, extracts of burdock fruit, extracts, anthocyanins, N-methyl-L-serine (- α -serine or α -glucan, such as for example, 62 m 83, d-myrrh, and 52 b. Preferred actives are selected from the group consisting of hyaluronic acid and its derivatives or salts, (-) - α -bisabolol or synthetic α -bisabolol, such as Dragosantol and Dragosantol from Symrise, oat glucan, echinacea extract, sinorhizobium meliloti fermentation filtrate, calcium ketogluconate, galangal leaf extract and tetradecyl aminobutyric acid valyl urea trifluoroacetate, for example.
Anti-inflammatory Agents the compositions according to the invention are preferably combined with anti-inflammatory and/or redness and/or itching improving ingredients, in particular steroid substances selected from the group consisting of hydrocortisone, dexamethasone phosphate, prednisone Long Huoke, pine are advantageously used as anti-inflammatory active ingredients or active ingredients for reducing redness and itching, the list of which can be extended by the addition of other steroidal anti-inflammatory agents. Non-steroidal anti-inflammatory drugs may also be used. More specifically:
(i) Steroid anti-inflammatory substances of the corticosteroid type, in particular hydrocortisone, hydrocortisone derivatives such as hydrocortisone 17-butyrate, dexamethasone phosphate, methylprednisolone or cortisone,
(Ii) Non-steroidal anti-inflammatory substances, in particular oxicams such as piroxicam or tenoxicam, salicylates such as aspirin, bissalicylic acid, solprin or Fenolsalate, acetic acid derivatives such as diclofenac, chlorfenamic acid, indomethacin, sulindac, tolmetin or clindanac, fenamic acid esters such as mefenamic acid, meclofenamic acid, flufenamic acid or niflumic acid, propionic acid derivatives such as ibuprofen, naproxen or benoxaprofen, pyrazoles such as phenylbutazone, oxyphenbutazone, fepraat Zong Huoa zapropion,
(Iii) Naturally occurring or naturally occurring anti-inflammatory substances or substances which relieve redness and/or itching, in particular extracts or fractions from chamomile, aloe vera, myrrh substances, madder substances, willow, oat, calendula, arnica, san Jose Johns, honeysuckle, rosemary, passion flower, witch hazel, ginger or echinacea, or single active compounds thereof,
(Iv) Histamine receptor antagonists, serine protease inhibitors (e.g., of soybean extract), TRPV1 antagonists (e.g., 4-t-butylcyclohexanol), NK1 antagonists (e.g., aprepitant, hydroxyphenylpropionamide benzoic acid), cannabinoid receptor agonists (e.g., palmitoylethanolamine), and TRPV3 antagonists.
Examples which may be cited here are oxicams, such as piroxicam or tenoxicam, salicylates, such as aspirin, bissalicylic acid, solprin or Fendolac, acetic acid derivatives, such as diclofenac, fentanyl, indomethacin, sulindac, tolmetin or gram Lin Shansuan, fenamic salts, such as mefenamic, meclofenamic, flufenamic or niflumide, propionic acid derivatives, such as ibuprofen, naproxen or benoxaprofen, or pyrazoles, such as phenylbutazone, oxyphenbutazone, feprazone Zong Huoa zapropine. Anthranilic acid derivatives are preferred antipruritic ingredients in the compositions according to the invention.
Also useful are mixtures of naturally occurring or naturally occurring anti-inflammatory substances or mixtures of substances that alleviate redness and/or itching, in particular extracts or fractions from chamomile, aloe vera, myrrh, madder, willow, oat, calendula, arnica, san jojojose, honeysuckle, rosemary, passion flower, witch hazel, ginger or echinacea; preferably selected from the group consisting of extracts or fractions from chamomile, aloe vera, oat, calendula, arnica, honeysuckle, rosemary, witch hazel, ginger or echinacea, and/or pure substances, preferably alpha-bisabolol, apigenin-7-glucoside, gingerol, shogaol, dehydrogingerol, gingerol, natural or naturally occurring oat anthracene amides, preferably tranilast, oat anthracene amide a, oat anthracene amide B, oat anthracene amide C, non-natural or non-naturally occurring oat anthracene amides, preferably dihydro oat anthracene amide D, dihydro oat anthracene amide E, oat anthracene amide D, oat anthracene amide E, oat anthracene amide F, boswellic acid, phytosterol, glycyrrhizin, glabridin and licorice chalcone a, preferably selected from the group consisting of alpha-bisabolol, natural oat anthracene amide, non-oat anthracene amide, preferably dihydro anthracene amide D (as described in WO 2004 7878a 1), boswellic acid, plant and neotame, methyl-and licorice, methyl-2-propyl-ceramide, palmitoyl-methoxy-propyl-ceramide, palmitolein-propyl-2-methoxy-propyl-ceramide N- (1-hexadecanoyl) -4-hydroxy-L-proline (1-hexadecanoyl) ester, hydroxyethyl palmitoyl hydroxypropyl palmitamide ], glycosphingolipids, phytosterols, chitosan, mannose, lactose and-glucans, in particular 1,3- >1, 4-beta-glucans from oat.
TRPV1 antagonists preferred compositions according to the invention comprise one or more TRPV1 antagonists. Suitable compounds which reduce cutaneous nerve hypersensitivity based on their action as TRPV1 antagonists encompass, for example, trans-4-tert-butylcyclohexanol, or compounds which indirectly modulate TRPV1 by activating μ -receptors (e.g., acetyl tetrapeptide-15) are preferred.
Antimicrobial agents: the sunscreen product, cosmetic or pharmaceutical preparation or home care product according to the invention may advantageously be combined with an antimicrobial agent which acts mainly against microorganisms, in particular bacteria, yeasts and/or fungi, and comprises one or more antimicrobial agents, such as octanoyl hydroxamic acid, o-cymene-5-ol, propylparaben, octanoylglycine, phenylpropanol, tropone, ethyl cocoyl arginine ester of PCA, 2-methyl-5-cyclohexylpentanol, phenoxyethanol, disodium EDTA, methyl paraben and salts thereof, sodium benzoate, benzyl alcohol, potassium sorbate, benzyl salicylate, propylparaben, sodium methyl paraben, methylisothiazolinone, ethylhexyl glycerol, butylparaben, ethyl paraben, sodium propylparaben, DMDM hydantoin, dehydroacetic acid, salicylic acid, chlorphenamine, butylparaben, sodium ethyl paraben, diazolidinyl urea, farnesol, bisabolol, glyceryl octoate, sodium phytate or phytic acid, sodium levulinate or levulinic acid and their esters and/or ketals, chlorhexidine, lauric acid and salts thereof, chlorhexidine digluconate, teasalicylate, ethanol, sodium sorbate, sodium glutamate, oxyethyl acrylate, sodium glutamate, methyl-4-hydroxy-ethyl-acrylate, sodium octoate, methyl-4-hydroxy-ethyl-glycolate, methyl-4-hydroxy-ethyl-acrylate, methyl-n, sodium-4-hydroxy-ethyl-glycolate, methyl-n-4-ethyl-hydroxyethyl-glycolate, methyl-n, methyl-4-n-ethyl-hydroxyethyl-oleate, methyl-5-n-ethyl-oleate, methyl-n-ethyl-carboxylate, and their esters, dimethyl octanoate, 3-hydroxypropyl benzoate, 3-hydroxypropyl anisoate, 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 mixtures thereof.
Preferably, the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention comprises one or more antimicrobial agents selected from the group consisting of 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-heptanediol, 1, 2-octanediol, 1, 2-nonanediol, 1, 2-decanediol, 1, 2-undecanediol, 1, 2-dodecanediol, 2, 3-pentanediol, 2, 3-hexanediol, 2, 3-heptanediol, 2, 3-octanediol, 2, 3-nonanediol, 2, 3-decanediol, 2, 3-undecanediol, 2, 3-dodecanediol, 2-benzylheptanol, 2-hydroxyacetophenone, 2-methyl 5-cyclohexylpentanol, 3-hydroxypropyl 2-hydroxybenzoate, 4-hydroxyacetophenone, and any mixtures thereof. More preferably, the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention comprises one or more antimicrobial agents selected from the group consisting of 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-heptanediol, 1, 2-octanediol, 1, 2-nonanediol, 1, 2-decanediol, 1, 2-undecanediol, 1, 2-dodecanediol, 1, 2-tridecanediol, 4-hydroxyacetophenone, and any mixtures thereof.
To further enhance antimicrobial efficacy, a sunscreen product, cosmetic or pharmaceutical formulation or home care product as defined herein is advantageously combined with at least one other antimicrobial agent other than the antimicrobial agents specified above. The combination with another antimicrobial agent provides reliable protection against microbial degradation and deterioration of the formulation, especially during storage. In addition, a different antimicrobial agent provides reliable protection against other microorganisms as described above, such as corynebacteria, anaerobcoccus, gordonia, moraxella, porphyromonas, fusobacterium, malassezia, dyspepsia, streptococcus, lactobacillus, gardnerella, van, epidermophyton, trichophyton, dermatophytes. Thus, the combination with another different antimicrobial agent allows antimicrobial protection against different microbiota and thus against a wider range of microorganisms. Another different antimicrobial agent in the context of the present invention is preferably selected from the group consisting of: 2-benzylheptanol, alkyl (C12-C22) trimethylammonium bromide and chloride, ascorbic acid and salts thereof, benzalkonium bromide, benzalkonium chloride, benzalkonium bromide, benzethonium chloride, benzoic acid, camphor, cetylpyridinium chloride, chlorhexidine diacetate, chlorhexidine dihydrochloride, chlorocresol, chloroxylenol, cyclohexylglycerol, dimethylbutylbutanol, dimethylphenylpropanol, ethanol, ethyllaurylarginine salt HCl, ethyllaurylarginine salt laurate, eucalyptol, gluconic acid and salts thereof, glycerol, hexamidine diisocynate, hexylglycerol, iodopropynyl butylcarbamate, jasmonic alcohol, laurinol, levulinic acid and esters and/or ketals thereof, mannitol, menthol, methyl salicylate, octenyldine HCl, polyarginine, polyglycerin-10 laurate, polyglyceryl-2 caprate, polyglyceryl-3 caprylate, polylysine, carnosil oil, silver chloride, silver citrate, sodium caproyl lactate, sodium caproyl/lauroyl lactate, sodium lauroyl lactate, sorbitol, sorbic acid, zinc octoate, zinc triclosan, zinc octoate, zinc sesquioxide, zinc citrate, and mixtures thereof.
The aforementioned antimicrobial agents are used as a single component in a sunscreen product, cosmetic or pharmaceutical formulation or home care product or preferably in combination with two or more of said antimicrobial agents as specified above.
The antimicrobial agent is present in the sunscreen product, cosmetic or pharmaceutical formulation, or home care product in an amount of from 0.01 wt% to 25.0 wt%, preferably from 0.02 wt% to 15.0 wt%, most preferably from 0.05 wt% to 6.0 wt%, based on the total weight of the final formulation.
Advantageously, the at least one antimicrobial alkanediol is present in the sunscreen product, the cosmetic or pharmaceutical preparation or the home care product in an amount of from 0.1 to 5% by weight based on the total weight of the final formulation and/or the 4-hydroxyacetophenone is present in the sunscreen product, the cosmetic or pharmaceutical preparation or the home care product in an amount of from 0.01 to 2% by weight based on the total weight of the final formulation.
Preservative for the purpose of preservation the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention preferably comprises one or more preservatives suitable for or commonly used in sunscreen products, cosmetic or pharmaceutical formulations or home care products. Suitable and advantageous preservatives are, for example, benzoic acid, sodium benzoate, ammonium benzoate, butyl benzoate, calcium benzoate, ethyl benzoate, isobutyl benzoate, isopropyl benzoate, magnesium benzoate, benzoic acid mea, 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, mea salicylate, sodium salicylate, potassium salicylate, teas of salicylic acid, sorbic acid, calcium sorbate, sodium sorbate, potassium sorbate, phenylphenol, sodium sulfite, ammonium bisulphite, potassium bisulphite, sodium bisulphite, metabisulfite, potassium metabisulfite, chlorobutanol, 4-hydroxybenzoic acid, methyl paraben, potassium ethylparaben Potassium nipagin, sodium methyl benzoate, sodium ethyl benzoate, sodium nipagin, potassium methyl benzoate, calcium nipagin, butyl nipagin, propyl nipagin, sodium butyl nipagin, potassium propyl nipagin, dehydroacetic acid, sodium dehydroacetate, formic acid, sodium formate, dibromohexamidine isethionate, thimerosal, phenylmercuric acetate, phenylmercuric benzoate, undecylenic acid, potassium undecylenate, sodium undecylenate, calcium undecylenate, undecylenate mea, undecylenate teas, hexamidine, 5-bromo-5-nitro-1, 3-dioxane, 2-bromo-2-nitropropane-1, 3-diol, dichlorobenzyl alcohol, triclosan, chloroxylenol, imidazolidinyl urea, polyaminopropyl alcohol, urotropine, chloroimidazole biguanide, phenoxyethanol, DMDM hydantoin, benzyl alcohol, 1-hydroxy-4-methyl-6- (2, 4-trimethylpentyl) -2-pyridone, piroctone olamine, bromochlorobenzene, o-cymene-5-ol, methyl chloroisothiazolinone and methyl isothiazolinone, chlorhexidine diacetate, chlorhexidine digluconate, chlorhexidine dihydrochloride, phenoxyisopropanol, anisodamine chloride (1), cetrimide bromide, cet Qu An (2) chloride, dodecyltrimethylammonium bromide, octadecyltrimethylammonium chloride (2), dimethyl oxazolidine, diazolidinyl urea, hexamidine diisoisothiocyanate, hexamidine di-p-hydroxybenzoate, hexamidine p-hydroxybenzoate, glutaraldehyde, 7-ethyldicyclooxazolidine, chlorobenzeneglycerol ether, sodium hydroxymethylglycinate, silver chloride, benzethonium chloride, benzalkonium bromide, ammonium benzoate, benzyl hemiformal, iodopropynyl butylcarbamate, methylisothiazolinone, citric acid, silver citrate, hydroxyethoxyphenyl butanone (HEPB), and any mixture thereof.
