Antimicrobial mixtures
A synergistic mixture of acetophenone derivatives and secondary antimicrobial agents addresses the challenge of broad-spectrum antimicrobial activity in cosmetic and pharmaceutical products, providing enhanced stability and efficacy against molds like Aspergillus species.
Patent Information
- Application Number
- JP2024189987
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-10-29
- Publication Date
- 2025-01-20
- Estimated Expiration
- 2038-08-27
AI Technical Summary
Existing antimicrobial agents face challenges in achieving broad-spectrum activity against various microorganisms, particularly molds, while being stable, non-toxic, and easily formulated in cosmetic and pharmaceutical products, with limited understanding of the relationship between chemical structure and biological activity.
A synergistic mixture of acetophenone derivatives and secondary antimicrobial agents, such as 1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantane chloride, enhances broad-spectrum activity against microorganisms, including molds like Aspergillus species, by forming stable emulsions that maintain efficacy across different pH and temperature conditions.
The mixture demonstrates superior antimicrobial performance against a range of microorganisms, including Aspergillus species, with improved stability and reduced side effects, making it suitable for cosmetic and pharmaceutical formulations.
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Abstract
Description
[Technical field]
[0001] The present invention is in the field of antimicrobial agents for personal care, detergents and nutritionals and refers to new antimicrobial agents and their use in various areas of consumer products. [Background technology]
[0002] In the cosmetics, pharmaceutical and food industries, there is a constant need for agents with antibacterial properties, especially for the preservation of otherwise perishable products (cosmetics, pharmaceuticals, food, etc.), but also for the direct cosmetic or therapeutic treatment of microorganisms that may have a negative effect on the human or animal body. As examples, we can refer to microorganisms that may cause body odor, acne, mycoses, etc.
[0003] Although in the referred technical field a large number of antibacterial active compounds are already in use in practice, there is still a need for alternatives, so that targeted specific treatment can be performed and / or side effects can be reduced.However, in this context, in the search for alternative agents with antibacterial properties, especially preservative action, there is a need for substances used in the cosmetics, pharmaceutical and / or food sectors that: Toxicologically acceptable. Easily tolerated by skin. · Stable (especially in conventional cosmetic and / or pharmaceutical formulations). · Mostly, completely odorless, if possible. · They are inexpensive to prepare (i.e., they employ standard processes and / or start from standard precursors). · It is easy to formulate (i.e. preferably liquid) and is not harmful to the final product.
[0004] In addition, they should have antibacterial activity properties that meet a variety of criteria. Provides broad-spectrum antibacterial activity against gram-positive and gram-negative bacteria, yeasts, and molds; - Particularly active against the fungus Aspergillus braziliensis, · It should be active in various cosmetic formulations at various pH values. [Prior art documents] [Non-patent literature]
[0005] From the state of the art, many publications are known dealing with various types of products active against microorganisms. For example, Schenk et al. evaluated various fungicides for preserving moist alfalfa hay (Laboratory evaluation of fungicides for preserving moist hay). 4-Hydroxyacetophenone was one of the compounds tested, but it was found not to inhibit the growth of molds and is therefore not suitable for preserving hay. The main toxicological properties of the cosmetic formulations were not disclosed. (Agronomy Journal, 47, 64-69, 1955).
[0006] Zauner et al. reported impurities in beet molasses that inhibit respiration and fermentation of the yeast Saccharomyces cerevisiae (Inhibitory activity of impurities in beet molasses and plant protection agents on respiration and fermentation of the yeast (Saccharomyces cerevisiae)). No other microorganisms than Saccharomyces cerevisiae were investigated, in particular no molds or bacteria. There are no references to the potential use of the inhibitors in the cosmetics field.
[0007] investigated the aroma composition of cranberries and found one component, 4-hydroxyacetophenone. No mention was made of the antibacterial activity of the cranberry aroma or its components (Zeitschrift fur Lebensmittel-Untersuchung und-Forschung, 172(5), 365-7, 1981).
[0008] Alvarez et al. studied the anti-inflammatory properties of different components of the plant Lampayahieronymi. 4-hydroxyacetophenone was one of the active compounds that reduced subcutaneous inflammation when administered intraperitoneally. The drugs were not applied topically and no data on antibacterial activity were disclosed for any of the compounds presented (Il Farmaco, 55, 502-5, 2000).
[0009] Schmeda-Hirschmann et al. identified components of Tagetes mendocina that reveal antioxidant activity in chemical in vitro assays. Among others, 4-hydroxyacetophenone proved to be one of the active ingredients. No data on antibacterial activity and cosmetic application were disclosed for any of the presented compounds (Zeitschrift fur Naturforschung, 59c, 345-353, 2004).
[0010] Reference is also made here to DE-OS 3629056 (Celamerck), which discloses the extraction of mixtures of substances containing p-hydroxyacetophenone from the cuticle of spruce needles using non-polar solvents. These mixtures of substances are claimed to be effective in neutralizing phytopathogenic fungi, namely Cladosporium cucumerinum and Rhizosphaera kalkhoffii. Other microorganisms, such as the non-phytopathogenic yeast C. albicans or bacteria, are included. Furthermore, no specific applications, such as product preservation of cosmetic formulations, are mentioned.
[0011] US2008 / 0254130AA (Bioderm Research) discloses a topical method for the treatment of dysfunction of certain skin enzymes and for the treatment of skin conditions or disorders caused by said dysfunction. The antibacterial activity of different acetophenone derivatives is not described.
[0012] JP07 206645 A (POLA) discloses acetophenone derivatives as hair growth agents. The antibacterial activity of different acetophenone derivatives is not described.
[0013] EP 2774481 B1 (SYMRISE) proposes an antimicrobial composition comprising (a) at least one acetophenone derivative of formula (I) in which R1 represents hydrogen or methyl, R2 represents hydrogen, a hydroxyl or an -OCH3 group, or a cosmetically or pharma- ceutically acceptable salt thereof, and (b) at least one second antimicrobial agent. However, it was found that the synergistic effect between components (a) and (b) is not always significant and is strongly dependent on the weight ratio. Summary of the Invention [Problem to be solved by the invention]
[0014] The search for a suitable (active) substance with one or more of the mentioned properties to an appropriate degree is made difficult for the skilled person, on the one hand, by the absence of a clear dependency between the chemical structure of the substance, on the other hand, in terms of its biological activity against certain microorganisms (bacteria, yeasts, fungi, small eukaryotes). This makes the testing of the substance in the laboratory inevitable. Moreover, the antibacterial performance in cosmetic formulations cannot be derived from standard antibacterial screening tests, such as growth inhibition experiments as described in DIN 58940 or ISO 20776. Many antibacterial substances, characterized by a low minimum inhibitory concentration (MIC), do not work in more highly applied assays. The preservation of the product requires the use of very laborious and time-consuming "challenge tests" according to ISO 11930, the European Pharmacopoeia 7-5.1.3 or the United States Pharmacopoeia 35. Moreover, there is no predictable relationship between the chemical structure and other physicochemical parameters relevant in the field of cosmetics, namely toxicological acceptability, skin tolerance, stability, solubility and formulation properties, as well as the odor of the substance.
[0015] The problem underlying the present invention is therefore to develop new antimicrobial agents that meet the complex profile described above and are particularly active at low concentrations against a variety of different microorganisms. Another object of the present invention is to provide emulsions containing such antimicrobial agents that have improved stability. [Means for solving the problem]
[0016] The object of the present invention is to provide an antimicrobial mixture comprising (a) a first antibacterial agent selected from the group consisting of at least one acetophenone derivative of formula (I), wherein R1 represents hydrogen or methyl, R2 represents hydrogen, hydroxyl, or an -OCH3 group or a cosmetically or pharma- ceutically acceptable salt thereof; [ka] (I) R1 represents hydrogen or methyl; R2 represents hydrogen, hydroxyl, or an -OCH3 group. or a cosmetically or pharma- ceutically acceptable salt thereof, and (b) at least one second antimicrobial agent selected from the group consisting of preservatives selected from the group consisting of: 1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantane chloride, 1-(4-chlorophenoxy)-1-(1H-imidazol-1-yl)-3,3-dimethyl-2-butanone, 1-Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridone, 2-aminoethanol (Octopirox), 1,1'-methylene-bis(3-(1-hydroxymethyl-2,4-dioxyimidazolidin-5-yl)urea), 1,2-benzisothiazol-3(2H)-one, 1,2-Decanediol, 1,3-Decanediol, 1,2-dibromo-2,4-dicyanobutane, 1,3-bis(hydroxymethyl)-1-(1,3,4-tris(hydroxy-methyl)-2,5-dioxoimidazolidin-4-yl)urea (diazolidinyl urea), 1,3-bis-(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione, 1,3-bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione, 1,5-pentanediol, 1,6-bis(4-amidino-2-bromophenoxy)-n-hexane and its salts, 1,6-bis(4-amidino-phenoxy)-n-hexane and its salts, 1,6-Hexanediol, 1,8-octanediol, 10-Undecylenic acid and its salts, 1-phenoxy-propan-2-ol, 2,2'-methylene-bis(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), 2,4-Dichlorobenzyl alcohol, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 2,4-Hexadienoic acid (sorbic acid) and its salts (e.g. potassium salt), 2-benzyl-4-chlorophenol, 2-benzylheptan-1-ol, 2-Bromo-2-(bromomethyl)pentanedinitrile, 2-Bromo-2-nitro-1,3-propanediol (Bronopol), 2-Butyloctanoic acid, 2-Chloroacetamide, Chlorhexidine, 2-Hydroxybiphenyl ether and its salts, Contains 2-methyl-3(2H)-isothiazolinone and magnesium chloride and magnesium nitrate, 2-Octyl-2H-isothiazol-3-one, 2-phenoxyethanol, 2-Zinc-sulfidopyridine N-oxide, 3-(4-chlorophenoxy)-1,2-propanediol, 3-(4-chlorophenoxy)-1,2-propanediol (chlorphenesin), 3-Acetyl-2-hydroxy-6-methyl-4H-pyran-4-one, 3-benzyloxy-propane-1,2-diol, 3-iodo-2-propynyl butylcarbamate, 3-phenoxy-propane-1,2-diol, 3-phenoxypropanol, 4,4-dimethyl-1,3-oxazolidine, 4-chloro-3,5-dimethylphenol, 4-chloro-m-cresol, 4-Ethylmercury(II) 5-amino-1,3-bis(2-hydroxybenzoic acid), its salts and esters, 4-hydroxybenzaldehyde, 5-amino-1,3-bis(2-ethylhexyl)-5-methyl-hexahydropyrimidine, 5-bromo-5-nitro-1,3-dioxane, 5-chloro-2-methyl-3(2H)-isothiazolinone, 5-ethyl-1-aza-3,7-dioxabicyclo(3.3.0)octane, Alkyl-(C8-C18)-dimethyl-benzylammonium bromide, Alkyl-(C8-C18)-dimethyl-benzyl-ammonium chloride, Alkyl-(C8-C18)-dimethyl-benzyl-ammonium saccharinate, Anisic acid and its salts, Benzoic acid and parahydroxybenzoic acid, their esters and salts, Benzyl alcohol, Benzyl benzoate, Benzyl Hemiformal, benzyloxymethanol, benzyloxymethoxy-methanol hexamethylenetetramine, Bis(2-pyridylthio)zinc 1,1'-dioxide, N,N'-(decane-1,10-diyldipyridin-1-yl-4-ylidene)-dioctan-1-amine dihydrochloride (octenidine dihydrochloride), Bromochlorophene, Caprylhydroxamic acid, Capryloyl glycine, Cetylpyridinium chloride, Chitosan, Chlorhexidine acetate, Chlorhexidine gluconate, Chlorhexidine hydrochloride, Chlorobutanoram, Cinnamic acid and its salts, Cinnamyl alcohol, Cinnamaldehyde, Climasol, Dehydroacetic acid, Diazolidinyl urea, DMDM hydantoin, Ethylenediaminetetraacetic acid (EDTA) Ethylenedioxy-dimethanol, Ethyl Lauroyl Arginate HCL Ethylmercury-(II)-thiosalicylic acid sodium salt, Eugenol, Farnesol, Formaldehyde and paraformaldehyde, Formic acid, Glutaraldehyde, Glyceryl Monolaurate, Glyceryl Caprylate Glyceryl Caprate Hyamine, Imidazolidinyl urea, Inorganic sulfites and bisulfites, Levulinic acid and its salts, N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine, N-Alkyl (C12-C22) trimethyl-ammonium bromides and chlorides, N-hydroxymethyl-N-(1,3-di(hydroxymethyl)-2,5-dioxoimidazolidin-4-yl)-N'-hydroxymethylurea, Ortho-, meta-, and para-anisic aldehyde, Pericrylic acid and its salts, Phenylmercury and its salts, Poly-(hexamethylenediguanide) hydrochloride, Propionic acid and its salts, salicylic acid and its salts, pyridine-2-thiol-1-oxide, Sodium Benzoate Sodium hydroxymethylaminoacetate, Sodium hydroxymethylglycinate, Sodium iodate, Sorbitan caprylate, Sorbohydroxamic acid, Tetrahydro-1,3,4,6-tetrakis(hydroxymethyl)imidazo[4,5-d]imidazole-2,5(1H,3H)-dione, Thymol, Tropolone, Undecenoyl glycine α,α',α”-trimethyl-1,3,5-triazine-1,3,5(2H,4H,6H)-triethanol, and mixtures thereof.
[0017] The present invention is based on the surprising discovery that the compounds of formula (I) according to the invention show very good broad-spectrum activity as agents for preserving various preparations against microbial spoilage. Moreover, the compounds of formula (I) have a synergistically enhanced antimicrobial effect against at least selected microorganisms, in particular against mold species of the genus Aspergillus, such as Aspergillus braziliensis, Aspergillus niger, Aspergillus flavus, Aspergillus fumigatus and other microorganisms. Molds are known to be very difficult to deal with, due to their high resistance to various pH, temperature, osmotic pressure, nutritional conditions, and their ability to resist and decompose various chemicals.
[0018] In particular, it has been found that the mixtures according to the invention can be used outstandingly as antimicrobially active compound mixtures, in particular for preserving otherwise perishable articles.
[0019] More specifically, the synergistically active mixture according to the invention has been found to have good action against Staphylococcus epidermidis, Corynebacterium xerosis, Brevibacterium epidermidis, Propionibacterium acnes, and against Trichophyton and Epidermophyton species. It is generally used as an agent for the treatment or combating underarm and foot or body odor, as an agent for combating acne, as an antidandruff agent, and as an agent for the treatment of fungal infections, in particular dermatophytosis. Acetophenone Derivatives
[0020] The acetophenone derivatives according to the invention represent known compounds that can be obtained by conventional methods of organic chemistry. It is understood that both the substituents OR1 and R2 can be located in the ortho, meta, or para position relative to the methyl keto group.
[0021] Preferably, the species is [ka] (1a): 2-Hydroxyacetophenone [ka] (Ib): 3-Hydroxyacetophenone [ka] (Ic): 4-Hydroxyacetophenone or mixtures thereof. Insofar as the definition refers to cosmetically or pharma- ceutically acceptable salts of said derivatives, it means that these salts can be safely used for pharmaceutical purposes. This does not mean that the present invention or any of its aspects is limited to the use of compounds of formula (I) or corresponding mixtures for medicinal purposes. In general, if a salt can be used for medicinal purposes, it can be used for cosmetic purposes as well or in food or beverage formulations. In particular, sodium and potassium and ammonium salts of compounds of formula (I) are considered to be (pharmaceutical) acceptable salts. In some cases, the use of the respective ionic compounds or solvate carriers proves to be superior to the unmodified derivatives. The (pharmaceutical) acceptable salts (and the corresponding solvates) of compounds of formula (I) can be prepared by standard procedures. Hereinafter, reference to compounds of formula (I) or corresponding mixtures as defined above should be understood to include an additional reference to the corresponding (pharmaceutical) acceptable salts.
