WO2022128057A1 - Medicament for prevention and treatment of collagen degradation in human connecting tissue - Google Patents

Medicament for prevention and treatment of collagen degradation in human connecting tissue Download PDF

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Publication number
WO2022128057A1
WO2022128057A1 PCT/EP2020/085972 EP2020085972W WO2022128057A1 WO 2022128057 A1 WO2022128057 A1 WO 2022128057A1 EP 2020085972 W EP2020085972 W EP 2020085972W WO 2022128057 A1 WO2022128057 A1 WO 2022128057A1
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peg
sodium
dimethicone
acid
acetate
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PCT/EP2020/085972
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French (fr)
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Uwe SCHAAR
Emilie Singer
Dominik Stuhlmann
Michael DOSSI
Marcus-Rudolf GÖTZ
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Symrise Ag
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Priority to PCT/EP2020/085972 priority Critical patent/WO2022128057A1/en
Publication of WO2022128057A1 publication Critical patent/WO2022128057A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/11—Aldehydes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
    • A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
    • A61K31/216—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids of acids having aromatic rings, e.g. benactizyne, clofibrate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/28—Asteraceae or Compositae (Aster or Sunflower family), e.g. chamomile, feverfew, yarrow or echinacea
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/53—Lamiaceae or Labiatae (Mint family), e.g. thyme, rosemary or lavender
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/54—Lauraceae (Laurel family), e.g. cinnamon or sassafras
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/75—Rutaceae (Rue family)
    • A61K36/752—Citrus, e.g. lime, orange or lemon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/74—Biological properties of particular ingredients
    • A61K2800/78—Enzyme modulators, e.g. Enzyme agonists
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations

Definitions

  • the present invention refers to the area of pharmaceutical compositions and relates to specific medicaments for preventing and/or treating degradation of macromolecules in human connecting tissue.
  • the connective tissue which consists of elastic and collagen fibres, normally sur- rounds supports and strengthens every organ of the body like a scaffold and connects the structures in the human body.
  • MMP1 to MMP23 matrix metalloproteases
  • the subgroup of collagenases plays an important role in this process, since they are the only native collagen that can cleave in its helical regions. Tissue collagenases cleave the collagen molecules through a single cut through the entire helix. The resulting fragments denature and can be broken down to the individual amino acids by non-specific proteases. It is well known that the expression of MMPs is regulated by a complex system of inductors (e.g.
  • IL-1 IL-1
  • PFGF PFGF
  • UVB-radiation TNF- ⁇
  • growth factors PFGF
  • suppressors or inhibitors e.g. retinoids, hepa- rin, TIMPs.
  • MMP inhibitors and down regulators are known as the following examples show:
  • WO 2012 157587 A1 (SHISEIDO) relates to a matrix metalloproteinase (MMP) inhibi- tor and/or laminin 5 production promoter, as well as an anti-wrinkle agent, each of which comprises 1 -piperidine propionate and/or a salt thereof.
  • MMP matrix metalloproteinase
  • US 6,455,569 B (UNIVERSITY MANCHESTER) proposes the use of Matrix Metallopro- teinase Inhibitors in the prevention or treatment of connective tissue softening and also for the maintenance of sutures in such connective tissues.
  • US 2002 119107 A refers to the selective inhibition of the enzyme (MMP-1), which causes the dermal matrix damage in humans, while sparing the en- zyme(s) (MMP-9 and perhaps MMP-2) which not only do not cause the damage (based on extrapolation from our in vitro collagen gel system to real skin) but actually "clear away" the damage produced by MMP-1 to restore normal function to the skin.
  • MMP-1 the selective inhibition of the enzyme
  • US 2002 164319 A (MOORFIELD HOSPITAL) concerns the use of an MMP inhibitor, especially a collagenase inhibitor, in the manufacture of a medicament for the treatment of a natural or artificial tissue comprising extracellular matrix components to inhibit contraction of the tissue and methods for the treatment of tissue comprising extracellular matrix compo- nents to inhibit contraction.
  • MMP inhibitor especially a collagenase inhibitor
  • MMP matrix metalloproteinase
  • MMP in- hibitors may be used in both cosmetic compositions and pharmaceutical compositions for application to skin.
  • MMP inhibitors are formulated with a cosmetically suitable vehicle or pharmaceutically acceptable excipient for application to the skin as creams, lotions, oint- ments, solutions, face masks, etc.
  • inventive MMP inhibitor compositions are applied to the skin to prevent or reduce the appearance of wrinkles, pigmentation changes, loss of elasticity, or other effects associated with aging or sun damage.
  • the inventive MMP inhibitor compositions may also be applied to the skin to treat or prevent a skin disease (e.g., proliferative disease, inflammatory disease)
  • US 2012 058140 A (BATH & BODY WORKS) concerns a topical composition for use in a skin care regimen that provides matrix metalloprotease (MMP) inhibiting activity, tissue inhibitor of metalloprotease (TIMP) inducing activity, and immediate and delayed antioxida- tive activity.
  • MMP matrix metalloprotease
  • TIMP tissue inhibitor of metalloprotease
  • the topical composition comprises at least one MMP inhibitor, a TIMP inducing agent, Tremella fuciformis (snow fungus) extract, Camellia sinensis (green tea) leaf extract, and Eugenia caryophyllus (clove) extract.
  • the compositions are useful in anti-wrinkle
  • SUBSTITUTE SHEET (RULE 26) and anti-aging products, providing elasticity, firmness, tone and texture to the skin, amelio- rating fine lines and preventing skin damage
  • a first object of the present invention refers to a agonists of olfactory receptors, par- ticularly OR2AT4, showing a molecular weight ranging from about 50 to about 300 Dalton, preferably from about 75 to about 250 Dalton and an evaporation rate versus butyl acetate of about 3 to about 15, preferably from about 5 to about 10, for use as a medicament for preventing or treating degradation of macromolecules, particularly collagen in human con- nective tissue by inhibition or reduction of MMP and/or TIMP expression.
  • Another advantage is that these molecules are already known as cosmetic additives, particularly as fragrances. They are easy to obtain and can be formulated into cosmetic or pharmaceutical preparations without problems.
  • Olfactory receptors also known as odorant receptors
  • ORs are expressed in the cell membranes of olfactory receptor neurons and are responsible for the detection of air-borne odour molecules that enter the nasal cavity.
  • Activated olfactory receptors trigger nerve im- pulses which transmit information about odour to the brain.
  • These receptors are members of the class A rhodopsin-like family of G protein-coupled receptors (G PC Rs).
  • G PC Rs G protein-coupled receptors
  • the olfactory re- ceptors form a multigene family consisting of around 800 genes in humans. Particularly, the human nose has roughly 400 types of scent receptors that can detect at least 1 trillion different odours.
  • olfactory receptors display affinity for a range of odour molecules, and conversely a single odorant molecule may bind to a number of ol- factory receptors with varying affinities, which depend on physio-chemical properties of mol- ecules like their molecular volumes. Once the odorant has bound to the odour receptor, the receptor undergoes structural changes and it binds and activates the olfactory-type G pro- tein on the inside of the olfactory receptor neuron.
  • the G protein (G oif and/or G s ) in turn acti- vates the lyase - adenylate cyclase - which converts ATP into cyclic AMP (cAMP).
  • the cAMP opens cyclic nucleotide-gated ion channels which allow calcium and sodium ions to enter into the cell, depolarizing the olfactory receptor neuron and beginning an action poten- tial which carries the information to the brain.
  • OR is the root name (Olfactory Receptor superfamily)
  • n an integer representing a family (e.g., 1 -56) whose members have greater than 40% sequence identity
  • OR1 A1 is the first isoform of subfamily A of olfactory receptor family.
  • An overview on olfactory receptors can be found in the following paper submitted by Gaillard I, Rouquier S, Giorgi: D "Olfactory receptors”. Cellular and Molecular Life Sciences. 61 (4): 456-69 (2004).
  • the evaporation rate is the rate at which a material will vaporize (evaporate, change from liquid to vapor) compared to the rate of vaporization of butyl acetate, which is set as 1. This quantity is a ratio, therefore it is unitless.
  • Suitable agonists according to the present invention are selected from the group con- sisting of:
  • the preferred agonists show an aldehyde, ketone, ester or terpene structure.
  • the agonists can be applied in a concentration of from 0.1 to 100 pg/ml, and prefera- bly of from 0.5 to 10 pg/ml.
  • Another object of the present invention refers to a cosmetic or pharmaceutical com- position comprising the agonists as defined above, preferably in amounts of from 0.0001 to about 1 wt. -percent, more preferably from about 0.001 to about 0.1 wt.-percent and most preferred from about 0.02 to 0.05 wt.-percent.
  • compositions may represent a lotion, a cream, an emulsion, an ointment or any other form for topical application on skin.
  • compositions may comprise a cosmetically or phar- maceutically acceptable carrier or solvent, such as for example water, ethanol, isopropyl alco- hol, butanol, glycerol, ethylene glycol, propylene glycol and diethylene glycol or mixtures thereof.
  • the carriers may be present in quantities of 99 wt.-percent, preferably 99.9 wt.- percent or more.
  • compositions may comprise at least one bio- genic agent or antioxidant.
  • Biogenic active substances include, for example, tocopherol, to- copherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and its frag- mentation products, ⁇ -glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as such as prunus extract, bambaranus extract and vitamin complexes.
  • Antioxidants interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin.
  • Typical examples are amino acids (e.g. glycine, histidine, tyro- sine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives,
  • SUBSTITUTE SHEET (RULE 26) peptides like D,L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. -carotene, lycopene) and their derivates, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g. dihydrolic acid), aurothioglucose, propylthiou- racil and other thiols (e.g.
  • thioredoxin glutathione, cysteine, cystine, cystamin and their gly- cosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, linoleyl, choles- teryl and glyceryl esters) and their salts
  • Dilaurylthiodipropionate, ditearylthiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleo- sides and salts) as well as sulfoximine compounds e.g. (e.g.
  • buthionine sulfoximines in very low tolerated dosages (e.g. pmol to mol/kg), furthermore (metal) chelators (e.g. hydroxy fatty acids, palmitic acid, phytinic acid, lactoferrin), hydroxy acids (e.g. (e.g. (e.g.
  • citric acid citric acid, lactic acid, malic acid
  • humic acid gallic acid
  • bile extracts bilirubin, biliverdin, EDTA, EGTA and their derivatives
  • unsaturated fatty acids and their derivatives e.g. linolenic acid, linoleic acid, oleic acid
  • folic acid and its derivatives ubiquinone and ubiquinol and their derivatives
  • vitamin C and its derivatives e.g. ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbylacetate
  • tocoph- erols and derivatives e.g.
  • vitamin E acetate
  • vitamin A and derivates vitamin A palmitate
  • conifer aryl benzoate of benzoic resin rutinic acid and its derivatives, glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butylhydroxyanisole, nor- dihydroguaiac resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (e.g. e.g. ZnO, ZnSO4) selenium and its derivatives (e.g. selenium-methionine), stilbenes and their derivatives (e.g. styrene oxide, trans-stilbene oxide) and the derivatives suitable for the invention (salts, esters, ethers, sugars
  • agonists according to the present invention are incorporated in or deliv- ered to human skin by means of a cosmetic or pharmaceutical composition, these may con- tain further additives which are typical for skin care applications, as for example:
  • auxiliaries and additives are anionic and/or amphoteric or zwitterionic sur- factants.
  • Non-ionic and cationic surfactants can be also present in the composition. Suitable examples are mentioned along with the paragraph dealing with emulsifiers.