Medicament the sunscreen product or cosmetic or pharmaceutical formulation according to the invention is preferably combined with one or more medicaments. In certain such embodiments, the pharmaceutically active agent is selected from the group consisting of anti-acne agents, agents for treating rosacea, analgesics, anesthetics, anorectal agents, antihistamines, anti-inflammatory agents including non-steroidal anti-inflammatory agents, antibiotics, antifungals, antiviral agents, antimicrobial agents, anticancer actives, scabies killing agents, pediculicides, antitumor agents, antiperspirant agents, antipruritics, antipsoriatic agents, anti-sebum agents, bioactive proteins and peptides, burn treatments, cauterizing agents, depilatory agents, diaper rash treatments, enzymes, hair growth stimulants, hair growth retardants, including difluroornithine and salts and analogs thereof, hemostatic agents, corneal solutions, oral ulcer treatments, cold sore treatments, dental and periodontal treatments, photosensitive actives, skin protectants/barriers, steroids including hormones and corticosteroids, sunburn treatments, sun protection agents, transdermal actives, nasal actives, vaginal actives, wart treatments, wound healing agents, and the like.
Particularly useful are mixtures of naturally occurring or naturally occurring anti-inflammatory substances or mixtures of substances that alleviate redness and/or itching, in particular extracts or fractions from chamomile, aloe vera, myrrh, madder, willow, oat, calendula, arnica, san jojojose, honeysuckle, rosemary, passion flower, witch hazel, ginger or echinacea; preferably selected from the group consisting of chamomile, aloe vera, oat, calendula, arnica, honeysuckle, rosemary, witch hazel, ginger or echinacea extract or fraction, and/or pure substances, preferably alpha-bisabolol, apigenin-7-glucoside, gingerol, shogaol, jiang Erchun, dehydrogingerol, gingerol, natural or naturally occurring oat alkaloids, preferably tranilast, oat alkaloid a, oat alkaloid B, oat alkaloid C, non-natural or non-naturally occurring oat alkaloids, preferably dihydro oat alkaloid D, dihydro oat alkaloid E, oat alkaloid D, oat alkaloid E, oat alkaloid F, boswellic acid, phytosterol, glycyrrhizin, glabridin and glycyrrhizin a, preferably selected from the group consisting of alpha-bisabolol, natural oat alkaloids, non-natural oat alkaloids, preferably dihydro oat alkaloids D, boswellin, phytosterol, glycyrrhizin and licochalcone a, and/or neotame, preferably methoxy-propyl-2-ceramide, palmitoyl-2-propyl-ceramide N- (1-hexadecyl) -4-hydroxy-L-proline (1-hexadecyl) ester, hydroxyethyl palmitoyloxy hydroxypropyl palmitamide ], glycosphingolipids, phytosterols, chitosan, mannose, lactose and beta-glucans, in particular 1,3- >1, 4-beta-glucans from oat.
In addition to the above, additional ingredients commonly used in sunscreen products, cosmetic or pharmaceutical formulations or household care products, suitable for or commonly used in the compositions of the present invention, may be used.
The sunscreen product or cosmetic or pharmaceutical (in particular dermatological) formulation according to the first aspect of the invention is intended for topical application. The term "topical" is understood to mean external application to the skin or mucous membranes of mammals, 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.
For topical application, the cosmetic or pharmaceutical formulation may be a rinse-off or leave-on formulation.
The sunscreen products according to the present invention may be in the form of aqueous solutions, dispersions, aqueous alcoholic vehicles, sticks, ointments, gels, aerosols (foams, sprays, propellant pumps) and the like.
The sunscreen product, cosmetic or pharmaceutical (in particular dermatological) formulation or home care product according to the first aspect of the invention may be present in different forms, for example in the form of a dispersion, in the form of an anhydrous formulation, or in the form of a solution based on water, water/alcohol, in particular water/ethanol, water/glycol or alcohol/glycol, in particular ethanol/glycol.
In a preferred variant, the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the first aspect of the invention is a dispersion. The term "dispersion" in the context of the present invention means that the sunscreen product, cosmetic or pharmaceutical preparation or household care product is a dispersed two-phase system consisting of colloidal particles (dispersed phase) and a medium in which they are suspended (dispersion medium). The two phases are not miscible with each other but only with the emulsifier. Such dispersions (e.g. emulsions) comprise at least one oil component (free of UV filters) preferably in an amount of ≡1 wt.%, more preferably in an amount of ≡3 wt.%.
Preferably, the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the first aspect of the invention takes various forms such as emulsions, in particular O/W emulsions, W/O emulsions, multiple emulsions, water dispersed gels, sesame oils, multiple emulsions of water-in-oil (W/O/WO) or oil-in-water (O/W/O), PIT emulsions, pickering emulsions, microemulsions, liquids, lotions, suspensions, milk, ointments, pastes, gels, cream-based, oil-based or liposome-based formulations or aerosols, such as foams and sprays, including all types of silicone-based emulsions.
In a most preferred variant, the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention is in the form of an emulsion as defined herein, advantageously in the form of an oil-in-water (O/W) emulsion comprising an oil phase dispersed in an aqueous phase in the presence of O/W or a polymeric emulsifier.
If the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention is a dispersion, preferably an emulsion, the oil component (without UV filter) is present in the cosmetic or pharmaceutical formulation in an amount of 0.01 to 50.0 wt. -%, based on the total weight of the composition. In a preferred variant, the cosmetic or pharmaceutical formulation comprises an oil component in an amount of 0.1 to 45.0% by weight, based on the total weight of the composition. In a particularly preferred variant, the oil component is advantageously used in cosmetic or pharmaceutical preparations in an amount of from 1.0% to 40% by weight, based on the total weight of the composition.
In another variant, the sunscreen product, the cosmetic or pharmaceutical (preferably dermatological) formulation or the home care product according to the first of the invention is an anhydrous formulation, i.e. an oil formulation.
If the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the invention is an anhydrous formulation, i.e. an oil formulation, the oil component is present in the cosmetic or pharmaceutical formulation in an amount of ≡60 wt%, preferably ≡75 wt%, more preferably ≡90 wt%, based on the total weight of the composition.
Such anhydrous formulations include, for example, oils, skin creams, powders, lipsticks, antiperspirant/deoxidizers, and decorative cosmetics.
In addition, other anhydrous formulations are likewise ethanol/glycol/triol/glycol based formulations, such as sprays or gels.
Alternatively, the sunscreen product, cosmetic or pharmaceutical formulation or home care product as disclosed herein is a water or water/alcohol, preferably water/ethanol, water/glycol, or alcohol/glycol, preferably ethanol/glycol solution. Typically, this may be a combination of glycerol in water or alcohol. The solution is a homogeneous single phase system of water/alcohol/glycol and additional components. The solution comprises fatty alcohols or glycols in an amount of 0.1 to 70.0 wt%, preferably 0.5 to 60.0 wt%, more preferably 1.0 to 50.0 wt%, based on the total weight of the solution. The fatty alcohol is preferably selected from the group consisting of ethanol, isopropanol, n-propanol. The ethylene glycol is preferably selected from the group consisting of glycerol, propylene glycol, 1, 3-propanediol, 1,2-C5 to C10 alkanediol, butanediol or dipropylene glycol.
Preferably, the total water content in the final aqueous-based solution may be ≡30 wt%, more preferably ≡40 wt%, most preferably ≡50 wt%.
Such water or water/alcohol or water/glycol or alcohol/glycol based solutions include, for example, deoxidizing/antiperspirant formulations, post-shave formulations, cleansing formulations or anti-acne formulations.
In a preferred variant, the composition of the invention is an impregnating solution in the form of an emulsion spray or an ethanol/oil spray for wet wipes.
The above formulations or compositions are prepared according to usual and known methods.
Cosmetic formulations are formulations for cosmetic and/or non-therapeutic use in personal care, skin protection, skin care, scalp protection, scalp care, hair care, nail care, in particular for the prevention and treatment of skin disorders, intolerant or sensitive skin, skin irritation, skin redness, rubella, itching (itching), skin ageing, wrinkle formation, loss of skin volume, loss of skin elasticity, pigmentation spots, pigmentary anomalies, dry skin, flaking, greasiness, hypopigmentation and/or hyperpigmentation of the skin, or for animal care.
Examples of personal care products are preferably anti-aging preparations, skin care lotions, body oils, body lotions, cleansing lotions, facial or body balms, post-shave balms, post-sun balms, deodorant lotions, cationic lotions, body gels, treatment creams, skin protection ointments, moisturizing gels, facial and/or body moisturizers, photoprotective preparations (sunscreens), micellar water, hair gels, color protection hair care products, skin lightening products, anti-black spot repair products, and the like.
Cosmetic formulations also include cosmetics, eye care formulations, eye shadows, mascaras, eyeliners, lip care formulations (such as lipstick, lip gloss), mail care formulations (such as nail polish, nail polish remover),
Alternatively, the formulation according to the invention is a medical formulation.
The pharmaceutical (in particular dermatological) composition according to the invention is preferably a formulation for the prevention and treatment of skin, mucous membrane, nail or hair conditions.
For use, a sufficient amount of the sunscreen product or cosmetic or pharmaceutical (in particular dermatological) composition according to the first aspect of the invention is applied to the skin, hair, scalp and/or nails in the usual manner for sunscreen products or cosmetic and dermatological products.
In addition, the products and formulations according to the present invention are home care products. Home care products typically include laundry detergents (powders, liquids and tablets), fabric conditioners, dishwashing detergents (liquids and tablets), hard floor and surface cleaners, glass cleaners, carpet cleaners, oven cleaners, air fresheners, disinfectants, soil release agents, and car wash products. These products are typically manufactured in the form of liquids, powders, sprays, granules, and the like.
Surprisingly, it was found that the addition of a retinoid amino acid compound or a salt thereof as defined in the present application has the effect of improving the SPF of a formulation comprising an inorganic UV filter and promoting UVA photoprotection of the formulation. The higher the SPF or UVA-PF, the more protective the sunscreen.
Furthermore, by adding a retinoid amino acid compound or a salt thereof, the critical wavelength of a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising an inorganic UV filter can be increased to provide broad spectrum coverage with critical wavelengths greater than 370 nm.
These effects have the advantage that a sunscreen product or cosmetic or pharmaceutical product with a broader spectrum protection covering both UVA and UVB can be provided. Furthermore, improved UV filter performance, in particular UVA photoprotection, allows reducing the amount of UV filters (in particular inorganic UV filters) without affecting the envisaged SPF.
As demonstrated in the examples below, SPF and UVA photoprotection is highly improved, i.e. increased by the addition of a retinoid amino acid compound as defined therein. Control samples without the retinoid amino acid compound exhibited average or lower SPF.
Improvements in SPF and/or UVA photoprotection can be observed when the retinoid amino acid compounds according to formula (V) or formula (VI) as defined herein are added to sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters.
By adding a retinoid amino acid compound according to formula (VI), wherein X is S, SO or SO 2, particularly pronounced SPF and/or UVA photoprotection promoting effects can be achieved.
Surprisingly, when the retinoid amino acid compounds are in acid form or salt form as described in detail above, these retinoid amino acid compounds are particularly effective in improving SPF and/or UVA photoprotection of sunscreen products, cosmetic or pharmaceutical formulations or home care products.
The SPF of a sunscreen product or cosmetic or pharmaceutical formulation comprising an inorganic UV filter may be increased by at least 10%, preferably at least 30%, and more preferably at least 50%, by the addition of a retinoid amino acid compound as defined herein, as demonstrated in the examples below.