[0022] It is worth mentioning that those skilled in the art have already addressed, for example, the antibacterial properties of aromatic alcohols, namely benzyl alcohol, 2-phenylethyl alcohol, 3-phenylpropanol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxy-propan-2-ol, 3-phenoxy-propane-1,2-diol, benzyloxymethanol and (benzyloxymethoxy)-methanol. Up to now, there are no indications that mixtures of acetophenone derivatives have a significantly improved antibacterial action in individual cases (at least against selected microorganisms). It was therefore particularly surprising that the mixture according to the invention showed a very synergistic activity, significantly superior to that of the therapeutic fungus of the genus Aspergillus. an individually administered compound of formula (I), or · further antimicrobially active compounds administered individually which are not compounds of the formula (I), in particular, for example, diols and aromatic alcohols administered individually, such as 1,3-propanediol, methylpropanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, ethylhexylglycerin, hexoxy-propane-1,2-diol, heptoxy-propane-1,2-diol, octoxy-propane-1,2-diol, 3-benzyloxy-propane-1,2-diol, 3-phenylethyloxy-propane-1,2-diol, 3-phenylpropyloxy-propane-1,2-diol, 3-methylbenzyloxy-propane-1,2-diol, 3-phenylpropanol, 2-phenoxy-ethanol and mixtures of these compounds at the same concentrations, in particular with regard to the reduction in the number of microorganisms and the rate of reduction in the number of microorganisms.
[0023] In a preferred embodiment, the antibacterial agent comprises or comprises two or three compounds (Ia), (Ib) and (Ic), such as, for example, 2-hydroxyacetophenone and 3-hydroxyacetophenone, or 2-hydroxyacetophenone and 4-hydroxyacetophenone, 3-hydroxyacetophenone and 4-hydroxyacetophenone.
[0024] The mixture may contain components (a) and (b) in a weight ratio of about 1:99 to about 99:1, preferably about 20:80 to about 80:20, and more preferably about 40:60 to about 60:40. Secondary Antimicrobial Agent
[0025] Preferred secondary preservatives include the compounds summarized in Table A. Also provided are the preferred weight ratios (4-HAP:activity) for strongest synergistic effect. [Table A]
[0026] A mixture of 4-hydroxyacetophenone with one of the preferred secondary antimicrobial agents (particularly within the preferred range) exhibits additional beneficial effects with regard to the storage stability of the emulsion at temperatures below 5°C and above 25°C, facilitating the formulation of cosmetic products containing said mixture. Additives to storage mixtures
[0027] In a preferred embodiment, the performance of the mixture is improved by adding a specific hydroxy compound selected from the group consisting of 1,3-propanediol, methylpropanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, ethylhexylglycerin, hexoxy-propane-1,2-diol, heptoxy-propane-1,2-diol, octoxy-propane-1,2-diol, 3-benzyloxy-propane-1,2-diol, 3-phenylethyloxy-propane-1,2-diol, 3-phenylpropyloxy-propane-1,2-diol, 3-methylbenzyloxy-propane-1,2-diol, 3-phenylpropanol, 2-phenoxyethanol and mixtures thereof. The addition of 2-phenoxyethanol is particularly preferred. The additive may be present in an amount of about 1 to 25, preferably 2 to 20, more preferably about 5 to 10% by weight, calculated on the total mixture. Personal Care Compositions
[0028] Another embodiment of the present invention covers a personal care or cosmetic composition comprising a working amount of at least one acetophenone derivative or mixtures thereof and an additional preservative and / or antimicrobial agent, which may be present in an amount of about 0.01 to about 10% by weight, about 0.05 to about 5% by weight, and more preferably about 0.1 to about 1% by weight, calculated on the total composition.
[0029] The personal care or cosmetic composition may contain abrasives, anti-acne agents, agents against aging of the skin, anti-cell inflammation agents, anti-dandruff agents, anti-inflammatory agents, irritation prevention agents, irritation inhibitors, antioxidants, astringents, antiperspirants, preservatives, antistatic agents, binders, buffers, carrier materials, chelating agents, cell stimulants, cleaning agents, care agents, depilatories, surface active substances, deodorants, antiperspirants, softeners, emulsifiers, enzymes, essential oils, fibers, film formers, fixatives, foam formers, foam stabilizers, foam prevention substances, foam boosters, gelling agents, gel forming agents, hair care agents, hair setting agents, straightening agents, moisturizing agents, moisturizing agents, moisturizing agents, bleaching agents, strengthening agents, stain removers, optical brighteners, impregnating agents, antifouling agents, friction reducers, lubricants, moisturizing creams, ointments, opacifiers, soluble All auxiliary substances and additives may be included such as plasticizers, coating agents, abrasives, polishing agents, polymers, powders, proteins, re-oiling agents, polishing agents, silicones, skin soothing agents, skin cleansing agents, skin care agents, skin healing agents, skin whitening agents, skin protection agents, skin softeners, cooling agents, skin cooling agents, warming agents, skin warming agents, stabilizers, UV absorbers, UV filters, detergents, fabric conditioning agents, suspending agents, skin tanning agents, thickeners, vitamins, oils, waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, alpha-hydroxy acids, polyhydroxy fatty acids, liquefying agents, dyes, color inhibitors, pigments, corrosion inhibitors, fragrances, flavoring substances, aromatic substances, polyols, surfactants, electrolytes, organic solvents or silicone derivatives. Surfactants
[0030] Other preferred auxiliaries and additives are anionic and / or amphoteric or zwitterionic surfactants.Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ethersulfonates, glycerol ethersulfonates, methyl estersulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ethers, sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinic acids, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamic acid and acyl aspartic acid, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based plant products) and alkyl (ether) phosphates. If the anionic surfactant contains a polyglycol ether chain, it preferably has a narrow range homolog distribution, but may have a conventional homolog distribution. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolium betaines and sulfobetaines. All of the above surfactants are known compounds. Information on their structure and production can be found in relevant synopsis studies such as J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124, or J. Falbe (ed.), "Katalysatoren, Tenside und Mineraloladditive (Catalysts, Surfactants and Mineral Oil Additives)", Thieme Verlag, Stuttgart, 1978, pp. 123-217. The percentage content of surfactants in the preparation is between 0.1 and 10% by weight, preferably between 0.5 and 5% by weight, based on the preparation.
[0031] B. Oil body Suitable oil bodies which form a constituent of the O / W emulsions are, for example, gelbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6-C13-carboxylic acids with linear or branched C6-C22-fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, peristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl ... stearate, stearyl oleate, stearyl behenate, stearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate, and erucyl erucate. Further suitable oil bodies are the esters of linear C6-C22-fatty acids with branched alcohols, in particular 2-ethylhexanol, also suitable are the esters of C18-C38-alkylhydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols, in particular dioctyl malate.Also suitable are esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and / or Guerbet alcohols, liquid mono- / di- / triglyceride mixtures based on C6-C10-fatty acids, esters of C6-C22-fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid. Also suitable are esters of C2-C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups. Also suitable are vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alcohol carbonates, such as dicaprylyl carbonate (Cetiol® CC), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and / or branched C6-C22-alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 hydrocarbon atoms per alkyl group, such as dicaprylyl ether (Cetiol® OE), epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.) and / or aliphatic or naphthenic hydrocarbons, such as squalene, squalene or dialkylcyclohexanes. emulsifier
[0032] Other surfactants may also be added to the formulation as emulsifiers including, for example: · Products of the addition of 2-30 mol of ethylene oxide and / or 0-5 mol of propylene oxide to linear C8-22 fatty alcohols, C12-22 fatty acids, and alkylphenols containing 8-15 carbon atoms in the alkyl group. ·C12 / 18 fatty acid mono- and diesters of addition products of 1-30 moles of ethylene oxide to glycerol. Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and their ethylene oxide addition products. Addition products of 15 to 60 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil, Polyol esters, in particular polyglycerol esters such as polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate isostearate. Mixtures of compounds from several of these classes are also suitable. ·Addition products of 2-15 mol of ethylene oxide onto castor oil and / or hydrogenated castor oil. · Linear, branched, unsaturated or saturated C6 / 22 fatty acids, ricinoleic acid, 12-hydroxystearic acid and partial esters based on glycerol, polyglycerol, pentaerythritol, -dipentaerythritol, sugar alcohols (such as sorbitol), alkyl glucosides (such as methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose). Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts. · Wool wax alcohol. ·Polysiloxane / polyalkyl polyether copolymers and corresponding derivatives. Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols, and / or mixed esters of C6-22 fatty acids, methyl glucose and a polyol, preferably glycerol or polyglycerol. Polyalkylene glycols, and Glycerol carbonate.
[0033] The addition products of ethylene oxide and / or propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol monoesters and diesters, sorbitan monoesters and diesters of fatty acids, or castor oil are known commercial products. They are homogeneous mixtures whose average degree of alkoxylation corresponds to the ratio between the amount of ethylene oxide and / or propylene oxide and the substrate with which the addition reaction is carried out. C12 / 18 fatty acid monoesters and diesters of the addition products of ethylene oxide to glycerol are known as lipid layer enhancers in cosmetic formulations. Preferred emulsifiers are described in more detail as follows.
[0034] Partial glycerides. Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride. Linoleic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride and other mixtures thereof, which may contain small amounts of triglycerides from the production process. Also suitable are addition products of 1 to 30, preferably 5 to 10 mol of ethylene oxide to the above partial glycerides.
[0035] Sorbitan esters. Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan diisostearate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan dicitrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Also suitable are addition products of 1 to 30 mol, preferably 5 to 10 mol, of ethylene oxide onto the abovementioned sorbitan esters.
[0036] Polyglycerol ester. Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI34), polyglyceryl-3 oleate, diisostearoyl polyglyceryl-3 diisostearate (Diisostearoyl Polyglyceryl-3 Diisostearate). Polyglyceryl-3 methylglucose distearate (Isolan® PDI), polyglyceryl-3 methylglucose distearate (TegoCare® 450), polyglyceryl-3 beeswax (CeraBellina®), polyglyceryl-4 caprate (polyglycerin caprate T2010 / 90), polyglyceryl-3 cetyl ether (Chimexane® NL), polyglyceryl-3 distearate (Cremophor® GS32) and polyglyceryl polyricinoleate (Admul® WOL1403), polyglyceryl dimerate isostearate and mixtures thereof. Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coco fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid, etc., optionally reacted with 1 to 30 mol of ethylene oxide.
[0037] Anionic emulsifier. Typical anionic emulsifiers are aliphatic C12-22 fatty acids, such as palmitic acid, stearic acid or behenic acid, and C12-22 dicarboxylic acids, such as azelaic acid or sebacic acid.
[0038] Amphoteric emulsifier. 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 carboxylic acid group and one sulfonic acid group in the molecule. Particularly suitable zwitterionic surfactants are N-alkyl-N,N-dimethylammonium glycinates, such as cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, such as cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. Particularly preferred are fatty acid amide derivatives known under the CTFA name of cocamidopropyl betaine. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds that contain at least one free amino group and at least one -COOH- or -SO3H- group in the molecule in addition to a C8 / 18 alkyl or acyl group and can form internal salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl amino butyric acids, N-alkyl imino dipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl amino propionic acids, alkyl amino acetic acids containing about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coco alkyl amino propionates, coco acyl amino ethyl amino propionates and C12 / 18 acyl sarcosines. Superfatting agents and consistency factors
[0039] Superfatting agents can be selected from materials such as lanolin and lecithin, and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, fatty acid alkanolamides which also function as foam stabilizers.
[0040] The consistency factors mainly used are fatty alcohols or hydroxyfatty alcohols containing 12 to 22, preferably 16 to 18, carbon atoms, as well as partial glycerides, fatty acids or hydroxyfatty acids. Combinations of these substances with alkyl oligoglucosides of the same chain length and / or fatty acid N-methylglucamides and / or polyglycerol poly-12-hydroxystearates are preferably used. Thickeners and Rheology Additives
[0041] Suitable thickening agents are polymeric thickening agents such as Aerosil® types (hydrophilic silicas), polysaccharides, more particularly xanthan gum, guar guar, agar-agar, alginates and tyros, carboxymethylcellulose and hydroxyethylcellulose, also of relatively high molecular weight; polyethylene glycol monoesters and diesters of fatty acids, polyacrylates (for example Carbopols® [Goodrich] or Synthalens® [Sigma]), polyacrylamides, polyvinyl alcohols and polyvinylpyrrolidones; surfactants, for example ethoxylated fatty acid glycerides, esters of fatty acids; polyols, for example pentaerythritol or trimethylolpropane, narrow range fatty alcohol ethoxylates and electrolytes, such as sodium chloride or ammonium chloride, are used. polymer
[0042] Suitable cationic polymers are, for example, cationic cellulose derivatives such as quaternized hydroxyethylcellulose available from Amercol under the name Polymer JR400®, cationic starch, copolymers of diallyl ammonium salts and acrylamide, quaternized vinylpyrrolidone / vinylimidazole polymers such as, for example, Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat® L, Grunau), quaternized wheat polypeptides, polyethyleneimine, Cationic silicone polymers such as, for example, amodimethicone, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine®, Sandoz), copolymers of acrylic acid and dimethyldiallylammonium chloride (Merquat® 550, Chemviron), polyaminopolyamides and their crosslinked water-soluble polymers, cationic chitin derivatives such as, for example, quaternized chitosan, optionally in microcrystalline distribution, dihaloalkyls such as dibromo Condensation products of butane with bis-dialkylamines, such as bis-dimethylamino-1,3-propane, cationic guar gums, such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Milanol, and various polyquaternium types (e.g. 6, 7, 32, or 37). They can be found on the market under the trade names Rheocare® CC or Ultragel® 300.
[0043] Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate / crotonic acid copolymers, pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, non-crosslinked and polyol-crosslinked polyacrylic acids, acrylamidopropyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylic acid copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam terpolymers and optionally derivatized cellulose ethers and silicones. Pearl Wax
[0044] Suitable pearl waxes are, for example, alkylene glycol esters, in particular ethylene glycol distearate; fatty acid alkanolamides, in particular coco fatty acid diethanolamide; partial glycerides, in particular stearic acid monoglyceride; esters of polybasic and hydroxy-substituted carboxylic acids, optionally with fatty alcohols containing 6 to 22 carbon atoms, in particular long-chain esters of tartaric acid; fatty compounds, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates containing at least 24 carbon atoms in total, in particular laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides containing 12 to 22 carbon atoms with fatty alcohols containing 12 to 22 carbon atoms and / or polyols containing 2 to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof. silicone
[0045] Suitable silicone compounds are, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic silicones, and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside-, and / or alkyl-modified silicone compounds, which may be both liquid and resinous at room temperature. Another suitable silicone compound is simethicone, which is a mixture of dimethicone and hydrogenated silicate with an average chain length of 200 to 300 dimethylsiloxane units. A detailed overview of suitable volatile silicones can be found in Todd et al. Cosm. Toil. 91, 27 (1976). Waxes and stabilizers
[0046] In addition to the use of natural oils, waxes are also present in the preparation, more particularly natural waxes such as, for example, candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice oil wax, sugarcane wax, olicurea wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial fat, ceresin, ozocerite (earth wax), petrolatum, paraffin wax and microwaxes, and synthetic waxes such as, for example, montan ester wax, sasol wax, hydrogenated jojoba wax (hard wax), and polyalkylene waxes and polyethylene glycol waxes.