  • Typical examples for anionic and zwitterionic surfactants encompass: Almondami- dopropylamine Oxide, Almondamidopropyl Betaine, Aminopropyl Laurylglutamine, Ammoni- um C12-15 Alkyl Sulfate, Ammonium C12-16 Alkyl Sulfate, Ammonium Capryleth Sulfate, Ammonium Cocomonoglyceride Sulfate, Ammonium Coco-Sulfate, Ammonium Cocoyl Isethionate, Ammonium Cocoyl Sarcosinate, Ammonium C12-15 Pareth Sulfate, Ammonium
  • SUBSTITUTE SHEET (RULE 26) C9-10 Perfluoroalkylsulfonate, Ammonium Dinonyl Sulfosuccinate, Ammonium Dodecylben- zenesulfonate, Ammonium Isostearate, Ammonium Laureth-6 Carboxylate, Ammonium Lau- reth-8 Carboxylate, Ammonium Laureth Sulfate, Ammonium Laureth-5 Sulfate, Ammonium Laureth-7 Sulfate, Ammonium Laureth-9 Sulfate, Ammonium Laureth-12 Sulfate, Ammonium Lauroyl Sarcosinate, Ammonium Lauryl Sulfate, Ammonium Lauryl Sulfosuccinate, Ammoni- um Myreth Sulfate, Ammonium Myristyl Sulfate, Ammonium Nonoxynol-4 Sulfate, Ammoni- um Nonoxynol-30 Sulfate, Ammonium Oleate, Ammoni
  • SUBSTITUTE SHEET (RULE 26) um Chloride, Coco- Hydroxysultaine, Coco-Morpholine Oxide, coconut Acid, Coconut Oil Glycereth-8 Esters, Coco/Oleamidopropyl Betaine, Coco-Sultaine, Co- co/Sunfloweramidopropyl Betaine, Cocoylcholine Methosulfate, Cocoyl Glutamic Acid, Cocoyl Hydrolyzed Collagen, Cocoyl Hydrolyzed Keratin, Cocoyl Hydrolyzed Oat Protein, Cocoyl Hy- drolyzed Rice Protein, Cocoyl Hydrolyzed Silk, Cocoyl Hydrolyzed Soy Protein, Cocoyl Hydro- lyzed Wheat Protein, Cocoyl Sarcosine, Corn Acid, Cottonseed Acid, Cottonseed Oil Glycer- eth-8 Esters, C10-16 Pareth-1, CIO-16 Pareth-2, C11 -13 Pareth-6, Cl 1-13 Pareth-9, C11 -13 Pareth-10, C
  • SUBSTITUTE SHEET (RULE 26) Sulfosuccinate, Disodium Cocamido MIPA PEG-4 Sulfosuccinate, Disodium Cocamido MIPA- Sulfosuccinate, Disodium Cocamido PEG-3 Sulfosuccinate, Disodium Coceth-3 Sulfosuccin- ate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiace- tate, Disodium Cocoamphodipropionate, Disodium Coco-Glucoside Sulfosuccinate, Disodi- um Coco-Sulfosuccinate, Disodium Cocoyl Butyl Gluceth-10 Sulfosuccinate, Disodium Cocoyl Glutamate, Disodium C12-14 Pareth-1 Sulfosuccinate, Disodium C12-14 Pareth-2 Sulfosuc- cinate, Disodium C12-15 Pareth Sulf
  • SUBSTITUTE SHEET (RULE 26) Myristoyl Sarcosinate, Sodium Myristyl Sulfate, Sodium Nonoxynol-6 Phosphate, Sodium Nonoxynol-9 Phosphate, Sodium Nonoxynol-1 Sulfate, Sodium Nonoxynol-3 Sulfate, Sodium Nonoxynol-4 Sulfate, Sodium Nonoxynol-6 Sulfate, Sodium Nonoxynol-8 Sulfate, Sodium Nonoxynol-10 Sulfate, Sodium Nonoxynol-25 Sulfate, Sodium Octoxynol-2 Ethane Sulfonate, Sodium Octoxynol-2 Sulfate, Sodium Octoxynol-6 Sulfate, Sodium Octoxynol-9 Sulfate, Sodi- um Oleate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate
  • SUBSTITUTE SHEET (RULE 26) Glycine, Undecylenoyl Hydrolyzed Collagen, Undecylenoyl Wheat Amino Acids, Undecyl Glu- coside, Wheat Germ Acid, Wheat Germamidopropylamine Oxide, Wheat Germamidopropyl Betaine, Yucca Schidigera Leaf/Root/Stem Extract, Yucca Schidigera Stem Extract, Zinc Coceth Sulfatea and Zinc Coco-Sulfate.
  • the percentage content of surfactants in the preparations may be from 0.1 to 10% by weight and is preferably from 0.5 to 5% by weight, based on the preparation.
  • Suitable oil bodies which form constituents of the O/W emulsions, are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C 6 -C 22 -fatty acids with linear or branched C 6 -C 22 -fatty alcohols or esters of branched C 6 -C 13 -carboxylic acids with linear or branched C 6 -C 22 -fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, ce- tyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate,
  • esters of linear C 6 -C 22 -fatty acids with branched alcohols in particular 2-ethylhexanol
  • esters of C 18 -C 38 - alkylhydroxy carboxylic acids with linear or branched C 6 -C 22 -fatty alcohols in particular Dioctyl Malate
  • esters of linear and/or branched fatty acids with polyhydric alcohols such as, for example, propylene glycol, dimerdiol or trimertriol
  • Guerbet alcohols triglycerides based on C 6 -C 10 -fatty acids, liquid mono-/di-/triglyceride mixtures based on C 6 -C 18 -fatty acids
  • esters of C 6 - C 22 -fatty al- cohols and/or Guerbet alcohols with aromatic carboxylic acids in particular benzoic acid, es- ters of C 2 - C 12 -dicarboxylic acids with linear or branched
  • Finsolv ® TN linear or branched, sym- metrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol ® OE), ring-opening products of epoxidized fatty acid
  • silicone oils cyclomethicones, silicone methicone grades, etc.
  • aliphatic or naphthenic hydrocarbons such as, for example, squalane, squalene or dialkylcy- clohexanes.
  • non-ionic or cationic surfactants may also be added to the preparations as emulsifiers, including for example:
  • polyol esters and, in particular, polyglycerol esters such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate isos- tearate. Mixtures of compounds from several of these classes are also suitable;
  • 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 monoglycer- ide, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyc- eride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quantities
  • Sorbitan esters are sorbitan monoisostearate, sorbitan ses- quiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquieru- cate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricino- leate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan tri hydroxystea rate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritart
  • Polyglycerol esters are Polyglyceryl- 2 Dipolyhydroxystearate (Dehymuls ® PGPH), Polyglycerin-3-Diisostearate (Lameform ® TGI), Polyglyceryl-4 Isostearate (Isolan ® Gl 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan ® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care ® 450), Poly- glyceryl-3 Beeswax (Cera Beilina ® ), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane ® NL), Polyglyceryl-3 Distearate (Cremophor ® GS 32) and Polyglyceryl Polyric
  • SUBSTITUTE SHEET (RULE 26) mitic acid, stearic acid, oleic acid, behenic acid and the like optionally reacted with 1 to 30 mol ethylene oxide.
  • Tetraalkyl ammonium salts comprise the hydrophobic high molecular group required for the surface activity in the cation by dissociation in aqueous solution.
  • a group of important representatives of the cationic surfactants are the tetraalkyl ammonium salts of the general formula: (R 1 R 2 R 3 R 4 N + ) X-.
  • R1 stands for C 1 -C 8 alk(en)yl, R 2 , R 3 and R 4 , independently of each other, for alk(en)yl radicals having 1 to 22 carbon atoms.
  • X is a counter ion, preferably selected from the group of the halides, alkyl sulfates and alkyl carbonates.
  • Cationic surfactants in which the nitrogen group is substituted with two long acyl groups and two short alk(en)yl groups, are particularly preferred.
  • Esterquats A further class of cationic surfactants particularly useful as co-surfactants for the present invention is represented by the so-called esterquats.
  • Esterquats are generally understood to be quaternised fatty acid triethanolamine ester salts. These are known compounds which can be obtained by the relevant methods of preparative organic chemistry. Reference is made in this connection to International patent application WO 91/01295 A1, according to which triethanolamine is partly esterified with fatty acids in the presence of hypophosphorous acid, air is passed through the reaction mixture and the whole is then quaternised with dimethyl sulphate or ethylene oxide.
  • German patent DE 4308794 C1 describes a process for the production of solid esterquats in which the quaternisation of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.
  • esterquats suitable for use in accordance with the invention are products of which the acyl component derives from monocarboxylic acids corresponding to formula RCOOH in which RCO is an acyl group containing 6 to 10 carbon atoms, and the amine component is triethanolamine (TEA).
  • monocarboxylic acids are caproic acid, caprylic acid, capric acid and technical mixtures thereof such as, for example, so- called head-fractionated fatty acid.
  • Esterquats of which the acyl component derives from monocarboxylic acids containing 8 to 10 carbon atoms are preferably used.
  • esterquats are those of which the acyl component derives from dicarboxylic acids like 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.
  • esterquats of which the acyl component derives from mixtures of monocarboxylic acids containing 6 to 22 carbon atoms, and adipic acid are preferably used.
  • the molar ratio of mono and dicarboxylic acids in the final esterquat may be in the range from 1 :99 to 99:1 and is preferably in the range from 50:50 to 90:10 and more particularly in the range from 70:30 to 80:20.
  • other suitable esterquats are quaternized ester salts of mono-/dicarboxylic acid mixtures with diethanolalkyamines or 1,2- dihydroxypropyl dialkylamines.
  • the esterquats may be obtained both from fatty acids and
  • SUBSTITUTE SHEET (RULE 26) from the corresponding triglycerides in admixture with the corresponding dicarboxylic acids.
  • One such process which is intended to be representative of the relevant prior art, is proposed in European patent EP 0750606 B1.
  • the mixtures of mono- and dicarboxylic acids and the triethanolamine - based on the available carboxyl functions - may be used in a molar ratio of 1.1 :1 to 3:1.
  • a ratio of 1.2:1 to 2.2:1 and preferably 1.5:1 to 1.9:1 has proved to be particularly advantageous.
  • the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9.
  • Superfatting agents may be selected from such substances as, for example, lanolin and lecithin and also polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the fatty acid alkanolamides also serving as foam stabilizers.
  • the consistency factors mainly used are fatty alcohols or hydroxyfatty alcohols con- taining 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxyfatty acids.
  • a combination of these substances with alkyl oligoglucosides and/or fatty acid N-methyl glucamides of the same chain length and/or polyglycerol poly-12- hydroxystea rates is preferably used.
  • Suitable thickeners are polymeric thickeners, such as Aerosil ® types (hydrophilic sili- cas), polysaccharides, more especially xanthan gum, guar-guar, agar-agar, alginates and tylo- ses, carboxymethyl cellulose and hydroxyethyl cellulose, also relatively high molecular weight polyethylene glycol monoesters and diesters of fatty acids, polyacrylates (for example Carbo- pols ® [Goodrich] or Synthalens ® [Sigma]), polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, for example pentaerythritol or trimethylol propane, narrow-range fatty alcohol ethoxylates and electrolytes, such as sodium chloride and ammonium chloride.
  • Aerosil ® types hydrophilic
  • Suitable cationic polymers are, for example, cationic cellulose derivatives such as, for example, the quaternized hydroxyethyl cellulose obtainable from Amerchol under the name of Polymer JR 400 ® , cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone/vinyl imidazole 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,
  • cationic cellulose derivatives such as, for example, the quaternized hydroxyethyl cellulose obtainable from Amerchol under the name of Polymer JR 400 ® , cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrroli
  • quaternized wheat polypeptides polyethyleneimine
  • cationic silicone polymers such as, for example, amodimethicone, copolymers of adipic acid and dimethylaminohy- droxypropyl diethylenetriamine (Carta retine ® , Sandoz), copolymers of acrylic acid with dime- thyl diallyl ammonium chloride (Merquat ® 550, Chemviron), polyaminopolyamides and cross- linked water-soluble polymers thereof, cationic chitin derivatives such as, for example, quaternized chitosan, optionally in microcrystalline distribution, condensation products of dihaloalkyls, for example dibromobutane, with bis-dialkylamines, for example bis- dimethylamino-1,3-propane, cationic guar gum such as, for example, Jaguar ® CBS, Jaguar ® C-
  • Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl ace- tate/butyl maleate/isobornyl acrylate copolymers, methyl vinylether/maleic anhydride copol- ymers and esters thereof, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamido- propyl trimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacry- late/tert.-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, vinyl pyrroli- done/dimethylaminoethyl methacrylate/vinyl
  • Suitable pearlising waxes are, for example, alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially cocofatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polybasic, optionally hydroxy- substituted carboxylic acids with fatty alcohols containing 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; fatty compounds, such as for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates which contain in all at least 24 carbon atoms, especially laurone and distea rylether; fatty acids, such as stearic acid, hy- droxystearic 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 con-
  • Suitable silicones can be chosen from the group consisting of: Acefylline Methylsilanol Mannuronate, Acetylmethionyl Methylsilanol Elastinate Acrylates/Behenyl, Acry- late/Dimethicone Methacrylate Copolymer, Acrylates/Behenyl Methacrylate/Dimethicone
  • Butyloxyamodimethicone/PEG-60 Copolymer Bis(C13-15 Alkoxy) Hydroxybutamidoamodi- methicone, Bis(C13-15 Alkoxy) PG- Amodimethicone, Bis-(C1 -8 Alkyl Lauroyl Lysine Decyl- carboxamide) Dimethicone, Bis-Cetyl Cetyl Dimethicone, Bis-Cetyl/PEG-8 Cetyl PEG-8 Dime- thicone, Bis-Diphenylethyl Disiloxane, Bis-Ethyl Ethyl Methicone, Bis- Gluconamidoethylaminopropyl Dimethicone, Bis-Hydrogen Dimethicone, Bis- Hydroxyethox- ypropyl Dimethicone Bis-Hydroxylauryl, Dimethicone/IPDI Copolymer, Bis- Hydroxy/Methoxy Amodime
  • SUBSTITUTE SHEET (RULE 26) Butyl Dimethyl Silyl Grape Seed Extract, Butyl Polydimethylsiloxyl Eth- ylene/Propylene/Vinylnorbornene Copolymer, C6-8 Alkyl C3-6 Alkyl Glucoside Dimethicone, C20-24 Alkyl Dimethicone, C24-28 Alkyl Dimethicone, C26-28 Alkyl Dimethicone, C30-45 Al- kyl Dimethicone, C30-60 Alkyl Dimethicone, C32 Alkyl Dimethicone, C30-45 Alkyl Dimethi- cone/Polycyclohexene Oxide Crosspolymer, C26-28 Alkyldimethylsilyl Polypropylsilsesquiox- ane, C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane, C20-24 Alkyl Methicone, C24-28
  • SUBSTITUTE SHEET (RULE 26) 8, Silicone Quaternium-9, Silicone Quaternium-10, Silicone Quaternium-11, Silicone Quater- nium-12, Silicone Quaternium-15, SiliconeQuaternium-16, Silicone Quaternium-16/Glycidoxy Dimethicone Crosspolymer, Silicone Quaternium-17, Silicone Quaternium- 18, Silicone Qua- ternium-19, Silicone Quaternium-20, Silicone Quaternium-21, Silicone Quaternium- 22, Sili- cone Quaternium-24, Silicone Quaternium-25, Siloxanetriol Alginate, Siloxanetriol Phytate, Simethicone, Sodium Carboxydecyl PEG-8 Dimethicone, Sodium Dimethicone PEG-7 Acetyl Methyltaurate, Sodium Hyaluronate Dimethylsilanol, Sodium Lactate Methylsilanol, Sodium Mannuronate Me
  • silicones to be contained in the mixture according to the inven- tions are Dimethicone, Cyclomethicone, Phenyl Trimethicone, Cyclohexasiloxane and Cyclo- pentasiloxane.