Addition of MAA-1 in an amount of 1.0 wt.% to the O/W ZnO emulsion as specified in Table 4 resulted in an in vitro SPF of 44.0, which was 42% higher than that of the reference sample (i.e., the sample to which the retinoid amino acid compound was not added). Addition of MAA-1 in an amount of 3.0 wt.% even resulted in an in vitro SPF of 49.8, which was 60.6% higher than that of the control sample (i.e., without the retinoid amino acid compound). Addition of MAA-13 in an amount of 1.0% resulted in an in vitro SPF of 45.2, which was 45.8% higher than that of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound). Addition of MAA-13 in an amount of 3.0 wt% even resulted in an in vitro SPF of 44.0, which was 41.9% higher compared to the in vitro SPF of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound).
Furthermore, in addition to improving SPF, the addition of certain retinoid amino acid compounds to sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters also produces UVA photoprotection (UVA-PF) promotion. In particular, adding MAA-13 in an amount of 1.0% to the O/W ZnO emulsion as specified in Table 4 resulted in an improvement in UVA-PF of 8.4% compared to the control sample (i.e., without the retinoid amino acid compound). Addition of MAA-13 in an amount of 3.0% even resulted in a 30.9% improvement in UVA-PF compared to the control sample (i.e., without the retinoid amino acid compound).
Depending on the concentration of MAA-13, the addition of MAA-13 also increases the broad-spectrum protection from the critical wavelength of 374nm to critical wavelengths of 378nm and 379 nm. Thus, the addition of MAA-13 results in an improvement of SPF as well as UVA-PF in sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters in the form of oil-in-water emulsions.
Addition of MAA-1 in an amount of 1.0 wt% to the W/O ZnO emulsion as specified in table 5 resulted in an in vitro SPF of 26.45, which was 20.2% higher than the in vitro SPF of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound). Addition of MAA-1 in an amount of 3.0 wt.% even resulted in an in vitro SPF of 42.8, which was 94.5% higher than that of the control sample (i.e., without the retinoid amino acid compound). Addition of MAA-13 in an amount of 1.0% resulted in an in vitro SPF of 25.1, which was 14% higher than that of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound). Addition of MAA-1 in an amount of 3.0 wt% even resulted in an in vitro SPF of 44.4, which was up to twice the in vitro SPF (101.8%) of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound).
Furthermore, in addition to improving SPF, the addition of certain retinoid amino acid compounds to sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters also produces UVA-PF promotion. Addition of MAA-1 at 1.0% resulted in a 5.7% improvement in UVA-PF over the control sample (i.e., without the retinoid amino acid compound). Addition of MAA-1 in an amount of 3.0% even resulted in a 15.2% improvement in UVA-PF compared to the control sample (i.e., without the retinoid amino acid compound). In particular, the addition of MAA-13 at 1.0% resulted in a 6.5% improvement in UVA-PF compared to the control sample (i.e., without the retinoid amino acid compound). Addition of MAA-13 in an amount of 3.0% even resulted in a 30.6% improvement in UVA-PF compared to the control sample (i.e., without the retinoid amino acid compound).
Depending on the concentration of MAA-13, the addition of MAA-1 and MAA-13 also increased the broad-spectrum protection from critical wavelengths of 373nm to critical wavelengths of 379nm and 380 nm.
In addition, the addition of MAA-20 in an amount of 1.0 wt% in the O/W sunscreen formulation comprising ZnO resulted in an in vitro SPF of 51.0, which was 19.2% higher than that of the reference sample (i.e., the control example without the addition of the retinoid amino acid compound).
Furthermore, the addition of MAA-20 at 1.0% resulted in a 0.16 improvement in UVA-PF over the control sample (i.e., without the retinoid amino acid compound).
The addition of MAA-20 also increased the broad-spectrum protection from 373nm critical wavelength to 374 nm.
Thus, the addition of MAA-20 results in an improvement of SPF as well as UVA-PF in sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters in the form of oil-in-water emulsions.
As demonstrated by the examples below, the addition of MAA-20 to the W/O ZnO sunscreen formulation also resulted in an increase in SPF as compared to the W/O ZnO sunscreen formulation without MAA-20.
Similar SPF and/or UVA photoprotection improving effects may be exhibited for the retinoid compounds MAA-2, MAA-3, MAA-4, MAA-5, MAA-6, MAA-7, MAA-8, MAA-9, MAA-11, MAA-12, MAA-13, MAA-14, MAA-16, MAA-17, and MAA-20 to MAA-39. The compound exhibits at least a 10% increase in SPF and at least a 5% increase in UVA-PF relative to an otherwise identical sunscreen product, cosmetic or pharmaceutical formulation, or home care product that does not contain the retinoid amino acid compound (b).
Thus, the addition of a retinoid amino acid compound results in an improvement of SPF as well as UVA photoprotection (UVA-PF) in sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters.
Thus, with the formulation according to the invention, it is possible to provide a sunscreen product or cosmetic or pharmaceutical product with a significant increase in SPF, a significant increase in UVA photoprotection (UVA-PF) and an increase in critical wavelength, and thus a broad spectrum of protection well above the minimum critical wavelength of 370nm compared to a product or formulation without the addition of the specified retinoid amino acid compound.
Accordingly, the present invention provides a sunscreen product, cosmetic or pharmaceutical formulation or home care product wherein the SPF is increased by at least 10%, preferably at least 15% and more preferably at least 20% compared to a sunscreen product, cosmetic or pharmaceutical formulation or home care product which does not contain the retinoid amino acid compound (b).
Furthermore, the sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention provides at least a 5% increase in UVA photoprotection (UVA-PF) relative to an otherwise identical formulation without the retinoid amino acid compound (b). In some cases, the sunscreen product, cosmetic or pharmaceutical formulation, or home care product provides at least a 10%, more preferably at least a 15%, increase in UVA-PF relative to an otherwise identical formulation that does not contain a retinoid amino acid compound.
Thus, improved/enhanced UV filter performance allows for a reduction in the amount of inorganic UV filter without affecting the envisaged Sun Protection Factor (SPF).
Due to such benefits as described previously, the present invention in a further aspect relates to the use of a retinoid amino acid compound as defined herein or a mixture thereof for improving the SPF, UVA photoprotection (UVA-PF) and increasing the critical wavelength of a sunscreen product, a cosmetic or pharmaceutical formulation or a home care product comprising at least one inorganic UV filter.
By mixing a retinoid amino acid compound as defined herein or a mixture thereof, the SPF of a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising an inorganic UV filter may be enhanced by at least 10%, preferably at least 15%, and more preferably even at least 20% relative to a sunscreen product, cosmetic or pharmaceutical formulation or home care product without the retinoid amino acid compound (b). In addition, UVA photoprotection (UVA-PF) in a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising an inorganic UV filter may be enhanced by at least 5%, preferably at least 10%, and most preferably at least 15% relative to an otherwise identical formulation without the retinoid amino acid compound.
In a further aspect, the invention relates to a method of enhancing or promoting SPF performance and UVA photoprotection of a sunscreen product, a cosmetic or pharmaceutical formulation or a home care product. In this method, an effective amount of at least one retinoid amino acid, or a mixture thereof, as defined herein, is added to the sunscreen product, cosmetic or pharmaceutical formulation, or home care product comprising an inorganic UV filter.
Due to its enhanced SPF and/or UVA photoprotection, the present invention in a further aspect relates to a method of providing anti-aging benefits to skin, whitening skin or preventing skin darkening, improving skin appearance, reducing visible signs of skin aging and improving the gloss and firmness of skin by topically applying a sunscreen product, cosmetic or pharmaceutical formulation or home care product according to the present invention.
The present invention will now be described in detail with reference to the following examples, which are only for illustration of the present invention, and thus the content of the present invention is not limited by the following examples.
Examples
Example 1 determination of SPF in vitro
SPF promotion and UVA-PF promotion tests were performed as in vitro determinations of SPF.
Principle the formulation to be tested (emulsion, solution) is weighed on a PMMA plate by means of an analytical balance. The formulation was distributed and bonded to the board using a method corresponding to the formulation. The plates thus prepared were then measured on a Labsphere apparatus and the results calculated as SPF with appropriate software.
1. Sample preparation:
A PMMA plate (polymethyl methacrylate) (based on ISOethA 24443:2012"Determination of UVA photoprotection in vitro", WW5 plate with 5 mu roughness, GmbH & co.ag) for SPF measurement.
1.1 Preparation of reference samples:
The reference sample was obtained by distributing 25mg to 28mg glycerol (99.5%) with the index finger over the roughened surface of the PMMA plate. The glycerol film must be very thin and uniform. Subsequently, the plate is stored for at least 2 hours.
The reference plate was measured with the following transmission values:
A transmission of >60% at 290nm;
300nm >69% transmission, and
320Nm >82% transmission.
1.2 Application of the sample to be measured:
The sample to be measured should be mixed well with a spatula before application. Samples of 1.2mg/cm2 were uniformly distributed in several rows of spots on the PMMA plate. In order to minimize evaporation of the sample during the weighing process, the process must be performed quickly. The sample is then distributed by hand evenly with a finger pre-impregnated with sample material. The distribution is performed in two stages:
stage 1-rapid and uniform distribution under slight pressure until the emulsion breaks.
Stage 2 the sample is massaged with strong pressure into the roughened surface and the process should last 30 seconds. In this context, under strong pressure means when massaging on a scale, this means at least 200m.
With the exception:
Sunscreen oil the amount of product is typically 1.3mg/cm 2. For strongly spread oils, less product is applied because the amount of oil is not "absorbed" from the plate. The amount applied should then be reduced to 1.0mg/cm 2-0.75mg/cm2. The application methods herein are also 30s fast/light and 30s strong methods.
A "30/30 method" is suitable for use herein (particularly for thicker sprays).
For very liquid sprays (like water):
Rapidly and uniformly distribute under slight pressure until the emulsion "breaks".
The process should take 45s.
The finished sample plates were stored dust-free and the measurement was performed at the earliest after 15 minutes.
2. Measurement on Labsphere:
Samples were measured using a UV-200S apparatus using the method specified Colipa. Labsphere user handbook is also suitable.
2.1 Basic settings in software:
a new "study" is opened via a file, and then the "Colipa guide 2011" method is selected under the heading "study". In the new window "Colipa Method Options", the number of plates (3 plates), the number of measurement points per plate (5 measurement points) and the in-vivo SPF are entered, and if necessary, the irradiance intensity of the external irradiation device (solar simulator irradiance) is entered.
As a standard, the irradiance set on the external device was 765W/m2. Complete naming of samples is accomplished via "study", "study information".
2.2 Sample measurement:
At the beginning of the measurement, the blank value of the glycerol reference sample is measured ("scanning blank"). To determine the SPF of the sample, a total of 15 measurement points (3 plates 5 measurement points) were then generated ("scan positions"). The plate that has been scanned and the measurement point are checked in the upper right window, while the absorbance of the currently measured plate is displayed in the middle window.
The method comprises the following steps:
after the first measurement run, the apparatus calculates the irradiation dose (irradiation dose/J/cm 2) and the duration (exposure time) of each plate. The plates were irradiated in an external irradiation device (irradiation duration=average of 3 plates).
The calculation of the irradiation dose and exposure time was based on irradiance (765W/m 2) set on the external device.
No irradiation:
If no irradiation device is available or no irradiation is desired, the first plate is started again after 15 separate scans are completed and the measurement is repeated (background: no second measurement, no calculation of UVA/UVB balance by software).
After the measurement is completed, "study" is recorded and the data can be printed/output as "report".
3. Test sample:
example 1.1-O/W ZnO emulsion:
recipe samples a to E as specified in table 4 below and recipe samples a and B as specified in table 5 below were prepared as follows:
phase a the ingredients of phase a were heated to 85 ℃ to dissolve the ingredients.
Phase A the pigment is dissolved in the ingredients of phase B while stirring and homogenizing (UltraT25:10,000rpm/10 min). At the end of homogenization, add and disperse
Phase B the ingredients of phase B are mixed and dissolved with stirring. The aqueous phase combined with the sodium hydroxide solution will be cloudy. Thereafter, aqueous phase B was heated to 80 ℃. Then, hot phase B was added to hot phase a and homogenized (UltraT25:13,000rpm/3 min). Finally, the mixture was cooled to ambient temperature while stirring. Subsequently, the mixture was homogenized in a short time (UltraT25:13,000rpm/1,5min)。
The results of the in vitro SPF determinations are shown in tables 4 and 5.
Table 4:
As can be retrieved from table 4, in vitro SPF is highly improved, i.e. increased by the combination of the formulation with certain retinoid amino acid compounds. The control example without the retinoid amino acid compound exhibited an SPF of 31.0. However, the addition of MAA-1 in an amount of 1.0 wt.% resulted in an in vitro SPF of 44.0, which was 42% higher than that of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound). Addition of MAA-1 in an amount of 3.0 wt.% even resulted in an in vitro SPF of 49.8, which was 60.6% higher than that of the control sample (i.e., without the retinoid amino acid compound). Addition of MAA-13 in an amount of 1.0% resulted in an in vitro SPF of 45.2, which was 45.8% higher than that of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound). Addition of MAA-13 in an amount of 3.0 wt% even resulted in an in vitro SPF of 44.0, which was 41.9% higher compared to the in vitro SPF of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound).
