Particulate organic uv absorber compositions

Abstract

Disclosed is an aqueous dispersion (A) comprising a micronized organic UV filter (a) selected from the group consisting of: (a1) a micronized compound of formula (1); (a2) a micronized compound of formula (2); (a3) a micronized compound of formula (3a); (a4) a micronized compound of formula (4); (b) a vinylpyrrolidone copolymer or homopolymer. (1) (1a) (2) (3a) (3b) (4)

Description

[0001] This application is a divisional application of Chinese patent application filed on May 19, 2017, with application number 201780030007.X and invention title "Particulate Organic UV Absorber Composition". Technical Field

[0002] This invention relates to an improved aqueous dispersion of micronized organic UV filter and a novel sunscreen composition comprising an aqueous dispersion of micronized organic UV filter. Background Technology

[0003] It has long been known that prolonged exposure to UV radiation can lead to erythema or mild skin diseases, as well as an increased incidence of skin cancer or accelerated skin aging.

[0004] Various sunscreen formulations have been proposed that contain materials designed to combat UV radiation, thereby inhibiting the unwanted effects on the skin.

[0005] Numerous compounds have been proposed for use as UV filters in sunscreen formulations, particularly soluble organic UV absorbers and insoluble micronized organic compounds.

[0006] The micronized insoluble organic UV absorber prepared according to the method is used in sunscreen formulations to provide excellent UV protection, and the SPF rating is at least as high as that of corresponding sunscreen formulations containing known inorganic UV absorbers.

[0007] GB-A-2303549 describes a method for preparing a micronized insoluble organic UV absorber, and a sunscreen composition comprising an aqueous dispersion of the micronized insoluble organic UV absorber. The method includes grinding the insoluble organic UV absorber into coarse particles in a grinding apparatus in the presence of a polyglucoside.

[0008] WO 2007 071584 describes suitable anionic, nonionic, and amphoteric surfactants with HLB (hydrophilic-lipophilic balance) values ​​greater than 8, preferably greater than 10, as grinding aids in the micronization process of organic UV absorbers. This reference teaches that many cosmetic surfactants can be used for the micronization of insoluble organic UV filters, with sodium alkyl sulfate or sodium alkyl ether sulfate being the most preferred dispersants. However, these surfactants, primarily used in rinse-off surfactants, are not well-accepted by the skin and can be irritating. More preferably are skin-friendly, no-rinse dispersants.

[0009] WO 2009 068469 discloses numerous exemplary compositions for micronized dispersions. All formulations contain a thickener (e.g., xanthan gum) to prevent UV filter particles from settling, thereby extending the shelf life of the dispersion. However, the use of xanthan gum requires the preparation of a concentrated thickener dispersion in a suitable solvent as an additional process step. This thickener dispersion is then incorporated into the micronized UV filter dispersion to obtain a homogeneous UV filter dispersion. For this solvent, a water / diol mixture is frequently used. Therefore, the use of xanthan gum as a thickener in micronized UV filter dispersions may also result in a certain level of diol in sunscreen products, which is not always desirable in cosmetic formulations.

[0010] Thickeners used in cosmetics include viscous liquids such as polyethylene glycol, synthetic polymers such as carbomer (a trade name for polyacrylic acid), and plant gums such as xanthan gum. Some thickeners also act as stabilizers when used to maintain the stability of emulsions.

[0011] Finally, due to their specific properties, the use of organic micronized filters offers new benefits to consumers. Their UV protection spectrum can extend to longer UVA wavelengths, even exceeding UV light to reach blue visible light (up to 500 nm), without causing severe skin whitening, thus enhancing protection and providing new areas of protection: for example, very long UVA and near-VIS light are known to effectively induce free radicals in the skin [Zastrow 2007]. Furthermore, short-wavelength visible light has been reported to be involved in specific pigmentation mechanisms, such as tanning in dark skin types [Mahmoud 2010], post-inflammatory hyperpigmentation, and the formation of melasma. Castanedo-Cazares JP 1 wait; Photodermatol Photoimmunol Photomed. February 2014; 30(1): 35-42, doi: 10.1111 / phpp.12086. Epub, December 3, 2013]. Therefore, enhancing skin protection at longer wavelengths is a very important and beneficial effect.

[0012] Therefore, the problem of the present invention is to overcome the disadvantages of the aforementioned micronized organic UV filter formulations and to provide new benefits for cosmetic and pharmaceutical formulations. Summary of the Invention

[0013] Surprisingly, it was found that the use of diols in aqueous dispersions of micronized organic UV filters could be avoided by using a thickener system based on polyvinylpyrrolidone.

[0014] Therefore, a first aspect of the present invention relates to an aqueous dispersion (A) comprising a micronized organic UV filter selected from the following: (a1) Micronized compounds of the following formula:

[0015] in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; divalent groups; or hydroxyl groups -B- It should be in the following formula:

[0016] in: n1 is a number between 1 and 3; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula:

[0017] in: T1 is hydrogen; C1-C 12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula:

[0018] in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 Alkyl groups; or groups of the following formula:

[0019] in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula:

[0020] in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18 Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; and (b) Vinylpyrrolidone copolymers or homopolymers. Attached Figure Description

[0021] Figure 1 The emission spectrum of the LED array is shown.

[0022] Figure 2 The UV spectrum of the film absorbance is shown.

[0023] Figure 3 and 4 The values ​​at 150 J / cm were displayed respectively. 2 Results of cell survival rates at 385 nm and 405 nm after dose administration.

[0024] Figure 5 and 6 The figures show the results at 385 nm and 50 J / cm. 2 Results of UV dose and ROS formation in cells after 100 J / cm² light dose at 405 nm.

[0025] Figure 7 This shows gene expression experiments of HMOX-1 and MMP-1 under 385 nm irradiation.

[0026] Figure 8 This study demonstrates gene expression experiments of IL-1a and IL-6 under 385 nm irradiation.

[0027] Figure 9 The gene expression experiments of HMOX-1 and MMP-1 after 405 nm irradiation are shown.

[0028] Figure 10 The gene expression experiments after 405 nm irradiation of IL-1a and IL-6 are shown. Detailed Implementation

[0029] C1-C 20Alkyl groups refer to straight-chain or branched, unsubstituted or substituted alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, n-hexyl, cyclohexyl, n-decyl, n-dodecyl, n-octadecyl, eicosyl, methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl, N,N-diethylaminopropyl, cyanoethyl, phenethyl, benzyl, p-tert-butylphenethyl, p-tert-octylphenoxyethyl, 3-(2,4-ditert-pentylphenoxy)propyl, ethoxycarbonylmethyl-2-(2-hydroxyethoxy)ethyl, or 2-furanylethyl.

[0030] C2-C 20 Alkenyl groups include, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-pent-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl, or n-octadec-4-enyl.

[0031] C3-C 10 The cycloalkyl group is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, preferably cyclohexyl. These groups can be substituted, for example, by one or more identical or different C1-C4 alkyl groups, preferably by methyl and / or hydroxyl groups. If the cycloalkyl group is substituted by one or more groups, they are preferably substituted by 1, 2, or 4, preferably 1 or 2 identical groups.