[0047] For example, magnesium, aluminum and / or zinc stearate or metal salts of fatty acids such as ricinoleic acid can be used as stabilizers. Primary Sun Protection Factors
[0048] Primary sun protection agents in the context of the present invention are, for example, organic substances (light filters) that are liquid or crystalline at room temperature and are capable of absorbing ultraviolet radiation and releasing the absorbed energy in the form of long-wave radiation, e.g. heat.
[0049] The formulations according to the invention advantageously comprise at least one UV-A filter and / or at least one UV-B filter and / or a broadband filter and / or at least one inorganic pigment. The preparations according to the invention preferably comprise at least one UV-B filter or a broadband filter, more particularly at least one UV-A filter and at least one UV-B filter.
[0050] Preferred cosmetic compositions, preferably topical formulations according to the invention, comprise one, two, three or more sun protection factors selected from the group consisting of 4-aminobenzoic acid and derivatives, salicylic acid derivatives, benzophenone derivatives, dibenzoylmethane derivatives, diphenylacrylates, 3-imidazol-4-ylacrylic acid and its esters, benzofuran derivatives, benzylidene malonate derivatives, polymeric UV absorbers comprising one or more organosilicone radicals, cinnamic acid derivatives, camphor derivatives, trianilinostriazine derivatives, 2-hydroxyphenylbenzotriazole derivatives, phenylbenzimidazolesulfonic acid derivatives and salts thereof, anthranilic acid menthyl esters, benzotriazole derivatives and indole derivatives.
[0051] Moreover, it is advantageous to combine the compound of formula (I) with an active ingredient that penetrates into the skin, protects skin cells from the inside against damage induced by sunlight, and reduces the level of skin matrix metalloproteinase.Preferred respective ingredients, so-called aryl hydrocarbon receptor antagonists, are described in WO2007 / 128723, which is incorporated herein by reference.Preferred is 2-benzylidene-5,6-dimethoxy-3,3-dimethylindan-1-one.
[0052] The UV filters cited below which can be used within the context of the present invention are preferred but of course are not limiting.
[0053] Preferably used UV filters are selected from the group consisting of: p-Aminobenzoic acid p-Aminobenzoic acid ethyl ester (25 mol) ethoxylated (INCI name: PEG-25 PABA) p-Dimethylaminobenzoic acid-2-ethylhexyl ester p-Aminobenzoic acid ethyl ester (2 mol) N-propoxylated p-Aminobenzoic acid glycerol ester Salicylic acid homomenthyl ester (homosalate) (NeoHeliopan® HMS) Salicylic acid-2-ethylhexyl ester (NeoHeliopan® OS) Triethanolamine salicylate 4-Isopropylbenzyl Salicylate Anthranilic acid menthyl ester (NeoHeliopan® MA) Diisopropyl cinnamate ethyl ester p-Methoxycinnamic acid-2-ethylhexyl ester (NeoHeliopan® AV) Diisopropyl cinnamate methyl ester p-Methoxycinnamic acid isoamyl ester (NeoHeliopan® E1000) p-Methoxycinnamic acid diethanolamine salt p-Methoxycinnamic acid isopropyl ester 2-Phenylbenzimidazole sulfonic acid and salts (NeoHeliopan® Hydro) 3-(4'-trimethylammonium)benzylidenebornan-2-one methyl sulfate Beta-imidazole-4(5)-acrylic acid (urocanic acid) 3-(4'-sulfo)benzylidenebornan-2-one and salts 3-(4'-Methylbenzylidene)-D,L-Camphor (NeoHeliopan® MBC) 3-Benzylidene-D,L-camphor N-[(2and4)-[2-(oxo-3-ylidene)methyl]benzyl]acrylamide polymer 4,4'-[(6-[4-(1,1-dimethyl)aminocarbonyl)phenylamino]-1,3,5-triazine-2,4-diyl)diimino]-bis-(benzoic acid-2-ethylhexyl ester) (Uvasorb® HEB) Benzylidenemalonic acid polysiloxane (Parsol® SLX) Glyceryl ethylhexanoate dimethoxycinnamate Dipropylene glycol salicylate Tris(2-ethylhexyl)-4,4',4'-(1,3,5-triazine-2,4,6-triyltriimino)tribenzoate (=2,4,6-trianilino-(p-carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine) (Uvinul® T150)
[0054] The broadband filters which are preferably combined with one or more compounds of formula (I) in the preparation according to the invention are selected from the group consisting of: 2-Ethylhexyl-2-cyano-3,3-diphenylacrylate (NeoHeliopan® 303) Ethyl 2-cyano-3,3'-diphenylacrylate 2-Hydroxy-4-methoxybenzophenone (NeoHeliopan® BB) 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid Dihydroxy-4-methoxybenzophenone 2,4-Dihydroxybenzophenone Tetrahydroxybenzophenone 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone 2-Hydroxy-4-n-octoxybenzophenone 2-Hydroxy-4-methoxy-4'-methylbenzophenone Hydroxymethoxybenzophenone Sodium Sulfonate Disodium-2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(1,3,3,3-tetramethyl-1-(trimethylsilyl)oxy)disiloxyanyl)propyl) (Mexolyl® XL) 2,2'-Methylenebis-(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)phenol) (Tinosorb® M) 2,4-Bis-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-1,3,5-triazine 2,4-Bis-[{(4-(2-ethylhexyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (Tinosorb® S) 2,4-bis-[{(4-(3-sulfonato)-2-hydroxypropyloxy)-2-hydroxyphenyl-6-(4-methoxyphenyl)-1,3,5-triazine sodium salt 2,4-Bis-[{(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine 2,4-Bis-[{4-(2-ethylhexyloxy)-2-hydroxy}phenyl]-6-[4-(2-methoxyethylcarbonyl)phenylamino]-1,3,5-triazine 2,4-Bis-[{4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy}phenyl]-6-[4-(2-ethylcarboxyl)phenylamino]-1,3,5-triazine 2,4-Bis-[{4-(2-ethylhexyloxy)-2-hydroxy}phenyl]-6-(1-methylpyrrol-2-yl)-1,3,5-triazine 2,4-Bis-[{4-tris-(trimethylsiloxysilylpropyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine 2,4-Bis-[{4-(2''-methylpropenyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine 2,4-Bis-[{4-(1',1',1',3',5',5',5'-heptamethylsiloxy-2''-methylpropyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine The UV-A filters which are preferably combined with one or more compounds of formula (I) in the preparations according to the invention are selected from the group consisting of: 4-Isopropyldibenzoylmethane Terephthalylidene dibornane sulfonic acid and salts (Mexoryl® SX) 4-t-Butyl-4'-methoxydibenzoylmethane (Avobenzone) / (NeoHeliopan® 357) 4-t-Butyl-4'-methoxydibenzoylmethane (Avobenzone) / (NeoHeliopan® 357) Phenylenebis-benzimidazyltetrasulfonic acid disodium salt (NeoHeliopan® AP) 2,2'-(1,4-phenylene)-bis-(1H-benzimidazole-4,6-disulfonic acid), monosodium salt 2-(4-Diethylamino-2-hydroxybenzoyl)benzoic acid hexyl ester (Uvinul® APlus) Indanylidene compounds according to DE100 55 940A1 (=WO2002 038537A1)
[0055] UV filters which are more preferably combined with one or more compounds of formula (I) in the preparations according to the invention are selected from the group consisting of: p-Aminobenzoic acid 3-(4'-trimethylammonium)benzylidenebornan-2-one methyl sulfate Salicylic acid homomenthyl ester (NeoHeliopan® HMS) 2-Hydroxy-4-methoxybenzophenone (NeoHeliopan® BB) 2-Phenylbenzimidazole sulfonic acid (NeoHeliopan® Hydro) Terephthalylidene dibornane sulfonic acid and salts (Mexoryl® SX) 4-tert-Butyl-4'-methoxydibenzoylmethane (NeoHeliopan® 357) 3-(4'-sulfo)benzylidenebornan-2-one and salts 2-Ethylhexyl-2-cyano-3,3-diphenylacrylate (NeoHeliopan® 303) N-[(2 and 4)-[2-(oxoborn-3-ylidene)methyl]benzyl]acrylamide polymer p-Methoxycinnamic acid-2-ethylhexyl ester (NeoHeliopan® AV) p-Aminobenzoic acid ethyl ester (25 mol) ethoxylated (INCI name: PEG-25 PABA) p-Methoxycinnamic acid isoamyl ester (NeoHeliopan® E1000) 2,4,6-Trianilino-(p-carbo-2'-ethylhexyl-1'-oxy)-1,3,5-triazine (Uvinul® T150) Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3(1,3,3,3-tetramethyl-1-(trimethylsilyl)oxy)disiloxyanyl)propyl) (Mexolyl® XL) 4,4'-[(6-[4-(1,1-dimethyl)aminocarbonyl)phenylamino]-1,3,5-triazine-2,4-diyl)diimino]-bis-(benzoic acid-2-ethylhexyl ester) (Uvasorb HEB) 3-(4'-Methylbenzylidene)-D,L-Camphor (NeoHeliopan® MBC) 3-Benzylidene camphor Salicylic acid-2-ethylhexyl ester (NeoHeliopan® OS) 4-Dimethylaminobenzoic acid-2-ethylhexyl ester (Padimate O) Hydroxy-4-methoxybenzophenone-5-sulfonic acid and sodium salt 2,2'-Methylene bis-(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)phenol) (Tinosorb® M) Phenylenebis-benzimidazyltetrasulfonic acid disodium salt (NeoHeliopan® AP) 2,4-Bis-(4-(2-ethylhexyloxy)-2-hydroxyphenyl-6-(4-methoxyphenyl)-1,3,5-triazine (Tinosorb® S) Benzylidenemalonic acid polysiloxane (Parsol® SLX) Menthyl anthranilate (NeoHeliopan® MA) 2-(4-Diethylamino-2-hydroxybenzoyl)benzoic acid hexyl ester (Uvinul® APlus) Indanylidene compounds according to DE 100 55 940 (= WO / 02 / 38537).
[0056] Advantageous primary and secondary sun protection factors are described in WO2005 / 123101 / A1. Advantageously, these preparations contain at least one UVA filter and / or at least one UVB filter and / or at least one inorganic pigment. The preparations may be present here in various forms as are conventionally used in sunscreen preparations. Thus, they may be in the form of a water-in-oil (W / O) or oil-in-water (O / W) emulsion, multiple emulsions, for example water-in-oil-in-water (W / O / W), gels, aqueous dispersions, solid sticks, or solutions of aerosols.
[0057] In a further preferred embodiment, the formulations according to the invention comprise a total amount of sunscreens, i.e. in particular UV filters and / or inorganic pigments (UV filtering pigments), so that the formulations according to the invention have a light protection factor of 2 or more (preferably 5 or more). Such preparations according to the invention are particularly suitable for protecting the skin and hair. Secondary Sun Protection Factors
[0058] In addition to the above group of primary sunscreen factors, secondary sunscreen factors of the antioxidant type can also be used. Secondary sunscreen factors of the antioxidant type interrupt the photochemical reaction chain that is initiated when ultraviolet radiation penetrates the skin. Typical examples are amino acids (e.g., glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g., urocanic acid) and their derivatives, peptides, e.g., D,L-carnosine, D-carnosine, L-carnosine. and its derivatives (e.g. anserine), carotenoids, carotenes (e.g. alpha-carotene, beta-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, liponic acid and its derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, α-linoleyl, cholesteryl and glyceryl esters) and their salts, dilaurylthiodipropionate, distearyl-thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and very Small compatible doses of sulfoximine compounds (e.g. buthionine sulfoximine, homocysteine sulfoximine, buthionine sulfone, penta-, hexa- and hepta-thionine sulfoximine), as well as (metal) chelating agents (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferulin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acids, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. linoleic acid), oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherol and its derivatives (e.g. vitamin E acetate),Vitamin A and its derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin resin, rutinic acid and its derivatives, glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, titanium dioxide (for example dispersion in ethanol), zinc and its derivatives (for example ZnO, ZnSO 4), selenium and its derivatives (for example selenium methionine), stilbene and its derivatives (for example stilbene oxide, trans-stilbene oxide), and derivatives (salts, esters, ethers) of these active substances suitable for the purposes of the present invention, sugars, nucleotides, nucleosides, peptides and lipids).
[0059] Advantageous inorganic secondary shading pigments are finely dispersed metal oxides and metal salts, which are also disclosed in WO 2005 123101 A1. The total amount of inorganic pigments, in particular hydrophobic inorganic micropigments, in the finished cosmetic preparation prepared according to the invention is advantageously 0.1 to 30% by weight, preferably 0.5 to 10.0% by weight, each based on the total weight.
[0060] Also preferred are particulate UV filters or inorganic pigments, which can optionally be hydrophobized, oxides of titanium (TiO2), zinc (ZnO), iron (Fe2O3), zirconium (ZrO2), silicon (SiO2) manganese (e.g. MnO), aluminum (Al2O3), cerium (e.g. Ce2O3), and / or mixtures thereof. Anti-Aging Activity
[0061] In the context of the present invention, anti-aging or biogenic agents are, for example, antioxidants, matrix metalloproteinase inhibitors (MMPIs), skin moisturizers, glycosaminoglycan stimulators, anti-inflammatory agents, TRPV1 antagonists and plant extracts.
[0062] Antioxidant.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), carnosine, creatine, matrikin peptides (preferably lysyl-threonyl-threonyl-lysyl-serine) and palmitoylated pentapeptides, carotenoids, carotenes (preferably alpha-carotene, beta-carotene, lycopene) and derivatives thereof, lipoic acid and derivatives thereof (preferably dihydrolipoic acid), aurothioglucose glucose, propylthiouracil and other thiols (preferably thioredoxin, glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, gamma-linoleyl, cholesteryl, glyceryl and oligoglyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (preferably esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and in very small tolerated amounts (e.g. pmol to μmol / kg) of sulfoximine compounds (preferably buthionine sulfoximine, homocysteine sulfoximine, buthionine sulfone, penta-, hexa-, heptathionine sulfoximine), also (metal) chelating agents (preferably α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin, α-hydroxy acids (preferably citric acid, lactic acid, malic acid), humic acid, bile acids, bile extracts, tannins, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof), unsaturated fatty acids and derivatives thereof (preferably gamma-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and derivatives thereof, ubiquinol and derivatives thereof, vitamin C and derivatives (preferably ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate, ascorbyl glucoside), tocopherol and derivatives (preferably vitamin E acetate),Vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoic acid resin, rutinic acid and its derivatives, flavonoids and their glycosylated precursors, in particular quercetin and its derivatives, preferably α-glucosylrutin, rosmarinic acid, carnosol, carnosolic acid, r-esveratrol, caffeic acid and its derivatives, sinapic acid and its derivatives, ferulic acid and its derivatives, curcuminoids, chlorogenic acid and its derivatives, retinoids, preferably retinyl palmitate, retinol or tretinoin, ursolic acid, levulinic acid, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (preferably ZnO, ZnSO4), selenite, glycerol ... selenium and its derivatives (preferably selenium methionine), superoxide dismutase, stilbene and its derivatives (preferably stilbene oxide, trans-stilbene oxide) and derivatives of these cited active ingredients that are suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) or extracts or fractions of plants having antioxidant action, preferably green tea, rooibos, honeybush, grape, rosemary, sage, melissa, thyme, lavender, olive, oat, cocoa, ginkgo, ginseng, licorice, honeysuckle, sophora, pueraria, pinus, citrus, phyllanthus emblica or St. John's wort, 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, tocopherol and derivatives, preferably tocopheryl acetate, and ubiquinone.