Furthermore, the addition of certain retinoid amino acid compounds in sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters not only results in improved SPF, but also in enhanced UVA-PF. In particular, the addition of MAA-13 at 1.0% resulted in an 8.4% improvement in UVA-PF over the control sample (i.e., without the retinoid amino acid compound). Addition of MAA-13 in an amount of 3.0% even resulted in a 30.9% improvement in UVA-PF compared to the control sample (i.e., without the retinoid amino acid compound).
Depending on the concentration of MAA-13, the addition of MAA-13 also increases the broad-spectrum protection from the critical wavelength of 374nm to critical wavelengths of 378nm and 379 nm. Thus, the addition of MAA-13 results in an improvement of SPF as well as UVA-PF in sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters in the form of oil-in-water emulsions.
Table 5:
As can be seen from table 5, in vitro SPF is highly improved by the combination of the formulation with the retinoid MAA. The control example without the retinoid amino acid compound exhibited an SPF of 42.8. However, the addition of MAA-20 in an amount of 1.0 wt.% resulted in an in vitro SPF of 51.0, which was 19.2% higher than that of the reference sample (i.e., the control example without the addition of the retinoid amino acid compound).
Furthermore, the addition of MAA-20 at 1.0% resulted in a 0.16 improvement in UVA-PF over the control sample (i.e., without the retinoid amino acid compound).
The addition of MAA-20 also increased the broad-spectrum protection from 373nm critical wavelength to 374 nm.
Thus, the addition of MAA-20 results in an improvement of SPF as well as UVA-PF in sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters in the form of oil-in-water emulsions.
Example 1.2-W/O ZnO emulsion:
recipe samples a to E as specified in table 6 below and recipe samples a and B as specified in table 7 below were prepared as follows:
phase a the ingredients of phase a were heated to 85 ℃ without pigment to dissolve the ingredients.
Phase A the pigment in the oil phase is dissolved while stirring and homogenizing (UltraT25:10,000rpm/10min)。
Phase B the ingredients of phase B are mixed and dissolved with stirring. The aqueous phase combined with the sodium hydroxide solution will be cloudy. Thereafter, aqueous phase B was heated to 80 ℃. Then, hot phase B was added to hot phase a and homogenized (UltraT25:13,000rpm/3 min). Finally, the mixture was cooled to ambient temperature while stirring. Subsequently, the mixture was homogenized in a short time (UltraT25:13,000rpm/1,5min)。
The results of the in vitro SPF determinations are shown in tables 6 and 7.
Table 6:
As can be retrieved from table 6, in vitro SPF is highly improved, i.e. increased by the combination of the formulation with certain retinoid amino acid compounds. The control example without the retinoid amino acid compound exhibited an SPF of 22.0. However, the addition of MAA-1 in an amount of 1.0 wt.% resulted in an in vitro SPF of 26.45, which was 20.2% higher than that of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound). Addition of MAA-1 in an amount of 3.0 wt.% even resulted in an in vitro SPF of 42.8, which was 94.5% higher than that of the control sample (i.e., without the retinoid amino acid compound). Addition of MAA-13 in an amount of 1.0% resulted in an in vitro SPF of 25.1, which was 14% higher than that of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound). Addition of MAA13 in an amount of 3.0 wt% even resulted in an in vitro SPF of 44.4, which was up to twice (101.8%) that of the reference sample (i.e., the sample without the addition of the retinoid amino acid compound).
Furthermore, the addition of certain retinoid amino acid compounds in sunscreen products, cosmetic or pharmaceutical formulations or home care products comprising inorganic UV filters not only results in improved SPF, but also in enhanced UVA-PF. Addition of MAA-1 at 1.0% resulted in a 5.7% improvement in UVA-PF over the control sample (i.e., without the retinoid amino acid compound). Addition of MAA-1 in an amount of 3.0% even resulted in a 15.2% improvement in UVA-PF compared to the control sample (i.e., without the retinoid amino acid compound). In particular, the addition of MAA-13 at 1.0% resulted in a 6.5% improvement in UVA-PF compared to the control sample (i.e., without the retinoid amino acid compound).
Addition of MAA-13 in an amount of 3.0% even resulted in a 30.6% improvement in UVA-PF compared to the control sample (i.e., without the retinoid amino acid compound).
Depending on the concentration of MAA-13, the addition of MAA-13 also increased the broad-spectrum protection from the 373nm critical wavelength to the 379nm and 380nm critical wavelengths.
Table 7:
As can be seen from table 7, in vitro SPF is highly improved by the combination of the formulation with the retinoid amino acid compound MAA-20. The control example without the retinoid amino acid compound exhibited an SPF of 24.6. However, the addition of MAA-20 in an amount of 1.0 wt.% resulted in an in vitro SPF of 29.5, which was 19.9% higher than that of the reference sample (i.e., the control example without the addition of the retinoid amino acid compound).
Thus, the addition of MAA-20 results in an improvement of SPF in a sunscreen product, cosmetic or pharmaceutical formulation or home care product comprising an inorganic UV filter in the form of a water-in-oil emulsion.
Formulation examples
In the formulation examples below, the following five perfume oils PFO1, PFO2, PFO3, PFO4 or PFO5 were each used as fragrances.
Table F1 composition of perfume oil 1 (PO 1; amounts in wt.%)
Table F2 composition of perfume oil 2 (PO 2; amounts in wt.%)
Table F3 composition of perfume oil 3 (PO 3; amounts in wt.%)
Table F4 composition of perfume oil 4 (PO 4; amounts in wt.%)
Table F5 composition of perfume oil 5 (PO 5; amounts in wt.%)
The above perfume oils PO1, PO2, PO3, PO4 or PO5 were incorporated into the formulations presented below.
Sunscreen products, cosmetic and pharmaceutical formulations and household care products (formulations), the amounts of all formulations being expressed in weight%:
Sunscreen oil spray with ethanol, expected SPF 30, UVA/UVB balance
Urban sunscreen spray, expected spf50+
Sun-protection spray (O/W), expected SPF 30 (all in one pot/cold manufacturing process)
UV protective Water spray SPF 50
Sunscreen spray, spf50+, very water resistant
Sun protection lotion (O/W), expected SPF 50 (Cold/Cold manufacturing Process)
Beach time lotion SPF 30
Antiperspirant and sunscreen lotions
Sun protection emulsion (w/o)
Face-care water mousse, expected SPF 30
Comprehensively protecting drops, expected SPF 50
Luminescent brighteners, expected spf50+
SPF 30 was expected with Yu Yichang sunscreens for acne skin
De-gloss liquid, expected SPF 50
Light sunscreens, expected SPF 50
Refreshing gel sunscreens, expected SPF 30, UVA/UVB balance
Sun-blocking balsam, SPF 40
Anti-pollution hair care agent (SPF 15)
Perfect hand, expected SPF 15, UVA/UVB equilibrium
Colored sunscreens to prevent hyperpigmentation, expected SPF 50 ×
Dark-toned Bb cream, spf-20 (expectation)
Daily healthy aging, SPF 30, UVA/UVB balance
Anti-wrinkle daily emulsion, expected SPF 15
Daily tattoo care, expected SPF 10, UVA/UVB balance
Sensitive daytime care cream, expected SPF15
Cream, expected SPF 15, UVA/UVB
General purpose cleaners
APC alkalinity
Light liquid detergents
Dish washing liquid, manual
Fabric softener
Fabric softener concentrate, encapsulation
Hand cleanser
Fragrance lotion, encapsulation
Detergent, liquid, citric acid
Table F6 ethanol containing sunscreen spray, expected SPF 30, UVA/UVB balance
Table F7 City sunscreen spray, o/w emulsion, expected SPF50+
Table F8 Sun protection spray (O/W), expected SPF 30 x (Cold manufacturing Process)
TABLE F9 UV protective Water spray SPF 50
Table f10 sun protection spray spf50+, very water repellent
Table F11 Sun protection lotion (O/W), expected SPF 50 (Cold/Cold manufacturing Process)
Table F12 beach time lotion SPF30
Exterior F13 sweat-proof sun-proof lotion
Table F14 Sun block (w/o)
Table F15 protective water mousse, expected SPF30 ×
TABLE F16 full protective emulsion, expected SPF50
Table F17 whitening emulsion, expected SPF50+
Table F18 Sun-screening liquid for acne prone skin, SPF 30 is expected
Table F19 De-gloss liquid, expected SPF50
Table F20 light Sun-screening liquid, expected SPF50
Table F21 refreshing gel sunscreens, expected SPF 30, UVA/UVB equilibrium
Table F22 Sun cream, SPF40
Table F23 anti-pollution hair care agent (SPF 15)
Table F24 perfect hand emulsion, expected SPF 15, UVA/UVB equilibrium
Table F25 colored sunscreens to prevent hyper-pigmentation
Table F26 dark-tone BB cream, SPF-20 (expected)
TABLE F27 daily health aging, SPF 30, UVA/UVB balance, w/o octyl cyanobiphenyl acrylate
Table F28 anti-wrinkle daily emulsion, expected SPF 15
Table F29 daily tattoo care, expected SPF10, UVA/UVB balance
TABLE F30 sensitive daytime care cream, expected SPF15
TABLE F31 cream, expected SPF15, UVA/UVB
Table F32 general purpose cleaners
Whether or not Composition of the components Measuring amount
1 Fatty alcohol ethers 4
2 Sulfonic acid, C13-C17-secondary alkyl, sodium salt 6.2
3 2-Octyl-2H-isothiazol-3-one 0.1
4 Aromatic agent 3.5
5 MAA-13 1.0
6 1, 2-Heptanediol 0.9
7 Water aqua To 100
Colorless liquid, pH 7
TABLE F33 APC alkaline detergents
Whether or not Composition of the components Measuring amount
1 Coconut glycoside 1
2 Benzalkonium chloride 0.2
3 Sodium bicarbonate 0.1
4 Trisodium citrate dihydrate 0.1
5 Methyl glycine diacetic acid 0.1
6 1, 2-Benzisothiazol-3 (2H) -one 0.1
7 Aromatic agent 0.1
8 1, 2-Heptanediol 0.5
9 MAA-2 0.5
10 Hydroxy acetophenone 0.3
11 Water aqua To 100
Colorless liquid, pH 9
Table F34 light liquid detergent
Whether or not Composition of the components Measuring amount
1 Cocoa fatty acids 0.85
2 Potassium hydroxide 0.45
3 2-Octyl-2H-isothiazol-3-one 0.2
4 Sulfonic acid, C13-C17-secondary alkyl, sodium salt 20
5 Sodium lauryl polyoxyethylene ether sulfate 3
6 Tridecyl polyoxyethylene ether-9 5
7 Sodium chloride 1.3
8 MAA-20 0.1
9 1, 2-Heptanediol 0.9
10 Aromatic agent 0.5
11 Water aqua To 100
12 Hydroxy acetophenone 0.2
Liquid, pH 7.3
Table F35 dishwashing liquid, manual
Whether or not Composition of the components Measuring amount
1 Sodium lauryl polyoxyethylene ether sulfate To 100
2 Ethanol 2.9
3 Laurylamine oxides 7.7
4 Propylene glycol 1.9
5 Phenoxyethanol 0.1
6 Benzisothiazolinone, process for preparing benzisothiazolinone methyl isothiazolinone lauramine dipropylene diamine 0.1
7 1, 2-Heptanediol 0.5
8 Sodium chloride 3.85
9 Aromatic agent 0.3
10 Benzyl alcohol 0.2
11 MAA-13 1.5
Colorless liquid, pH 8.5
Table F36 softener
Liquid, pH 3
TABLE F37 microencapsulated softener concentrate
Whether or not Composition of the components Measuring amount
1 Di- (talcarboxyethyl) hydroxyethyl methyl ammonium methyl sulfate 16.6
2 2-Octyl-2H-isothiazol-3-one 0.1
3 Dimethicone 0.3
4 Magnesium chloride 0.8
5 Microencapsulated perfume oil 0.3
6 Crosslinked cationic polymers 0.15
7 MAA-1 0.9
8 1, 2-Heptanediol 0.5
9 Aromatic agent 0.6
10 Water aqua To 100
11 Glycerol octanoate 0.1
White liquid, pH 2.5
Table F38 hand cleanser
Whether or not Composition of the components Measuring amount
1 Sodium lauryl polyoxyethylene ether sulfate 18
2 Cocamidopropyl betaine 6
3 Cocamide DEA 3
4 Citric acid 0.5
5 Sodium chloride 1.9
6 Glycerol 2
7 Aromatic agent 0.2
8 MAA-20 0.25
9 Water aqua To 100
10 Propylene glycol octanoate 0.3
Slightly colored liquid, pH 6
Table F39 fragrance lotion with capsules
Whether or not Composition of the components Measuring amount
1 Microcrystalline cellulose/cellulose gum 1
2 PEG-40 hydrogenated castor oil/tridecyl polyoxyethylene ether-9 0.5
3 Microencapsulated perfume oil 1
4 2-Octyl-2H-isothiazol-3-one 0.1
5 Aromatic agent 5
6 1, 2-Heptanediol 1
7 Water aqua To 100
8 MAA-12 0.4
Whitening emulsion, pH neutral
Table F40 citric acid liquid detergent
Whether or not Composition of the components Measuring amount
1 Sulfonic acid, C13-C17-secondary alkyl, sodium salt 1
2 Xanthan gum 0-3;
3 Citric acid 5
4 1,2 Pentanediol 0.25
5 Aromatic agent 0.3
6 Water aqua To 100
7 Fennel acid 0.1
8 MAA-1 0.3
Liquid, pH 2.