[0032] C3-C 10 The cycloalkenyl group is, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, or cyclodecenyl, preferably cyclohexenyl. These groups may be substituted with one or more identical or different C1-C4 alkyl groups, preferably with methyl and / or hydroxyl groups. If the cycloalkenyl group is substituted with one or more groups, they are preferably substituted with 1, 2, 3, or 4, preferably 1 or 2 identical or different groups.

[0033] The hydroxyl-substituted C1-C5 alkyl group is, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, or hydroxypentyl.

[0034] Alkylene is preferably C1-C 12 Alkylenes, such as methylene, ethylene, propylene, butylene, hexylene, or octylene.

[0035] Cycloalkylene is preferably cyclo-C3-C 12 Alkylenes, such as cyclopropylene, cyclobutylene, cyclohexylene, or cyclooctylene.

[0036] The alkylene or cycloalkylene group may optionally be substituted with one or more C1-C5 alkyl groups.

[0037] If R1 and R2 are heterocyclic groups, they contain 1, 2, 3, or 4 identical or different cyclic heteroatoms. Heterocyclic rings containing 1, 2, or 3, especially 1 or 2 identical or different heteroatoms are particularly preferred. The heterocycles can be monocyclic or polycyclic, for example, monocyclic, bicyclic, or tricyclic. They are preferably monocyclic or bicyclic, especially monocyclic. The rings preferably contain 5, 6, or 7 ring members. Examples of monocyclic and bicyclic heterocyclic systems from which groups present in compounds of formula (1) or (2) can be derived include, for example, pyrrole, furan, thiophene, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyridazine, pyrimidine, pyrazine, pyran, thioran, 1,4-dioxane, etc. Alkane, 1,2- Azine, 1,3- Azine, 1,4- Azides, indole, benzothiophene, benzofuran, pyrrolidine, piperidine, piperazine, morpholine, and thiomorpholine.

[0038] Preferably, the dispersion (A) of the present invention does not contain any thickener, and is preferably selected from propylene glycol, carbomer and plant gum, and most preferably xanthan gum.

[0039] The preferred compound is of formula (1), wherein:

[0040] R1 and R2 are hydrogen independently of each other; or C1-C 20 Alkyl group; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; B is an alkylene group, which may optionally be spaced with a carbonyl or carboxyl group; or a group of formula (1b); A is -O-; or -N(R3)-; or a direct bond, and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl.

[0041] The compound of formula (1) is of preferred interest, wherein: R1 and R2 are C1-C 20 Alkyl group, preferably C1-C5 alkyl group, and most preferably ethyl group.

[0042] Preferably, R1 and R2 in equation (1) have the same definition.

[0043] The most preferred compound is of formula (1), wherein: B corresponds to equation (1b).

[0044] Very preferably, the micronized organic UV filter (a1) corresponds to the following formula:

[0045] Preferably, the micronized organic UV filter (a2) corresponds to the following formula:

[0046] Preferably, the micronized organic UV filter (a3) ​​corresponds to the following formula:

[0047] Preferably, the micronized organic UV filter (a4) corresponds to the following formula:

[0048] The vinylpyrrolidone copolymer or homopolymer of component (b) within the scope of this invention refers to a water-soluble polymer containing 1-vinyl-2-pyrrolidone monomer and accepted in cosmetic formulations for use in leave-on skin applications to thicken micronized UV filter dispersions.

[0049] Polyvinylpyrrolidone or poly[1-(2-oxo-1-pyrrolyl)ethylene] (PVP; CAS No.: 9003-39-8) is preferably used as component (b) of the present invention. PVP is a linear polymer composed of 1-vinyl-2-pyrrolidone monomers that generally conform to the following formula:

[0050] Preferably, the dispersion (A) of the present invention comprises: Micronized organic UV filters corresponding to the following formula (a1):

[0051] and

[0052] (b) Polyvinylpyrrolidone of the following formula:

[0053] Preferably, the dispersion of the present invention does not contain any diol (diol) compound.

[0054] Diols are chemical compounds containing two hydroxyl groups (-OH groups). This pair of functional groups is ubiquitous and many subclasses have been identified. The most common industrial diol is ethylene glycol. Examples of diols in which the hydroxyl functional groups are more widely separated include 1,2-, 1,3-, 1,4-, 1,5-, and longer diols, such as 1,4-butanediol HO-(CH2)4-OH, 1,5-pentanediol HO-(CH2)5-OH and bisphenol A, propylene-1,3-diol or β-propanediol, HO-CH2-CH2-CH2-OH, 2-methyl-2-propyl-1,3-propanediol, and neopentanediol.

[0055] Further examples of diol compounds include arachidonic ethylene glycol, benzyl ethylene glycol, butoxydiethylene glycol, octyl ethylene glycol, cetyl / octadecyl ethylene glycol polyoxyethylene (60) ether myristyl ethylene glycol, cetyl ethylene glycol, C14-30 ethylene glycol, decanediol, diethylene glycol, dimethoxydiethylene glycol, dimethylol ethylene glycol, dipropylene glycol, ethoxydiethylene glycol, hexadecyl ethylene glycol, hexanediol, lauryl glycol, methoxydiethylene glycol, methylene glycol, myristyl ethylene glycol, octadecyl ethylene glycol, pentylene glycol, poly(1,2-butanediol)-6-propylene glycol, polybutylene glycol-10, stearyl ethylene glycol, triethylene glycol, or tripropylene glycol.

[0056] The UV filters (a1)-(a4) used in this invention exist in a micronized state and are preferably prepared by wet milling. Any known method suitable for preparing microparticles can be used to prepare micronized UV absorbers, for example: - Wet milling in water or in a suitable organic solvent using hard grinding media (e.g., zirconium silicate balls in a ball mill) and protective surfactants or protective polymers (for low-viscosity micronization methods of pumpable dispersions); - Wet kneading using continuous or intermittent (batch) kneaders (for high-viscosity micronization of non-pumpable pastes). For wet kneading methods, solvents (water or cosmetically acceptable oils), grinding aids (surfactants, emulsifiers), and polymer grinding aids can be used.

[0057] - Spray dried with a suitable solvent, such as an aqueous suspension or condensate containing an organic solvent, or a true solution in water, ethanol, dichloroethane, toluene, or N-methylpyrrolidone.

[0058] - Expanding according to the RESS (rapid expansion of supercritical solution) method of supercritical fluid (e.g., CO2) in which UV filter is dissolved, or expanding liquid carbon dioxide together with a solution of one or more UV filter in a suitable organic solvent. - By reprecipitation with a suitable solvent (including supercritical fluid) (GASR method = gaseous antisolvent recrystallization / PCA method = precipitation with compressed antisolvent).

[0059] Wet grinding and wet kneading are the preferred methods.

[0060] As the grinding apparatus for preparing the micronized organic UV absorbers (a1)-(a4), a jet mill, ball mill, vibratory mill, or hammer mill can be used, preferably a high-speed mixing mill. Even more preferred are modern ball mills; manufacturers of these types of mills include, for example, Netzsch (LMZ mills), Drais (DCP-Viscoflow or Cosmo), Bühler AG (centrifugal mills), or Bachhofen. Grinding is preferably performed using a grinding aid.