  • Dimethicone, Cyclomethicone, Phenyl Trimethicone, Cyclohexasiloxane and Cyclo- pentasiloxane are Dimethicone, Cyclomethicone, Phenyl Trimethicone, Cyclohexasiloxane and Cyclo- pentasiloxane.
  • suitable volatile silicones can be found in Todd et al. in Cosm. Toil. 91. 27 (1976).
  • waxes may also be present in the preparations, more espe- cially natural waxes such as, for example, candelilla wax, carnauba wax, Japan wax, espar- tograss wax, cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffin waxes and microwaxes; chemically modified waxes (hard waxes) such as, for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxes and syn- thetic waxes such as, for example, polyalkylene waxes and polyethylene glycol waxes.
  • candelilla wax carnauba wax, Japan wax, espar- tograss wax, cork wax, guaruma wax, rice oil
  • Metal salts of fatty acids such as, for example, magnesium, aluminium and/or zinc stearate or ricinoleate may be used as stabilizers.
  • Primary sun protection factors in the context of the invention are, for example, organ- ic substances (light filters) which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet radiation and of releasing the energy absorbed in the form of longer-wave radiation, for example heat.
  • organ- ic substances light filters
  • light filters which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet radiation and of releasing the energy absorbed in the form of longer-wave radiation, for example heat.
  • the formulations according to the invention advantageously contain 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.
  • Formulations according to the invention preferably contain at least one UV-B filter or a broadband filter, more particularly preferably at least one UV-A filter and at least one UV-B filter.
  • Preferred cosmetic compositions preferably topical formulations according to the present invention comprise one, two, three or more sun protection factors selected from the group consistiung of 4-aminobenzoic acid and derivatives, salicylic acid derivatives, benzo- phenone derivatives, dibenzoylmethane derivatives, diphenyl acrylates, 3-imidazol-4-yl acryl- ic acid and esters thereof, benzofuran derivatives, benzylidene malonate derivatives, poly- meric UV absorbers containing one or more organosilicon radicals, cinnamic acid derivatives, camphor derivatives, trianilino-s-triazine derivatives, 2-hydroxyphenylbenzotriazole deriva- tives, phenylbenzimidazole sulfonic acid derivatives and salts thereof, anthranilic acid menthyl esters, benzotriazole derivativesand indole derivatives.
  • sun protection factors selected from the group consistiung of 4-amin
  • SUBSTITUTE SHEET (RULE 26) light-induced damage and reduce the level of cutaneous matrix metalloproteases.
  • Preferred respective ingredients, so called arylhydrocarbon receptor antagonists, are described in WO 2007/128723, incorporated herein by reference.
  • Preferred is 2-benzylidene-5,6-dimethoxy- 3,3-dimethylindan-1 -one.
  • UV filters cited below which can be used within the context of the present inven- tion are preferred but naturally are not limiting.
  • UV filters which are preferably used are selected from the group consisting of
  • Broadband filters which are preferably combined with one or more compounds of formula (I) in a preparation according to the present invention are selected from the group consisting of
  • compositions can comprise further typical detergent and cleansing composition ingredients such as UV-A filters filters which are preferably combined with one or more com- pounds of formula (I) in a preparation according to the present invention are selected from the group consisting of
  • compositions can comprise further typical detergent and cleansing composition ingredients such as UV filters which are more preferably combined with one or more com- pounds of formula (I) in a preparation according to the present invention are selected from the group consisting of
  • menthyl anthranilate (Neo Heliopan ® MA)
  • compositions 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 such as are conventionally used for sun protection prepara-
  • SUBSTITUTE SHEET (RULE 26) tions.
  • they may be in form of a solution, an emulsion of the water-in-oil type (W/O) or of the oil-in-water type (O/W) or a multiple emulsion, for example of the water-in-oil-in- water type (W/O/W), a gel, a hydrodispersion, a solid stick or else an aerosol.
  • a formulation according to the invention contains a total amount of sunscreen agents, i.e. in particular UV filters and/or inorganic pigments (UV filtering pigments) so that the formulation according to the invention has a light protection factor of greater than or equal to 2 (preferably greater than or equal to 5).
  • sunscreen agents i.e. in particular UV filters and/or inorganic pigments (UV filtering pigments) so that the formulation according to the invention has a light protection factor of greater than or equal to 2 (preferably greater than or equal to 5).
  • UV filters and/or inorganic pigments UV filtering pigments
  • Secondary sun protection factors of the antioxidant type interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin.
  • Typical examples are amino acids (for example glycine, histidine, tyrosine, tryptophane) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (for example anserine), carotinoids, carotenes (for example alpha- carotene, beta-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, liponic acid and derivatives thereof (for example dihydroliponic acid), aurothioglu- cose, propylthiouracil and other thiols (for example thioredoxine, glutathione, cysteine,
  • amino acids for example glycine, histidine, tyrosine, tryptophane
  • SUBSTITUTE SHEET (RULE 26) pie stilbene oxide, trans-stilbene oxide) and derivatives of these active substances suitable for the purposes of the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids).
  • Advantageous inorganic secondary light protection pigments are finely dispersed metal oxides and metal salts which are also mentioned in WO 2005 123101 A1.
  • the total quantity of inorganic pigments, in particular hydrophobic inorganic micro-pigments in the finished cosmetic preparation according to the present invention is advantageously from 0.1 to 30% by weight, preferably 0.5 to 10.0% by weight, in each case based on the total weight of the preparation.
  • particulate UV filters or inorganic pigments which can optionally be hydrophobed, can be used, such as the oxides of titanium (TiO 2 ), zinc (ZnO), iron (Fe 2 O 3 ), zirconium (ZrO 2 ), silicon (SiO 2 ), manganese (e.g. MnO), aluminium (AI 2 O 3 ), cerium (e.g. Ce 2 O 3 ) and/or mixtures thereof.
  • Suitable anti-inflammatory agent encompass in particular steroidal substances of the corticosteroid type selected from the group consisting of hydrocortisone, dexamethasone, dexamethasone phosphate, methyl prednisolone or cortisone, are advantageously used as anti-inflammatory active ingredients or active ingredients to relieve reddening and itching, the list of which can be extended by the addition of other steroidal anti-inflammatories.
  • Non- steroidal anti-inflammatories can also be used. More particularly:
  • steroidal anti-inflammatory substances of the corticosteroid type in particular hydro- cortisone, hydrocortisone derivatives such as hydrocortisone 17-butyrate, dexame- thasone, dexamethasone phosphate, methylprednisolone or cortisone,
  • non-steroidal anti-inflammatory substances in particular oxicams such as piroxicam or tenoxicam, salicylates such as aspirin, disalcid, solprin or fendosal, acetic acid deriv- atives such as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or clindanac, fenamates such as mefenamic, meclofenamic, flufenamic or niflumic, propionic acid derivatives such as ibuprofen, naproxen or benoxaprofen, pyrazoles such as phenyl- butazone, oxyphenylbutazone, febrazone or azapropazone,
  • oxicams such as piroxicam or tenoxicam
  • salicylates such as aspirin, disalcid, solprin or fendosal
  • acetic acid deriv- atives such as diclofenac,
  • histamine receptor antagonists include serine protease inhibitors (e.g. of Soy extracts), TRPV1 antagonists (e.g. 4-t-Butylcyclohexanol), NK1 antagonists (e.g. Aprepitant, Hydroxy-
  • SUBSTITUTE SHEET (RULE 26) phenyl Propamidobenzoic Acid), cannabinoid receptor agonists (e.g. Palmitoyl Ethan- olamine) and TRPV3 antagonists.
  • oxicams such as piroxicam or tenoxicam
  • salicy- lates such as aspirin, disalcid, solprin or fendosal
  • acetic acid derivatives such as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or clindanac
  • fenamates such as mefenamic, meclofenamic, flufenamic or niflumic
  • propionic acid derivatives such as ibuprofen, naproxen, benoxaprofen or pyrazoles such as phenylbutazone, oxyphenylbutazone, febrazone or azapropazone.
  • Anthranilic acid derivatives in particular avenanthramides described in WO 2004 047833 A1, are also preferred in a composition according to the present invention.
  • bisabolol when used in the context of the present invention it can be of natural or synthetic origin, and is preferably "alpha-bisabolol".
  • the bisabolol used is syn- thetically prepared or natural (-)-alpha-bisabolol and/or synthetic mixed-isomer alpha- bisabolol.
  • natural (-)-alpha-bisabolol is used, this can also be employed as a constituent of an essential oil or of a plant extract or of a fraction thereof, for example as a constituent of (fractions of) oil or extracts of camomile or of Vanillosmopsis (in particular Vanillosmopsis erythropappa or Vanillosmopsis arborea).
  • Synthetic alpha-bisabolol is obtainable, for exam- ple, under the name "Dragosantol" from Symrise.
  • ex- tracts of the fresh or dried ginger root are used which are prepared by extraction with meth- anol, ethanol, iso-propanol, acetone, ethyl acetate, carbon dioxide (CO2), hexane, methylene chloride, chloroform or other solvents or solvent mixtures of comparable polarity.
  • the ex- tracts are characterized by the presence of active skin irritation-reducing amounts of constit- uents such as e.g. gingerols, shogaols, gingerdiols, dehydrogingerdiones and/or paradols.
  • compositions may also contain one or more substances with a physiological cool- ing effect (cooling agents), which are preferably selected here from the following list: men- thol and menthol derivatives (for example L-menthol, D-menthol, racemic menthol, isomen- thol, neoisomenthol, neomenthol) menthylethers (for example (l-menthoxy)-1,2-propandiol, (l-menthoxy)-2-methyl-1,2-propandiol, l-menthyl-methylether), menthylesters (for example menthylformiate, menthylacetate, menthylisobutyrate, menthyllactates, L-menthyl-L-lactate, L-menthyl-D-lactate, menthyl-(2-methoxy)acetate, menthyl-(2-methoxyethoxy)acetate, menthylpyroglutamate), menthyl-(2-
  • 2-(2-propyl)-butyric acid derivatives for example 2,3-dimethyl-2-(2-propyl)-butyric acid-N- methylamide [WS23]
  • isopulegol or its esters l-(-)-isopulegol, l-(-)-isopulegolacetate
  • men- thane derivatives for example p-menthane-3,8-diol
  • cubebol or synthetic or natural mix- tures containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (for example
  • Suitable anti-microbial agents are, in principle, all substances effective against Gram- positive bacteria, such as, 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 (triclo- san), 4-chloro-3,5-dimethyl-phenol, 2,2'-methylenebis(6-bromo-4- chlorophenol), 3-methyl-
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of compounds listed in Appendix 6, Parts A and B of the Kosmetikverowski ("Cosmetics Directive").