[0063] Matrix metalloproteinase inhibitors (MMPIs). Preferred compositions include matrix metalloproteinase inhibitors, in particular ursolic acid, retinyl palmitate, propyl gallate, precocenes, 6-hydroxy-7-methoxy-2,2-dimethyl-1(2H)-benzopyran, 3,4-dihydro-6-hydroxy-7-methoxy-2,2-dimethyl-1(2H)-benzopyran, benzamidine hydrochloride, the cysteine proteinase inhibitor N-ethylmalemide and the serine protease inhibitor epsilon-amino-n-caproic acid; phenylmethyl-thyrsufonyl-fluoride, colhibin (Pentapharm; INCI: Hydrolyzed Rice Protein), oenotherol (Soliance; INCI: Propylene Glycol, Aqua, Oenothera biennis root extract, el-lagic acid and ellagitannins, e.g. from pomegranate), phosphoramidone hinokitiol, EDTA, galardin, EquiStat (Collaborative Group Inc.; apple fruit extract, soybean seed extract, ursolic acid, soy isoflavones and soy protein), sage extract, MDI (Atrium Inc.; INCI: glycosaminoglycans), fermiskin (Silab / Mawi Inc.; INCI: water and lentinus edodes extract), actimp 1.9.3 (Expanscience / Rahn, INCI: hydrolyzed lupin proteins), lipobelle soyaglycone (Mibelle, INCI: alcohol, polysorbate 80, lecithin and soy isoflavones), extracts from green and black tea and further plant extracts described in WO02 069992 A1 (see Tables 1 to 12, which are incorporated herein by reference), proteins or glycoproteins from soybeans, hydrolyzed proteins from rice, pea or lupin, extracts that inhibit MMPs from plants, preferably extracts from Shitake mushrooms, extracts from leaves of the family Rosaceae, subfamily Rosoideae, in particular blackberry leaf extracts (preferably as described in WO2005 / 123101 / A1, which are incorporated herein by reference), SymMatrix (Symrise, INCI: maltodextrin, Rubus Fruticosus (blackberry) leaf extract), preferred active substances include those that inhibit matrix metalloproteinases that enzymatically cleave collagen, selected from the group consisting of retinyl palmitate, ursolic acid, extracts from the leaves of the Rosaceae family, subfamily Rosaceae, genistein and daidzein.
[0064] Skin moisturizer. Preferred skin moisturizers are selected from the group consisting of alkanediols or alkanetriols containing 3 to 12 carbon atoms, preferably C3-C10-alkanediols and C3-C10-alkanetriols.More preferably, the skin moisturizer is selected from the group consisting of glycerol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol and 1,2-decanediol.
[0065] Glycosaminoglycan stimulator. Preferred compositions are substances stimulating the synthesis of glycosaminoglycans selected from the group consisting of hyaluronic acid and derivatives or salts, including Subliskin (Sederma, INCI: Sinorhizobium meliloti ferment filtrate, cetyl hydroxyethylcellulose, lecithin), Hyalufix (BASF, INCI: water, butylene glycol, Alpinia galanga leaf extract, xanthan gum, caprylic / capric triglyceride). Stimulants (Soliance, INCI: Calcium ketogluconate), Synglican (DSM, INCI: Tetradecylaminobutyroylvalyl-aminobutyric acid urea trifluoroacetate, glycerin, magnesium chloride), Kalpariane (Biotech Marine), DC Upregulex (Characteristic cosmetic ingredient, INCI: Water, Butylene glycol, Phospholipids, Hydrolyzed sericin), Glucosamine, N-acetylglucosamine, Retinoids, preferably retinol and vitamin A, Arctium lappa fruit extract, Eriobotrya japonica extract, Genkwanin, N-methyl-L-serine, (-)-alpha-bisabolol or synthetic alpha-bisabolol (e.g. Dragosantol and Dragosantol 100 from Symrise, Oat glucan, Echinacea purpurea extract, Soy protein hydrolysate). Preferred active substances are selected from the group consisting of hyaluronic acid and derivatives or salts, retinol and derivatives, (-)-alpha-bisabolol or synthetic alpha-bisabolol, e.g. Dragosantol and Dragosantol 100 from Symrise, oat glucan, Echinacea purpurea extract, Sinorhizobium meliloti ferment filtrate, calcium ketogluconate, Alpinia galanga leaf extract and tetradecylaminobutyroylvalylaminobutyric acid urea trifluoroacetate.
[0066] Anti-inflammatory. The composition may also contain anti-inflammatory and / or redness and / or itching relieving ingredients. In particular, steroid substances of the corticosteroid type selected from the group consisting of hydrocortisone, dexamethasone, dexamethasone phosphate, methylprednisolone or cortisone are advantageously used. As anti-inflammatory active ingredients or active ingredients that relieve redness and itching, the list can be expanded by the addition of other steroidal anti-inflammatory agents. Non-steroidal anti-inflammatory drugs can also be used. Examples which may be cited here are oxicams such as piroxicam or tenoxicam, salicylates such as aspirin, disalcid, solprin or fendosal, acetic acid derivatives such as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or clindanac, fenamates such as mefenamic acid, meclofenamic acid, flufenamic acid or niflumic acid, propionic acid derivatives such as ibuprofen, naproxen, benoxaprofen, or pyrazoles such as phenylbutazone, oxyphenylbutazone, febrazone or azapropazone. Anthranilic acid derivatives, in particular the avenanthramides described in WO2004 / 047833 / A1, are preferred antipruritic ingredients in the compositions according to the invention.
[0067] Useful are natural or naturally occurring anti-inflammatory mixtures of substances that reduce redness and / or itching, in particular extracts or fractions from chamomile, aloe vera, Commiphora species, Rubia species, willow, willow herb, oats, calendula, arnica, St. John's wort, honeysuckle, rosemary, Passiflora incarnata, witch hazel, ginger or echinacea; chamomile, aloe vera, oats, calendula, arnica, honeysuckle, rosemary , witch hazel, ginger or echinacea, and / or pure substances, preferably alpha-bisabolol, apigenin, apigenin-7-glucoside, gingerol, shogaol, gingerdiol, dehydrogingerdione, paradol, natural or naturally occurring avenanthramides, preferably tranilast, avenanthramide A, avenanthramide B, avenanthramide C, non-natural or non-naturally occurring avenanthramides, preferably dihydroavenanthramide D, dihydroavenan avenanthramide E, avenanthramide F, boswellic acid, phytosterols, glycyrrhizin, glabridin, licochalcone A; preferably alpha-bisabolol, natural avenanthramides, non-natural avenanthramides, preferably dihydroavenanthramide D (described in WO 2004 / 047833 / A1), boswellic acid, phytosterols, glycyrrhizin, and licochalcone A, and / or allantoin, panthenol, lanolin, (pseudo)ceramides ( Preferably, the extract or fraction comprises ceramide 2, hydroxypropyl bispalmitamide MEA, cetyloxypropyl glyceryl methoxypropyl myristamide, N-(1-hexadecanoyl)-4-hydroxy-L-proline (1-hexadecyl) ester, hydroxyethyl palmityloxyhydroxypropyl palmitamide, glycosphingolipids, phytosterols, chitosan, mannose, lactose and β-glucan, in particular 1,3-1,4-β-glucan derived from oats.
[0068] TRPV1 antagonists. Suitable compounds that reduce the hypersensitivity of skin nerves based on their action as TRPV1 antagonists include, for example: trans-4-tert-butylcyclohexanol, as described in WO2009 / 087242 / A1, or indirect modulators of TRPV1 by activating the μ receptor, such as E. acetyl tetrapeptide-15, are preferred.
[0069] plant extract. The compositions may also include extracts of, for example, Ginkgo biloba, Osmanthus europensis, Glycyrrhiza glabra, Vaccinium myrtillus, Red clover, Litchi sinensis, Vitis vinifera, Brassica napus, Pomegranate, Parsley, Centella asiatica, Passiflora incarnata, Medicago sativa, Melissa officinalis, Valeriana officinalis, Castanea sativa, Salix alba, and Hapagophytum procumbens. coolant
[0070] The composition may also contain one or more substances having a physiological cooling effect (cooling agents), which are preferably selected here from the following list: menthol and menthol derivatives (e.g. L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol), menthyl ethers (e.g. (I-menthol)-1,2-propanediol, (l-menthoxy)-2-methyl-1,2-propanediol, l-menthyl-methyl ether), menthyl esters (e.g. menthyl formate, menthyl acetate, menthyl isobutyrate, menthyl lactate, L-menthyl-L-lactate, L-menthyl-D-lactate, menthyl -(2-methoxy)acetate, menthyl-(2-methoxyethoxy)acetate, menthyl pyroglutamate), menthol carbonates (e.g., menthol propylene glycol, menthol ethylene glycol carbonate, menthol glycerol carbonate or mixtures thereof), semiesters of menthol with dicarboxylic acids or their derivatives (e.g., monomenthyl succinate, monomenthyl glutarate, monomenthyl malonate, O-menthyl succinate-N,N-(dimethyl)amide, O-menthyl succinic acid acid ester amides), menthane carboxylic acid amides (in this case preferably menthane carboxylic acid-N-ethyl amides [WS3] or Nα-(menthanecarbonyl)glycine ethyl esters [WS5] as described in US 4,150,052, menthane carboxylic acid-N-, methane carboxylic acid-N-(alkoxyalkyl) amides, menthane carboxylic acid-N-(4-cyanophenyl) amides or menthane-carboxylic acid-N- as described in WO2005049553A1 (4-cyanomethylphenyl)amide, methanecarboxylic acid-N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g., L-menthone glycerol ketal), 2,3-dimethyl-2-(2-propyl)-butyric acid derivatives (e.g., 2,3-dimethyl-2-(2-propyl)-butyric acid-N-methylamide [WS23]), isopulegol or its esters (I-(-)-isopulegol, I-(-)-isopulegolacetate), menthane derivatives (e.g., p-menthane-3,8-diols), cubols or synthetic or natural mixtures containing pyrrolidone derivatives of cubols or cycloalkyldione derivatives (e.g. 3-methyl-2(1-pyrrolidinyl)-2-cyclopenten-1-one) or tetrahydropyrimidin-2-ones (e.g. icilin or related compounds as described in WO2004 / 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)cyclohexane-carboxamide [WS12], oxamates (preferably those described in EP 2033688A2). Antibacterial agents
[0071] Suitable antibacterial agents are in principle, for example, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)urea, 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), 4-chloro-3,5-dimethyl-phenol, 2,2'-methylenebis(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-1,2-propanediol, 3-iodo-4-chlorophenol, 4-chloro-3,5-dimethyl- ... do-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid N-alkylamides, e.g., n-octyl salicylamide or n-decyl salicylamide, are all substances effective against. Enzyme inhibitors
[0072] Suitable enzyme inhibitors are, for example, esterase inhibitors. These are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, and especially triethyl citrate (HydagenCAT). These substances inhibit enzyme activity, thereby reducing the formation of odor. Other substances that are suitable esterase inhibitors are, for example, sterol sulfates or phosphates, such as lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as tartaric acid, monoethyl. Glutaric acid, diethyl glutarate, adipic acid, monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters, such as citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate. Odor absorbents and antiperspirants
[0073] Suitable odor absorbers are substances that are able to absorb odor-forming compounds and retain a large part of them. They reduce the partial pressure of the individual components and therefore also their diffusion rate. In this process, it is important that the perfume is not spoiled. Odor absorbers are ineffective against bacteria. They contain, for example, as the main ingredient, complex zinc salts of ricinoleic acid or certain storax or certain abietic acid derivatives known to the skilled artisan as "fixatives", such as, for example, extracts of labdanum, mainly odor-neutral fragrances. The odor masking agents are fragrances or perfume oils which, in addition to their function as odor masking agents, give the deodorants their respective fragrance notes. Perfume oils that may be mentioned are, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts from flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches, resins and balsams. Also suitable are animal products, such as, for example, civet or beaver incense. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type. Ester type fragrance compounds are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styrallyl propionate, and benzyl salicylate. Ethers include, for example, benzyl ethyl ether, and aldehydes include, for example, linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial, and brujonal. Ketones include, for example, ionones and methyl cedryl ketone, and alcohols include anethofol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol, and terpineol. The hydrocarbons include mainly terpenes and balsams. However, preference is given to using mixtures of different fragrances which together produce a pleasant fragrance note.Relatively low volatility essential oils that are primarily used as aroma ingredients include perfume oils, namely sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil, and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, alpha-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, clary sage oil, beta-damascene, geranium oil bourbon, cyclohexyl salicylate, Vertofix coeur, iso-E-super, Fixolide NP, evernyl, iraldine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romirat, irotyl and floramat alone or in mixtures.
[0074] The preferred astringent antiperspirant active ingredient is mainly a salt of aluminum, zirconium or zinc.Such suitable anti-hydration active ingredients include, for example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds, for example, aluminum, 1,2-propylene glycol, aluminum hydroxyalantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds, for example, amino acids such as glycine. Film formers and anti-dandruff agents
[0075] Standard film-forming agents are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid and its salts, and similar compounds.
[0076] Suitable antidandruff agents include Piroctone Olamine (1-hydroxy-4-methyl-6-(2,4,4-trimethyl-pentyl)-2-(1H)-pyridinone monoethanolamine salt), Baypival® (Climbazole), Keto-conazol® (4-acetyl-1-{4-[2-(2,4-dichlorophenyl)r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxiran-c-4-ylmethoxyphenyl}-piperazine, ketoconazole, elbiphenyl, ethylhexyl ether ... ol, selenium disulfide, colloidal sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, sulfur tar distillate, salicylic acid (or in combination with hexachlorophene), undecylenic acid, monoethyl-anoramide sulfosuccinic acid sodium salt, Lamepon® UD (protein / undecylenic acid condensate), zinc pyrithione, aluminum pyrithione and magnesium pyrithione / dipyrithione magnesium sulfate. Carriers and hydrotropes
[0077] Preferred cosmetic carrier. The material is solid or liquid at 25°C and 1013 mbar (including high viscosity substances), such as, for example, glycerol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-propylene glycol 1,3-butylene glycol, ethanol, water, and mixtures of two or more of the above liquid carrier materials with water. Optionally, these preparations according to the invention can be produced using preservatives or solubilizers. Other preferred liquid carrier substances that can be components of the preparations according to the invention are selected from the group consisting of oils, such as vegetable oils, neutral oils and mineral oils.
[0078] Preferred solid carrier materials which may be a component of the preparation according to the invention are starch, degraded starch, chemically or physically modified starch, dextrin, (powdered) maltodextrin (preferably with a dextrose equivalent value of 5 to 25, preferably 10 to 20), lactose, silicon dioxide, glucose, modified cellulose, gum arabic, gum ghatti, tragacanth, karaya, carrageenan, pullulan, curdlan, xanthan gum, gellan gum, guar flour, carob flour, alginates, agar, pectin, inulin, and mixtures of two or more of these solids, in particular maltodextrin (preferably with a dextrose equivalent value of 15 to 20), lactose, silicon dioxide, and / or glucose.