[0061] Examples of kneading apparatuses used for preparing micronized organic UV absorbers (a1)-(a4) are typical sigma-blade batch kneaders, as well as series batch kneaders (IKA-Werke) or continuous kneaders (from Werner und Pfleiderer's Continua).

[0062] For each example of the aqueous dispersion of the present invention, the preparation method is as follows: UV filters (a1)-(a4) were added separately to a homogeneous aqueous dispersion containing an aqueous dispersant. The slurry was then ground together with zirconium silicate beads (0.1-4 mm in diameter) as grinding media in a ball mill (as described above) until d... 50 The average particle size is 100-170 nm. After obtaining the fine pigment dispersions of UV filters (a1)-(a4) respectively, they can be pH adjusted and / or formulated with a preservation system, and polyvinylpyrrolidone (PVP) (b) can be added as a thickener system.

[0063] PVP is essentially water-soluble, allowing for the preparation of stock solutions with high polymer levels. Therefore, the preparation of pre-dispersions of thickeners in organic solvents such as propylene glycol becomes obsolete.

[0064] The grinding of the slightly soluble organic compounds used in this invention is preferably carried out in the presence of a grinding aid.

[0065] The grinding aid can be any surfactant that can be used as a dispersant. This surfactant may include anionic, nonionic, amphoteric, and / or cationic surfactants, or mixtures thereof.

[0066] Preferably, the grinding aid is used at a concentration of 0.1-20% by weight, more preferably 0.4-15% by weight, based on the total weight of the UV protection composition.

[0067] The grinding aid that can be used is alkyl polyglucosides (GAO).

[0068] Available grinding aids are carboxylic acids and their salts (ga1), for example: - Organic-based soaps, such as linear C6-C24 Fatty acids (capric / capric acid, myristic acid, palmitoleic acid, isostearic acid, linoleic acid, arachidic acid, sorbic acid) (Acids, such as erucic acid) or branched carboxylic acids or hydroxycarboxylic acids.

[0069] Other available grinding aids are fatty acid esters (ga2), for example: - Straight chain C3-C7 or C 23 -C 24 Fatty alcohols and esters of straight-chain fatty acids having 6-11 carbon atoms or more than 22 carbon atoms in an alkyl group.

[0070] The preferred formulation is isochetyl isostearate or ethylene glycol oleate.

[0071] Other available grinding aids (ga3) are alkyl phosphates or phosphates, such as DEA-oil-based polyoxyethylene (3) ether phosphate.

[0072] Other available grinding aids (ga4) are ethoxylated carboxylic acids or polyethylene glycol (PEG) esters such as PEG-n acylates (excluding PEG-n stearate, PEG-n oleate, and PEG-n cocoate), wherein the carboxylic acid has an alkyl group containing 8-22 carbon atoms (ethoxylated or non-ethoxylated), such as butyric acid, hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, myristone acid, palmitic acid, palmitoleic acid, linoleic acid, arachidic acid, arachidonic acid, and so on. Acids, eicosapentaenoic acid, erucic acid, or docosahexaenoic acid.

[0073] The preferred formulation is PEG-20 lauryl ester.

[0074] Other available grinding aids (ga5) are fatty alcohol polyethylene glycol (PEG) ethers.

[0075] Straight-chain or branched fatty alcohols have 8-22 carbon atoms (isopropyl, ethylhexyl, octyl, isothiazyl, myristyl, palmityl, isostearyl, linoleyl, linolenic acid, arachidyl, etc.). Group or erucic acid group.

[0076] Preferably, it is hexadecyl polyoxyethylene (10) ether, lauryl polyoxyethylene (7) ether, or PEG-10 ether. basal ether (mountain) (Based polyoxyethylene (10) ether).

[0077] Other available grinding aids (ga7) are ethoxylated alkylphenols or ethoxylated alkylphenyl ethers, such as PEG-10 nonylphenyl ether.

[0078] Other available grinding aids (ga8) are esters of polyols and mono-, di-, or tri-glycerides of glycerol, such as PEG-10 polyglycerol (2) laurate.

[0079] Other available grinding aids (ga9) are esters of fatty acids and sucrose, such as PEG-120 methyl gluconate dioleate or polyglycerol (3) methyl gluconate distearate.

[0080] Other available grinding aids (ga) 10 ) are sorbitol monoesters and diesters of saturated and / or unsaturated fatty acids, such as PEG-20 sorbitol isostearate and sorbitol polyoxyethylene (20) ether oleate (polysorbate-80).

[0081] Other available grinding aids (ga) 11 ( ) refers to surfactants commonly used in detergents or cleaning agents. Examples are listed below: A. Anionic surfactants Anionic surfactants are so named because they contain a negatively charged fatty structural moiety. This ionized structural moiety can be a carboxyl group, sulfate group, sulfonate group, or phosphate group.

[0082] The general form of anionic surfactants is:

[0083] RX - M +

[0084] in: R defines the carbon chain length; X is a negatively charged species, such as carboxylate (RCOO). - ), sulfate radical (ROSO2O - ), sulfonate (RSO2O) - ) or phosphate (ROPO(OH)O - ); M is a neutralizing group, such as sodium, ammonium, TEA, or magnesium.

[0085] a. Sulfates; sulfuric acid and salts

[0086] The preferred option is sodium dioctyl ethylenediamine PEG-15 sulfate.

[0087] b. Sulfonates; sulfonic acids and salts

[0088] Acyl hydroxyethyl sulfonates, such as sodium acyl hydroxyethyl sulfonate and sodium cocoyl hydroxyethyl sulfonate; alkyl aryl sulfonates, such as sodium alkylbenzene sulfonate and sodium dodecylbenzene sulfonate; alkyl sulfonates, such as sodium alkyl ether sulfonate (C12-15 polyoxyethylene (15) ether sulfonate); C14 -C 16 Sodium olefin sulfonate, sodium decyl glucoside hydroxypropyl sulfonate, or sodium lauryl glucoside hydroxypropyl sulfonate.

[0089] Hydroxypropylsulfonic acid is preferred. compounds .

[0090] c. Sulfosuccinate; sulfosuccinic acid and its salt

[0091] The preferred formulation is alkylamide-based PEG-n disodium sulfosuccinate (oleamide-based MEA-disodium sulfosuccinate).

[0092] d. Phosphates; phosphoric acid and salts

[0093] PEG-n alkyl phosphates such as DEA oil-based polyoxyethylene (10) ether phosphate, and diPEG-n alkyl phosphates (diesters) such as dilauryl polyoxyethylene (4) ether phosphate.

[0094] e. Acyl amino acids and salts

[0095] Acyl glutamate salts, such as diTEA palmitoyl aspartate, hydrogenated tallow glutamate; sodium stearoyl glutamate; sodium cocoyl glutamate; disodium cocoyl glutamate; acyl peptides, such as palmitoyl hydrolyzed milk protein, sodium cocoyl hydrolyzed soy protein, TEA cocoyl hydrolyzed collagen; sarcosine salts or acyl sarcosine salts, such as myristoyl sarcosine, sodium lauroyl sarcosine, sodium myristoyl sarcosine, TEA lauroyl sarcosine; taurine salts and sodium methyl acyl taurate, such as sodium lauroyl taurate or sodium methyl cocoyl taurate.