  • compositions according to the present inventions are selected from the group of products for treatment, protecting, care and cleansing of the skin and/or hair or as a make-up product, preferably as a leave-on product (meaning that the one or more com- pounds of formula (I) stay on the skin and/or hair for a longer period of time, compared to rinse-off products, so that the moisturizing and/or anti-ageing and/or wound healing pro- moting action thereof is more pronounced).
  • the formulations according to the invention are preferably in the form of an emul- sion, e.g. 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) emulsion, PIT emulsion, Pickering emulsion, emulsion with a low oil content, micro- or nanoemulsion, a solution, e.g.
  • a gel including hydrogel, hydrodisper- sion gel, oleogel
  • spray e.g. pump spray or spray with propellant
  • a foam or an impreg- nating solution for cosmetic wipes e.g. soap, synthetic detergent, liquid wash- ing, shower and bath preparation, bath product (capsule, oil, tablet, salt, bath salt, soap, etc.), effervescent preparation, a skin care product such as e.g.
  • an emulsion as described above, ointment, paste, gel (as described above), oil, balsam, serum, powder (e.g. face powder, body powder), eau de perfume, eau de toilette, after-shave, a mask, a pencil, stick, roll-on, pump, aerosol (foaming, non-foaming or post-foaming), a deodorant and/or antiperspirant, mouthwash and mouth rinse, a foot care product (including keratolytic, deodorant), an insect repellent, a sunscreen, aftersun preparation, a shaving product, aftershave balm, pre- and aftershave lotion, a depilatory agent, a hair care product such as e.g.
  • shampoo including 2- in-1 shampoo, anti-dandruff shampoo, baby shampoo, shampoo for dry scalps, concentrated shampoo
  • conditioner hair tonic, hair water, hair rinse, styling creme, pomade, perm and setting lotion
  • hair spray e.g. gel or wax
  • hair smoothing agent detangling agent, relaxer
  • hair dye such as e.g. temporary direct-dyeing hair dye, semi-permanent hair dye, permanent hair dye, hair conditioner, hair mousse, eye care product, make-up, make-up remover or baby product.
  • the formulations according to the invention are particularly preferably in the form of an emulsion, in particular in the form of a W/O, O/W, W/O/W, O/W/O emulsion, PIT emul- sion, Pickering emulsion, emulsion with a low oil content, micro- or nanoemulsion, a gel (in- cluding hydrogel, hydrodispersion gel, oleogel), a solution e.g. in oil (fatty oils or fatty acid
  • SUBSTITUTE SHEET (RULE 26) esters, in particular C 6 -C 32 fatty acid C 2 -C 30 esters)) or silicone oil, or a spray (e.g. pump spray or spray with propellant).
  • Auxiliary substances and additives can be included in quantities of 5 to 99 % b.w., preferably 10 to 80 % b.w., based on the total weight of the formulation.
  • the amounts of cosmetic or dermatological auxiliary agents and additives and perfume to be used in each case can easily be determined by the person skilled in the art by simple trial and error, de- pending on the nature of the particular product.
  • the preparations can also contain water in a quantity of up to 99 % b.w., preferably 5 to 80 % b.w., based on the total weight of the preparation
  • Another object of the present invention concerns a non-therapeutical method for strengthening human connective tissue comprising or consisting of the following steps:
  • the present invention covers the use of agonists as defined above for strengthening human tissue, particular female skin.
  • the present invention also refers to the use of said agonists of olfactory recep- tors as cosmetic ingredients.
  • cosmetic ingredients for the sake of good order it is emphasized that all preferred embodiments, ranges, combinations and compositions as described above are also valid with respective to the claimed industrial applications. Any repretition is therefor superfluous.

Abstract

Suggested are agonists of olfactory receptors, particularly OR2AT4, showing (i) a molecular weight ranging from about 50 to about 300 Dalton and (ii) an evaporation rate versus butyl acetate of about 3 to about 15 for use as a medicament for preventing and/or treating collagen degradation in human connective tissue.

Description

Medicament for prevention and treatment of collagen degradation in human connecting tissue
AREA OF INVENTION
[0001] The present invention refers to the area of pharmaceutical compositions and relates to specific medicaments for preventing and/or treating degradation of macromolecules in human connecting tissue.
BACKGROUND OF THE INVENTION
[0002] The connective tissue, which consists of elastic and collagen fibres, normally sur- rounds supports and strengthens every organ of the body like a scaffold and connects the structures in the human body. The fewer tightening fibres (collagen fibres) are present in the connective tissue, the less tissue tension there is. This then leads to a slackening of the outer skin, blood vessels can dilate (varicose veins) and the firm anchoring of individual organs in their actual place can weaken (lowering of organs, such as in the case of a vaginal prolapse or a shifting of the uterus are the frequent consequences). Connective tissue weakness - which needs to be distinguished from cellulite- can occur due to lack of physical exertion, due to age or already at a young age due to predisposition. Finally, the disease is caused by an in- sufficient biosynthesis of macromolecules in the tissue, particularly collagen.
[0003] A decisive contribution to collagen degradation in human tissue is made by the group of 23 matrix metalloproteases (MMP1 to MMP23), which are secreted as inactive zymogens. The subgroup of collagenases plays an important role in this process, since they are the only native collagen that can cleave in its helical regions. Tissue collagenases cleave the collagen molecules through a single cut through the entire helix. The resulting fragments denature and can be broken down to the individual amino acids by non-specific proteases. It is well known that the expression of MMPs is regulated by a complex system of inductors (e.g. IL-1, PFGF, UVB-radiation, TNF-α, growth factors) or suppressors or inhibitors (e.g. retinoids, hepa- rin, TIMPs). In order to fight degradation of collagen in the connecting tissue, a constant need exists for substances capable of inhibiting or at least reducing the expression of MMPs.
RELEVANT PRIOR ART
[0004] From the state of the art numerous examples for MMP inhibitors and down regulators are known as the following examples show:
SUBSTITUTE SHEET (RULE 26) [0005] WO 2012 157587 A1 (SHISEIDO) relates to a matrix metalloproteinase (MMP) inhibi- tor and/or laminin 5 production promoter, as well as an anti-wrinkle agent, each of which comprises 1 -piperidine propionate and/or a salt thereof.
[0006] US 6,455,569 B (UNIVERSITY MANCHESTER) proposes the use of Matrix Metallopro- teinase Inhibitors in the prevention or treatment of connective tissue softening and also for the maintenance of sutures in such connective tissues.
[0007] US 2001 053347 A (UNIVERSITY MICHIGAN) teaches that the deleterious effects of the passage of time on human skin (i.e., chronological aging of human skin) can be prevent- ed and treated with the topical application of a MMP inhibitor such as a retinoid, preferably retinol.
[0008] US 2002 119107 A (UNIVERSITY MICHIGAN) refers to the selective inhibition of the enzyme (MMP-1), which causes the dermal matrix damage in humans, while sparing the en- zyme(s) (MMP-9 and perhaps MMP-2) which not only do not cause the damage (based on extrapolation from our in vitro collagen gel system to real skin) but actually "clear away" the damage produced by MMP-1 to restore normal function to the skin.
[0009] US 2002 164319 A (MOORFIELD HOSPITAL) concerns the use of an MMP inhibitor, especially a collagenase inhibitor, in the manufacture of a medicament for the treatment of a natural or artificial tissue comprising extracellular matrix components to inhibit contraction of the tissue and methods for the treatment of tissue comprising extracellular matrix compo- nents to inhibit contraction.
[0010] US 2009 068255 A (BEDFORD) refers to the application of matrix metalloproteinase (MMP) inhibitors to the skin inhibits the degradation of proteins found in the skin including collagen, elastin, and other basement membrane and extracellular matrix protein. MMP in- hibitors may be used in both cosmetic compositions and pharmaceutical compositions for application to skin. MMP inhibitors are formulated with a cosmetically suitable vehicle or pharmaceutically acceptable excipient for application to the skin as creams, lotions, oint- ments, solutions, face masks, etc. As cosmetics, the inventive MMP inhibitor compositions are applied to the skin to prevent or reduce the appearance of wrinkles, pigmentation changes, loss of elasticity, or other effects associated with aging or sun damage. As pharmaceuticals, the inventive MMP inhibitor compositions may also be applied to the skin to treat or prevent a skin disease (e.g., proliferative disease, inflammatory disease)
[0011] US 2012 058140 A (BATH & BODY WORKS) concerns a topical composition for use in a skin care regimen that provides matrix metalloprotease (MMP) inhibiting activity, tissue inhibitor of metalloprotease (TIMP) inducing activity, and immediate and delayed antioxida- tive activity. Preferably, the topical composition comprises at least one MMP inhibitor, a TIMP inducing agent, Tremella fuciformis (snow fungus) extract, Camellia sinensis (green tea) leaf extract, and Eugenia caryophyllus (clove) extract. The compositions are useful in anti-wrinkle
SUBSTITUTE SHEET (RULE 26) and anti-aging products, providing elasticity, firmness, tone and texture to the skin, amelio- rating fine lines and preventing skin damage
OBJECT OF THE INVENTION
[0012] Therefore, it has been the object of the present invention identifying compounds ca- pable of inhibiting or at least significantly reducing the expression of MMPs and TIMPs, par- ticularly of TIMP1, MMP1 and MMP9. In other words, there is a need for a medicament which is useful for preventing or treating weakness of human connective tissue.
[0013] Another task was to look for molecules that are already available in the market and are known for their toxicological safety.
BRIEF DESCRIPTION OF THE INVENTION
[0014] A first object of the present invention refers to a agonists of olfactory receptors, par- ticularly OR2AT4, showing a molecular weight ranging from about 50 to about 300 Dalton, preferably from about 75 to about 250 Dalton and an evaporation rate versus butyl acetate of about 3 to about 15, preferably from about 5 to about 10, for use as a medicament for preventing or treating degradation of macromolecules, particularly collagen in human con- nective tissue by inhibition or reduction of MMP and/or TIMP expression.
[0015] Surprisingly it has been found that small and volatile molecules capable of activating olfactory receptors, in particular OR2AT4, which is found in human skin, solve the above- identified problem. In assays with HaCat keratinocytes a reduction in the activation of MMP1, MMP9 and TIMP9 versus PolylC of 30 to 50 % was achieved.
[0016] Another advantage is that these molecules are already known as cosmetic additives, particularly as fragrances. They are easy to obtain and can be formulated into cosmetic or pharmaceutical preparations without problems.
Olfactory receptors
[0001] Olfactory receptors (ORs), also known as odorant receptors, are expressed in the cell membranes of olfactory receptor neurons and are responsible for the detection of air-borne odour molecules that enter the nasal cavity. Activated olfactory receptors trigger nerve im- pulses which transmit information about odour to the brain. These receptors are members of the class A rhodopsin-like family of G protein-coupled receptors (G PC Rs). The olfactory re- ceptors form a multigene family consisting of around 800 genes in humans. Particularly, the human nose has roughly 400 types of scent receptors that can detect at least 1 trillion different odours.
SUBSTITUTE SHEET (RULE 26) [0002] Rather than binding specific ligands, olfactory receptors display affinity for a range of odour molecules, and conversely a single odorant molecule may bind to a number of ol- factory receptors with varying affinities, which depend on physio-chemical properties of mol- ecules like their molecular volumes. Once the odorant has bound to the odour receptor, the receptor undergoes structural changes and it binds and activates the olfactory-type G pro- tein on the inside of the olfactory receptor neuron. The G protein (Goif and/or Gs) in turn acti- vates the lyase - adenylate cyclase - which converts ATP into cyclic AMP (cAMP). The cAMP opens cyclic nucleotide-gated ion channels which allow calcium and sodium ions to enter into the cell, depolarizing the olfactory receptor neuron and beginning an action poten- tial which carries the information to the brain.
[0003] A nomenclature system has been devised for the olfactory receptor family and is the basis for the official Human Genome Project (HUGO) symbols for the genes that encode these receptors. The names of individual olfactory receptor family members are in the format "ORnXm" where:
• OR is the root name (Olfactory Receptor superfamily)
• n = an integer representing a family (e.g., 1 -56) whose members have greater than 40% sequence identity,
• X = a single letter (A, B, C, ...) denoting a subfamily (>60% sequence identity), and
• m = an integer representing an individual family member (isoform).
[0004] For example, OR1 A1 is the first isoform of subfamily A of olfactory receptor family. An overview on olfactory receptors can be found in the following paper submitted by Gaillard I, Rouquier S, Giorgi: D "Olfactory receptors". Cellular and Molecular Life Sciences. 61 (4): 456-69 (2004).