Claims (24)

1.一种防晒剂产品、化妆品或药物制剂或家庭护理产品,所述防晒剂产品、化妆品或药物制剂或家庭护理产品包含以下或由以下组成:1. A sunscreen product, a cosmetic or pharmaceutical preparation or a home care product, comprising or consisting of: (a)至少一种无机UV滤光剂;和(a) at least one inorganic UV filter; and (b)至少一种类菌胞素氨基酸化合物,(b) at least one mycosporine-like amino acid compound, 所述至少一种类菌胞素氨基酸化合物,由通式(V)表示The at least one mycosporin-like amino acid compound is represented by the general formula (V): 其中in -Z选自由O-R2'或酰胺'组成的组;-Z is selected from the group consisting of O-R2' or amide'; -R1'选自由以下组成的组:CH2、未经取代的或经取代的CH(烷基)、未经取代的或经取代的C(烷基)2、未经取代的或经取代的CH(环烷基)、未经取代的或经取代的CH(芳基)、未经取代的或经取代的CH(杂环烷基)、未经取代的或经取代的CH(杂芳基)、CR7'R8'、C=O、卤素、O、S、SO、SO2、NH、未经取代的或经取代的N(烷基)、未经取代的或经取代的N(烯基)、未经取代的或经取代的N(炔基)、未经取代的或经取代的N(烷氧基)、未经取代的或经取代的N(烷硫基)、未经取代的或经取代的N(环烷基)、未经取代的或经取代的N(芳基)、未经取代的或经取代的N(杂环烷基)和未经取代的或经取代的N(杂芳基)和未经取代的或经取代的C-螺环;-R1' is selected from the group consisting of CH2 , unsubstituted or substituted CH(alkyl), unsubstituted or substituted C(alkyl) 2 , unsubstituted or substituted CH(cycloalkyl), unsubstituted or substituted CH(aryl), unsubstituted or substituted CH(heterocycloalkyl), unsubstituted or substituted CH(heteroaryl), CR7'R8', C=O, halogen, O, S, SO, SO2 , NH, unsubstituted or substituted N(alkyl), unsubstituted or substituted N(alkenyl), unsubstituted or substituted N(alkynyl), unsubstituted or substituted N(alkoxy), unsubstituted or substituted N(alkylthio), unsubstituted or substituted N(cycloalkyl), unsubstituted or substituted N(aryl), unsubstituted or substituted N(heterocycloalkyl), and unsubstituted or substituted N(heteroaryl), and unsubstituted or substituted C-spiro; -R2'选自由以下组成的组:H、未经取代的或经取代的烷基、未经取代的或经取代的烯基、未经取代的或经取代的炔基、未经取代的或经取代的烷氧基、未经取代的或经取代的烷硫基、未经取代的或经取代的环烷基、未经取代的或经取代的芳基、未经取代的或经取代的杂环烷基、未经取代的或经取代的杂芳基;-R2' is selected from the group consisting of H, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl; -酰胺'选自由以下组成的组:NH2、未经取代的或经取代的NH(烷基)、未经取代的或经取代的NH(烯基)、未经取代的或经取代的NH(炔基)、未经取代的或经取代的NH(烷氧基)、未经取代的或经取代的NH(烷硫基)、未经取代的或经取代的NH(环烷基)、未经取代的或经取代的NH(芳基)、未经取代的或经取代的NH(杂环烷基)、未经取代的或经取代的NH(杂芳基)和未经取代的或经取代的NR9'R10'、未经取代的或经取代的-N(O-烷基)(烷基)(Weinreb酰胺)、-N(OH)(H)(异羟肟酸)和未经取代的或经取代的-N(OH)(烷基)(烷基化异羟肟酸);-amide' is selected from the group consisting of NH2 , unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), and unsubstituted or substituted NR9'R10', unsubstituted or substituted -N(O-alkyl)(alkyl)(Weinreb amide), -N(OH)(H)(hydroxamic acid), and unsubstituted or substituted -N(OH)(alkyl)(alkylated hydroxamic acid); -R3'选自由以下组成的组:H、OH、卤素、未经取代的或经取代的烷基、未经取代的或经取代的烯基、未经取代的或经取代的炔基、未经取代的或经取代的烷氧基、未经取代的或经取代的烷硫基、未经取代的或经取代的烷酰基/酰基R-C(=O)-、-CH2-OH、-R-CH2-OH、-C(=O)-O-Y、-R-C(=O)-O-Y、未经取代的或经取代的环烷基、未经取代的或经取代的芳基、未经取代的或经取代的杂环烷基、未经取代的或经取代的杂芳基、SO、SO2、NH2、未经取代的或经取代的NH(烷基)、未经取代的或经取代的NH(环烷基)、未经取代的或经取代的NH(芳基)、未经取代的或经取代的NH(杂环烷基)、未经取代的或经取代的NH(杂芳基)、未经取代的或经取代的NR9'R10'和未经取代的或经取代的C-螺环;-R3' is selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl RC(=O)-, -CH2- OH, -R- CH2- OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2 , NH2 , unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9'R10', and unsubstituted or substituted C-spiro; -能够相同或不同的取代基R4'、R5'和R6'彼此独立地选自由以下组成的组:H、OH、卤素、未经取代的或经取代的烷基、未经取代的或经取代的烯基、未经取代的或经取代的炔基、未经取代的或经取代的烷氧基、未经取代的或经取代的烷硫基、未经取代的或经取代的烷酰基/酰基R-C(=O)-、-CH2-OH、-R-CH2-OH、-C(=O)-O-Y、-R-C(=O)-O-Y、未经取代的或经取代的环烷基、未经取代的或经取代的芳基、未经取代的或经取代的杂环烷基、未经取代的或经取代的杂芳基、SO、SO2、-S(=O)2OH、磺酰基、NH2、未经取代的或经取代的NH(烷基)、未经取代的或经取代的NH(烯基)、未经取代的或经取代的NH(炔基)、未经取代的或经取代的NH(烷氧基)、未经取代的或经取代的NH(烷硫基)、未经取代的或经取代的NH(环烷基)、未经取代的或经取代的NH(芳基)、未经取代的或经取代的NH(杂环烷基)和未经取代的或经取代的NH(杂芳基)、未经取代的或经取代的NR9'R10'和未经取代的或经取代的C-螺环;- the substituents R4', R5' and R6' which may be the same or different are independently selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl RC(=O)-, -CH2 -OH, -R- CH2 -OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2 , -S(=O) 2OH , sulfonyl, NH2 , unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), and unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9'R10', and unsubstituted or substituted C-spiro; -能够相同或不同的R7'和R8'彼此独立地选自由以下组成的组:H、OH、卤素、未经取代的或经取代的烷基、未经取代的或经取代的烯基、未经取代的或经取代的炔基、未经取代的或经取代的烷氧基、未经取代的或经取代的烷硫基、未经取代的或经取代的烷酰基/酰基R-C(=O)-、-CH2-OH、-R-CH2-OH、-C(=O)-O-Y、-R-C(=O)-O-Y、未经取代的或经取代的环烷基、未经取代的或经取代的芳基、未经取代的或经取代的杂环烷基、未经取代的或经取代的杂芳基、SO、SO2、NH2、未经取代的或经取代的NH(烷基)、未经取代的或经取代的NH(烯基)、未经取代的或经取代的NH(炔基)、未经取代的或经取代的NH(烷氧基)、未经取代的或经取代的NH(烷硫基)、未经取代的或经取代的NH(环烷基)、未经取代的或经取代的NH(芳基)、未经取代的或经取代的NH(杂环烷基)、未经取代的或经取代的NH(杂芳基)和未经取代的或经取代的NR9'R10';- R7' and R8', which may be the same or different, are independently selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl RC(=O)-, -CH2 -OH, -R- CH2- OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2 , NH2 , unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), and unsubstituted or substituted NR9'R10'; -能够相同或不同的R9'和R10'彼此独立地选自由以下组成的组:H、OH、未经取代的或经取代的烷基、未经取代的或经取代的烯基、未经取代的或经取代的炔基、未经取代的或经取代的烷氧基、未经取代的或经取代的烷硫基、未经取代的或经取代的烷酰基/酰基R-C(=O)-、未经取代的或经取代的环烷基、未经取代的或经取代的芳基、未经取代的或经取代的杂环烷基和未经取代的或经取代的杂芳基;- R9' and R10', which may be identical or different, are independently selected from the group consisting of H, OH, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heteroaryl; -Y选自由H和未经取代的或经取代的烷基组成的组;并且-Y is selected from the group consisting of H and unsubstituted or substituted alkyl; and -R是未经取代的或经取代的烷基;-R is unsubstituted or substituted alkyl; 或上述化合物的互变异构体或立体异构体或盐;or a tautomer or stereoisomer or salt of the above compound; 或者由通式(VI)表示Or represented by general formula (VI) 其中in -R1”选自由以下组成的组:CH2、未经取代的或经取代的CH(烷基)、未经取代的或经取代的C(烷基)2、未经取代的或经取代的CH(环烷基)、未经取代的或经取代的CH(芳基)、未经取代的或经取代的CH(杂环烷基)、未经取代的或经取代的CH(杂芳基)、-CR7”R8”、C=O、卤素、O、S、SO、SO2、NH、未经取代的或经取代的N(烷基)、未经取代的或经取代的N(烯基)、未经取代的或经取代的N(炔基)、未经取代的或经取代的N(烷氧基)、未经取代的或经取代的N(烷硫基)、未经取代的或经取代的N(环烷基)、未经取代的或经取代的N(芳基)、未经取代的或经取代的N(杂环烷基)、未经取代的或经取代的N(杂芳基)和未经取代的或经取代的C-螺环;-R1" is selected from the group consisting of CH2 , unsubstituted or substituted CH(alkyl), unsubstituted or substituted C(alkyl) 2 , unsubstituted or substituted CH(cycloalkyl), unsubstituted or substituted CH(aryl), unsubstituted or substituted CH(heterocycloalkyl), unsubstituted or substituted CH(heteroaryl), -CR7"R8", C=O, halogen, O, S, SO, SO2 , NH, unsubstituted or substituted N(alkyl), unsubstituted or substituted N(alkenyl), unsubstituted or substituted N(alkynyl), unsubstituted or substituted N(alkoxy), unsubstituted or substituted N(alkylthio), unsubstituted or substituted N(cycloalkyl), unsubstituted or substituted N(aryl), unsubstituted or substituted N(heterocycloalkyl), unsubstituted or substituted N(heteroaryl), and unsubstituted or substituted C-spiro; -R2”选自由以下组成的组:H、OH、卤素、未经取代的或经取代的烷基、未经取代的或经取代的烯基、未经取代的或经取代的炔基、未经取代的或经取代的烷氧基、未经取代的或经取代的烷硫基、未经取代的或经取代的烷酰基/酰基R-C(=O)-、-CH2-OH、-R-CH2-OH-C(=O)-O-Y、-C(=O)-酰胺”、未经取代的或经取代的环烷基、未经取代的或经取代的芳基、未经取代的或经取代的杂环烷基、未经取代的或经取代的杂芳基、SO、SO2、NH2、未经取代的或经取代的NH(烷基)、未经取代的或经取代的NH(烯基)、未经取代的或经取代的NH(炔基)、未经取代的或经取代的NH(烷氧基)、未经取代的或经取代的NH(烷硫基)、未经取代的或经取代的NH(环烷基)、未经取代的或经取代的NH(芳基)、未经取代的或经取代的NH(杂环烷基)、未经取代的或经取代的NH(杂芳基)、未经取代的或经取代的NR9”R10”和未经取代的或经取代的C-螺环;-R2" is selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl RC(=O)-, -CH2 -OH, -R-CH2- OH -C(=O)-OY, -C(=O)-amide", unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2 , NH2 , unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9"R10", and unsubstituted or substituted C-spiro; -X选自由以下组成的组:CH2、未经取代的或经取代的CH(烷基)、未经取代的或经取代的CH(烯基)、未经取代的或经取代的CH(炔基)、未经取代的或经取代的CH(烷氧基)、未经取代的或经取代的CH(烷硫基)、未经取代的或经取代的CH(环烷基)、未经取代的或经取代的CH(芳基)、未经取代的或经取代的CH(杂环烷基)、未经取代的或经取代的CH(杂芳基)、-CR7”R8”、C=O、O、S、SO、SO2、NH、未经取代的或经取代的N(烷基)、未经取代的或经取代的N(烯基)、未经取代的或经取代的N(炔基)、未经取代的或经取代的N(烷氧基)、未经取代的或经取代的N(烷硫基)、未经取代的或经取代的N(环烷基)、未经取代的或经取代的N(芳基)、未经取代的或经取代的N(杂环烷基)、未经取代的或经取代的N(杂芳基)和未经取代的或经取代的C-螺环;-X is selected from the group consisting of CH2 , unsubstituted or substituted CH(alkyl), unsubstituted or substituted CH(alkenyl), unsubstituted or substituted CH(alkynyl), unsubstituted or substituted CH(alkoxy), unsubstituted or substituted CH(alkylthio), unsubstituted or substituted CH(cycloalkyl), unsubstituted or substituted CH(aryl), unsubstituted or substituted CH(heterocycloalkyl), unsubstituted or substituted CH(heteroaryl), -CR7"R8", C=O, O, S, SO, SO2 , NH, unsubstituted or substituted N(alkyl), unsubstituted or substituted N(alkenyl), unsubstituted or substituted N(alkynyl), unsubstituted or substituted N(alkoxy), unsubstituted or substituted N(alkylthio), unsubstituted or substituted N(cycloalkyl), unsubstituted or substituted N(aryl), unsubstituted or substituted N(heterocycloalkyl), unsubstituted or substituted N(heteroaryl), and unsubstituted or substituted C-spiro; -能够相同或不同的取代基R4”、R5”和R6”彼此独立地选自由以下组成的组:H、OH、卤素、未经取代的或经取代的烷基、未经取代的或经取代的烯基、未经取代的或经取代的炔基、未经取代的或经取代的烷氧基、未经取代的或经取代的烷硫基、未经取代的或经取代的烷酰基/酰基R-C(=O)-、-CH2-OH、-R-CH2-OH、-C(=O)-O-Y、-R-C(=O)-O-Y、未经取代的或经取代的环烷基、未经取代的或经取代的芳基、未经取代的或经取代的杂环烷基、未经取代的或经取代的杂芳基、SO、SO2、-S(=O)2OH、磺酰基、NH2、未经取代的或经取代的NH(烷基)、未经取代的或经取代的NH(烯基)、未经取代的或经取代的NH(炔基)、未经取代的或经取代的NH(烷氧基)、未经取代的或经取代的NH(烷硫基)、未经取代的或经取代的NH(环烷基)、未经取代的或经取代的NH(芳基)、未经取代的或经取代的NH(杂环烷基)和未经取代的或经取代的NH(杂芳基)、未经取代的或经取代的NR9”R10”和未经取代的或经取代的C-螺环;- the substituents R4", R5" and R6" which may be the same or different are independently selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl RC(=O)-, -CH2 -OH, -R- CH2 -OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2 , -S(=O) 2OH , sulfonyl, NH2 , unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), and unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9"R10", and unsubstituted or substituted C-spiro; -能够相同或不同的R7”和R8”彼此独立地选自由以下组成的组:H、OH、卤素、未经取代的或经取代的烷基、未经取代的或经取代的烯基、未经取代的或经取代的炔基、未经取代的或经取代的烷氧基、未经取代的或经取代的烷硫基、未经取代的或经取代的烷酰基/酰基R-C(=O)-、-CH2-OH、-R-CH2-OH、-C(=O)-O-Y、-R-C(=O)-O-Y、未经取代的或经取代的环烷基、未经取代的或经取代的芳基、未经取代的或经取代的杂环烷基、未经取代的或经取代的杂芳基、SO、SO2、NH2、未经取代的或经取代的NH(烷基)、未经取代的或经取代的NH(烯基)、未经取代的或经取代的NH(炔基)、未经取代的或经取代的NH(烷氧基)、未经取代的或经取代的NH(烷硫基)、未经取代的或经取代的NH(环烷基)、未经取代的或经取代的NH(芳基)、未经取代的或经取代的NH(杂环烷基)、未经取代的或经取代的NH(杂芳基)和未经取代的或经取代的NR9”R10”;- R7" and R8" which may be the same or different are independently selected from the group consisting of H, OH, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl RC(=O)-, -CH2- OH, -R- CH2- OH, -C(=O)-OY, -RC(=O)-OY, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl, unsubstituted or substituted heteroaryl, SO, SO2 , NH2 , unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), and unsubstituted or substituted NR9"R10"; -酰胺”选自由以下组成的组:NH2、未经取代的或经取代的NH(烷基)、未经取代的或经取代的NH(烯基)、未经取代的或经取代的NH(炔基)、未经取代的或经取代的NH(烷氧基)、未经取代的或经取代的NH(烷硫基)、未经取代的或经取代的NH(环烷基)、未经取代的或经取代的NH(芳基)、未经取代的或经取代的NH(杂环烷基)、未经取代的或经取代的NH(杂芳基)、未经取代的或经取代的NR9”R10”、未经取代的或经取代的-N(O-烷基)(烷基)(Weinreb酰胺)、-N(OH)(H)(异羟肟酸)和未经取代的或经取代的-N(OH)(烷基)(烷基化异羟肟酸);-amide" is selected from the group consisting of NH2 , unsubstituted or substituted NH(alkyl), unsubstituted or substituted NH(alkenyl), unsubstituted or substituted NH(alkynyl), unsubstituted or substituted NH(alkoxy), unsubstituted or substituted NH(alkylthio), unsubstituted or substituted NH(cycloalkyl), unsubstituted or substituted NH(aryl), unsubstituted or substituted NH(heterocycloalkyl), unsubstituted or substituted NH(heteroaryl), unsubstituted or substituted NR9"R10", unsubstituted or substituted -N(O-alkyl)(alkyl)(Weinreb amide), -N(OH)(H)(hydroxamic acid), and unsubstituted or substituted -N(OH)(alkyl)(alkylated hydroxamic acid); -能够相同或不同的R9”和R10”彼此独立地选自由以下组成的组:H、OH、未经取代的或经取代的烷基、未经取代的或经取代的烯基、未经取代的或经取代的炔基、未经取代的或经取代的烷氧基、未经取代的或经取代的烷硫基、未经取代的或经取代的烷酰基/酰基R-C(=O)-、未经取代的或经取代的环烷基、未经取代的或经取代的芳基、未经取代的或经取代的杂环烷基和未经取代的或经取代的杂芳基;- R9" and R10" which may be identical or different are independently selected from the group consisting of H, OH, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkanoyl/acyl R-C(=O)-, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycloalkyl and unsubstituted or substituted heteroaryl; -Y选自由H和未经取代的或经取代的烷基组成的组;并且-Y is selected from the group consisting of H and unsubstituted or substituted alkyl; and -R是未经取代的或经取代的烷基;-R is unsubstituted or substituted alkyl; 或上述化合物的互变异构体或立体异构体或盐;or a tautomer or stereoisomer or salt of the above compound; 或上述化合物的任何混合物;or any mixture of the foregoing compounds; 前提是以下化合物被拒绝/被排除:The following compounds are rejected/excluded: 化合物1:Compound 1: 化合物2:Compound 2: 化合物3:Compound 3: 化合物4:Compound 4: 化合物5:Compound 5: 化合物6:Compound 6: 化合物7:Compound 7: 化合物8:Compound 8: 化合物9:Compound 9: and 化合物10:Compound 10: 2.根据权利要求1所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中所述类菌胞素氨基酸化合物(b)由通式(VII)表示2. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to claim 1, wherein the mycosporin-like amino acid compound (b) is represented by the general formula (VII): 其中R1'、R2'、R3'、R4'、R5'和R6'具有与针对式(V)定义的相同的含义;wherein R1′, R2′, R3′, R4′, R5′ and R6′ have the same meanings as defined for formula (V); 或者由通式(VIII)表示Or represented by general formula (VIII) 其中R1'、酰胺'、R3'、R4'、R5'和R6'具有与针对式(V)定义的相同的含义。wherein R1′, Amide′, R3′, R4′, R5′ and R6′ have the same meanings as defined for formula (V). 3.根据权利要求1或权利要求2所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中在所述通式(VI)中,X选自由以下组成的组:CH2、未经取代的或经取代的CH(烷基)、未经取代的或经取代的C(烷基)2、未经取代的或经取代的CH(烯基)、未经取代的或经取代的CH(炔基)、未经取代的或经取代的CH(烷氧基)、未经取代的或经取代的CH(烷硫基)、未经取代的或经取代的CH(环烷基)、未经取代的或经取代的CH(芳基)、未经取代的或经取代的CH(杂环烷基)、未经取代的或经取代的CH(杂芳基)、-CR7”R8”、C=O、S、SO、SO2、NH、未经取代的或经取代的N(烷基)、未经取代的或经取代的N(烯基)、未经取代的或经取代的N(炔基)、未经取代的或经取代的N(烷氧基)、未经取代的或经取代的N(烷硫基)、未经取代的或经取代的N(环烷基)、未经取代的或经取代的N(芳基)、未经取代的或经取代的N(杂环烷基)、未经取代的或经取代的N(杂芳基)和未经取代的或经取代的C-螺环。3. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to claim 1 or claim 2, wherein in the general formula (VI), X is selected from the group consisting of: CH2 , unsubstituted or substituted CH(alkyl), unsubstituted or substituted C(alkyl) 2 , unsubstituted or substituted CH(alkenyl), unsubstituted or substituted CH(alkynyl), unsubstituted or substituted CH(alkoxy), unsubstituted or substituted CH(alkylthio), unsubstituted or substituted CH(cycloalkyl), unsubstituted or substituted CH(aryl), unsubstituted or substituted CH(heterocycloalkyl), unsubstituted or substituted CH(heteroaryl), -CR7"R8", C=O, S, SO, SO2 , NH, unsubstituted or substituted N(alkyl), unsubstituted or substituted N(alkenyl), unsubstituted or substituted N(alkynyl), unsubstituted or substituted N(alkoxy), unsubstituted or substituted N(alkylthio), unsubstituted or substituted N(cycloalkyl), unsubstituted or substituted N(aryl), unsubstituted or substituted N(heterocycloalkyl), unsubstituted or substituted N(heteroaryl), and unsubstituted or substituted C-spiro. 4.根据权利要求1至3中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中在所述通式(V)中,4. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 3, wherein in the general formula (V), -Z为-O-R2'或酰胺';并且/或者-Z is -O-R2' or amide'; and/or -R1'选自由以下组成的组:CH2、C(烷基)2、O、S、SO、SO2、NH和N(烷基);并且/或者- R1' is selected from the group consisting of CH2 , C(alkyl) 2 , O, S, SO, SO2 , NH and N(alkyl); and/or -R2'选自由以下组成的组:H、甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、 (2-乙基己基)和苯基;或者-R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl; or -酰胺'选自由以下组成的组:NH2、NH(烷基)、N(烷基)2、-N(O-烷基)(烷基)(Weinreb酰胺)和-N(OH)(H)(异羟肟酸);并且/或者-amide' is selected from the group consisting of: NH2 , NH(alkyl), N(alkyl) 2 , -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and/or -R3'选自由以下组成的组:H、甲基、乙基、-O-甲基、-C(=O)-OH、-C(=O)-CH3、-C(=O)-C3H7和-C(=O)-O-甲基;并且/或者-R3' is selected from the group consisting of H, methyl, ethyl, -O-methyl, -C(=O)-OH, -C(=O) -CH3 , -C(=O) -C3H7 and -C(=O)-O-methyl ; and/or -所述取代基R4'、R5'和R6'具有与针对式(V)定义的相同的含义;- the substituents R4', R5' and R6' have the same meanings as defined for formula (V); -其中烷基选自由以下组成的组:甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基;- wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; 或者其中在所述通式(VII)或(VIII)中,Or wherein in the general formula (VII) or (VIII), -R1'选自由以下组成的组:CH2、C(烷基)2、O、S、SO、SO2、NH和N(烷基);并且/或者- R1' is selected from the group consisting of CH2 , C(alkyl) 2 , O, S, SO, SO2 , NH and N(alkyl); and/or -R2'选自由以下组成的组:H、甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、 (2-乙基己基)和苯基;或者-R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl; or -酰胺'选自由以下组成的组:NH2、NH(烷基)、N(烷基)2、-N(O-烷基)(烷基)(Weinreb酰胺)和-N(OH)(H)(异羟肟酸);并且/或者-amide' is selected from the group consisting of: NH2 , NH(alkyl), N(alkyl) 2 , -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and/or -R3'选自由以下组成的组:H、甲基、乙基、-O-甲基、-C(=O)-OH、-C(=O)-CH3、-C(=O)-C3H7和-C(=O)-O-甲基;并且/或者-R3' is selected from the group consisting of H, methyl, ethyl, -O-methyl, -C(=O)-OH, -C(=O) -CH3 , -C(=O) -C3H7 and -C(=O)-O-methyl ; and/or -所述取代基R4'、R5'和R6'具有与针对式(VII)和(VIII)定义的相同的含义;- the substituents R4', R5' and R6' have the same meanings as defined for formulae (VII) and (VIII); -其中烷基选自由以下组成的组:甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基;- wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; 或者其中在所述通式(VI)中,Or wherein in the general formula (VI), -R1”选自由以下组成的组:CH2、C(烷基)2、O、S、SO、SO2、NH和N(烷基);并且/或者-R1" is selected from the group consisting of CH2 , C(alkyl) 2 , O, S, SO, SO2 , NH and N(alkyl); and/or -R2”选自由以下组成的组:-CH2-OH、-C(=O)-O-Y和-C(=O)-酰胺”;并且/或者-R2" is selected from the group consisting of: -CH2 -OH , -C(=O)-OY and -C(=O)-amide"; and/or -X选自由以下组成的组:CH2、C=O、O、S、SO、SO2、NH和N(烷基);并且/或者- X is selected from the group consisting of CH2 , C=O, O, S, SO, SO2 , NH and N(alkyl); and/or -Y选自由以下组成的组:H、甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、 (2-乙基己基)和苯基;并且/或者-Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl; and/or -酰胺”选自由以下组成的组:NH2、NH(烷基)、N(烷基)2、-N(O-烷基)(烷基)(Weinreb酰胺)和-N(OH)(H)(异羟肟酸);并且/或者-amide" is selected from the group consisting of: NH2 , NH(alkyl), N(alkyl) 2 , -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and/or -所述取代基R4”、R5”和R6”具有与针对式(VI)定义的相同的含义;- the substituents R4", R5" and R6" have the same meanings as defined for formula (VI); -其中烷基选自由以下组成的组:甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基。- wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl. 5.根据权利要求1至4中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中在所述通式(V)中,5. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 4, wherein in the general formula (V), -Z为-O-R2'或酰胺';并且/或者-Z is -O-R2' or amide'; and/or -R1'选自由CH2和C(甲基)2组成的组;并且/或者-R1' is selected from the group consisting of CH2 and C(methyl) 2 ; and/or -R2'选自由以下组成的组:H、甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、 (2-乙基己基)和苯基;或者-R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl; or -酰胺'选自由以下组成的组:NH2、NH(烷基)、N(烷基)2、-N(O-烷基)(烷基)(Weinreb酰胺)和-N(OH)(H)(异羟肟酸);并且/或者-amide' is selected from the group consisting of: NH2 , NH(alkyl), N(alkyl) 2 , -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and/or -R3'选自由以下组成的组:H、甲基、乙基、-O-甲基、-C(=O)-OH、-C(=O)-CH3、-C(=O)-C3H7和-C(=O)-O-甲基;并且/或者-R3' is selected from the group consisting of H, methyl, ethyl, -O-methyl, -C(=O)-OH, -C(=O) -CH3 , -C(=O) -C3H7 and -C(=O)-O-methyl ; and/or -所述取代基R4'、R5'和R6'具有与针对式(V)定义的相同的含义;- the substituents R4', R5' and R6' have the same meanings as defined for formula (V); -其中烷基选自由以下组成的组:甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基;- wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; 或者其中在所述通式(VII)或(VIII)中,Or wherein in the general formula (VII) or (VIII), -R1'选自由CH2和C(甲基)2组成的组;-R1' is selected from the group consisting of CH2 and C(methyl) 2 ; -R2'选自由以下组成的组:H、甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、 (2-乙基己基)和苯基;或者-R2' is selected from the group consisting of: H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl; or -酰胺'选自由以下组成的组:NH2、NH(烷基)、N(烷基)2、-N(O-烷基)(烷基)(Weinreb酰胺)和-N(OH)(H)(异羟肟酸);并且/或者-amide' is selected from the group consisting of: NH2 , NH(alkyl), N(alkyl) 2 , -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and/or -R3'选自由以下组成的组:H、甲基、乙基、-O-甲基、-C(=O)-OH、-C(=O)-CH3、-C(=O)-C3H7和-C(=O)-O-甲基;并且/或者-R3' is selected from the group consisting of H, methyl, ethyl, -O-methyl, -C(=O)-OH, -C(=O) -CH3 , -C(=O) -C3H7 and -C(=O)-O-methyl ; and/or -所述取代基R4'、R5'和R6'具有与针对式(VII)和(VIII)定义的相同的含义;- the substituents R4', R5' and R6' have the same meanings as defined for formulae (VII) and (VIII); -其中烷基选自由以下组成的组:甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基;并且/或者- wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; and/or 或者其中在所述通式(VI)中,Or wherein in the general formula (VI), -R1”选自由CH2和C(甲基)2组成的组;并且/或者-R1" is selected from the group consisting of CH2 and C(methyl) 2 ; and/or -R2”选自由以下组成的组:-CH2-OH、-C(=O)-O-Y和-C(=O)-酰胺”;并且/或者-R2" is selected from the group consisting of: -CH2 -OH , -C(=O)-OY and -C(=O)-amide"; and/or -X选自由以下组成的组:CH2、C=O、O、S、SO、SO2、NH和N(烷基);并且/或者- X is selected from the group consisting of CH2 , C=O, O, S, SO, SO2 , NH and N(alkyl); and/or -Y选自由以下组成的组:H、甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、 (2-乙基己基)和苯基;并且/或者-Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, (2-ethylhexyl) and phenyl; and/or -酰胺”选自由以下组成的组:NH2、NH(烷基)、N(烷基)2、-N(O-烷基)(烷基)(Weinreb酰胺)和-N(OH)(H)(异羟肟酸);并且/或者-amide" is selected from the group consisting of: NH2 , NH(alkyl), N(alkyl) 2 , -N(O-alkyl)(alkyl)(Weinreb amide) and -N(OH)(H)(hydroxamic acid); and/or -所述取代基R4”、R5”和R6”具有与针对式(VI)定义的相同的含义;- the substituents R4", R5" and R6" have the same meanings as defined for formula (VI); -其中烷基选自由以下组成的组:甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基。- wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl. 6.根据权利要求1至5中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中所述类菌胞素氨基酸化合物(b)选自由根据所述通式(V)所述的以下化合物I-1至I-128和根据所述通式(VI)所述的以下化合物II-1至II-192组成的组:6. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 5, wherein the mycosporin-like amino acid compound (b) is selected from the group consisting of the following compounds I-1 to I-128 according to the general formula (V) and the following compounds II-1 to II-192 according to the general formula (VI): 其中在上述类菌胞素氨基酸化合物中,苯环能够是未经取代的或经取代的,并且R4'、R5'、R6'、R4”、R5”、R6”、酰胺'、Y、酰胺”和烷基具有与根据前述权利要求中任一项所述的相同的含义,或上述化合物的互变异构体或立体异构体或盐;wherein in the above-mentioned mycosporin-like amino acid compound, the benzene ring can be unsubstituted or substituted, and R4', R5', R6', R4", R5", R6", amide', Y, amide", and alkyl have the same meanings as in any one of the preceding claims, or a tautomer or stereoisomer or salt of the above-mentioned compound; 或者其中所述类菌胞素氨基酸化合物选自由以下组成的组:Or wherein the mycosporin-like amino acid compound is selected from the group consisting of: MAA-A:MAA-A: MAA-B:MAA-B: and MAA-C:MAA-C: 其中烷基是甲基或乙基或丙基或丁基、优选地甲基,wherein alkyl is methyl or ethyl or propyl or butyl, preferably methyl, 或上述化合物的互变异构体或立体异构体或盐;or a tautomer or stereoisomer or salt of the above compound; 或上述化合物的任何混合物。or any mixture of the above compounds. 7.根据权利要求1至6中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中在所述通式(VI)、(IX)和(X)中,X为S、SO或SO2,并且/或者其中在所述通式(V)至(X)中,n=1。7. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 6, wherein in the general formulae (VI), (IX) and (X), X is S, SO or SO2, and / or wherein in the general formulae (V) to (X), n=1. 8.根据权利要求1至7中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中在所述通式(V)、(VII)和(VIII)中,能够相同或不同的取代基R4'、R5'和R6'彼此独立地选自由以下组成的组:H、OH、烷基、优选地甲基、乙基、丙基、异丙基、丁基、异丁基或叔丁基、烷氧基、优选地O-甲基、O-乙基或O-丁基、-S(=O)2OH和磺酰基;8. A sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 7, wherein in the general formulae (V), (VII) and (VIII), the substituents R4', R5' and R6', which can be the same or different, are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O) 2OH and sulfonyl; 或者or 其中在所述通式(VI)、(IX)和(X)中,能够相同或不同的取代基R4”、R5”和R6”彼此独立地选自由以下组成的组:H、OH、烷基、优选地甲基、乙基、丙基、异丙基、丁基、异丁基或叔丁基、烷氧基、优选地O-甲基、O-乙基或O-丁基、-S(=O)2OH和磺酰基。In the general formulae (VI), (IX) and (X), the substituents R4", R5" and R6" which may be identical or different are independently selected from the group consisting of H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O) 2OH and sulfonyl. 9.根据权利要求1至8中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中在所述通式(V)至(X)中,与亚氨基官能团结合的经取代的苯基选自由以下组成的组:9. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 8, wherein in the general formulae (V) to (X), the substituted phenyl group bonded to the imino functional group is selected from the group consisting of: 其中虚线表示结合位点。The dotted lines indicate the binding sites. 10.根据权利要求1至9中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中在所述通式(V)、(VII)和(VIII)中,能够相同或不同的所述取代基R4'、R5'、R6'彼此独立地选自由以下组成的组:H、OH、烷基,优选地甲基、乙基、丙基、异丙基、丁基、异丁基或叔丁基、和烷氧基,优选地O-甲基、O-乙基或O-丁基、-S(=O)2OH和磺酰基;前提是如果经取代的苯环被单取代,则所述取代基位于所述亚氨基官能团的邻位或间位;或者其中在所述通式(VI)、(IX)和(X)中,能够相同或不同的所述取代基R4”、R5”、R6”彼此独立地选自由以下组成的组:H、OH、烷基,优选地甲基、乙基、丙基、异丙基、丁基、异丁基、或叔丁基、和烷氧基,优选地O-甲基、O-乙基或O-丁基、-S(=O)2OH和磺酰基;前提是如果经取代的苯环被单取代,则所述取代基位于所述亚氨基官能团的邻位或间位。10. A sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 9, wherein in the general formulae (V), (VII) and (VIII), the substituents R4', R5', R6', which can be the same or different, are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, and alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O) 2 OH and sulfonyl; provided that if the substituted benzene ring is monosubstituted, the substituent is located in the ortho-position or meta-position to the imino function; or wherein in the general formulae (VI), (IX) and (X), the substituents R4", R5", R6", which can be identical or different, are independently selected from the group consisting of: H, OH, alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl, and alkoxy, preferably O-methyl, O-ethyl or O-butyl, -S(=O) 2 OH and sulfonyl; provided that if the substituted benzene ring is monosubstituted, the substituent is located in the ortho-position or meta-position to the imino function. 11.根据权利要求1至10中任一项所述的防晒剂、化妆品或药物制剂或家庭护理产品,其中所述类菌胞素氨基酸化合物(b)选自由以下组成的组:11. The sunscreen, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 10, wherein the mycosporin-like amino acid compound (b) is selected from the group consisting of: 或上述化合物的互变异构体或立体异构体或盐;or a tautomer or stereoisomer or salt of the above compound; 或上述化合物的任何混合物。or any mixture of the above compounds. 12.根据权利要求1至11中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中所述至少一种无机UV滤光剂(a)选自由以下组成的组:二氧化钛(TiO2)(无定形的或结晶的,金红石和/或锐钛矿形式)、氧化锌(ZnO)、氧化铁(Fe2O3)、氧化锆(ZrO2)、二氧化硅(SiO2)、氧化锰(例如,MnO)、氧化铝(Al2O3)、氧化铈(Ce2O3)、碳酸钡(BaCO3)、碳酸钙(CaCO3),非纳米颜料、纳米颜料、处理的非纳米颜料和处理的纳米颜料形式的所有上述无机UV滤光剂、以及它们的混合物。12. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 11, wherein the at least one inorganic UV filter (a) is selected from the group consisting of titanium dioxide ( TiO2 ) (amorphous or crystalline, rutile and / or anatase form), zinc oxide (ZnO), iron oxide ( Fe2O3 ), zirconium oxide ( ZrO2 ), silicon dioxide ( SiO2 ), manganese oxide (e.g. MnO ), aluminum oxide ( Al2O3 ), cerium oxide ( Ce2O3 ), barium carbonate ( BaCO3 ), calcium carbonate ( CaCO3 ), all of the above inorganic UV filters in non-nanopigments, nanopigments, treated non-nanopigments and treated nanopigments form, and mixtures thereof. 13.根据权利要求1至12中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,还包含至少一种附加初级有机UV滤光剂,其中另外初级有机UV滤光剂选自由以下组成的组:樟脑苯扎铵甲基硫酸盐、胡莫柳酯、二苯甲酮-3、苯基苯并咪唑磺酸、对苯二亚甲基二樟脑磺酸、丁基甲氧基二苯甲酰基甲烷、亚苄基樟脑磺酸、氰双苯丙烯酸辛酯、聚丙烯酰胺甲基亚苄基樟脑、甲氧基肉桂酸乙基己酯、PEG-25PABA、对甲氧基肉桂酸异戊酯、乙基己基三嗪酮、甲酚曲唑三硅氧烷、二乙基己基丁酰胺基三嗪酮、4-甲基亚苄基樟脑、水杨酸乙基己酯、二甲基PABA乙基己酯、二苯甲酮-4、二苯甲酮-5、亚甲基双-苯并三唑基四甲基丁基苯酚(纳米)、苯基二苯并咪唑四磺酸酯二钠、双-乙基己氧基苯酚甲氧基苯基三嗪、聚硅氧烷-15、二乙基氨基羟基苯甲酰基苯甲酸己酯、三-联苯基三嗪(纳米)、亚苯基双-二苯基三嗪、甲氧基丙基氨基亚环己烯基乙氧基乙基氰基乙酸酯、双-(二乙基氨基羟基苯甲酰基苯甲酰基)哌嗪、TEA-水杨酸盐、二苯甲酮-8、PABA、二甲基PABA乙基己酯、邻氨基苯甲酸薄荷酯,以及它们的任何混合物。13. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 12, further comprising at least one additional primary organic UV filter, wherein the additional primary organic UV filter is selected from the group consisting of: camphor benzalkonium methyl sulfate, homosalate, benzophenone-3, phenylbenzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, butyl methoxydibenzoylmethane, benzalkonium camphor sulfonic acid, octocrylene, polyacrylamidomethylbenzylidene camphor, ethylhexyl methoxycinnamate, PEG-25 PABA, isoamyl p-methoxycinnamate, ethylhexyl triazone, drometrizole trisiloxane, diethylhexyl butamido triazone, 4-methylamino Benzyl camphor, ethylhexyl salicylate, dimethyl PABA ethylhexyl ester, benzophenone-4, benzophenone-5, methylene bis-benzotriazolyl tetramethylbutylphenol (nano), disodium phenyl dibenzimidazole tetrasulfonate, bis-ethylhexyloxyphenol methoxyphenyl triazine, polysilicone-15, diethylamino hydroxybenzoyl hexyl benzoate, tris-biphenyl triazine (nano), phenylene bis-diphenyl triazine, methoxypropylaminocyclohexenylene ethoxyethyl cyanoacetate, bis-(diethylamino hydroxybenzoyl benzoyl) piperazine, TEA-salicylate, benzophenone-8, PABA, dimethyl PABA ethylhexyl ester, menthyl anthranilate, and any mixture thereof. 14.根据权利要求1至13中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,基于所述产品或制剂的总重量计,以0.5重量%至60.0重量%的量、特别地以0.3重量%至55.0重量%的量、更特别地以0.1重量%至50.0重量%的量、最特别地以1.0重量%至45重量%的量包含所述无机UV滤光剂(a)或其混合物。14. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 13, comprising the inorganic UV filter (a) or a mixture thereof in an amount of 0.5 to 60.0 wt.-%, particularly in an amount of 0.3 to 55.0 wt.-%, more particularly in an amount of 0.1 to 50.0 wt.-%, most particularly in an amount of 1.0 to 45 wt.-%, based on the total weight of the product or preparation. 15.根据权利要求1至14中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,基于所述产品或制剂的所述总重量计,以0.001重量%至15.0重量%的量、特别地以0.01重量%至10.0重量%的量、更特别地以0.05重量%至7.5重量%的量、最特别地以0.1重量%至5.0重量%的量包含所述类菌胞素氨基酸化合物(b)或其混合物。15. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 14, comprising the mycosporin-like amino acid compound (b) or a mixture thereof in an amount of 0.001 to 15.0 wt.-%, particularly in an amount of 0.01 to 10.0 wt.-%, more particularly in an amount of 0.05 to 7.5 wt.-%, most particularly in an amount of 0.1 to 5.0 wt.-%, based on the total weight of the product or preparation. 16.根据权利要求1至15中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,还包含具有5个至12个碳原子的至少一种1,2-链烷二醇或一种2,3-链烷二醇,其中所述1,2-链烷二醇优选地选自由以下组成的组:1,2-戊二醇、1,2-己二醇、1,2-庚二醇、1,2-辛二醇、1,2-壬二醇、1,2-癸二醇、1,2-十一烷二醇、1,2-十二烷二醇,并且其中所述2,3-链烷二醇选自由以下组成的组:2,3-戊二醇、2,3-己二醇、2,3-庚二醇、2,3-辛二醇、2,3-壬二醇、2,3-癸二醇、2,3-十一烷二醇、2,3-十二烷二醇和它们的任何混合物。16. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 15, further comprising at least one 1,2-alkanediol or one 2,3-alkanediol having 5 to 12 carbon atoms, wherein the 1,2-alkanediol is preferably selected from the group consisting of 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, and wherein the 2,3-alkanediol is selected from the group consisting of 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 2,3-octanediol, 2,3-nonanediol, 2,3-decanediol, 2,3-undecanediol, 2,3-dodecanediol and any mixtures thereof. 17.根据权利要求1至16中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,还包含一种或多种抗微生物剂,优选地其中所述抗微生物剂选自由以下组成的组:1,2-戊二醇、1,2-己二醇、1,2-庚二醇、1,2-辛二醇、1,2-壬二醇、1,2-癸二醇、1,2-十一烷二醇、1,2-十二烷二醇、2,3-戊二醇、2,3-己二醇、2,3-庚二醇、2,3-辛二醇、2,3-壬二醇、2,3-癸二醇、2,3-十一烷二醇、2,3-十二烷二醇、2-苄基庚醇、2-羟基苯乙酮、2-甲基5-环己基戊醇、2-羟基苯甲酸3-羟丙酯、4-羟基苯乙酮和它们的任何混合物。17. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 16, further comprising one or more antimicrobial agents, preferably wherein the antimicrobial agent is selected from the group consisting of 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 2,3-octanediol, 2,3-nonanediol, 2,3-decanediol, 2,3-undecanediol, 2,3-dodecanediol, 2-benzylheptanol, 2-hydroxyacetophenone, 2-methyl 5-cyclohexylpentanol, 3-hydroxypropyl 2-hydroxybenzoate, 4-hydroxyacetophenone and any mixture thereof. 18.根据权利要求1至17中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,还包含至少一种赋形剂和/或活性物质,所述至少一种赋形剂和/或活性物质选自由以下组成的组:载剂、油组分、流变添加剂、水溶助长剂、增溶剂、粉末、成膜剂、耐水性改进剂、皮肤保湿和/或保水物质、缓和剂物质、生理冷却剂、链烷二醇、抗氧化剂、抗皮肤老化剂、基质-金属蛋白酶抑制剂(MMPI)、抗炎剂、TRPV1拮抗剂、乳化剂、抗微生物、防腐剂、抗细菌或抗真菌活性物质、螯合剂、表面活性剂、芳香剂/香味剂或香料油以及上述物质中的两者或更多者的任何混合物。18. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 17, further comprising at least one excipient and/or active substance selected from the group consisting of: carriers, oil components, rheological additives, hydrotropes, solubilizers, powders, film formers, water resistance improvers, skin moisturizing and/or water retention substances, emollient substances, physiological cooling agents, alkanediols, antioxidants, anti-skin aging agents, matrix-metalloproteinase inhibitors (MMPI), anti-inflammatory agents, TRPV1 antagonists, emulsifiers, antimicrobials, preservatives, antibacterial or antifungal active substances, chelating agents, surfactants, fragrances/fragrances or perfume oils and any mixtures of two or more of the above substances. 19.根据权利要求1至18中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,所述防晒剂产品、化妆品或药物制剂或家庭护理产品的形式为19. The sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 18, which is in the form of (i)分散体,优选地其中所述化妆品或药物制剂的形式为乳液、特别是O/W乳液、W/O乳液、多重乳液、水分散凝胶、香油、油包水型(W/O/W)或水包油型(O/W/O)的多重乳液、PIT乳液、皮克林乳液、微乳液、液体、洗液、悬浮液、牛奶、软膏、糊剂、凝胶、基于乳膏、基于油或基于脂质体的调配物或气雾剂、特别是泡沫和喷雾剂,包括所有类型的硅基乳液;(i) dispersions, preferably wherein the cosmetic or pharmaceutical preparation is in the form of an emulsion, in particular an O/W emulsion, a W/O emulsion, a multiple emulsion, an aqueous dispersion gel, a balm, a water-in-oil (W/O/W) or oil-in-water (O/W/O) multiple emulsion, a PIT emulsion, a Pickering emulsion, a microemulsion, a liquid, a lotion, a suspension, a milk, an ointment, a paste, a gel, a cream-based, oil-based or liposome-based formulation or an aerosol, in particular a foam and a spray, including all types of silicone-based emulsions; (ii)无水调配物;或(ii) anhydrous formulations; or (iii)基于水或水/醇、特别是水/乙醇、或水/甘醇、或醇/甘醇、特别是乙醇/甘醇的溶液。(iii) Solutions based on water or water/alcohol, in particular water/ethanol, or water/glycol, or alcohol/glycol, in particular ethanol/glycol. 20.根据权利要求1至19中任一项所述的防晒剂产品或化妆品或药物制剂,其作为化妆品用于个人护理,特别是用于皮肤护理、皮肤保护、防晒、头皮保护、头皮护理、毛发护理、指/趾甲护理,作为药物用于动物护理或用于家庭护理。20. The sunscreen product or cosmetic or pharmaceutical preparation according to any one of claims 1 to 19 for use as a cosmetic in personal care, in particular for skin care, skin protection, sun protection, scalp protection, scalp care, hair care, nail care, as a medicament in animal care or for household care. 21.根据权利要求1至20中任一项所述的防晒剂产品、化妆品或药物制剂或家庭护理产品,其中相对于不含所述类菌胞素氨基酸化合物(b)的防晒剂产品、化妆品或药物制剂或家庭护理产品,SPF增加至少10%,优选地至少15%,更优选地至少20%;并且/或者其中相对于不含所述类菌胞素氨基酸化合物(b)的防晒剂产品、化妆品或药物制剂或家庭护理产品,UVA光防护(UVA-PF)增加至少5%,优选地至少10%,并且更优选地至少15%。21. A sunscreen product, cosmetic or pharmaceutical preparation or home care product according to any one of claims 1 to 20, wherein the SPF is increased by at least 10%, preferably at least 15%, more preferably at least 20% relative to a sunscreen product, cosmetic or pharmaceutical preparation or home care product not containing the mycosporin-like amino acid compound (b); and/or wherein the UVA light protection (UVA-PF) is increased by at least 5%, preferably at least 10%, and more preferably at least 15% relative to a sunscreen product, cosmetic or pharmaceutical preparation or home care product not containing the mycosporin-like amino acid compound (b). 22.如权利要求1至11中任一项中所限定的类菌胞素氨基酸化合物或其混合物用于增加包含至少一种无机UV滤光剂的防晒剂产品、化妆品或药物制剂或家庭护理产品的SPF和/或UVA光防护(UVA-PF)的用途。22. Use of a mycosporin-like amino acid compound as defined in any one of claims 1 to 11 or a mixture thereof for increasing the SPF and/or UVA photoprotection (UVA-PF) of a sunscreen product, a cosmetic or pharmaceutical preparation or a home care product comprising at least one inorganic UV filter. 23.增强或促进包含至少一种无机UV滤光剂的防晒剂产品、化妆品或药物制剂或家庭护理产品的SPF性能和UVA光防护的方法,所述方法包括向所述防晒剂产品、化妆品或药物制剂或家庭护理产品中添加有效量的如权利要求1至11中任一项中所限定的类菌胞素氨基酸化合物或其混合物。23. A method for enhancing or boosting the SPF performance and UVA photoprotection of a sunscreen product, a cosmetic or pharmaceutical preparation or a home care product comprising at least one inorganic UV filter, said method comprising adding to said sunscreen product, cosmetic or pharmaceutical preparation or home care product an effective amount of a mycosporin-like amino acid compound as defined in any one of claims 1 to 11 or a mixture thereof. 24.通过局部施用根据权利要求1至20中任一项所述的防晒剂产品、化妆品或药物制剂来向皮肤提供抗老化益处、增白皮肤或防止皮肤变黑、改善皮肤外观、减少皮肤老化的可见迹象和改善皮肤的光泽和紧致度的方法。24. A method of providing anti-aging benefits to the skin, whitening the skin or preventing skin darkening, improving the appearance of the skin, reducing visible signs of skin aging and improving the radiance and firmness of the skin by topically applying a sunscreen product, cosmetic or pharmaceutical formulation according to any one of claims 1 to 20.
CN202380054705.9A 2022-08-05 2023-08-07 Compositions with improved SPF and UVA photoprotection Pending CN119604267A (en)

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EPPCT/EP2023/071719 2023-08-04
PCT/EP2023/071719 WO2025031562A1 (en) 2023-08-04 2023-08-04 Mycosporine-like amino acid analogue compounds and use thereof
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