[0096] B. Nonionic surfactants

[0097] Amine oxide

[0098] Examples include cocamidopropylamine oxide or laurylamine oxide.

[0099] C. Amphoteric or zwitterionic surfactants

[0100] Surfactants that carry a positive charge in strongly acidic media carry a negative charge in strongly alkaline media and form zwitterionic species at moderate pH.

[0101] C1. Acyl / dialkylethylenediamine

[0102] Examples include disodium acryloazidopropionate, sodium acryloazidohydroxypropylsulfonate, disodium acryloazidodiacetate, and sodium acryloazidopropionate.

[0103] D. Cationic surfactants

[0104] Positively charged surfactants; of primary interest are those used in hair care for conditioning and antistatic effects.

[0105] D1. Alkylamine

[0106] Examples include dimethylalkylamine (dimethyl laurylamine), dihydroxyethylalkylamine dioleate, and acylaminopropyl dimethylamine lactate (cocamidopropyl dimethylamine lactate).

[0107] D2. Alkyl imidazoline

[0108] For example, alkylhydroxyethylimidazoline, ethylhydroxymethyl oleoyl Azoline, alkylaminoethylimidazoline.

[0109] D3. Quaternary ammonium compounds

[0110] Examples include dialkyl dimethyl ammonium chloride (hydroxyethyl hexadecyl dimethyl ammonium chloride) and alkylamidopropyl alkyl dimethyl ammonium toluenesulfonate (cocamidopropyl ethyl dimethyl ammonium ethyl sulfate).

[0111] Other available grinding aids (ga) 12 ) is a siloxane or an organically substituted polysiloxane, that is, any organosilicon polymer or oligomer having a linear or cyclic, branched or cross-linked structure of variable molecular weight and being substantially based on repeating structural units in which silicon atoms are connected to each other by oxygen atoms (siloxane bond SiOSi), wherein optionally substituted hydrocarbon groups are directly linked to silicon atoms via carbon atoms.

[0112] E. Silicon-containing compounds

[0113] E1. Silanol compounds or polydimethylsiloxane alcohol

[0114] The following are dimethylsiloxanes with hydroxyl (-OH)-terminated caps:

[0115] E2. Siloxane elastomers and resins

[0116] Siloxane structures such as crosslinking of polydimethylsiloxane

[0117] Elastomer: Moderately crosslinked with a density that allows for molecular elongation / deformation. Excludes PEG-modified polydimethylsiloxane crosslinked polymers.

[0118] Resin: Provides molecules with a certain degree of rigidity and high cross-linking density.

[0119] E3. Siloxane elastomer as a co-emulsifier system

[0120] Polydimethylsiloxane crosslinked polymer in cyclopentasiloxane; DC 9045 siloxane elastomer blend (Dow Corning); Polydimethylsiloxane crosslinked polymer in polydimethylsiloxane; DC 9041 siloxane elastomer blend (Dow Corning); composed of C3-C 20 Alkyl crosslinked polydimethylsiloxane (qv) polymers; polydimethylsiloxane / vinyl polydimethylsiloxane crosslinked polymers; DC 9506 powder (Dow Corning); polydimethylsiloxane / vinyl polydimethylsiloxane crosslinked polymers in cyclopentasiloxane; SFE 839 (GE silicones) or KSG15 (Shin-Etsu); dimethyl polysiloxane copolymers crosslinked from vinyl dimethyl polysiloxane.

[0121] E4. Resin siloxane

[0122] Examples include dispersants such as KP-545 (Shin-Etsu); acrylate / polydimethylsiloxane copolymers in cyclopentasiloxane; copolymers of polydimethylsiloxane with one or more monomers of acrylic acid, methacrylic acid, or their simple esters; siloxysilicates such as trimethylsiloxysilicate; T-resins; branched polymers of T-units; Q-resins; branched polymers of Q-units.

[0123] Film-forming and waterproofing agents such as trimethylsiloxysilicate; SR 399 (GE Silicones) or Wacker-Belsil TMS803 (Wacker Chemie); mixtures derived from Dow Corning, such as DC 749 cosmetic fluid (trimethylsiloxysilicate in cyclopentasiloxane) or DC 593 fluid (trimethylsiloxysilicate in polydimethylsiloxane); alkyl-modified siloxanes (AMS); AMS improves spreadability and washability.

[0124] For inorganic sunscreens, they can improve particle dispersion, reduce reagglomeration, and provide a longer-lasting effect on the skin.

[0125] Alkyl polydimethylsiloxanes of the following general formula:

[0126] Where R stands for -(CH2) n -CH3.

[0127] For example: bis-phenylpropyl polydimethylsiloxane (SF 1555 fluid; GE Silicone).

[0128] Alkyl polymethylsiloxanes of the following general formula:

[0129] Where R stands for -(CH2) n -CH3.

[0130] Silicone waxes such as DC 2503 cosmetic wax (Dow Corning); stearyl polydimethylsiloxane; DC 2502 fluid (Dow Corning); hexadecyl polydimethylsiloxane; DC AMS-C30 wax (Dow Corning); C 30 -C 45 Alkyl polymethylsiloxane; DC 580 wax (Dow Corning); stearoxytrimethylsilane and stearyl alcohol.

[0131] Another suitable option is simethicone, a mixture of polydimethylsiloxane with an average chain length of 200-300 dimethylsiloxane units and hydrogenated silicate. Furthermore, a detailed investigation by Todd et al. on suitable volatile siloxanes can be found in Cosm. Toil. 91, 27 (1976).

[0132] The silicone emulsifiers particularly suitable for this type of emulsion are those corresponding to the following formula: (2)

[0133] in: m is a number between 1 and 20; n is a number between 0 and 500; and p is a number between 0 and 50; R1 is a straight-chain or branched C1-C 30 Alkyl or phenyl; R2 is -C c H 2c (-O-C2H4) a -(-O-C3H6) b -(-O-C4H8) d -R3; R3 is H, -OH; straight-chain or branched C1-C 12 Alkyl, straight-chain or branched C1-C6 alkoxy, or straight-chain or branched C2-C 12 Acyloxy group; -NHCH2CH2COOM; optional aminoalkyl group substituted with an amine functional group; -NHCO(CH2) d -COOM, C1-C 30 Carboxyl acyl group; M is H; Na; K; Li; NH4; or an organic amine; optionally substituted phosphonoyl group; -NHCO(CH2) d OH; NH3Y; Y is a monovalent organic or inorganic anion, such as Cl, Br, sulfate, carboxylate (acetate, lactate, citrate); a is a number between 0 and 100; c is a number between 0 and 5; b is a number between 0 and 50; and d is a number between 0 and 10.

[0134] These compounds represent oxidatively olefinically modified organic siloxanes. Other names used, such as PEG / PPG polydimethylsiloxane (polydimethylsiloxane copolyol) or siloxane polyether, clearly demonstrate the surface-active properties required for emulsification.