[0005] The evaporation rate is the rate at which a material will vaporize (evaporate, change from liquid to vapor) compared to the rate of vaporization of butyl acetate, which is set as 1. This quantity is a ratio, therefore it is unitless. agonists of olfactory receptors
[0006] Suitable agonists according to the present invention are selected from the group con- sisting of:
• (-) CBD
• (-) CBG
• (+) CBDV
• Acetophenone
• Agrunitrile
SUBSTITUTE SHEET (RULE 26) • Aldehyde C8
• Aldehyde C11
• Aldehyde C12
• Aldehyde C16
• Aldehyde C18
• Allyl caproate
• Allyl cyclohexylpropionate
• Allyl heptoate
• Allyl phenoxyacetate
• Amalia oil
• Amarocit
• Amber Core
• Ambrocenide
• Ambrostar
• Ambroxide
• Amyl butyrate
• Anethole
• Anisic aldehyde
• Benzaldehyde
• Benzophenone
• Benzyl acetone
• Benzyl cinnamate
• Benzyl isobutyrate
• Benzyl isobutyrate
• Benzyl propionate
• Borneol/lsoborneol
• Bourgeonal
• Bows bioactive bullet 1
• Brahmanol
SUBSTITUTE SHEET (RULE 26) • Butyl acetate
• Butyl butyrate
• Butyl cyclohexanol, p-tert.
• Camphor
• Cedar wood oil
• Cedryl acetate
• Ceylanil
• Cinnamic alcohol
• Citral diethyl acetal
• Citronellyl acetate
• Citronellyl isobutyrate
• Citronellyl tiglate
• Citronitril
• Clove bud oil
• Cresyl methyl ether
• Cyclabute
• Cyclamen aldehyde
• Cyclohexyl magnol
• Cyclohexyl salicylate
• Decalactone, gamma
• Decyl acetate
• Diethyl malonate
• Dihydro myrcenyl acetate
• Dimethyl anthranilate
• Dimethyl benzyl carbonyl butyrate
• Ethyl acetoacetate
• Ethyl butyl butyrate
• Ethyl butyrate
• Ethyl cinnamate
• Ethyl linalool
• Eucalyptus oil
• Eugenol
SUBSTITUTE SHEET (RULE 26) • Fenchol
• Florazon
• Fragolan
• Frambionon
• Frambinon methyl ether
• Fresiol
• Frutinat
• Geranyl acetate
• Geranyl butyrate
• Geranyl tiglate
• Geranyl tiglate
• Globalide
• Globanone
• Guaiac wood oil
• Heliotropin
• Herbarome
• Hexyl acetate
• Hexenyl acetate
• Hydrocitronitrile
• Indole
• Intreleven aldehyde
• Ionone
• Isoborneol
• Isoamyl acetate
• Isoamyl butyrate
• Isoamyl salicylate
• Isoeugenol
• Isoeugenyl methyl ether
• Isotridecyl acetate
• Jasmol
• Jasmopyrane
• Jessemal
SUBSTITUTE SHEET (RULE 26) • Koavone
• Labdanum extract
• Lavandine Espieur
• Lavender oil
• Lemonile
• Leovovert
• Limonene
• Limoneal
• Macrolide supra
• Magnolan
• Majantol
• Mandaril
• Manzanate
• Melonal
• Menthol
• Menthone/lsomenthone
• Menthyl acetate
• Menthanyl acetate
• Methyl anthranilate
• Methyl benzoate
• Methyl naphthyl ketone
• Methyl phenylacetate
• Mintonat
• Mugetanol
• Neononyl acetate
• Nerol
• Nerolin
• Nopyl acetate
• Octahydro coumarin
• Octalactone, gamma
• Orange Oil
• Palisandal
SUBSTITUTE SHEET (RULE 26) Pearadise
Peonile
Phenoxanol
Phenoxyethyl alcohol
Phenyl acetaldehyde dimethyl acetal
Phenylethyl acetate
Phenylethyl acetate
Phenylethyl dimethyl carbinol
Phenylethyl isobutyrate
Phenylethyl isovalerate
Phenylethyl phenylacetate
Pinene
Poivrol
Prenyl acetate
Profarnesal
Projasmone
Resedafol
Resedylacetal
Rosaphen
Rose oxide L
Sandalore
Sandalwood oil
Sy m rose
Tagetes oil
Terpineol
Tetrahydrogeraniol
Tonka lactone
Thyme oil
Thymol
Timberol
Timberol
Undecavertrol
SUBSTITUTE SHEET (RULE 26) • Vanillin
• Verdolea
• Vertomugal
• Ylang Ylang oil
• Ysamber K and mixtures thereof.
[0007] The preferred agonists show an aldehyde, ketone, ester or terpene structure.
[0008] The agonists can be applied in a concentration of from 0.1 to 100 pg/ml, and prefera- bly of from 0.5 to 10 pg/ml.
COSMETIC AND PHARMACEUTICAL COMPOSITIONS
[0017] Another object of the present invention refers to a cosmetic or pharmaceutical com- position comprising the agonists as defined above, preferably in amounts of from 0.0001 to about 1 wt. -percent, more preferably from about 0.001 to about 0.1 wt.-percent and most preferred from about 0.02 to 0.05 wt.-percent.
[0018] Said compositions may represent a lotion, a cream, an emulsion, an ointment or any other form for topical application on skin.
Carriers or solvents
[0019] In a preferred embodiment the compositions may comprise a cosmetically or phar- maceutically acceptable carrier or solvent, such as for example water, ethanol, isopropyl alco- hol, butanol, glycerol, ethylene glycol, propylene glycol and diethylene glycol or mixtures thereof. The carriers may be present in quantities of 99 wt.-percent, preferably 99.9 wt.- percent or more.
Biogenic agents and antioxidants
[0020] In another preferred embodiment the compositions may comprise at least one bio- genic agent or antioxidant. Biogenic active substances include, for example, tocopherol, to- copherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and its frag- mentation products, β -glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as such as prunus extract, bambaranus extract and vitamin complexes.
[0021] Antioxidants interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples are amino acids (e.g. glycine, histidine, tyro- sine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives,
SUBSTITUTE SHEET (RULE 26) peptides like D,L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. -carotene, lycopene) and their derivates, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g. dihydrolic acid), aurothioglucose, propylthiou- racil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamin and their gly- cosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, linoleyl, choles- teryl and glyceryl esters) and their salts Dilaurylthiodipropionate, ditearylthiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleo- sides and salts) as well as sulfoximine compounds (e.g. (e.g. buthionine sulfoximines, homo- cysteine sulfoximines, butionine sulfones, penta-, hexa-, heptathionine sulfoximines) in very low tolerated dosages (e.g. pmol to mol/kg), furthermore (metal) chelators (e.g. hydroxy fatty acids, palmitic acid, phytinic acid, lactoferrin), hydroxy acids (e.g. (e.g. citric acid, lactic acid, malic acid), humic acid, gallic acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (e.g. ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbylacetate), tocoph- erols and derivatives (e.g. vitamin E acetate), vitamin A and derivates (vitamin A palmitate) as well as conifer aryl benzoate of benzoic resin, rutinic acid and its derivatives, glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butylhydroxyanisole, nor- dihydroguaiac resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (e.g. e.g. ZnO, ZnSO4) selenium and its derivatives (e.g. selenium-methionine), stilbenes and their derivatives (e.g. styrene oxide, trans-stilbene oxide) and the derivatives suitable for the invention (salts, esters, ethers, sugars
Further additives for cosmetic and pharmaceutical compositions
[0022] In case the agonists according to the present invention are incorporated in or deliv- ered to human skin by means of a cosmetic or pharmaceutical composition, these may con- tain further additives which are typical for skin care applications, as for example:
Surfactants
[0023] Preferred auxiliaries and additives are anionic and/or amphoteric or zwitterionic sur- factants. Non-ionic and cationic surfactants can be also present in the composition. Suitable examples are mentioned along with the paragraph dealing with emulsifiers.
[0024] Typical examples for anionic and zwitterionic surfactants encompass: Almondami- dopropylamine Oxide, Almondamidopropyl Betaine, Aminopropyl Laurylglutamine, Ammoni- um C12-15 Alkyl Sulfate, Ammonium C12-16 Alkyl Sulfate, Ammonium Capryleth Sulfate, Ammonium Cocomonoglyceride Sulfate, Ammonium Coco-Sulfate, Ammonium Cocoyl Isethionate, Ammonium Cocoyl Sarcosinate, Ammonium C12-15 Pareth Sulfate, Ammonium
SUBSTITUTE SHEET (RULE 26) C9-10 Perfluoroalkylsulfonate, Ammonium Dinonyl Sulfosuccinate, Ammonium Dodecylben- zenesulfonate, Ammonium Isostearate, Ammonium Laureth-6 Carboxylate, Ammonium Lau- reth-8 Carboxylate, Ammonium Laureth Sulfate, Ammonium Laureth-5 Sulfate, Ammonium Laureth-7 Sulfate, Ammonium Laureth-9 Sulfate, Ammonium Laureth-12 Sulfate, Ammonium Lauroyl Sarcosinate, Ammonium Lauryl Sulfate, Ammonium Lauryl Sulfosuccinate, Ammoni- um Myreth Sulfate, Ammonium Myristyl Sulfate, Ammonium Nonoxynol-4 Sulfate, Ammoni- um Nonoxynol-30 Sulfate, Ammonium Oleate, Ammonium Palm Kernel Sulfate, Ammonium Stearate, Ammonium Tallate, AMPD-lsostearoyl Hydrolyzed Collagen, AMPD-Rosin Hydro- lyzed Collagen, AMP-lsostearoyl Hydrolyzed Collagen, AMP-lsostearoyl Hydrolyzed Keratin, AMP-lsostearoyl Hydrolyzed Soy Protein, AMP-lsostearoyl Hydrolyzed Wheat Protein, Apri- cotamidopropyl Betaine, Arachidic Acid, Arginine Hexyldecyl Phosphate, Avocadamidopropyl Betaine, Avocado Oil Glycereth-8 Esters, Babassu Acid, Babassuamidopropylamine Oxide, Babassuamidopropyl Betaine, Beeswax Acid, Behenamidopropyl Betaine, Behenamine Oxide, Beheneth-25, Beheneth-30, Behenic Acid, Behenyl Betaine, Bis- Butyldimethicone Polyglycer- yl-3, Butoxynol-5 Carboxylic Acid, Butoxynol-19 Carboxylic Acid, Butyldimoniumhydroxypro- pyl Butylglucosides Chloride, Butyldimoniumhydroxypropyl Laurylglucosides