[0079] In addition, hydrotropes such as ethanol, isopropyl alcohol or polyols can be used to improve the flow behavior. Suitable polyols preferably contain 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, more particularly amino groups, or may be modified with nitrogen. A typical example is as follows: Glycerol; Alkylene glycols, such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycol, with an average molecular weight between 100 and 1000 Daltons. Technical oligoglycerol mixtures having a degree of self-condensation of 1.5 to 10, such as, for example, technical diglycerol mixtures having a diglycerol content of 40 to 50% by weight. Particularly methylol compounds such as trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol. ·Lower alkyl glucosides, especially those containing 1 to 8 carbon atoms in the alkyl group, such as methyl and butyl glucoside. · Sugar alcohols containing 5 to 12 carbon atoms (such as sorbitol and mannitol). ·Sugars containing 5 to 12 carbon atoms, e.g. glucose and sucrose. Amino sugars, e.g. glucamine. · Dialcoholamines such as diethanolamine and 2-aminopropane-1,3-diol. Perfume Oils and Fragrances
[0080] Suitable perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances include extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peels (juniper, bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom, costus, iris, calamus), woods (pinewood, sandalwood, guaiacwood, cedarwood, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and branches (spruce, fir, pine, dwarf pine), resins, and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal sources such as civet and beaver can also be used. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type. Examples of fragrance compounds of the ester type include benzyl acetate, phenoxyethyl isobutyrate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propionate, and benzyl salicylate. Ethers include, for example, benzyl ethyl ether, while aldehydes include, for example, linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial, and bourgeonal. Examples of suitable ketones are ionone, -isomethylionone, and methyl cedryl ketone. Suitable alcohols are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol. Hydrocarbons include mainly terpenes and balsams. However, it is preferred to use mixtures of different fragrance compounds which together produce a pleasant fragrance. Other suitable perfume oils are relatively low volatility essential oils which are mainly used as aroma ingredients.Examples include sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, ladanum oil, and lavendin oil. The following are preferably used individually or in the form of a mixture: bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, citrus oil, mandarin oil, orange oil, allyl glycolate, cyclovertal, lavendin oil, clary oil, damascene, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romirat, irotyl, floramat. dye
[0081] Suitable dyes are any of the substances suitable and approved for cosmetic purposes, as described, for example, in the publication "Kosmetische Farbemittel" of the Farbstoff-kommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81-106. Examples are cochineal red A (CI 16255), patent blue V (CI 42051), indigotine (CI 73015), chlorophyllin (CI 75810), quinoline yellow (CI 47005), titanium dioxide (CI 77891), indanthrene blue RS (CI 69800) and madder lake (CI 58000). Luminol may also be present as a luminescent pigment. Advantageous color pigments are, for example, titanium dioxide, mica, iron oxides (e.g. Fe2O3 Fe3O4, FeO(OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet.
[0082] Preferred compositions according to the invention are from the group of products for the treatment, protection, care and cleansing of the skin and / or hair or make-up products, preferably leave-on products (wherein the compound or compounds of formula (I) remain on the skin and / or hair for a longer period of time compared to rinse-off products, and therefore their moisturizing and / or anti-aging and / or wound healing promoting action is more pronounced).
[0083] The formulations according to the invention are preferably in the form of emulsions, such as W / O (water in oil), O / W (oil in water), W / O / W (water in oil in water), O / W / O (oil in water-in-oil) emulsions, PIT emulsions, Pickering emulsions, low oil emulsions, micro- or nanoemulsions, solutions, e.g. in oil (fatty acids or fatty acid esters, in particular C6-C32 fatty acid C2-C30 esters) or silicone oils, dispersions, suspensions, creams, lotions or milk, gels (water-dispersible gels, including hydrogels), depending on the production method and ingredients. oils, oleogels), sprays (e.g. pump sprays or sprays with propellants) or foams or impregnating solutions for cosmetic wipes, detergents, e.g. soaps, detergents, liquid washes, shower and bath additives, bath additives (capsules, oils, tablets, salts, bath additives, soaps, etc.), foaming agents, skin care products (e.g. emulsions (as above), ointments, pastes, gels (as above), oils, balsams, serums, powders (e.g. face powders, body powders), masks, pencils, sticks hair care products such as shampoos (including 2-in-1 shampoos, anti-dandruff shampoos, baby shampoos, shampoos for dry scalp, concentrated shampoos), conditioners, hair tonics, hair waters, hair rinses, styling creams, pomades, perms, setting lotions, hair sprays, styling aids (such as gels or waxes), hair smoothing agents (detanglers, relaxers), hair dyes, temporary direct hair dyes, semi-permanent hair dyes, permanent hair dyes, hair conditioners, hair mousses, eye care products, makeup, makeup removers or baby products.
[0084] The formulations according to the invention are particularly preferably in the form of an emulsion, in particular a W / O, O / W, W / O / W, O / W / O emulsion, PIT emulsion, Pickering emulsion, low-oil emulsion, micro- or nano-emulsion, a gel (including hydrogels, water-dispersed gels, oleogels), a solution, such as in oil (fatty acids or fatty acid esters, in particular C6-C32 fatty acid C2-C30 esters)) or silicone oil, or a spray (e.g. pump spray or spray with propellant).
[0085] The auxiliary substances and additives may be present in an amount of 5 to 99% by weight, preferably 10 to 80% by weight, based on the total weight of the formulation. The amount of cosmetic or dermatological auxiliaries and additives and fragrances to be used in each case can be easily determined by the skilled artisan by simple trial and error, depending on the nature of the particular product.
[0086] The preparation may also contain water in an amount of up to 99% by weight, preferably from 5 to 80% by weight, based on the total weight of the preparation. Detergent Composition
[0087] Another embodiment of the present invention covers detergent compositions comprising an effective amount of at least one acetophenone derivative or mixtures thereof and additional preservatives and / or antimicrobial agents, which may be present in an amount of from about 0.01 to about 10% by weight, preferably from about 0.05 to about 5% by weight, more preferably from about 0.1 to about 1% by weight, calculated on the total composition.
[0088] The detergent compositions according to the invention may comprise any of the commonly found ingredients such as, for example, compositions of anionic, nonionic, cationic, amphoteric or zwitterionic (co)surfactants, organic solvents, additional auxiliaries such as builders, enzymes, soil release agents, thickeners, colourants and fragrances. Anionic Co-Surfactants
[0089] Preferably, surfactants of the sulfonate type, alkyl(en)yl sulfonates, alkoxylated alkyl(en)yl sulfates, ester sulfonates and / or soaps are used as anionic surfactants. Suitable surfactants of the sulfonate type are advantageously C9-13 alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkenes and hydroxyalkanesulfonates, and disulfonates, for example terminal or internal double bonds of the sulfonation products obtained by sulfonation of C12-18 monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis.
[0090] Alkyl(en)yl sulfates. Preferred alkenyl sulfates are alkaline, in particular the sulfate half esters or sodium salts of C12-C18 fatty alcohols, for example from coconut butter alcohol, tallow alcohol, lauryl, myristyl, cetyl, stearyl alcohol or C8-C20 oxo alcohols and half esters of secondary alcohols of these chain lengths. Alkenyl sulfates of the cited chain lengths, including synthetic straight chain alkyl groups produced petrochemically, are also preferred. C12-C16 alkyl sulfates and C12-C15 alkyl sulfates, as well as C14-C15 alkyl sulfates and C14-C16 alkyl sulfates, are particularly preferred for reasons of laundry performance. 2,3-Alkyl sulfates available under the trade name DANTM from Shell Oil Company are also suitable anionic surfactants.
[0091] Alkyl(en)yl ether sulfates. Also suitable are sulfuric acid monoesters derived from linear or branched C7-C21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-C11 alcohols containing an average of 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 to 4 EO.
[0092] Ester sulfonates. Likewise suitable are the esters of alpha sulfo fatty acids (ester sulfonates), for example the alpha sulfonated methyl esters of hydrogenated coconut acid, palm nut acid, or tallow acid.
[0093] soap. Soaps in particular can be considered as further anionic surfactants. Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, especially soap mixtures derived from natural fatty acids such as coconut oil fatty acid, palm kernel oil fatty acid or tallow fatty acid, are particularly suitable. These soap mixtures are particularly preferred, especially 50-100% by weight of saturated C12-C24 fatty acid soaps and 0-50% by weight of oleic acid soaps.
[0094] Ether carboxylic acids. A further class of anionic surfactants is that of ether carboxylic acids, which are obtained by treating fatty alcohol ethoxylates with sodium chloroacetate in the presence of a basic catalyst. Their general formula is RO(CH2CH2O)pCH2COOH, R=C1-C18 and p=0.1-20. Ether carboxylic acids are not affected by water hardness and have excellent surfactant properties. Nonionic (CO-) Surfactants
[0095] Alcohol alkoxylates. The nonionic surfactants added are preferably alkoxylated and / or propoxylated, particularly preferably primary alcohols with 8 to 18 carbon atoms and an average of 1 to 12 mol ethylene oxide (EO) and / or 1 to 10 mol propylene oxide (PO) per mole of alcohol. C8-C16-alcohol alkoxylates, advantageously ethoxylated and / or propoxylated C10-C15-alcohol alkoxylates, in particular C12-C14 alcohol alkoxylates, with a degree of ethoxylation between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between -1 and 6, preferably between 1.5 and 5, are particularly preferred. The quoted degrees of ethoxylation and propoxylation constitute statistical average values which may be integers or fractions for a particular product. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used, examples of which are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
[0096] Alkyl glycosides (APG®). Furthermore, as additional nonionic surfactants, alkyl glycosides satisfying the general formula RO(G)x can be added, for example, as compounds, especially together with anionic surfactants, where R denotes a primary linear or methyl-branched, especially 2-methyl-branched, aliphatic group containing 8 to 22, preferably 12 to 18, carbon atoms; and G denotes a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which defines the distribution of monoglycosides and oligoglycosides, can be any number between 1 and 10, preferably between 1.1 and 1.4.
[0097] Fatty acid ester alkoxylates. Another class of preferred nonionic surfactants, to be used either as solo nonionic surfactants or in combination with other nonionic surfactants (especially with alkoxylated fatty alcohols and / or alkyl glycosides), are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acidic alkyl esters, preferably containing 1 to 4 carbon atoms in the alkyl chain, more particularly the methyl esters of fatty acids produced, for example, by the processes described in Japanese patent application JP-A-58 / 217598 or in International application WO-A-90 / 13533. Particularly preferred are the methyl esters of C12-C18 fatty acids containing an average of 3 to 15 EO, in particular an average of 5 to 12 EO.
[0098] Amine oxide. Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides, may also be suitable. The amount of these nonionic surfactants used is preferably equal to or less than the amount of the ethoxylated fatty alcohols used, and more preferably equal to or less than half that amount.
[0099] Gemini surfactants. The so-called gemini surfactants can be considered as further surfactants. Generally speaking, such compounds are understood to mean compounds with two hydrophilic and two hydrophobic groups per molecule. As a rule, these groups are separated from each other by a "spacer". The spacer is usually a hydrocarbon chain intended to be long enough so that the hydrophilic groups are separated by a sufficient distance so that they can act independently of each other. These types of surfactants are generally characterized by an unusually low critical micelle concentration and the ability to significantly reduce the surface tension of water. However, in exceptional cases, not only dimeric surfactants but also trimeric surfactants are meant by the term gemini surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German published patent DE 4321022 A1 or dimeric alcohol bis- and trimeric alcohol trisulfates and ether sulfates according to International published patent WO 96 / 23768 A1. Blocked end group dimeric and trimeric mixed ethers according to German Patent Publication DE 19513391 A1 are particularly characterized by their bifunctional and multifunctional nature. Gemini polyhydroxy fatty acid amides or polyhydroxy fatty acid amides such as those described in International Patent Publications WO 95 / 19953 A1, WO 95 / 19954 A1 and WO 95 / 19955 A1 can also be used. Cationic (CO)-Surfactants
[0100] Tetraalkylammonium salts. Cationic active surfactants contain a hydrophobic polymeric group necessary for the surface activity of the cation by dissociation in aqueous solution. An important representative group of cationic surfactants are tetraalkylammonium salts of the general formula (R1R2R3R4N+)X-, where R1 represents C1-C8 alkyl(alkenyl) and R2, R3 and R4, independently of each other, represent alkyl(alkenyl) radicals having 1 to 22 carbon atoms. X is a counterion, preferably selected from the group of halides, alkyl sulfates and alkyl carbonates. Particularly preferred are cationic surfactants in which the nitrogen group is substituted with two long acyl groups and two short alkyl(alkenyl) groups.
[0101] Esterquat. A further class of cationic surfactants that is particularly useful as a co-surfactant of the present invention is represented by the so-called esterquats. Esterquats are generally understood to be quaternized fatty acid triethanolamine ester salts. These are known compounds that can be obtained by the relevant methods of preparative organic chemistry. In this context, reference is made to International Patent Publication WO 91 / 01295 A1, according to which triethanolamine is partially esterified with fatty acid in the presence of hypophosphorous acid, air is passed through the reaction mixture, and then quaternized in its entirety with dimethyl sulfate or ethylene oxide. Furthermore, German Patent DE 4308794 C1 describes a method for preparing solid esterquats, in which the quaternization of triethanolamine esters is carried out in the presence of a suitable dispersant, preferably a fatty alcohol.
[0102] Typical examples of esterquats suitable for use according to the invention are products whose acyl component is derived from a monocarboxylic acid corresponding to the formula RCOOH, where RCO is an acyl group containing from 6 to 10 carbon atoms, and whose amine component is triethanolamine (TEA). Examples of such monocarboxylic acids are capric acid, caprylic acid, capric acid, and technical mixtures thereof, such as the so-called head fraction fatty acids. Esterquats whose acyl component is derived from a monocarboxylic acid containing from 8 to 10 carbon atoms are preferably used. Other esterquats are those whose acyl component is derived from a dicarboxylic acid such as malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanedioic acid, but preferably adipic acid. Overall, esterquats whose acyl component is derived from a mixture of a monocarboxylic acid containing from 6 to 22 carbon atoms and adipic acid are preferably used. The molar ratio of mono- and dicarboxylic acids in the final esterquat can range from 1:99 to 99:1, preferably from 50:50 to 90:10, more specifically from 70:30 to 80:20. Besides quaternized fatty acid triethanolamine ester salts, other suitable esterquats are quaternized ester salts of mono- / dicarboxylic acids with diethanolalkylamines or 1,2-dihydroxypropyldialkylamines. Esterquats can be obtained both from fatty acids and from the corresponding triglycerides mixed with the corresponding dicarboxylic acids. One such process, intended to be representative of the relevant prior art, is proposed in European patent EP0750606B1. To produce quaternized esters, a mixture of mono- and dicarboxylic acids and triethanolamine based on the available carboxylic acid functional groups can be used in a molar ratio of 1.1:1 to 3:1. Bearing in mind the performance properties of the esterquats, ratios of 1.2:1 to 2.2:1, preferably 1.5:1 to 1.9:1, have proven particularly advantageous. Preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9. Amphoteric or zwitterionic co-surfactants
[0103] Betaine. Amphoteric or amphoteric surfactants have multiple functional groups that can be ionized in aqueous solution, thereby giving the compound an anionic or cationic character, depending on the conditions of the medium (see DIN 53900, July 1972). Near the isoelectric point (around pH 4), amphoteric surfactants form internal salts and therefore become poorly soluble or insoluble in water. Amphoteric surfactants are subdivided into ampholytes and betaines, the latter being present as zwitterions in solution. Ampholytes are ampholytes; that is, compounds that have both acidic and basic hydrophilic groups and act as acids or bases depending on the conditions. Betaines in particular are known surfactants that are mainly produced by carboxyalkylation, preferably carboxymethylation, of amine compounds. The starting material is preferably condensed with a halocarboxylic acid or its salt, more specifically sodium chloroacetate, so that one mole of salt is formed per mole of betaine. The addition of unsaturated carboxylic acids, such as, for example, acrylic acid, is also possible. Examples of suitable betaines are the carboxyalkylation products of secondary and especially tertiary amines corresponding to the formula R1R2R3N-(CH2)qCOOX, where R1 is an alkyl radical having 6 to 22 carbon atoms, R2 is hydrogen or 1-4 carbon atoms, R3 is an alkyl radical containing 1-4 carbon atoms, q is a number from 1 to 6 and X is an alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, C12 / 14-cocoyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine, C16 / 18-tallowalkyl-dimethylamine and technical mixtures thereof, in particular dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine and technical mixtures thereof.