[0135] The specially recommended siloxane emulsifier corresponds to the following formula: (3)

[0136] in: R is a straight-chain or branched C1-C 30 Alkyl or phenyl; R2 is -C c H2 c -(-O-C2H4) a -(-O-C3H6) b -O(-C4H8) d -R3; n is a number between 1 and 500; and R3, a, b, c, and d have the same meaning as described above.

[0137] The preferred ester is polydimethylsiloxane PEG / PPG-7 / 4 phosphate.

[0138] Preferably, the average particle size of the micronized insoluble organic UV absorber prepared according to the method of the present invention is 0.01-2 μm, more preferably 0.02-1.5 μm, and especially 0.05-1.0 μm.

[0139] In another embodiment of the invention, the dispersion of the micronized UV filter is produced in a manner that eliminates the need for thickeners to adjust the desired viscosity level. These dispersions exhibit thixotropic behavior, meaning they are more fluid under high shear in the liquid and increase in viscosity under low shear. This slows the settling of the dispersed UV filter particles when storing the product, while the dispersion can be pumped or formulated into consumer products when removed from the container.

[0140] Several emulsifiers have been found to act as grinding aids and stabilize the final micronized dispersion during the micronization process. Specifically, the grinding aids are selected from glutamate, hydrolyzed proteins, cyclic acyl peptides, polyglycerol lactate, and sulfosuccinate. These materials are widely used in the formulation of sunscreens, day creams, and other leave-on cosmetics.

[0141] Therefore, another aspect of the present invention relates to an aqueous dispersion (B) comprising: At least one UV filter selected from the following: (a1) Micronized compounds of the following formula:

[0142] in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; divalent groups; or hydroxyl groups -B- It should be in the following formula:

[0143] in: n1 is a number between 1 and 3; A is -N(R3)-; or -O-; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula:

[0144] in: T1 is hydrogen; C1-C 12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula:

[0145] in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 Alkyl groups; or groups of the following formula:

[0146] in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula:

[0147] in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18 Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; At least one dispersant selected from glutamate, hydrolyzed protein, cyclic acyl peptide, polyglycerol lactate, and sulfosuccinate (c); and Add to 100% water.

[0148] This dispersion formulation enables the preparation of personal care products containing only at least one UV filter (a1)-(a4) and a "no-rinse" formulation additive.

[0149] Preferably, the aqueous dispersion (A) of the present invention comprises: 20-60% by weight of at least one micronized UV filter selected from the following: (a1) Micronized compounds of the following formula:

[0150] in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; divalent groups; or hydroxyl groups -B- It should be in the following formula:

[0151] in: n1 is a number between 1 and 3; A is -N(R3)-; or -O-; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula:

[0152] in: T1 is hydrogen; C1-C 12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula:

[0153] in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 Alkyl groups; or groups of the following formula:

[0154] in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula:

[0155] in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; At least one dispersant, in the form of 0.1-20% by weight; 0.1-2% by weight of vinylpyrrolidone copolymers or homopolymers (b); 0-1% by weight of polydimethylsiloxane / silica-based components; and Add to 100% water.

[0156] In another embodiment of the invention, the aqueous dispersion (B) comprises: 20-60% by weight of at least one micronized UV filter selected from the following: (a1) Micronized compounds of the following formula:

[0157] in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; divalent groups; or hydroxyl groups -B- It should be in the following formula:

[0158] in: n1 is a number between 1 and 3; A is -N(R3)-; or -O-; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula:

[0159] in: T1 is hydrogen; C1-C12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula:

[0160] in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 Alkyl groups; or groups of the following formula:

[0161] in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula:

[0162] in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18 Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; 0.1-20% by weight of at least one dispersant selected from glutamate, hydrolyzed protein, cyclic acyl peptide, polyglycerol lactate and sulfosuccinate (c); 0-1% by weight of polydimethylsiloxane / silica-based components; and Add to 100% water.

[0163] In yet another embodiment of the invention, the aqueous dispersion (C) comprises: 20-60% by weight of at least one micronized UV filter selected from the following: (a1) Micronized compounds of the following formula:

[0164] in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; divalent groups; or hydroxyl groups -B- It should be in the following formula:

[0165] in: n1 is a number between 1 and 3; A is -N(R3)-; or -O-; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula:

[0166] in: T1 is hydrogen; C1-C 12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula:

[0167] in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 alkyl; or groups of the following formula

[0168] in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula:

[0169] in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18 Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; At least one dispersant, in the form of 0.1-20% by weight; 0-1% by weight of the polydimethylsiloxane / silica-based (defoamer) component; and Add to 100% water.

[0170] The aqueous dispersions (A), (B) and (C) of the present invention preferably do not contain any additional thickeners, which are preferably selected from propylene glycol, carbomer and plant gums, and most preferably xanthan gum.

[0171] The aqueous dispersions (A), (B) and (C) of the present invention are particularly suitable for cosmetics, as well as dermatological and pharmaceutical preparations.

[0172] Therefore, the present invention also provides a sunscreen composition comprising: (i) Based on the sunscreen composition, 0.1-50% by weight, preferably 0.5-20% by weight, of the aqueous dispersion (A), (B), or (C) as defined above; and optionally... (ii) Dermatologically and pharmaceutically acceptable carriers.

[0173] The sunscreen composition of the present invention can be prepared by physically mixing a micronized formulation of an insoluble organic UV absorber and a carrier component using any conventional method, such as by simply stirring the two materials together. In a preferred procedure, a mixture of coarse insoluble organic UV absorber, abrasive aid, and abrasive media is ground until the coarse insoluble organic UV absorber is converted into a micronized form, as described above for the preparation of micronized insoluble organic UV absorbers. After filtering out the abrasive media such as quartz sand, glass beads, or zirconium silicate beads, the filtrate consisting of the micronized insoluble organic UV absorber and abrasive aid components can be mixed with a cosmetically compatible carrier.

[0174] The sunscreen composition of the present invention can be formulated into an oil-in-water or oil-in-water dispersion, an oil or oil-alcohol milk, a capsule dispersion of ionic or nonionic amphiphilic lipids, a gel, a solid rod, or an aerosol formulation.

[0175] When formulated into an oil-in-water or water-in-oil dispersion, the optional cosmetically acceptable carrier preferably comprises 5-50% oil phase, 5-20% emulsifier, and 30-90% water, each expressed by weight based on the total weight of the carrier. The oil phase may comprise any oil commonly used in cosmetic formulations, such as one or more of hydrocarbon oils, waxes, natural oils, silicone oils, fatty acid esters, or fatty alcohols. Preferred monohydric or polyhydric alcohols are ethanol, isopropanol, propylene glycol, hexane glycol, glycerol, and sorbitol. The emulsifier may also include any emulsifier commonly used in cosmetic formulations, such as ethoxylated esters of one or more natural oil derivatives, such as polyethoxylated esters of hydrogenated castor oil; silicone oil emulsifiers, such as siloxane polyols; optionally ethoxylated fatty acid soaps; ethoxylated fatty alcohols; optionally ethoxylated dehydrated sorbitol esters; ethoxylated fatty acids; or ethoxylated glycerides.