Chloride, Butyl Glucoside, Butylglucoside Caprate, Butylglucosides Hydroxypropyltrimonium Chloride, Bu- tyloctanoic Acid, C18-36 Acid, C20-40 Acid, C30-50 Acid, C16-22 Acid Amide MEA, Calcium Dodecylbenzenesulfonate, Calcium Lauroyl Taurate, C9-16 Alkane/Cycloalkane, C10-14 Alkyl Benzenesulfonic Acid, C12-14 Alkyl Diaminoethylglycine HCL, C9-15 Alkyl Phosphate, Can- dida Bombicola/Glucose/Methyl Rapeseedate Ferment, Canolamidopropyl Betaine, Capric Acid, Caproic Acid, Caproyl Ethyl Glucoside, Capryl/Capramidopropyl Betaine, Capryleth-4 Carboxylic Acid, Capryleth-6 Carboxylic Acid, Capryleth-9 Carboxylic Acid, Caprylic Acid, Capryloyl Collagen Amino Acids, Capryloyl Glycine, Capryloyl Hydrolyzed Collagen, Capryloyl Hydrolyzed Keratin, Capryloyl Keratin Amino Acids, Capryloyl Silk Amino Acids, Capry- lyl/Capryl Glucoside, Caprylyl/Capryl Wheat Bran/Straw Glycosides, Caprylyl Glucoside, Caprylyl Glyceryl Ether, Caprylyl Pyrrolidone, Carnitine, Ceteareth-20, Ceteareth-23, Ce- teareth-24, Ceteareth-25, Ceteareth-27, Ceteareth-28, Ceteareth-29, Ceteareth-30, Ce- teareth-33, Ceteareth-34, Ceteareth-40, Ceteareth-50, Ceteareth-55, Ceteareth-60, Ce- teareth-80, Ceteareth-100, Ceteareth-25 Carboxylic Acid, Ceteareth-2 Phosphate, Ceteareth-4 Phosphate, Ceteareth-5 Phosphate, Ceteareth-10 Phosphate, Ceteth-20, Ceteth-23, Ceteth- 24, Ceteth-25, Ceteth-30, Ceteth-40, Ceteth-45, Ceteth-150, Ceteth-8 Phosphate, Ceteth-10 Phosphate, Ceteth-20 Phosphate, Cetoleth-22, Cetoleth-24, Cetoleth-25, Cetoleth-30, Cetyl Betaine, Chrysanthemum Sinense Flower Extract, C12-14 Hydroxyalkyl Hydroxyethyl Beta- Alanine, C12-14 Hydroxyalkyl Hydroxyethyl Sarcosine, Cocamidoethyl Betaine, Cocami- dopropylamine Oxide, Cocamidopropyl Betainamide MEA Chloride, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Cocamine Oxide, Cocaminobutyric Acid, Cocaminopropi- onic Acid, Coceth-7 Carboxylic Acid, Coceth-4 Glucoside, Cocoamphodipropionic Acid, Co- cobetainamido Amphopropionate, Coco-Betaine, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydrox- ypropyl Hydrolyzed Wheat Protein, Coco-Glucoside, Cocoglucosides Hydroxypropyltrimoni-
SUBSTITUTE SHEET (RULE 26) um Chloride, Coco- Hydroxysultaine, Coco-Morpholine Oxide, Coconut Acid, Coconut Oil Glycereth-8 Esters, Coco/Oleamidopropyl Betaine, Coco-Sultaine, Co- co/Sunfloweramidopropyl Betaine, Cocoylcholine Methosulfate, Cocoyl Glutamic Acid, Cocoyl Hydrolyzed Collagen, Cocoyl Hydrolyzed Keratin, Cocoyl Hydrolyzed Oat Protein, Cocoyl Hy- drolyzed Rice Protein, Cocoyl Hydrolyzed Silk, Cocoyl Hydrolyzed Soy Protein, Cocoyl Hydro- lyzed Wheat Protein, Cocoyl Sarcosine, Corn Acid, Cottonseed Acid, Cottonseed Oil Glycer- eth-8 Esters, C10-16 Pareth-1, CIO-16 Pareth-2, C11 -13 Pareth-6, Cl 1-13 Pareth-9, C11 -13 Pareth-10, C11 -15 Pareth-30, Cl 1-15 Pareth-40, C12-13 Pareth-1, C12-13 Pareth- 23, C12-14 Pareth-5, C12-14 Pareth-9, C13-15 Pareth-21, C14-15 Pareth-8, C20-22 Pareth-30, C20- 40 Pareth-40, C20-40 Pareth-95, C22-24 Pareth-33, C30-50 Pareth-40, C9-11 Pareth-6 Carbox- ylic Acid, C9-11 Pareth-8 Carboxylic Acid, C11 -15 Pareth-7 Carboxylic Acid, C12-13 Pareth-5 Carboxylic Acid, C12-13 Pareth-7 Carboxylic Acid, C12-13 Pareth-8 Carboxylic Acid, C12-13 Pareth-12 Carboxylic Acid, C12-15 Pareth-7 Carboxylic Acid, C 12-15 Pareth-8 Carboxylic Acid, C12-15 Pareth- 12 Carboxylic Acid, C14-15 Pareth-8 Carboxylic Acid, C6-10 Pareth-4 Phos- phate, C12-13 Pareth-2 Phosphate, C12-13 Pareth-10 Phosphate, C12-15 Pareth-6 Phos- phate, C12-15 Pareth-8 Phosphate, C12-15 Pareth-10 Phosphate, C12-16 Pareth-6 Phos- phate, C4-18 Perfluoroalkylethyl Thiohydroxypropyltrimonium Chloride, Cupuassuamidopro- pyl Betaine, DEA-C12-13 Alkyl Sulfate, DEA-C12-15 Alkyl Sulfate, DEA-Ceteareth-2 Phos- phate, DEA-Cetyl Sulfate, DEA- Cocoamphodipropionate, DEA-C12-13 Pareth-3 Sulfate, DEA- Cyclocarboxypropyloleate, DEA- Dodecylbenzenesulfonate, DEA-lsostearate, DEA-Laureth Sulfate, DEA-Lauryl Sulfate, DEA- Linoleate, DEA-Methyl Myristate Sulfonate, DEA-Myreth Sulfate, DEA-Myristate, DEA-Myristyl Sulfate, DEA-Oleth-5 Phosphate, DEA-Oleth-20 Phos- phate, DEA PG-Oleate, Deceth-7 Carboxylic Acid, Deceth-7 Glucoside, Deceth-9 Phosphate, Decylamine Oxide, Decyl Betaine, Decyl Glucoside, Decyltetradeceth-30, Decyltetradecyla- mine Oxide, Diammonium Lauramido-MEA Sulfosuccinate, Diammonium Lauryl Sulfosuccin- ate, Diammonium Oleamido PEG-2 Sulfosuccinate, Dibutoxymethane, Di-CI 2-15 Pareth-2 Phosphate, Di-CI 2-15 Pareth-4 Phosphate, Di-CI 2-15 Pareth-6 Phosphate, Di- C12-15 Pa- reth-8 Phosphate, Di-CI 2-15 Pareth-10 Phosphate, Didodecyl Butanetetracarboxylate, Di- ethylamine Laureth Sulfate, Diethylhexyl Sodium Sulfosuccinate, Dihydroxyethyl C8-10 Alkox- ypropylamine Oxide, Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Dimethicone PEG-7 Phosphate, Dimethicone PEG-10 Phosphate, Dimethicone PEG/PPG-7/4 Phosphate, Dimethi- cone PEG/PPG-12/4 Phosphate, Dimethicone/Polyglycerin-3 Crosspolymer, Dimethicone Propyl PG- Betaine, Dimyristyl Phosphate, Dioleoylamidoethyl Hydroxyethyl monium Meth- osulfate, DIPA- Hydrogenated Cocoate, DIPA-Lanolate, DIPA-Myristate, Dipotassium Capryloyl Glutamate, Dipotassium Lauryl Sulfosuccinate, Dipotassium Undecylenoyl Gluta- mate, Disodium Babassuamido MEA-Sulfosuccinate, Disodium Caproamphodiacetate, Diso- dium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloam- phodipropionate, Disodium Capryloyl Glutamate, Disodium Cetearyl Sulfosuccinate, Disodi- um Cetyl Phenyl Ether Disulfonate, Disodium Cetyl Sulfosuccinate, Disodium Cocamido MEA-
SUBSTITUTE SHEET (RULE 26) Sulfosuccinate, Disodium Cocamido MIPA PEG-4 Sulfosuccinate, Disodium Cocamido MIPA- Sulfosuccinate, Disodium Cocamido PEG-3 Sulfosuccinate, Disodium Coceth-3 Sulfosuccin- ate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiace- tate, Disodium Cocoamphodipropionate, Disodium Coco-Glucoside Sulfosuccinate, Disodi- um Coco-Sulfosuccinate, Disodium Cocoyl Butyl Gluceth-10 Sulfosuccinate, Disodium Cocoyl Glutamate, Disodium C12-14 Pareth-1 Sulfosuccinate, Disodium C12-14 Pareth-2 Sulfosuc- cinate, Disodium C12-15 Pareth Sulfosuccinate, Disodium C12-14 Sec-Pareth-3 Sulfosuccin- ate, Disodium C12-14 Sec-Pareth-5 Sulfosuccinate, Disodium Cl 2-14 Sec-Pareth-7 Sulfosuc- cinate, Disodium C12-14 Sec-Pareth-9 Sulfosuccinate, Disodium C12-14 Sec-Pareth-12 Sul- fosuccinate, Disodium Deceth-5 Sulfosuccinate, Disodium Deceth-6 Sulfosuccinate, Disodium Decyl Phenyl Ether Disulfonate, Disodium Dihydroxyethyl Sulfosuccinylundecylenate, Disodi- um Ethylene Dicocamide PEG-15 Disulfate, Disodium Hydrogenated Cottonseed Glyceride Sulfosuccinate, Disodium Hydrogenated Tallow Glutamate, Disodium Hydroxydecyl Sorbitol Citrate, Disodium Isodecyl Sulfosuccinate, Disodium Isostearamido MEA-Sulfosuccinate, Disodium Isostearamido MIPA-Sulfosuccinate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Isostearyl Sulfosuccinate, Disodium Laneth-5 Sul- fosuccinate, Disodium Lauramido MEA-Sulfosuccinate, Disodium Lauramido MIPA Glycol Sulfosuccinate, Disodium Lauramido PEG-2 Sulfosuccinate, Disodium Lauramido PEG-5 Sul- fosuccinate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Laureth-7 Citrate, Diso- dium Laureth Sulfosuccinate, Disodium Laureth-6 Sulfosuccinate, Disodium Laureth-9 Sul- fosuccinate, Disodium Laureth-12 Sulfosuccinate, Disodium Lauriminobishydroxypropyl- sulfonate, Disodium Lauriminodiacetate, Disodium Lauriminodipropionate, Disodium Laurim- inodipropionate Tocopheryl Phosphates, Disodium Lauroamphodiacetate, Disodium Lauro- amphodipropionate, Disodium N- Lauroyl Aspartate, Disodium Lauroyl Glutamate, Disodium Lauryl Phenyl Ether Disulfonate, Disodium Lauryl Sulfosuccinate, Disodium Myristamido MEA- Sulfosuccinate, Disodium Nonoxynol-10 Sulfosuccinate, Disodium Oleamido MEA- Sulfosuccinate, Disodium Oleamido MIPA-Sulfosuccinate, Disodium Oleamido PEG-2 Sul- fosuccinate, Disodium Oleoamphodipropionate, Disodium Oleth-3 Sulfosuccinate, Disodium Oleyl Phosphate, Disodium Oleyl Sulfosuccinate, Disodium Palmitamido PEG-2 Sulfosuccin- ate, Disodium Palmitoleamido PEG-2 Sulfosuccinate, Disodium PEG-4 Cocamido MIPA- Sulfosuccinate, Disodium PEG-12 Dimethicone Sulfosuccinate, Disodium PEG-8 Palm Glycer- ides Sulfosuccinate, Disodium PPG-2-lsodeceth-7 Carboxyamphodiacetate, Disodium Ricino- leamido MEA-Sulfosuccinate, Disodium Sitostereth-14 Sulfosuccinate, Disodium Soyamphodiacetate, Disodium Stearamido MEA-Sulfosuccinate, Disodium Steariminodi- propionate, Disodium Stearoamphodiacetate, Disodium Stearoyl Glutamate, Disodium Stear- yl Sulfosuccinamate, Disodium Stearyl Sulfosuccinate, Disodium 2-Sulfolaurate, Disodium 2- Sulfopalmitate, Disodium Tallamido MEA-Sulfosuccinate, Disodium Tallowamido MEA- Sulfosuccinate, Disodium Tallowamphodiacetate, Disodium Tallowiminodipropionate, Disodi- um Tallow Sulfosuccinamate, Disodium Tridecylsulfosuccinate, Disodium Undecylenamido MEA-Sulfosuccinate, Disodium Undecylenamido PEG-2 Sulfosuccinate, Disodium Un- decylenoyl Glutamate, Disodium Wheat Germamido MEA-Sulfosuccinate, Disodium Wheat