[0104] Alkylamidobetaine. Other suitable betaines are carboxyalkylation products of amidoamines corresponding to the formula R1CO(R3)(R4)-NH-(CH2)pN-(CH2)qCOOX, where R1CO is an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R2 is hydrogen or an alkyl radical having 1 to 4 carbon atoms, R3 is an alkyl radical having 1 to 4 carbon atoms, p is a number from 1 to 6, q is a number from 1 to 3 and X is an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, eleostearic acid, arachidonic acid, gadoleic acid, behenic acid, erucic acid, and technical mixtures thereof with N,N-dimethylamino-noethylamine, N,N-dimethylaminopropylamine, N,N-diethylaminoethylamine and N,N-diethylaminopropylamine, condensed with sodium chloroacetate. Commercially available products include Dehyton® K and Dehyton® PK (Cognis Deutschland GmbH & Co., KG), and Tego® Betaine (Goldschmidt).
[0105] Imidazolines. Other suitable starting materials for the betaines used for the purposes of the present invention are imidazolines. These substances are also known and can be obtained, for example, by cyclizing the condensation of 1 or 2 moles of C6-C22 fatty acids with polyfunctional amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are the condensation products of the above fatty acids with AEEA, preferably imidazolines based on lauric acid, which are then contaminated with sodium chloroacetate. Commercially available products include Dehyton® G (Cognis Deutschland GmbH & Co., KG).
[0106] The amount of (co)surfactant contained in the composition according to the invention is advantageously between 0.1 and 90% by weight, in particular between 10 and 80% by weight and particularly preferably between 20 and 70% by weight. Organic Solvents
[0107] The liquid light or heavy duty detergents may contain organic solvents, preferably miscible with water. Polydiols, ethers, alcohols, ketones, amides and / or esters are preferably used as organic solvents for this purpose in amounts of 0 to 90% by weight, preferably 0.1% to 70% by weight, in particular 0.1% to 60% by weight. Low molecular weight polar substances, such as methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof, are preferred. enzyme
[0108] Suitable enzymes include in particular those from the class of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures thereof. In the wash, all these hydrolases remove dirt such as protein, fatty and starchy dirt and prevent greying. In addition, cellulases and other glycosyl hydrolases can contribute to increased fibre softness and colour retention by removing pilling and microfibrils. Oxidoreductases can also be added to the bleaching agent or to inhibit colour transfer. Enzyme active substances obtained from bacterial sources or fungi such as Bacillus subtilis, Bacillus licheniformis, streptomycin-producing bacteria and Humicola insolens are particularly suitable. Proteases of the subtilisin type are preferably used, in particular those obtained from Bacillus lentus. Here, mixtures of enzymes, such as protease and amylase or protease and lipase or lipolytic enzyme or protease and cellulase or cellulase and lipase or lipolytic enzyme or protease, amylase and lipase or lipolytic enzyme or protease, lipase or lipolytic enzyme and especially cellulase, are of particular interest, as are mixtures containing proteases and / or lipases or mixtures with lipolytic enzymes. An example of such a lipolytic enzyme is the known cutinase. Peroxidases or oxidases have also proven suitable in certain cases. Suitable amylases include in particular α-amylase, iso-amylase, pullulanase and pectinase. Cellobiohydrolases, also known as cellobiases, endoglucanases and β-glucosidases or mixtures thereof are preferred cellulases. The activity of CMCase and avicelase differs depending on the type of cellulase, so that the required activity can be adjusted by controlling the mixture of cellulases. The content of the enzyme or enzyme mixture may be, for example, from about 0.1 to 5% by weight, but is preferably from 0.1 to about 3% by weight. builder
[0109] Zeolite. Microcrystalline synthetic zeolites containing bound water can be used as builders, for example zeolite A and / or zeolite P are preferred. Zeolite MAP.RTM (a commercial product of Crosfield) is particularly preferred as zeolite P. However, zeolites X and mixtures of A, X, Y and / or P are also suitable. Co-crystallized sodium / potassium aluminum silicate from zeolite A and zeolite X, available as Vegobond® RX (a commercial product of Condea Augusta SpA), is of particular importance. Preferably, the zeolites can be used as spray-dried powders. If the zeolite is added as a suspension, it may contain small amounts of non-ionic surfactants as stabilizers, for example 1 to 3% by weight, based on the zeolite, of ethoxylated C12-C18 fatty alcohols with 2 to 5 ethylene oxide groups, C12-C14 fatty alcohols with 4 to 5 ethylene oxide groups, or ethoxylated isotridecanol. Suitable zeolites have an average particle size of less than 10 μm (test method: volume distribution Coulter Counter) and preferably contain 18-22% by weight, in particular 20-22% by weight, of bound water. Apart from this, phosphates can also be used as builders.
[0110] Layered silicate. A suitable substitute or partial substitute for phosphate and zeolite is crystalline layered sodium silicate.These types of crystalline layered silicate are described, for example, in EP 0164514 A1.Preferred crystalline layered silicate is obtained, for example, from the process described in WO 91 / 08171 A1.
[0111] Amorphous silicates. Preferred builders also include amorphous sodium silicates with a modulus (Na2O:SiO2 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8, more preferably 1:2 to 1:2.6, which dissolve with delay and show multiple wash cycle properties. The delay in dissolution compared to conventional amorphous sodium silicates can be obtained in various ways, for example by surface treatment, compounding, compaction / compression or overdrying. In the context of the present invention, the term "amorphous" also means "X-ray amorphous". In other words, silicates do not produce sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but produce one or more diffraction angle maxima of scattered X-rays with a width of several degrees. However, particularly good builder properties can be achieved even when silicate particles produce unclear or sharp diffraction maxima in electron diffraction experiments. This should be interpreted as meaning that the product has microcrystalline regions with a size of 10 to several hundreds of nm, with values of up to 50 nm and especially up to 20 nm being preferred. X-ray amorphous silicates of this type, which also have a delayed dissolution compared to normal water glass, are described, for example, in DE 4400024 A1. Compacted / densified amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.
[0112] Phosphates. Also commonly known phosphates can be added as builders, unless their use should be avoided for ecological reasons. Orthophosphates, pyrophosphates and especially sodium salts of tripolyphosphate are particularly suitable. Their content is generally 25% by weight, preferably 20% by weight or less, each based on the final composition. In some cases, especially already small amounts of tripolyphosphate, up to 10% by weight, based on the final composition, in combination with other builders leads to a synergistic improvement of the secondary detergency. The preferred amount of phosphate is especially less than 10% by weight. Cobuilder
[0113] Polycarboxylic acids. Useful organic cobuilders are polycarboxylic acids, which can be used in the form of sodium salts of polycarboxylic acids, and polycarboxylic acids are understood to be carboxylic acids with multiple acid functions.These include, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA) and their derivatives and their mixtures.Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and their mixtures.
[0114] organic acid. Acids themselves can also be used.In addition to their construction effect, acids also typically have the properties of acidifying components, and therefore also help to establish a relatively low and moderate pH in detergent or cleansing compositions.Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixture thereof are specifically mentioned in this regard.Furthermore suitable acidifying agents are known pH adjusters, such as sodium hydrogen carbonate and sodium hydrogen sulfate.
[0115] polymer. Particularly suitable polymeric cobuilders are polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Due to their good solubility, preferred representatives of this group are short-chain polyacrylates with a molecular weight of 2,000 to 10,000 g / mol, more particularly 3,000 to 5,000 g / mol. Suitable polymers may also include substances which consist partially or entirely of vinyl alcohol units or derivatives thereof.
[0116] Further suitable copolymeric polycarboxylates are in particular copolymers of acrylic acid and methacrylic acid, and of acrylic acid or methacrylic acid and maleic acid. Copolymers of acrylic acid and maleic acid with 50-90% by weight of acrylic acid and 50-10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight based on the free acid is generally in the range of 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, in particular 30,000 to 40,000 g / mol. The (co)polymeric polycarboxylates can be added as aqueous solutions or preferably as powders. To improve water solubility, the polymers can also contain allylsulfonic acid as monomer, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as in EP 0727448 B1.
[0117] Particularly preferred are biodegradable polymers which contain two or more different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, such as in DE 4300772 A1, or those which contain as monomers salts of acrylic acid and 2-alkylarylsulfonic acid and sugar derivatives.Further preferred copolymers are those described in DE 4303320 A1 and 4417734 A1, preferably containing acrolein and acrylic acid / acrylates or acrolein and vinyl acetate as monomers.
[0118] Likewise, other preferred builders are polymeric aminodicarboxylic acids, salts or precursors thereof. Particular preference is given to those polyaspartic acids or their salts and derivatives which are disclosed in DE 19540086 A1 as having a bleach stabilizing effect in addition to cobuilder properties.
[0119] Further suitable builders are the polyacetals which can be obtained by treating dialdehydes with polyol carboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups, as described in EP 0 280 223 A1. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde, and mixtures thereof, and polycarboxylic acids such as gluconic acid and / or glucoheptonic acid.
[0120] carbohydrates. Further suitable organic cobuilders are dextrins, oligomers or carbohydrate polymers obtainable by partial hydrolysis of starch. Hydrolysis can be carried out using typical processes, for example acid or enzyme catalyzed processes. The hydrolysis products preferably have an average molecular weight in the range of 400 to 500,000 g / mol. Polysaccharides with a dextrose equivalent (DE) of 0.5 to 40, more particularly 2 to 30, are preferred, DE being an accepted measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dried glucose syrups with a DE between 20 and 37 can be used, as well as so-called yellow dextrins and white dextrins of relatively high molecular weight between 2000 and 30,000 g / mol. Preferred dextrins are described in British Patent Application No. 94 19 091.
[0121] The oxidized derivatives of such dextrins refer to their reaction products with an oxidation composition capable of oxidizing at least one alcohol function of the saccharide ring to a carboxylic acid function. Such oxidized dextrins and methods for their preparation are known, for example, from EP 0 232 202 A1. Products oxidized at C6 of the saccharide ring may be particularly advantageous.
[0122] Other derivatives of oxydisuccinate and disuccinate, preferably ethylenediamine disuccinate, are also suitable cobuilders.Here, ethylenediamine-N,N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salt.In this context, glycerol disuccinate and glycerol trisuccinate are also particularly preferred, as described in US Pat. No. 4,524,009.The appropriate loading amount in zeolite-containing and / or silicate-containing formulations is in the range of 3 to 15% by weight.
[0123] Lactone. Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids and their salts, which may also be present in lactone form and contain at least 4 carbon atoms, at least one hydroxyl group and at most two acid groups. Such cobuilders are described, for example, in WO 95 / 20029 A1. Insect repellent
[0124] Furthermore, the composition may also contain ingredients (so-called soil release agents) that positively influence the removal of grease from the fibers during washing. This effect is particularly evident if the textile is soiled and has been washed several times previously with the detergent of the invention containing this grease-removing ingredient. Preferred grease-removing ingredients include, for example, non-ionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a content of 15 to 30% by weight of methoxy groups and 1 to 15% by weight of hydroxypropoxy groups, respectively, non-ionic cellulose ethers, as well as polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate, or modified derivatives thereof on anionic and / or nonionic basis. Of these, sulfonated derivatives of phthalic acid polymers and terephthalic acid polymers are particularly preferred. Inorganic salts
[0125] Further suitable components of the composition are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof. Alkaline carbonates and amorphous silicates are particularly used, mainly sodium silicates with a molar ratio Na2O:SiO2 of 1:1 to 1:4.5, preferably 1:2 to 1:3.5. Preferred compositions contain from 0.5 to 70% by weight, preferably from 0.5 to 50% by weight, of alkali salts, builders and / or cobuilders, preferably sodium carbonate, zeolite, crystalline layered sodium silicate and / or trisodium citrate, in particular from 0.5 to 30% by weight of anhydrous substances. Foam suppressor
[0126] It may be advantageous to add conventional foam inhibitors to the composition, especially when used in automatic cleaning processes. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin with a high content of C18-C24 fatty acids. Suitable non-surface-active type foam inhibitors are, for example, organopolysiloxanes and their mixtures with fine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisstearylethylenediamide. Mixtures of various foam inhibitors, for example mixtures of silicones, paraffins or waxes, are also advantageously used. Preferably, the foam inhibitors, in particular silicone-containing and / or paraffin-containing foam inhibitors, are loaded into a granular water-soluble or dispersible carrier material. In particular in this case, mixtures of paraffins and bisstearylethylenediamide are preferred. Sequestering Agents
[0127] The salts of polyphosphonic acids can be considered as sequestering agents or stabilizers, especially for peroxy compounds and enzymes that are sensitive to heavy metal ions, where, for example, the sodium salts of 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate are used in amounts of 0.1 to 5% by weight. Graying inhibitor
[0128] Graying inhibitors have the function of keeping the dirt removed from the fibers suspended in the wash liquor, thereby preventing the dirt from re-sedimenting. For this, mostly organic water-soluble colloids are suitable. For example, water-soluble salts of (co)polymeric carboxylic acids, adhesives, gelatin, salts of ether carboxylic or ether sulfonic acids of starch or cellulose, or salts of acidic sulfates of cellulose or starch. Water-soluble acid group-containing polyamides are also suitable for this purpose. In addition, soluble starch preparations and others, such as degraded starch, aldehyde starch, etc., can be used as the abovementioned starch products. Polyvinylpyrrolidone can also be used. However, preference is given to the use of cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose, as well as mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof. As polyvinylpyrrolidone, for example, based on the composition, it can be added in an amount of 0.1 to 5% by weight. Optical brighteners and UV absorbents
[0129] The composition may, for example, contain a derivative of diaminostilbene disulfonic acid or its alkali metal salt as an optical brightener. Suitable optical brighteners include, for example, salts of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or compounds of similar structure that contain diethanolamino, methylamino, anilino or 2-methoxyethylamino groups instead of morpholino groups. Substituted diphenylstyryl type brighteners may also be present, for example, alkali metal salts of 4,4'-bis(2-sulfostyryl)diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)diphenyl or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)diphenyl. Mixtures of the mentioned brighteners may also be used.
[0130] In addition, UV absorbers can be added. These are compounds with a clear absorption capacity against ultraviolet light, which not only act as UV stabilizers, but also improve the photostability of colorants and pigments, both in the textile and in the skin of the textile wearer, by protecting against UV radiation penetrating the fabric. In general, efficient radiationless inactivating compounds are derivatives of benzophenones, mainly substituted in the 2- and / or 4-positions with hydroxyl and / or alkoxy groups. Substituted benzotriazoles, as well as acrylates (cinnamic acid derivatives) substituted with phenyl in the 3-position, optionally with a cyano group in the 2-position, salicylates, organic Ni complexes, as well as natural substances such as umbelliferone and endogenous urocanic acid, are suitable. In a preferred embodiment, the UV absorbers absorb UV-A and UV-B radiation as well as possible UV-C radiation and re-emit light of blue wavelengths, so that they have an additional optical brightening effect. Preferred UV absorbers are triazine derivatives, such as hydroxyaryl-1,3,5-triazines, sulfonated 1,3,5-triazines, o-hydroxyphenyl-benzotriazoles and 2-aryl-2H-benzotriazoles, as well as bis(anilinotriazinyl-amino)stilbenedisulfonic acid and their derivatives. Ultraviolet absorbing pigments, such as titanium dioxide, can also be used as UV absorbers. Thickener
[0131] The compositions may also include common thickening and anti-deposition compositions, as well as viscosity modifiers such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized, and / or ethoxylated hexamethylenediamines, and any mixtures thereof. Preferred compositions have a viscosity of less than 10,000 mPa·s, measured with a Brookfield viscometer at a temperature of 20° C. and a shear rate of 50 min−1. Perfumes and colourants
[0132] The composition can include more typical detergent and cleansing composition components, such as fragrance and / or coloring agent, preferably coloring agent that leaves no or negligible coloring on the washed fabric.The total preferred amount of added coloring agent is less than 1% by weight, preferably less than 0.1% by weight, based on the composition.The composition can also include white pigment, such as TiO2. Food Composition
[0133] Another embodiment of the present invention covers food compositions comprising a processed amount of at least one acetophenone derivative or a mixture thereof with an additive, which may be present in an amount of about 0.01 to about 10% by weight, preferably about 0.05 to about 5% by weight, more preferably about 0.1 to about 1% by weight, calculated on the total composition.