[0176] The sunscreen compositions of the present invention may also contain other components known to function usefully in sunscreen compositions. Examples of such other components include, for example, emollients, skin moisturizers, skin tanning promoters, antioxidants, emulsion stabilizers, thickeners such as xanthan gum, humectants such as glycerin, film-forming agents, preservatives, fragrances, and colorants.

[0177] The UV absorber compositions of the present invention may contain one or more additional UV absorbers as described in Tables 1 and 2.

[0178]

[0179] Cosmetic or pharmaceutical preparations may be, for example, creams, gels, milks, alcohol and water / alcohol solutions, emulsions, wax / fat compositions, stick formulations, powders, or ointments. In addition to the UV filters described above, cosmetic or pharmaceutical preparations may also contain other adjuvants as described below.

[0180] As an emulsion containing water and oil (e.g., W / O, O / W, O / W / O, and W / O / W emulsions or microemulsions), the formulation comprises, for example, 0.1-60%, preferably 0.1-20% by weight, especially 0.5-10% by weight of the aqueous dispersion of the present invention (based on the total weight of the composition); 1-60% by weight, especially 5-50% by weight, preferably 10-35% by weight of at least one oil component (based on the total weight of the composition); 0-30% by weight, especially 1-30% by weight, preferably 4-20% by weight of at least one emulsifier (based on the total weight of the composition); 10-90% by weight, especially 30-90% by weight of water (based on the total weight of the composition); and 0-88.9% by weight, especially 1-50% by weight of other cosmetically acceptable adjuvants.

[0181] The cosmetic or pharmaceutical compositions / formulations of the present invention may also contain one or more additional compounds, such as fatty alcohols, fatty acid esters, natural or synthetic triglycerides (including glycerides and derivatives), pearlescent waxes; hydrocarbon oils; silicones or siloxanes, organically substituted fat enrichers, surfactants, consistency modifiers / thickeners and rheology modifiers, polymers, bioactive ingredients, deodorizing active ingredients, anti-dandruff agents, antioxidants, water-soluble growth promoters, preservatives and bacterial inhibitors, fragrance oils, colorants, polymer beads or hollow spheres as mineral therapy enhancers.

[0182] Cosmetic or pharmaceutical formulations are included in a broad range of cosmetic formulations. For example, the following formulations may be considered: - Skin care preparations, such as skin cleansing and cleansing preparations in tablet form or in the form of liquid soap, soap-free detergent, or cleansing paste. - Bath preparations, such as liquid (foam bath, milk, shower preparation) or solid bath preparations, such as bath blocks and bath salts; - Skin care preparations, such as skin lotions, multi-lotions, or skin oils; - Personal care cosmetic preparations, such as day creams or powder creams, face powders (loose or pressed), blush or cream cosmetics; eye care preparations, such as eyeshadow preparations, mascaras, eyeliner gels, eye creams or eye-fix creams; lip care preparations, such as lipsticks, lip balms, lip contour pencils; nail care preparations, such as nail polish, nail polish remover, nail hardeners or cuticle removers; - Foot care preparations, such as foot baths, foot powders, foot creams or foot balms, special deodorants and antiperspirants or callus removers; - Photoprotective agents, such as sunscreen milk, lotion, cream or oil, sunblock or tropical agents, pre-tanning agents or after-sun agents; - Skin tanning agents, such as self-tanning creams; - Bleaching agents, such as skin bleaching agents or skin brightening agents; - Insect repellents, such as insect repellent oil, lotion, spray or stick; - Deodorants, such as deodorizing sprays, pump-action sprays, deodorizing gels, sticks, or roll-ons; - Antiperspirants, such as antiperspirant sticks, creams, or roll-ons; - Preparations used to clean and care for dirty skin, such as synthetic detergents (solid or liquid), peeling or scrubbing preparations, or peel-off masks; - Hair removal preparations in chemical form (hair removal), such as hair removal powder, liquid hair removal preparations, hair removal preparations in cream or paste form, hair removal preparations in gel form or aerosol foam. - Shaving preparations, such as shaving soap, foaming shaving cream, non-foaming shaving cream, foam and gel, preshave preparations for dry shaving, aftershave products or aftershave. - Fragrance preparations, such as fragrances (eau de cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), aromatic oils or fragrance creams; - Hair treatment cosmetics, such as shampoo and conditioner in the form of shampoo, hair care products such as pre-treatment products, hair growth oils, styling creams, styling gels, hair balms, hair bleaching agents, treatment packs, intensive hair treatments, hair structuring products such as perming products for permanent perming (hot perm, warm perm, cold perm), hair straightening products, liquid hair styling products, hair foam, hairspray, bleaching products such as hydrogen peroxide solutions, shine-enhancing shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair coloring agents, and products containing self-oxidizing dyes or natural hair coloring agents such as henna dyes or chamomile.

[0183] Presentation format

[0184] The listed final formulations can exist in a wide range of forms, such as: - Liquid formulations, such as W / O, O / W, O / W / O, W / O / W, or PIT emulsions, and all types of microemulsions. - Gel form, - In oil, cream, lotion, or liquid form, - In powder, paint, tablet, or cosmetic form, - Rod form, - In the form of spray (spraying or pumping spray using aerosol gas) or aerosol. - In foam form, or - Paste form.

[0185] As cosmetic formulations for the skin, photoprotective formulations are of particular importance, such as sunscreens, lotions, creams, oils, sunblocks, or tropical formulations; pre-tanning or after-tanning formulations; and skin-tanning formulations, such as self-tanning creams. Of particular interest are sunscreens in the form of creams, lotions, emulsions, and sprays.

[0186] As hair cosmetic formulations, the aforementioned formulations for hair treatment are of particular importance, especially hair washing formulations in the form of shampoos, conditioners, and hair care formulations such as pre-treatment formulations, hair growth oils, styling creams, styling gels, hair pomades, hair bleaching agents, treatment packs, intensive hair treatments, hair straightening formulations, liquid hair styling formulations, hair foams, and hairsprays. Shampoo-based hair washing formulations are of particular interest.

[0187] The shampoo, for example, has the following composition: 0.01-5% by weight of the UV absorber composition of the present invention, 12.0% by weight of sodium lauryl polyoxyethylene (2) ether sulfate, 4.0% by weight of cocamidopropyl betaine, 3.0% by weight of sodium chloride, and water to 100%.

[0188] Other typical ingredients in this type of formulation include preservatives, bactericides and antimicrobial agents, fragrances, dyes, pigments, thickeners, wetting agents, humectants, fats, oils, waxes, or other typical ingredients in cosmetic and personal care formulations such as alcohols, polyols, polymers, electrolytes, organic solvents, silicone derivatives, emulsifiers or emulsifying surfactants, surfactants, dispersants, antioxidants, anti-irritants, and anti-inflammatory agents.

[0189] The cosmetic and / or dermatological / pharmaceutical formulations of the present invention are characterized by excellent protection of human skin from the damaging effects of sunlight.

[0190] Furthermore, the sunscreen composition of the present invention exhibits beneficial effects related to cell survival, inhibition of reactive oxygen species (ROS), and inhibition of the induction of gene expression associated with skin aging and inflammatory responses.