SUBSTITUTE SHEET (RULE 26) Germamido PEG-2 Sulfosuccinate, Disodium Wheatgermamphodiacetate, Di-TEA-Cocamide Diacetate, Di-TEA-Oleamido PEG-2 Sulfosuccinate, Di-TEA-Palmitoyl Aspartate, Ditridecyl Sodium Sulfosuccinate, Dodecylbenzene Sulfonic Acid, Erucamidopropyl Hydroxysultaine, Ethylhexeth-3 Carboxylic Acid, Ethyl PEG-15 Cocamine Sulfate, Glyceryl Capryl Ether, Hex- yldecanoic Acid, Hydrogenated Coconut Acid, Hydrogenated Laneth-25, Hydrogenated Menhaden Acid, Hydrogenated Palm Acid, Hydrogenated Palm Kernel Amine Oxide, Hydro- genated Tallow Acid, Hydrogenated Tallowamine Oxide, Hydrogenated Tallow Betaine, Hy- drogenated Talloweth-25, Hydrogenated Tallowoyl Glutamic Acid, Hydrolyzed Candida Bom- bicola Extract, Hydroxyceteth-60, Hydroxyethyl Acetomonium PG-Dimethicone, Hydroxyeth- ylbutylamine Laureth Sulfate, Hydroxyethyl Carboxymethyl Cocamidopropylamine, Hydroxy- ethyl Hydroxypropyl C12-15 Alkoxypropylamine Oxide, Hydroxylauryl/Hydroxy myristyl Beta- ine, Hydroxystearic Acid, Hydroxysuccinimidyl C10-40 Isoalkyl Acidate, Hydroxysuccinimidyl C21 -22 Isoalkyl Acidate, Hydroxysultaines, IPDI/PEG-15 Soyamine Oxide Copolymer, IPDI/PEG-15 Soyethonium Ethosulfate Copolymer, IPDI/PEG-15 Soy Glycinate Copolymer, lsoceteth-30, lsolaureth-4 Phosphate, lsopolyglyceryl-3 Dimethicone, lsopolyglyceryl-3 Dime- thiconol, Isopropanolamine Lanolate, Isopropylamine Dodecylbenzenesulfonate, Isostear- amidopropylamine Oxide, Isostearamidopropyl Betaine, Isostearamidopropyl Morpholine Oxide, Isostea reth-8, lsosteareth-16, Isostea reth-22, lsosteareth-25, lsosteareth-50, Isostearic Acid, Isostearoyl Hydrolyzed Collagen, Jojoba Oil PEG-150 Esters, Jojoba Wax PEG-80 Esters, Jojoba Wax PEG-120 Esters, Laneth-20, Laneth-25, Laneth-40, Laneth-50, Laneth-60, Laneth- 75, Lanolin Acid, Lauramidopropylamine Oxide, Lauramidopropyl Betaine, Lauramidopropyl Hydroxysultaine, Lauramine Oxide, Lauraminopropionic Acid, Laurdimoniumhydroxypropyl Decylglucosides Chloride, Laurdimoniumhydroxypropyl Laurylglucosides Chloride, Laureth- 16, Laureth-20, Laureth-21, Laureth-23, Laureth-25, Laureth-30, Laureth-38, Laureth-40, Lau- reth-3 Carboxylic Acid, Laureth-4 Carboxylic Acid, Laureth-5 Carboxylic Acid, Laureth- 6 Car- boxylic Acid, Laureth-8 Carboxylic Acid, Laureth-10 Carboxylic Acid, Laureth-11 Carboxylic Acid, Laureth-12 Carboxylic Acid, Laureth-13 Carboxylic Acid, Laureth-14 Carboxylic Acid, Laureth-17 Carboxylic Acid, Laureth-6 Citrate, Laureth-7 Citrate, Laureth-1 Phosphate, Lau- reth-2 Phosphate, Laureth-3 Phosphate, Laureth-4 Phosphate, Laureth-7 Phosphate, Laureth- 8 Phosphate, Laureth-7 Tartrate, Laurie Acid, Laurimino Bispropanediol, Lauriminodipropionic Acid, Lauroamphodipropionic Acid, Lauroyl Beta-Alanine, Lauroyl Collagen Amino Acids, Lau- royl Ethyltrimonium Methosulfate, Lauroyl Hydrolyzed Collagen, Lauroyl Hydrolyzed Elastin, Lauroyl Methyl Glucamide, Lauroyl Sarcosine, Lauroyl Silk Amino Acids, Lauryl Betaine, Lauryl Dimethicone/Polyglycerin-3 Crosspolymer, Lauryldimoniumhydroxypropyl Cocoglucosides Chloride, Lauryl Glucoside, Laurylglucosides Hydroxypropyltrimonium Chloride, Lauryl Glycol Hydroxypropyl Ether, Lauryl Hydroxysultaine, Lauryl Malamide, Lauryl Methylglucamide, Lau- ryl/Myristyl Glycol Hydroxypropyl Ether, Lauryl/Myristyl Wheat Bran/Straw Glycosides, Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone, Lauryl Pyrrolidone, Lauryl Sultaine, Lino- leic Acid, Linolenic Acid, Linseed Acid, Lysine Cocoate, Macadamia Seed Oil Glycereth-8 Es- ters, Magnesium Coceth Sulfate, Magnesium Coco-Sulfate, Magnesium Isododecylbenzene- sulfonate, Magnesium Laureth-11 Carboxylate, Magnesium Laureth Sulfate, Magnesium Lau-
SUBSTITUTE SHEET (RULE 26) reth-5 Sulfate, Magnesium Laureth-8 Sulfate, Magnesium Laureth-16 Sulfate, Magnesium Laureth-3 Sulfosuccinate, Magnesium Lauryl Hydroxypropyl Sulfonate, Magnesium Lauryl Sulfate, Magnesium Methyl Cocoyl Taurate, Magnesium Myreth Sulfate, Magnesium Oleth Sulfate, Magnesium/TEA-Coco-Sulfate, Manicouagan Clay, MEA-Cocoate, MEA-Laureth-6 Carboxylate, MEA- Laureth Sulfate, MEA-Lauryl Sulfate, MEA PPG-6 Laureth-7 Carboxylate, MEA-PPG-8-Steareth-7 Carboxylate, MEA-Undecylenate, Meroxapol 108, Meroxapol 174, Meroxapol 178, Meroxapol 254, Meroxapol 255, Meroxapol 258, Meroxapol 314, Methoxy PEG-450 Amidoglutaroyl Succinimide, Methoxy PEG-450 Amido Hydroxysuccinimidyl Suc- cinamate, Methoxy PEG-450 Maleimide, Methyl Morpholine Oxide, Milkamidopropyl Amine Oxide, Milkamidopropyl Betaine, Minkamidopropylamine Oxide, Minkamidopropyl Betaine, MIPA C12-15 Pareth Sulfate, MIPA-Dodecylbenzenesulfonate, MIPA-Laureth Sulfate, MIPA- Lauryl Sulfate, Mixed Isopropanolamines Lanolate, Mixed Isopropanolamines Lauryl Sulfate, Mixed Isopropanolamines Myristate, Morpholine Oleate, Morpholine Stearate, Myreth-3 Car- boxylic Acid, Myreth-5 Carboxylic Acid, Myristalkonium Chloride, Myristamidopropylamine Oxide, Myristamidopropyl Betaine, Myristamidopropyl Dimethylamine Phosphate, Myristami- dopropyl Hydroxysultaine, Myristamidopropyl PG-Dimonium Chloride Phosphate, Myrista- mine Oxide, Myristaminopropionic Acid, Myristic Acid, Myristoyl Ethyltrimonium Methosul- fate, Myristoyl Glutamic Acid, Myristoyl Hydrolyzed Collagen, Myristoyl Sarcosine, Myristyl Betaine, Myristyl/Cetyl Amine Oxide, Myristyldimoniumhydroxypropyl Cocoglucosides Chlo- ride, Myristyl Glucoside, Myristyl Phosphate, Nonoxynol-20, Nonoxynol-23, Nonoxynol-25, Nonoxynol-30, Nonoxynol-35, Nonoxynol-40, Nonoxynol-44, Nonoxynol-50, Nonoxynol- 100, Nonoxynol-120, Nonoxynol-5 Carboxylic Acid, Nonoxynol-8 Carboxylic Acid, Nonox- ynol-10 Carboxylic Acid, Nonoxynol-3 Phosphate, Nonoxynol-4 Phosphate, Nonoxynol-6 Phosphate, Nonoxynol-9 Phosphate, Nonoxynol-10 Phosphate, Nonyl Nonoxynol-30, Nonyl Nonoxynol-49, Nonyl Nonoxynol-100, Nonyl Nonoxynol-150, Nonyl Nonoxynol-7 Phos- phate, Nonyl Nonoxynol-8 Phosphate, Nonyl Nonoxynol-9 Phosphate, Nonyl Nonoxynol-10 Phosphate, Nonyl Nonoxynol-11 Phosphate, Nonyl Nonoxynol-15 Phosphate, Nonyl Nonox- ynol-24 Phosphate, Oatamidopropyl Betaine, Octoxynol-16, Octoxynol-25, Octoxynol-30, Octoxynol-33, Octoxynol-40, Octoxynol-70, Octoxynol-20 Carboxylic Acid, Octyldodeceth-20, Octyldodeceth-25, Octyldodeceth-30, Oleamidopropylamine Oxide, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysultaine, Oleamine Oxide, Oleic Acid, Oleoyl Hydrolyzed Collagen, Oleoyl Sarcosine, Oleth-20, Oleth-23, Oleth-24, Oleth-25, Oleth-30, Oleth-35, Oleth-40, Oleth-44, Oleth-50, Oleth-3 Carboxylic Acid, Oleth-6 Carboxylic Acid, Oleth-10 Carboxylic Acid, Oleyl Betaine, Olivamidopropylamine Oxide, Olivamidopropyl Betaine, Olive Acid, Oli- voyl Hydrolyzed Wheat Protein, Ophiopogon Extract Stearate, Ozonized Oleth-10, Ozonized PEG-10 Oleate, Ozonized PEG-14 Oleate, Ozonized Polysorbate 80, Palm Acid, Pal- mamidopropyl Betaine, Palmeth-2 Phosphate, Palmitamidopropylamine Oxide, Palmitami- dopropyl Betaine, Palmitamine Oxide, Palmitic Acid, Palmitoyl Collagen Amino Acids, Pal- mitoyl Glycine, Palmitoyl Hydrolyzed Collagen, Palmitoyl Hydrolyzed Milk Protein, Palmitoyl Hydrolyzed Wheat Protein, Palmitoyl Keratin Amino Acids, Palmitoyl Oligopeptide, Palmitoyl Silk Amino Acids, Palm Kernel Acid, Palm Kernelamidopropyl Betaine, Peach Kernel Oil
SUBSTITUTE SHEET (RULE 26) Glycereth-8 Esters, Peanut Acid, PEG-10 Castor Oil, PEG-40 Castor Oil, PEG-44 Castor Oil, PEG-50 Castor Oil, PEG-54 Castor Oil, PEG-55 Castor Oil, PEG-60 Castor Oil, PEG-80 Castor Oil, PEG-100 Castor Oil, PEG-200 Castor Oil, PEG-11 Cocamide, PEG-6 Cocamide Phosphate, PEG-4 Cocamine, PEG-8 Cocamine, PEG-12 Cocamine, PEG-150 Dibehenate, PEG-90 Diisos- tearate, PEG-75 Dilaurate, PEG-150 Dilaurate, PEG-75 Dioleate, PEG-150 Dioleate, PEG-75 Distearate, PEG-120 Distearate, PEG-150 Distearate, PEG-175 Distearate, PEG-190 Distearate, PEG-250 Distearate, PEG-30 Glyceryl Cocoate, PEG-40 Glyceryl Cocoate, PEG-78 Glyceryl Co- coate, PEG-80 Glyceryl Cocoate, PEG-30 Glyceryl Isostearate, PEG-40 Glyceryl Isostearate, PEG-50 Glyceryl Isostearate, PEG-60 Glyceryl Isostearate, PEG-90 Glyceryl Isostearate, PEG-23 Glyceryl Laurate, PEG-30 Glyceryl Laurate, PEG-25 Glyceryl Oleate, PEG-30 Glyceryl Oleate, PEG-30 Glyceryl Soyate, PEG-25 Glyceryl Stearate, PEG-30 Glyceryl Stearate, PEG-40 Glyceryl Stearate, PEG-120 Glyceryl Stearate, PEG-200 Glyceryl Stearate, PEG-28 Glyceryl Tallowate, PEG-80 Glyceryl Tallowate, PEG-82 Glyceryl Tallowate, PEG-130 Glyceryl Tallowate, PEG-200 Glyceryl Tallowate, PEG-45 Hydrogenated Castor Oil, PEG-50 Hydrogenated Castor Oil, PEG- 54 Hydrogenated Castor Oil, PEG-55 Hydrogenated Castor Oil, PEG-60 Hydrogenated Castor Oil, PEG-80 Hydrogenated Castor Oil, PEG-100 Hydrogenated Castor Oil, PEG-200 Hydro- genated Castor Oil, PEG-30 Hydrogenated Lanolin, PEG-70 Hydrogenated Lanolin, PEG-50 Hydrogenated Palmamide, PEG-2 Isostearate, PEG-3 Isostearate, PEG-4 Isostearate, PEG-6 Isostearate, PEG-8 Isostearate, PEG-10 Isostearate, PEG-12 Isostearate, PEG-20 Isostearate, PEG-30 Isostearate, PEG-40 Isostearate, PEG- 26 