[0134] Food compositions according to the invention are any preparations or compositions suitable for consumption and used for nutritional or recreational purposes, generally products intended to be introduced and remain in the oral cavity of humans or animals, where they are left for a certain period of time and then either eaten (e.g. ready-to-eat foods and foodstuffs, see also below) or removed again from the oral cavity (e.g. chewing gum). Such products include substances or products that are ingested by humans or animals in a treated, partially treated or untreated state. They also include substances that are added to orally consumable products during manufacture, preparation or treatment and that are intended to be introduced into the oral cavity of humans or animals.
[0135] Food compositions according to the invention also include substances that are swallowed and then digested by humans or animals in an unchanged, processed or prepared state. In this respect, orally consumable products according to the invention also include packaging, coatings or other encapsulations that are or can be expected to be swallowed at the same time. The expression "orally consumable products" encompasses ready-to-eat foods and foodstuffs, i.e. foods or foodstuffs that are already complete with respect to substances important for taste. The expressions "ready-to-eat foods" and "ready-to-eat foodstuffs" include beverages as well as solid or semi-solid ready-to-eat foods or foodstuffs. Examples that may be mentioned are frozen products, which must be thawed and heated to eating temperature before eating. Products such as yoghurt, ice cream, chewing gum and hard caramel are also included in ready-to-eat foods and foodstuffs.
[0136] Preferred food compositions according to the invention also include "semi-finished products". In the present context, semi-finished products are to be understood as orally consumable products, which, due to their high content of flavour and taste-imparting substances, are unsuitable for use as pre-prepared and ready-to-eat foods, eating orally ingestible products (particularly food or foodstuffs). By mixing with at least one additional ingredient (e.g. by reducing the concentration of the flavouring and taste-imparting substances in question), and optionally by additional process steps (e.g. heating, freezing), the semi-finished product is only transformed into a ready-to-eat product by eating an orally ingestible product (particularly food or foodstuff). Examples of semi-finished products that may be mentioned are:
[0137] The food composition according to the invention preferably comprises one or more preparations for nutritional or recreational purposes.These include, in particular, (low-calorie) baked goods (e.g. bread, dry biscuits, cakes and other baked goods), confectionery (e.g. chocolate, chocolate bars and other bar-shaped products, fruit gums, dragées, hard and soft caramels, chewing gum), non-alcoholic beverages (e.g. cocoa, coffee, green tea, black tea, tea drinks enriched with (green, black) tea extracts, rooibos tea, other herbal teas, soft drinks containing fruit, isotonic drinks, refreshing drinks, nectars, fruit and vegetable juices, fruit or vegetable juice preparations), instant drinks. instant drinks (e.g. instant cocoa drinks, instant tea drinks, instant coffee drinks), meat products (e.g. ham, fresh or raw sausage preparations, spiced or marinated raw or salted meat products), eggs or egg products (dried eggs, egg whites, egg yolks), cereal products (breakfast cereals, muesli bars, cooked ready-to-eat rice products, etc.), dairy products (e.g. full-fat or reduced-fat or non-fat milk drinks, rice pudding, yogurt, kefir, cream cheese, soft cheese, hard cheese, milk powder, whey, butter -, buttermilk, partially or fully hydrolyzed milk protein-containing products), products made from soy protein or other soy fractions (e.g. soy milk and products produced therefrom, beverages containing isolated or enzymatically treated soy protein, beverages containing soy flour, preparations containing soy lecithin, fermented products such as tofu or tempeh or products produced therefrom, as well as fruit preparations and mixtures with any flavours), preparations (e.g. jams, sorbets, fruit sauces, fruit fillings), vegetable preparations (e.g. ketchup, sauces, dried vegetables, frozen vegetables, cooked vegetables). , boiled vegetables), snack products (e.g. baked or fried potato crisps or potato dough), corn or groundnut based extrudates), fat and oil based products or emulsions thereof (e.g. mayonnaise, lemonades, dressings, in each case full fat or reduced fat), other ready-made dishes and soups (e.g. dry soups, instant soups, cooked soups), spices, spice mixtures, condiments used especially in the snack sector, sweetener preparations, tablets or sachets, other sweetening or whitening beverage conditioners and other food products.The preparations within the scope of the present invention can also be used in the form of semi-finished products for the manufacture of further preparations for nutritional or recreational purposes.The preparations within the scope of the present invention can also be in the form of capsules, tablets (uncoated and coated tablets, e.g. enteric coating), dragees, granules, pellets, solid mixtures, dispersions in liquid phases, emulsions.In the form of powders, solutions, pastes or other preparations that can be swallowed or chewed, and in the form of food supplements.
[0138] The preparations may also be in the form of capsules, tablets (uncoated and coated tablets, e.g. enteric coated), dragees, granules, pellets, solid mixtures, dispersions in liquid phases, emulsions, powder pellets, solutions, pastes, or other preparations that can be swallowed or chewed, e.g. food supplements.
[0139] Semi-finished products are generally used in the manufacture of ready-to-use or ready-to-eat preparations for nutritional or recreational purposes.
[0140] Further components of the ready-to-eat preparations or semi-finished products for nutritional or recreational purposes may be conventional base substances, auxiliary substances and additives for food or recreational foods, e.g. water, raw or professional mixtures, processed, vegetable or animal based or raw substances (e.g. raw, roasted, dried, fermented, smoked and / or boiled meat, bones, cartilage, fish, vegetables, herbs, nuts, vegetable juices, vegetable pastes or mixtures thereof), digestible or non-digestible carbohydrates (e.g. sucrose, maltose, fructose, malt ... sugar alcohols (e.g. sorbitol, erythritol), natural or hydrogenated fats (e.g. tallow, lard, palm fat, cocoa fat, hydrogenated vegetable fats), oils (e.g. sunflower oil, peanut oil, corn germ oil, olive oil, fish oil, soybean oil, sesame oil), fatty acids or their salts (e.g. potassium stearate), proteinaceous or non-proteinaceous amino acids and related compounds (e.g. -aminobutyric acid, taurine) ), peptides (e.g. glutathione), natural or processed proteins (e.g. gelatin), enzymes (e.g. peptidases), nucleic acids, nucleotides, unpleasant taste correctors - unpleasant taste impressions, more generally taste modifiers - not unpleasant taste impressions, other taste modulating substances (e.g. nucleotides such as inositol phosphate, guanosine monophosphate, adenosine monophosphate, or other substances such as sodium glutamate or 2-phenoxypropionic acid), emulsifiers (e.g. lecithin, diacylglycerol, gum arabic), stabilizers (e.g. glycerol, glycerol, glycerol), glycerols, ... Fixing agents (e.g. carrageenan, alginates), preservatives (e.g. benzoic acid and its salts, sorbic acid and its salts), antioxidants (e.g. tocopherol, ascorbic acid), chelating agents (e.g. citric acid), organic or inorganic acidifiers (e.g. acetic acid, phosphoric acid), additional bitter substances (e.g. quinine, caffeine, limonene, amarogentin, humulone, lupulone, catechol, tannins), substances preventing enzymatic browning (e.g. sulfite, ascorbic acid), essential oils, plant extracts, natural or synthetic colourings or colour pigments (e.g.The odorants may be selected from the group consisting of calcium iodate, flavonoids, anthocyanins, chlorophyll and derivatives thereof, spices, trigeminally active substances or plant extracts containing such trigeminally active substances, synthetic, natural or nature-identical flavors or odorants, and odor correctors.
[0141] The food composition according to the invention, for example in the form of a preparation or semi-finished product, preferably comprises a flavor composition for completing and refining the taste and / or odor. The preparation may comprise, as components, a solid carrier and a flavor composition. Suitable flavor compositions include, for example, synthetic, natural or nature-identical flavors, odorants and taste-imparting substances, reaction flavors, smoke flavors or other flavor-imparting preparations (e.g. protein (partial) hydrolysates, preferably protein (partial) hydrolysates with high arginine content, barbecue flavors, plant extracts, spices, spice preparations, vegetables and / or vegetable preparations, as well as suitable auxiliary substances and carriers. Particularly suitable here are roasted meats (in particular chicken, fish, seafood, beef, pork, lamb, mutton, goat), vegetables (in particular tomato, onion, garlic, celery, leek, mushrooms, aubergine, seaweed), condiments (in particular black and white pepper, cardamom, nutmeg, pimento, mustard, mustard products), fried, yeasty, boiled, fatty, salty and / or pungent flavor impressions and accordingly a spicy impression. The flavor composition generally comprises two or more of the abovementioned components.
[0142] The food composition of the present invention is preferably selected from the group comprising: Confectionery, preferably low-calorie or calorie-free confectionery, preferably Muesli bar products, fruit gums, dragees, hard caramel and chewing gum, Non-alcoholic drinks, preferably green tea, black tea, tea drinks enriched with tea extracts, rooibo tea, other herbal teas, soft drinks containing fruit and selected from the group of sugar-free, low-sugar or sugar-containing drinks, isotonic drinks, nectars, fruit and vegetable juices, fruit and vegetable juice preparations Instant drinks, preferably instant teas (green tea, black tea, rooibos, herbal) Cereal products: low-sugar and sugar-free breakfast cereals and muesli bars Dairy products. Preferably low-fat and non-fat milk, yogurt, kefir, whey, buttermilk, ice cream Products made from soy proteins or other soy fractions, preferably products made from soy milk, beverages containing isolated or enzymatically treated soy proteins, beverages containing soy flour, preparations containing soy lecithin, preparations containing soy lecithin, and mixtures with fruit preparations and optionally flavours, Sweetener preparations, tablets and sachets, Sugar-free dragees, Ice cream with or without milk derivatives, preferably unsweetened. Aroma or Fragrance Compounds
[0143] Aroma compounds and flavors (component d) well known in the art can be added to the flavor compositions of the present invention. These flavors can be selected from synthetic flavor liquids and / or oils derived from plant leaves, flowers, fruits, etc., and combinations thereof. Representative flavor liquids include artificial, natural, or synthetic fruit flavors such as eucalyptus, lemon, orange, banana, grape, lime, apricot, grapefruit oil, and fruit essences such as apple, strawberry, cherry, orange, pineapple, and the like. Coffee, cocoa, cola, flavors derived from beans and nuts such as peanut, almond, and flavors derived from roots such as licorice and ginger.
[0144] The flavouring agents are preferably selected from the group consisting of essential oils and extracts, tinctures and balsams, such as anisole, basil oil, bergamot oil, bitter almond oil, camphor oil, citronella oil, lemon oil, eucalyptus citriodora oil, eucalyptus oil, fennel oil, grapefruit oil, chamomile oil, spearmint oil, caraway oil, lime oil, mandarin oil, nutmeg oil (especially nutmeg blossom oil = mace oil, mace oil), mill oil, clove oil, clove blossom oil, orange oil, oregano oil, parsley (seed) oil, peppermint oil, rosemary oil, sage oil (clary sage, Dalmatian or Spanish sage oil), star anise oil, thyme oil, vanilla extract, juniper oil (especially juniper berry oil), wintergreen oil, cinnamon leaf oil; cinnamon bark oil, and fractions thereof or components isolated therefrom.
[0145] It is particularly advantageous if the flavour composition according to the invention comprises at least one flavouring agent, preferably 2, 3, 4, 5, 6, 7, 8 or more flavouring agents, selected from the following group: menthol (preferably l-menthol and / or racemic menthol), anethophol, anisole, anisaldehyde, anisyl alcohol, (racemic) neomenthol, eucalyptol (1,8-cineole), menthone (preferably L-menthone), isomenthone (preferably D-isomenthone), isopulegol, menthyl acetate (preferably L-menthol acetate), menthyl propionate, carvone (preferably (-)-carvone, optionally as a component of spearmint oil). (optionally as a component of wintergreen oil), methyl salicylate, eugenol acetate, isoeugenol methyl ether, beta homocyclocitral, eugenol, isobutyraldehyde, 3-octanol, dimethyl sulfide, hexanol, hexanal, trans-2-hexenal, cis-3-hexenol, 4-terpineol, piperitone, linalool, 8-ocimenyl acetate, isoamyl alcohol, isovaleraldehyde, alpha pinene, beta pinene, limonene ene (preferably D-limonene, optionally as a component of an essential oil), piperitone, trans-sabinene hydrate, menthofuran, caryophyllene, germacrene D, cinnamaldehyde, mint lactone, thymol, gamma-octalactone, gamma-nonalactone, gamma-decalactone, (1,3E,5Z)-undecatriene, 2-butanone, ethyl formate, 3-octyl acetate, isoamyl isovalerate, cis- and trans-carbyl acetate, p-cymol, dacarbazine, dacarbazine, dacarbazine-1, dacarbazine-2, dacarbazine-3, dacarbazine-4, dacarbazine-5, dacarbazine-6, dacarbazine-7, dacarbazine-8, dacarbazine-9, dacarbazine-11, dacarbazine-12, dacarbazine-13, dacarbazine-14, dacarbazine-15, dacarbazine-16, dacarbazine-17, dacarbazine-18, dacarbazine-19, dacarbazine-21, dacarbazine-22, dacarbazine-23, dacarbazine-24, dacarbazine-25, dacarbazine-25, dacarbazine-25, dacarbazine-25, dacarbazine-15, dacarbazine-16, dacarbazine-17, dacarbazine-18, dacarbazine-25, dacarbazine-19, dacarbazine-25, dacarbazine-19, dacarbazine-26, dacarbazine-27, dacarbazine-18, dacarbazine-28, dacarbazine-29, dacarbazine-30, dacarbazine-31, dacarbazine-32, dacarbazine-33, dacarbazine-34, dacarbazine-35, They are: macenone, damascone, cis-rose oxide, trans-rose oxide, fenchol, acetaldehyde diethyl acetal, 1-ethoxyethyl acetate, cis-4-heptenal, cis-jasmone, methyl dihydrojasmonate, 2'-hydroxypropiophenone, menthyl methyl ether, myrtenyl acetate, 2-phenylethyl alcohol, 2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, geraniol, nerol, and viridiflorol.
[0146] Particularly preferred aroma or flavoring compounds are menthol, cineole, eugenol, thymol, cinnamaldehyde, peppermint oil, spearmint oil, eucalyptus oil, thyme oil, cinnamon oil, clove oil, spruce needle oil, fennel oil, sage oil, anise oil, star anise oil, chamomile oil, caraway oil, and mixtures thereof. sweetener
[0147] The term "sweetener" in this specification means a substance having a relative sweetening power of at least 25, based on the sweetening power of sucrose, which has a sweetening power of 1. The sweeteners used in the orally consumable products (in particular food, feed or pharmaceuticals) according to the present invention (a) are preferably non-carcinogenic and / or have an energy content of less than or equal to 5 kcal per gram of the orally consumable product.