[0191] A. Preparation Examples

[0192] A1. Preparation of UV filter dispersion (washout type dispersant)

[0193] Dispersion 1

[0194] Slurry preparation: In a beaker equipped with a stirrer, dissolve 35.7 g of sodium tetradecyl polyoxyethylene ether sulfate (an aqueous paste containing 70 wt% active material) in 801.8 g of deionized water. Add 275 g of decyl glucoside (50 wt% active material, in water), and adjust the pH of the solution to 4.5 with 62.5 g of 20 wt% citric acid aqueous solution. Then add 25 g of simethicone (a mixture of polydimethylsiloxane and hydrated silica with an average chain length of 200-350 dimethylsiloxane units, 20 wt%, in water). After homogenization, add 1250 g of the following compound:

[0195] Pre-grinding process: The slurry was homogenized by passing it through a colloid mill (Fryma) twice. Then, the colloid mill was switched to circulation mode and the slurry was wet-milled for 5 minutes.

[0196] Precision grinding process: Fill the grinder with 440ml Draison grinding beads with a diameter of 0.3-0.4mm. Transfer the pre-ground slurry to a beaker equipped with an IKA stirrer. Circulate the slurry using a Watson-Marlow pump. Fill the grinding chamber with slurry without running the grinder at low speed with the Watson-Marlow pump. Once the initial pressure in the grinder has increased, turn on the grinder.

[0197] Fine grinding is performed using the following parameters: The grinding mill's rotation speed is 2389 rpm. Pump speed: 20-40 rpm IKA mixer speed: 80 rpm temperature 最高 48°C Pressure: 0.2-0.5 bar Current: 4.5-6A Grinding power: Initial: 1420W; End of process: 550-500W Energy consumption: 3000W / h After 5 hours, the fine grinding is complete. Empty the mill and store the final product at room temperature.

[0198] UV filter dispersion 1 contains a rinsing surfactant as a grinding aid.

[0199] UV filter dispersions 2-12 were prepared using the same procedure. Optionally, the preservation system was added to the UV filter dispersion.

[0200] The particle size of the micronized UV filter dispersion was characterized using a Mastersizer 2000 (Malvern Instruments) equipped with a wet dispersion unit. This instrument measures the particle size distribution of the dispersed particles by laser diffraction.

[0201] d 50 The value is a measure of the average particle size of micronized UV filter particles.

[0202] The compositions are summarized below:

[0203] UV filter dispersions 1-12 contain only mild, rinse-free dispersants and are suitable for the formulation of mild cosmetic sunscreens and skincare consumer products.

[0204] Thickening of UV filter dispersions: Thickened dispersions with polyvinylpyrrolidone 1-5, 8 and 9: Dissolve 5g of polyvinylpyrrolidone in 5g of water (preferably for 24 hours, before grinding) and mix it into the slurry with a stirrer.

[0205] Viscosity of UV filter dispersion: The viscosity of UV filter dispersions was analyzed using a Contrave Rheomat RM115 viscometer, which determined the flow behavior and viscosity of the samples.

[0206]

[0207] Data show that dispersions 6 and 7, based on a mild dispersant as a grinding aid, exhibit flow behavior similar to dispersion 2 with added PVP, and do not require a thickener.

[0208] B. Formulation Examples

[0209] The efficacy (SPF, UVA-PF) of the following formulations was evaluated using the BASF simulator (www.basf.com / sunscreensimulator; Herzog, B.; Osterwalder, U., In Silico Determination of Topical Sun Protection. Cosm Sci Tech. 2011; 62: 1-8).

[0210]

[0211] C. Application Examples

[0212] The survey investigated conventional sunscreen formulations and UV filters with comparable sun protection factors (SPF) but also containing formula (1c). Different protective effects of sunscreen formulations

[0213] Cell cultures of keratinocytes were irradiated through a UV-transparent PMMA substrate, on which different sunscreen agents or placebo formulations were distributed.

[0214] Use four types of endpoints: 1. Cell viability, 2. Formation of reactive oxygen species (ROS) 3. DNA damage, and 4. Gene induction.

[0215] As the light source, two light-emitting diode (LED) arrays (Loctite) are used, one emitting at 385 nm and the other at 405 nm. The emission spectrum is as follows: Figure 1 As shown, the 405nm LED array exhibits considerably high emission in the visible light range, exceeding 76%; conversely, the 385nm LED array has approximately 95% emission in the UVA range and only 5% in the visible light range.

[0216] A model sunscreen containing the filter composition shown in Table 3 was prepared. The SPF was calculated using BASF sunscreen simulator software. The UV spectrum of the film absorbance simulated using the same procedure is shown below. Figure 2 As shown.

[0217]

[0218] Results—Cell viability

[0219] Figure 3 and 4 The values ​​at 150 J / cm were displayed respectively.2 Results of cell viability at 385 nm and 405 nm after dose. A linear dose-response relationship has previously been shown up to this dose.

[0220] The negative control (no irradiation) was set at 100% cell viability. The positive control was defined as unprotected irradiation, yielding a reading of approximately 60% cell viability at 385 nm and 80% at 405 nm. In both cases, the cell viability of the negative control was obtained when using a sunscreen containing compound (1c).

[0221] Results—Reactive Oxygen Species (ROS)

[0222] Figure 5 and 6 The figures show the results at 385 nm and 50 J / cm. 2 Results of ROS formation in cells after UV dose and a light dose of 100 J / cm² at 405 nm were presented. Dose-response experiments were performed prior to both cases, demonstrating a linear relationship between ROS formation and the corresponding dose. The negative control was no irradiation, and the positive control was irradiation without any protection. Optimal results regarding ROS formation were obtained at both wavelengths using a sunscreen containing compound (1c).

[0223] Results—Gene expression experiment at 385nm

[0224] Figure 7 and Figure 8 Gene expression experiments for HMOX-1, MMP-1, IL-1a, and IL-6 under 385 nm irradiation are shown, all of which are involved in skin aging and inflammatory processes, all of which were performed at a dose of 60 J / cm² and 24 hours after irradiation termination.

[0225] The expression of these genes was induced by 385 nm irradiation, and a linear dose-response relationship had previously been demonstrated up to 100 J / cm². In each case, induction was best suppressed by application of a sunscreen containing compound (1c).

[0226] Results—Gene Expression Experiment at 405nm

[0227] Figure 9 and Figure 10 Gene expression experiments for HMOX-1, MMP-1, IL-1a, and IL-6 after 405 nm irradiation are shown, all of which involve skin aging and inflammatory processes, all of which were performed at a dose of 105 J / cm² and 24 hours after irradiation termination.

[0228] The expression of these genes was induced by 405 nm irradiation, and a linear dose-response relationship has been previously demonstrated up to 150 J / cm². In each case, induction was best suppressed by application of a sunscreen containing compound (1c).

[0229] in conclusion

[0230] Experimental work on cell cultures of keratinocytes showed that sunscreens containing compound (1c) at SPF 15 exhibited beneficial effects compared to conventional sunscreens at SPF 15. These beneficial effects involved cell viability, ROS production in cells, and gene expression associated with skin aging and inflammatory responses.