[0148] Advantageous sweeteners in the preferred food compositions according to the invention are selected from the following group:
[0149] Naturally occurring sweeteners, preferably selected from the group comprising: Miraculin, monellin, mabinlin, thaumatin, curculin, brazzein, pentaidine, D-phenylalanine, D-tryptophan and these amino acids and / or proteins, as well as the physiologically acceptable salts of these amino acids, extracts or fractions obtained from natural sources and / or proteins, in particular the sodium, potassium, calcium or ammonium salts. Neohesperidin dihydrochalcone, Naringin dihydrochalcone, Stevioside, Stevioside Bioside, Rebaudiosides, especially Rebaudioside A, Rebaudioside B, Rebaudioside C, Rebaudioside D, Rebaudioside E, Rebaudioside F, Rebaudioside G, Rebaudioside H, Dulcoside, Rubus, Sua Bioside G, suavioside H, suavioside I, suavioside J, baiyunoside 1, baiyunoside 2, phlomisoside 1, phlomisoside 2, phlomisoside 3 and phlomisoside 4, abrusoside A, abrusoside B, abrusoside C, abrusoside D, cyclocaryoside, osladin, polypodoside A, strogin 1, strogin 2, strogin 4, seligeain A, Dihydroquercetin 3-acetate, perillartine, telosmoside A15, periandrin IV, pterocaryosides, cyclocaryosides, mukuroziosides, trans-anethophor, trans-cinnamaldehyde, bryonodulcosides, carnosiflosides, scandenosides, gypenosides, trilobatin, phlorizin, dihydroflavanols, hematoxylin, cyanin, chlorogenic acid, albizia saponin, telosmosides, gaudiosides, mogrosides, mogroside V, hernandalusine, monatin, phyllodulcin, glycyrrhetinic acid and derivatives thereof, in particular their glycosides, such as glycyrrhizin, and physiologically acceptable salts of these compounds, in particular the sodium, potassium, calcium or ammonium salts. Extracts or concentrated fractions of extracts selected from the group including thaumatococcus extracts (katamfe plants), extracts from Stevia sp. (especially Stevia rebaudiana), swingle extracts (Momordica or Siratia grosvenorii, Monk fruit), extracts from Glycerrhyzia sp. (especially Glycerrhyzia glabra), extracts from Rubus genus (especially Rubus suavissimus), extracts of citrus fruits and extracts from Lippiadulcis.
[0150] Synthetic sweetener. Preferably, they are selected from the group comprising magap, sodium cyclamate or other physiologically acceptable salts of cyclamic acid, acesulfame K or other physiologically acceptable salts of aspartame, neotame dihydrochalcone, naringin dihydrochalcone, saccharin, sodium saccharin, aspartame, super aspartame, neotame, alitame, advantame, perillartine, sucralose, ragduname, carrelame, sucuronate and sucrooctate. Thickener
[0151] Advantageous thickeners in preferred orally consumable products (especially food, foodstuffs or medicaments) according to the invention are selected from the group comprising crosslinked polyacrylic acid and its derivatives, polysaccharides and their derivatives such as xanthan gum, agar, alginates or tyloses, cellulose derivatives such as carboxymethylcellulose or hydroxycarboxymethylcellulose, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrolidone.
[0152] According to the invention, preference is given to orally consumable products (in particular food or foodstuffs) comprising lactobacillus-thickened milk and / or lactobacillus-thickened cream, preferably selected from the group comprising yoghurt, kefir, quark.
[0153] The food composition according to the invention comprising milk thickened with lactic acid bacteria and / or cream thickened with lactic acid bacteria is advantageously an orally consumable product comprising probiotics, preferably selected from the group consisting of Bifidobacterium animalis subsp lactis BB-12, Bifidobacterium animalis subsp lactis DN-173010, Bifidobacterium animalis subsp lactis HN019, Lac-tobacillus acidophilus LA5, Lactobacillus acidophilus NCFM, Lactobacillus johnsonii La1, Lactobacillus casei immunitass / defensis, Lactobacillus casei Shirota (DSM 20312), Lactobacillus casei CRL431, Lactobacillus reuteri (ATCC 55730), and Lactobacillus rhamnosus (ATCC 55730). 53013). Chewing gum additives
[0154] Particular preference is given to orally consumable products (in particular food, foodstuffs or medicines) according to the invention which comprise chewing gum and a chewing gum base. The chewing gum base is preferably selected from the group comprising chewing gum or bubble gum bases, the latter being softer so that the gum bubbles can also be formed together. Preferred chewing gum bases according to the invention include, in addition to the traditionally used natural resins or natural latex chicles, elastomers such as vinyl acetate (PVA), polyethylene, (low or medium molecular weight) polyisobutene (PIB), polybutadiene, isobutene-isoprene copolymers (butyl rubber), polyvinyethylether (PVE), polyvinylbutylether, copolymers of vinyl esters and vinyl ethers, styrene-butadiene copolymers (styrene-butadiene rubber, SBR) or vinyl elastomers, e.g. vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate or ethylene / vinyl acetate, as well as mixtures of the mentioned elastomers, as described, for example, in EP 0 242 325, US Pat. No. 4,518,615, US Pat. No. 5,093,136, US Pat. No. 5,266,336, US Pat. No. 5,601,858, US Pat. No. 6,986,709. Furthermore, the chewing gum bases preferably used according to the invention comprise further ingredients such as, for example, (mineral) fillers, plasticizers, emulsifiers, antioxidants, waxes, and also fats or fatty oils, for example as hardened (hydrogenated) vegetable or animal fats, monoglycerides, diglycerides or triglycerides. Suitable (mineral) fillers are, for example, calcium carbonate, titanium dioxide, silicon dioxide, talcum, aluminum oxide, dicalcium phosphate, tricalcium phosphate, magnesium hydroxide, and mixtures thereof. Suitable plasticizers or agents for preventing adhesion (degreasing agents) are, for example, lanolin, stearic acid, sodium stearate, ethyl acetate, diacetin (glycerol diacetate), triacetin (glycerol triacetate), triethyl citrate. Suitable waxes are, for example, paraffin wax, candelilla wax, carnauba wax, microcrystalline wax, and polyethylene wax. Suitable emulsifiers are, for example, phosphatides such as lecithin, mono- and diglycerides of fatty acids, for example, glycerol monostearate.
[0155] The chewing gum according to the invention (particularly as disclosed above) may preferably contain different types of sugars, sugar substitutes, other sweet substances, sugar alcohols (particularly sorbitol, xylitol, mannitol), ingredients with a cooling effect, taste correctors for unpleasant taste impressions, further taste modulating substances (e.g. nucleotides such as inositol phosphate, guanosine monophosphate, adenosine monophosphate or other substances such as sodium glutamate or 2-phenoxypropionic acid), humic substances, thickeners, emulsifiers, stabilizers, odor correctors and flavours (e.g. eucalyptus-menthol, cherry, strawberry, grapefruit, vanilla, banana, citrus, peach, blackcurrant, tropical fruits, ginger, coffee, cinnamon, combinations (of the mentioned flavours) but also mint flavours such as spearmint and peppermint themselves). Above all, the combination of flavours with further substances having cooling, warming and / or appetising properties is of particular interest. How to Protect and Combat Body Odor
[0156] The acetophenone derivatives and the respective mixtures according to the invention show a synergistically enhanced antibacterial action against many gram-positive bacteria, gram-negative bacteria, moulds and yeasts, in particular, a potential for protection in the antibacterial treatment of many cosmetic preparations. They have a particularly good action against gram-positive bacteria such as Staphylococcus aureus, Staphylococcus epidermidis, Corynebacterium xerosis, Propionibacterium acnes, against gram-negative bacteria such as Escherichia coli and Pseudomonas aeruginosa, against yeasts such as Candida albicans, Malasseziafurfur, Globosa, and, as already mentioned, against fungi such as Aspergillus species. The very good activity of the mixtures according to the invention against Aspergillus species, a group of fungi that can only be combated in very difficult conditions, should be considered here as particularly advantageous.
[0157] Therefore, another object of the present invention relates to a method for preserving a personal care composition, a detergent composition or a food composition by adding an effective amount of a processing amount of at least one acetophenone derivative or a mixture thereof to a second preservative or antimicrobial agent.
[0158] Another object of the present invention refers to a method for combating microorganisms by adding an effective amount of at least one acetophenone derivative or a mixture thereof to a personal care, detergent or food composition with a second preservative or antimicrobial agent.
[0159] The present invention also encompasses the use of at least one acetophenone derivative or mixtures thereof as a preservative with a second preservative or antimicrobial agent, preferably at about 0.01 to about 10% by weight, preferably at about 0.05 to about 5% by weight, more preferably at about 0.1 to about 1% by weight, particularly for personal care, detergent or food compositions.
[0160] Another object of the present invention relates to a method for combating microorganisms by adding an effective amount of at least one acetophenone derivative or a mixture thereof with a second preservative or antimicrobial agent.
[0161] Acetophenone derivatives and mixtures thereof are particularly useful against microorganisms causing body odor, acne and / or mycoses. Advantageously, the preservative or preservative mixtures are applied to human skin in a concentration of 0.01 to about 10% by weight, preferably about 0.05 to about 5% by weight, more preferably about 0.1 to about 1% by weight, in each case based on the total weight of the cosmetic or pharmaceutical product constituting the mixture. Here, the synergistically active mixtures can be used (a) preventively or (b) as needed. The concentration of the amount of active compounds applied varies, for example, depending on daily variations, the physiological state of the subject and individual-specific parameters such as age and weight. The synergistically active mixtures according to the invention can be used on their own or in combination with further antibacterial active substances.
[0162] Another object of the present invention therefore encompasses the treatment of unpleasant body odor, in particular with a working amount of at least one acetophenone derivative or a mixture thereof with a second preservative or antibacterial agent on the skin.Finally, the present invention refers to the use of at least one acetophenone derivative or a mixture thereof with a second preservative or antibacterial agent as a deodorant.
[0163] It is understood that the above descriptions and preferred embodiments relating to acetophenone derivatives and mixtures thereof also apply mutatis mutandis to the claimed methods and uses, and therefore no further repetition is necessary. Working Example <Example 1>
[0164] The synergistic activity of 4-hydroxyacetophenone in combination with various secondary antibacterial agents against the microorganism A. braziliensis was determined. The Kull equation (notes 1 and 2) was used to calculate the synergistic effect between the compound of formula (I) and other antibacterial active substances. (I)SI=(Cmixture×PA) / CA+(Cmixture×PB) / CB, SI is the synergy index according to Kull (Notes 1 and 2). CA is the cell number of substance A. CB is the number of cells of substance B. Cmixture is the number of cells in the mixture of substance A and substance B. PA is the proportion of substance A in the mixture. PB is the proportion of substance B in the mixture. 1) Kull, FC, Eismann, PC, Sylvestrowicz, HD and RL Mayer (1961). Mixtures of quaternary ammonium compounds and long-chain fatty acids as antifungal agents. Applied Microbiology 9, 538-541. Note 2) Steinberg, DC (2000) Measuring synergy. Cosmetics & Toiletries 115(11), 59-62.
[0165] Antibacterial activity was assessed by determining the minimum inhibitory concentration (MIC), which represents the lowest concentration of a chemical that prevents visible growth of bacteria.
[0166] MIC values are determined by preparing solutions of increasing concentrations of a chemical in vitro, incubating the solutions with separate batches of cultured bacteria, and measuring the results using agar dilution or broth microdilution. Results are classified as susceptible (often called susceptible), intermediate, or resistant to a particular antibiotic using cut-off points. The cut-off points are agreed upon values and are published in guidelines from reference organizations such as the Clinical Laboratory Standards Institute (CLSI), the British Society for Antimicrobial Chemotherapy (BSAC), or the European Committee on Antimicrobial Susceptibility Testing (EUCAST). [Table 1]
[0167] The synergy index SI of the combination of 4-hydroxyacetophenone with a secondary active substance indicates a very strong synergistic effect between these two compounds. Formulation example
[0168] The present invention is further illustrated by the following examples. Unless otherwise indicated, reference to "substance of formula (I)" refers to 4-hydroxyacetophenone (compound of formula (Ic)). However, "substance of formula (I)" can be replaced with any other compound of formula (I). In particular, 4-hydroxyacetophenone can be replaced with 2-hydroxyacetophenone (compound of formula (Ia)) or 3-hydroxyacetophenone (compound of formula (Ib)). [Table 1A] [Table 1B] [Table 1C] [Table 1D] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9]
Table 10
Table 11
Table 12
Table 13
Table 14
Table 15
Table 16
Table 17
Table 18
Table 19
Table 20
Table 21
Table 22
Table 23
Table 24
Table 25
Table 26
Table 27
Table 28
Table 29
Table 30
Table 31
Table 32
Table 33
Table 34
Table 35
Table 36
Table 37
Table 38
Table 39
Table 40
Table 41
Table 42
Table 43
Table 44
[0169] Wet Cleansing Wipes A composition or mixture for neutralizing unpleasant odors and / or disinfecting with wet cleansing wipes is prepared by mixing the following ingredients to form a composition or mixture: 30% by weight of dipropylene glycol, 25% by weight of a substance of formula (I), 15% by weight isopropyl myristate, 15 weight percent triethyl citrate, and 15% by weight of benzyl benzoate. Using an emulsifier (Doracolin GOC), a 0.05% aqueous solution is produced from this composition and used to manufacture wet wipes. [Table 58A] [Table 58B] [Table 58C] [Table 58D] [Table 59] [Table 60] [Table 61] [Table 62] [Table 63] [Table 64] [Table 65] [Table 66] [Table 67]
Claims
1. 1. An antimicrobial mixture comprising: (a) a first antimicrobial agent selected from the group consisting of at least one acetophenone derivative of formula (I); 【Chemistry 1】 (I) R1 represents hydrogen or methyl; R2 represents hydrogen, hydroxyl, or an -OCH3 group, or a cosmetically or pharma- ceutically acceptable salt thereof; (b) at least one second antimicrobial agent selected from the group consisting of ethylenediaminetetraacetate (EDTA), capryloyl glycine, ethyl lauroyl arginate HCL, undecenoyl glycine, and mixtures thereof; 5. An antibacterial mixture comprising or consisting of:
2. The acetophenone derivative is selected from the group consisting of: 【Chemistry 2】 (Ia): 2-hydroxyacetophenone 【Chemistry 3】 (Ib): 3-hydroxyacetophenone 【Chemistry 4】 (Ic): 4-hydroxyacetophenone 2. The antimicrobial mixture of claim 1.
3. 3. The antimicrobial mixture of claim 1 or claim 2, wherein the first antimicrobial agent and the second antimicrobial agent are present in a weight ratio of about 1:99 to about 99:
1.
4. 4. The antimicrobial mixture of any one of claims 1 to 3, wherein the first antimicrobial agent is 4-hydroxyacetophenone.
5. 6. The antimicrobial mixture of claim 5, wherein the first and second antimicrobial agents are present in the weight ratios set forth in the table below. 【Table 1】
6. A personal care composition comprising an effective amount of the antimicrobial mixture of any one of claims 1 to 5.
7. A detergent composition comprising an effective amount of an antimicrobial mixture according to any one of claims 1 to 5.
8. A food composition comprising an effective amount of the antimicrobial mixture of any one of claims 1 to 5.
9. 9. The personal care composition of claim 6, the detergent composition of claim 7, or the food composition of claim 8, comprising the antimicrobial mixture of any one of claims 1 to 5 in an amount of from about 0.01 to about 10% by weight, calculated on the total composition.
10. 6. A method for preserving a personal care composition, a detergent composition, or a food composition by adding an effective amount of the mixture of any one of claims 1 to 5.
11. 6. A method of combating microorganisms by adding an effective amount of the mixture of any one of claims 1 to 5 to a personal care, detergent or food composition.
12. 6. A method of combating unwanted body odor by topically administering to human skin an effective amount of a mixture according to any one of claims 1 to 5.
13. 6. Use of an effective amount of a mixture according to any one of claims 1 to 5 as a preservative.
14. 14. Use according to claim 13, wherein the preservative is against Staphylococcus epidermidis, Corynebacterium xerosis, Brevibacterium epidermidis, Propionibacterium acnes, Trichophyton and Epidermophyton species.
15. Use of an effective amount of a mixture according to any one of claims 1 to 5 as a deodorant.
Citation Information
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