Claims

1. An aqueous dispersion (A) comprising a micronized organic UV filter selected from the following: (a1) Micronized compounds of the following formula: in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; or divalent groups -B- It should be in the following formula: in: n1 is a number between 1 and 3; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula: in: T1 is hydrogen; C1-C 12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula: in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 Alkyl groups; or groups of the following formula: in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula: in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18 Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; and (b) Vinylpyrrolidone copolymers or homopolymers.

2. The dispersion according to claim 1, characterized in that... It contains no additional thickeners.

3. The dispersion according to claim 2, characterized in that... It contains no additional thickeners selected from propylene glycol, carbomer, and plant gums.

4. The dispersion according to claim 2 or 3, characterized in that... It does not contain xanthan gum.

5. The dispersion (A) according to any one of claims 1-4, wherein the micronized organic UV filter (a1) corresponds to the following formula 6. The dispersion (A) according to any one of claims 1-5, wherein the micronized organic UV filter (a2) corresponds to the following formula 7. The dispersion (A) according to any one of claims 1-6, wherein the micronized organic UV filter (a3) ​​corresponds to the following formula:

8. The dispersion (A) according to any one of claims 1-7, wherein the micronized organic UV filter (a4) corresponds to the following formula:

9. The dispersion (A) according to any one of claims 1-8, wherein (b) is a polyvinylpyrrolidone of the following formula:

10. The dispersion (A) according to any one of claims 1-9, comprising a micronized organic UV filter (a1) corresponding to the following formula: (b) Polyvinylpyrrolidone of the following formula:

11. The dispersion according to any one of claims 1-10, characterized in that... It does not contain diol compounds as solvents.

12. The dispersion according to any one of claims 1-11, wherein the particle size of the micronized UV filter (a1)-(a4) is 0.01-2 μm.

13. A method for preparing an aqueous dispersion (A) as defined in claim 1, wherein at least one UV filter (a1)-(a4) is added to an aqueous homogeneous dispersion containing a dispersant, and the resulting slurry is milled together with a suitable dispersant using zirconium silicate beads to an average particle size d of 100-170 nm. 50 An aqueous solution of polyvinylpyrrolidone is introduced into the dispersion.

14. An aqueous dispersion (B) comprising: At least one UV filter selected from the following: (a1) Micronized compounds of the following formula: in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; or divalent groups -B- It should be in the following formula: in: n1 is a number between 1 and 3; A is -N(R3)-; or -O-; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula: in: T1 is hydrogen; C1-C 12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula: in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 Alkyl groups; or groups of the following formula: in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula: in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18 Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; At least one dispersant selected from glutamate, hydrolyzed protein, cyclic acyl peptide, polyglycerol lactate, and sulfosuccinate (c); and Add to 100% water.

15. An aqueous dispersion (A) comprising: 20-60% by weight of at least one UV filter selected from the following: (a1) Micronized compounds of the following formula: in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; or divalent groups -B- It should be in the following formula: in: n1 is a number between 1 and 3; A is -N(R3)-; or -O-; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula: in: T1 is hydrogen; C1-C 12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula: in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 Alkyl groups; or groups of the following formula: in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula: in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18 Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; At least one dispersant, in the form of 0.1-20% by weight; 0.1-2% by weight of polyvinylpyrrolidone (b); 0-1% by weight of polydimethylsiloxane / silica-based components; and Add to 100% water.

16. An aqueous dispersion (B) comprising: 20-60% by weight of at least one UV filter selected from the following: (a1) Micronized compounds of the following formula: in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; or divalent groups -B- It should be in the following formula: in: n1 is a number between 1 and 3; A is -N(R3)-; or -O-; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula: in: T1 is hydrogen; C1-C 12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula: in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 Alkyl groups; or groups of the following formula: in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula: in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18 Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; 0.1-20% by weight of at least one dispersant selected from glutamate, polyglycerol lactate and sulfosuccinate (c); 0-1% by weight of polydimethylsiloxane / silica-based components; and Add to 100% water.

17. An aqueous dispersion (C) comprising: 20-60% by weight of at least one UV filter selected from the following: (a1) Micronized compounds of the following formula: in: R1 and R2 are independent of each other as C1-C 20 Alkyl; C2-C 20 Alkenyl; C3-C 10 cycloalkyl; C3-C 10 Cycloalkenyl; or R1 and R2 together with the linked nitrogen atom to form a 5- or 6-membered heterocycle; A represents -N(R3)-; -O-; or a direct bond; B is a divalent group selected from alkylene, cycloalkylene, alkenylene, or phenylene, which may optionally be substituted with a carbonyl or carboxyl group; or divalent groups -B- It should be in the following formula: in: n1 is a number between 1 and 3; A is -N(R3)-; or -O-; and R3 is hydrogen; C1-C5 alkyl; or hydroxy-C1-C5 alkyl; (a2) Micronized compounds of the following formula: in: T1 is hydrogen; C1-C 12 Alkyl; preferably isooctyl, or C1-C4 alkyl substituted with phenyl; (a3) Micronized compounds of the following formula: in: R4 and R5 are hydrogen independently of each other; C1-C 18 Alkyl; or C6-C 12 Aryl; R6, R7, and R8 are hydrogens, which are independent of each other; C1-C 18 alkyl; or groups of the following formula in: R9, R 10 and R 11 They are hydrogen independently of each other; or C1-C 18 Alkyl; and (a4) Micronized compounds of the following formula: in: R 12 and R 13 Independently representing hydrogen; halogen; C1-C 12 Alkyl; C1-C 18 Hydroxyl group; C1-C 18 Alkyl groups; poly(ethoxy)-alkoxy groups having a C1-C4 alkyl segment and 1-4 ethoxy groups; C1-C4 mono- or dialkylamino groups. R 14 This indicates a halogen; hydroxyl group; amino group; phenyl group, which is optionally substituted 1-3 times with a hydroxyl group at least at the para or phenyl position, and possibly C1-C at the ortho, meta or para position. 12 Alkoxy or cyano or C1-C7 alkylamino substitution 1-3 times; At least one dispersant, in the form of 0.1-20% by weight; 0-1% by weight of polydimethylsiloxane / silica-based components; and Add to 100% water.

18. The aqueous dispersion according to any one of claims 14-17, characterized in that... It contains no additional thickeners.

19. The aqueous dispersion according to any one of claims 14-17, characterized in that... It does not contain thickeners selected from propylene glycol, carbomer and plant gums.

20. The aqueous dispersion according to any one of claims 14-17, characterized in that... It does not contain xanthan gum.

21. A sunscreen composition comprising: (i) 0.1-50% by weight, preferably 0.5-20% by weight, of the aqueous dispersion (A) as defined in claim 15, the aqueous dispersion (B) as defined in claim 16, or the aqueous dispersion (C) as defined in claim 17, based on the sunscreen composition; and optionally... (ii) A cosmetically acceptable carrier.

22. The sunscreen composition according to claim 21, for inhibiting reactive oxygen species (ROS).

23. The sunscreen composition of claim 21, used to inhibit the induction of gene expression associated with skin aging and inflammatory responses.

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