Jojoba Acid, PEG-40 Jojoba Acid, PEG-15 Jojoba Alcohol, PEG-26 Jojoba Alcohol, PEG-40 Jojoba Alcohol, PEG-35 Lanolin, PEG-40 Lanolin, PEG-50 Lanolin, PEG-55 Lanolin, PEG-60 Lanolin, PEG- 70 Lanolin, PEG-75 Lanolin, PEG-85 Lanolin, PEG-100 Lanolin, PEG-150 Lanolin, PEG-75 Lanolin Oil, PEG-2 Lauramide, PEG-3 Lauramine Oxide, PEG-20 Laurate, PEG-32 Laurate, PEG-75 Laurate, PEG-150 Laurate, PEG-70 Mango Glycerides, PEG-20 Mannitan Laurate, PEG-8 Methyl Ether Dimethicone, PEG- 120 Methyl Glucose Dioleate, PEG-80 Methyl Glucose Laurate, PEG-120 Methyl Glucose Trio- leate, PEG-4 Montanate, PEG-30 Oleamine, PEG-20 Oleate, PEG-23 Oleate, PEG-32 Oleate, PEG-36 Oleate, PEG-75 Oleate, PEG-150 Oleate, PEG-20 Palmitate, PEG-150 Polyglyceryl-2 Tristearate, PEG/PPG-28/21 Acetate Dimethicone, PEG/PPG-24/18 Butyl Ether Dimethicone, PEG/PPG-3/17 Copolymer, PEG/PPG-5/35 Copolymer, PEG/PPG-8/55 Copolymer, PEG/PPG- 10/30 Copolymer, PEG/PPG-10/65 Copolymer, PEG/PPG-12/35 Copolymer, PEG/PPG-16/17 Copolymer, PEG/PPG-20/9 Copolymer, PEG/PPG-20/20 Copolymer, PEG/PPG-20/60 Copoly- mer, PEG/PPG- 20/65 Copolymer, PEG/PPG-22/25 Copolymer, PEG/PPG-28/30 Copolymer, PEG/PPG-30-35 Copolymer, PEG/PPG-30/55 Copolymer, PEG/PPG-35/40 Copolymer, PEG/PPG-50/40 Copolymer, PEG/PPG-150/35 Copolymer, PEG/PPG- 160/30 Copolymer, PEG/PPG- 190/60 Copolymer, PEG/PPG-200/40 Copolymer, PEG/PPG-300/55 Copolymer, PEG/PPG-20/22 Methyl Ether Dimethicone, PEG-26-PPG-30 Phosphate, PEG/PPG-4/2 Propylheptyl Ether, PEG/PPG-6/2 Propylheptyl Ether, PEG-7/PPG-2 Propylheptyl Ether, PEG/PPG-8/2 Propylheptyl Ether, PEG/PPG- 10/2 Propylheptyl Ether, PEG/PPG-14/2 Propylheptyl Ether, PEG/PPG-40/2 Propylheptyl Ether, PEG/PPG- 10/2 Ricinoleate, PEG/PPG- 32/3 Ricinoleate, PEG-55 Propylene Glycol Oleate, PEG-25 Propylene Glycol Stearate, PEG-75
SUBSTITUTE SHEET (RULE 26) Propylene Glycol Stearate, PEG- 120 Propylene Glycol Stearate, PEG-5 Rapeseed Sterol, PEG- 10 Rapeseed Sterol, PEG-40 Ricinoleamide, PEG-75 Shea Butter Glycerides, PEG-75 Shorea Butter Glycerides, PEG-20 Sorbitan Cocoate, PEG-20 Sorbitan Isostearate, PEG-40 Sorbitan Lanolate, PEG-75 Sorbitan Lanolate, PEG-10 Sorbitan Laurate, PEG-40 Sorbitan Laurate, PEG- 44 Sorbitan Laurate, PEG-75 Sorbitan Laurate, PEG-80 Sorbitan Laurate, PEG-20 Sorbitan Oleate, PEG-80 Sorbitan Palmitate, PEG-40 Sorbitan Stearate, PEG-60 Sorbitan Stearate, PEG- 160 Sorbitan Triisostearate, PEG-40 Soy Sterol, PEG-2 Stearamide Carboxylic Acid, PEG-9 Stearamide Carboxylic Acid, PEG-20 Stearate, PEG-23 Stearate, PEG-25 Stearate, PEG-30 Stearate, PEG-32 Stearate, PEG-35 Stearate, PEG-36 Stearate, PEG-40 Stearate, PEG-45 Stea- rate, PEG-50 Stearate, PEG-55 Stearate, PEG-75 Stearate, PEG-90 Stearate, PEG-100 Stearate, PEG- 120 Stearate, PEG-150 Stearate, PEG-45 Stearate Phosphate, PEG-20 Tallate, PEG-50 Tallow Amide, PEG-2 Tallowamide DEA, PEG-20 Tallowate, PEG-66 Trihydroxystearin, PEG- 200 Tri hydroxystearin, PEG-60 Tsubakiate Glycerides, Pelargonic Acid, Pentadoxynol-200, Pheneth-6 Phosphate, Poloxamer 105, Poloxamer 108, Poloxamer 182, Poloxamer 183, Poloxamer 184, Poloxamer 188, Poloxamer 217, Poloxamer 234, Poloxamer 235, Poloxamer 237, Poloxamer 238, Poloxamer 288, Poloxamer 334, Poloxamer 335, Poloxamer 338, Polox- amine 908, Poloxamine 1508, Polydimethylsiloxy PEG/PPG-24/19 Butyl Ether Silsesquioxane, Polydimethylsiloxy PPG-13 Butyl Ether Silsesquioxane, Polyglyceryl-6 Caprate, Polyglyceryl-10 Dilaurate, Polyglyceryl-20 Heptacaprylate, Polyglyceryl-20 Hexacaprylate, Polyglyceryl-2 Lau- ryl Ether, Polyglyceryl- 10 Lauryl Ether, Polyglyceryl-20 Octaisononanoate, Polyglyceryl-6 Pen- tacaprylate, Polyglyceryl- 10 Pentacaprylate, Polyglyceryl-3 Polydimethylsiloxyethyl Dimethi- cone, Polyglyceryl-6 Tetracaprylate, Polyglyceryl-10 Tetralaurate, Polyglyceryl-6 Tricaprylate, Polyglyceryl-10 Trilaurate, Polyquaternium- 77, Polyquaternium-78, Polyquaternium-79, Polyquaternium-80, Polyquaternium-81, Polyquaternium- 82, Pomaderris Kumerahou Flow- er/Leaf Extract, Poria Cocos Extract, Potassium Abietoyl Hydrolyzed Collagen, Potassium Ba- bassuate, Potassium Behenate, Potassium C9-15 Alkyl Phosphate, Potassium C11 -15 Alkyl Phosphate, Potassium C12-13 Alkyl Phosphate, Potassium C12-14 Alkyl Phosphate, Potassi- um Caprate, Potassium Capryloyl Glutamate, Potassium Capryloyl Hydrolyzed Rice Protein, Potassium Castorate, Potassium Cocoate, Potassium Cocoyl Glutamate, Potassium Cocoyl Glycinate, Potassium Cocoyl Hydrolyzed Casein, Potassium Cocoyl Hydrolyzed Collagen, Po- tassium Cocoyl Hydrolyzed Corn Protein, Potassium Cocoyl Hydrolyzed Keratin, Potassium Cocoyl Hydrolyzed Oat Protein, Potassium Cocoyl Hydrolyzed Potato Protein, Potassium Co- coyl Hydrolyzed Rice Bran Protein, Potassium Cocoyl Hydrolyzed Rice Protein, Potassium Cocoyl Hydrolyzed Silk, Potassium Cocoyl Hydrolyzed Soy Protein, Potassium Cocoyl Hydro- lyzed Wheat Protein, Potassium Cocoyl Hydrolyzed Yeast Protein, Potassium Cocoyl PCA, Potassium Cocoyl Sarcosinate, Potassium Cocoyl Taurate, Potassium Cornate, Potassium Cy- clocarboxypropyloleate, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Dimethicone PEG-7 Phosphate, Potassium Dodecylbenzenesulfonate, Potassium Hempseed- ate, Potassium Hydrogenated Cocoate, Potassium Hydrogenated Palmate, Potassium Hydro- genated Tallowate, Potassium Hydroxystearate, Potassium Isostearate, Potassium Lanolate, Potassium Laurate, Potassium Laureth-3 Carboxylate, Potassium Laureth-4 Carboxylate, Po-
SUBSTITUTE SHEET (RULE 26) tassium Laureth-5 Carboxylate, Potassium Laureth-6 Carboxylate, Potassium Laureth-10 Car- boxylate, Potassium Laureth Phosphate, Potassium Lauroyl Collagen Amino Acids, Potassium Lauroyl Glutamate, Potassium Lauroyl Hydrolyzed Collagen, Potassium Lauroyl Hydrolyzed Pea Protein, Potassium Lauroyl Hydrolyzed Soy Protein, Potassium Lauroyl PCA, Potassium Lauroyl Pea Amino Acids, Potassium Lauroyl Sarcosinate, Potassium Lauroyl Silk Amino Acids, Potassium Lauroyl Wheat Amino Acids, Potassium Lauryl Phosphate, Potassium Lauryl Sul- fate, Potassium Linoleate, Potassium Metaphosphate, Potassium Methyl Cocoyl Taurate, Po- tassium Myristate, Potassium Myristoyl Glutamate, Potassium Myristoyl Hydrolyzed Collagen, Potassium Octoxynol-12 Phosphate, Potassium Oleate, Potassium Oleoyl Hydrolyzed Colla- gen, Potassium Olivate, Potassium Olivoyl Hydrolyzed Oat Protein, Potassium Olivoyl Hydro- lyzed Wheat Protein, Potassium Olivoyl/Lauroyl Wheat Amino Acids, Potassium Olivoyl PCA, Potassium Palmate, Potassium Palmitate, Potassium Palmitoyl Hydrolyzed Corn Protein, Po- tassium Palmitoyl Hydrolyzed Oat Protein, Potassium Palmitoyl Hydrolyzed Rice Protein, Po- tassium Palmitoyl Hydrolyzed Sweet Almond Protein, Potassium Palmitoyl Hydrolyzed Wheat Protein, Potassium Palm Kernelate, Potassium Peanutate, Potassium Rapeseedate, Potassium Ricinoleate, Potassium Safflowerate, Potassium Soyate, Potassium Stearate, Potassium Stea- royl Hydrolyzed Collagen, Potassium Tallate, Potassium Tallowate, Potassium Taurate, Potas- sium Taurine Laurate, Potassium Trideceth-3 Carboxylate, Potassium Trideceth-4 Carboxylate, Potassium Trideceth-7 Carboxylate, Potassium Trideceth-15 Carboxylate, Potassium Tride- ceth-19 Carboxylate, Potassium Trideceth-6 Phosphate, Potassium Trideceth-7 Phosphate, Potassium Tsubakiate, Potassium Undecylenate, Potassium Undecylenoyl Hydrolyzed Colla- gen, Potassium Undecylenoyl Hydrolyzed Rice Protein, PPG-30- Buteth-30, PPG-36-Buteth- 36, PPG-38-Buteth-37, PPG-30-Capryleth-4 Phosphate, PPG-10 Cetyl Ether Phosphate, PPG-2 C9-11 Pareth-8, PPG-1 -Deceth-5, PPG-3-Deceth-2 Carboxylic Acid, PPG-30 Ethylhexeth-4 Phosphate, PPG-20-Glycereth-30, PPG-2 Hydroxyethyl Coco/lsostearamide, PPG-2- Isode- ceth-8, PPG-2-lsodeceth-10, PPG-2-lsodeceth-18, PPG-2-lsodeceth-25, PPG-4-lsodeceth-10, Propyltrimonium Hydrolyzed Collagen, Quaternium-24, Quaternium-52, Quaternium-87, Rapeseed Acid, Rice Bran Acid, Rice Oil Glycereth-8 Esters, Ricinoleamidopropyl Betaine, Ric- inoleic Acid, Ricinoleth-40, Safflower Acid, Sapindus Oahuensis Fruit Extract, Saponaria Offici- nalis Root Powder, Saponins, Sekken-K, Sekken-Na/K, Sekken Soji, Sekken Soji-K, Sesame Oil Glycereth-8 Esters, Sesamidopropylamine Oxide, Sesamidopropyl Betaine, Shea Butterami- dopropyl Betaine, Shea Butter Glycereth-8 Esters, Sodium Arachidate, Sodium Arganam- pohoacetate, Sodium Astrocaryum Murumuruate, Sodium Avocadoate, Sodium Babassuam- phoacetate, Sodium Babassuate, Sodium Babassu Sulfate, Sodium Behenate, Sodium Bisgly- col Ricinosulfosuccinate, Sodium Bis- Hydroxyethylglycinate Coco-Glucosides Crosspolymer, Sodium Bis-Hydroxyethylglycinate Lauryl- Glucosides Crosspolymer, Sodium Borageami- dopropyl PG-Dimonium Chloride Phosphate, Sodium Butoxynol-12 Sulfate, Sodium Butylglu- cosides Hydroxypropyl Phosphate, Sodium Cl 3-17 Alkane Sulfonate, Sodium C14-18 Alkane Sulfonate, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium C10-16 Alkyl Sulfate, Sodium C11 -15 Alkyl Sulfate, Sodium C12-13 Alkyl Sulfate, Sodium C12-15 Alkyl Sulfate, So- dium C12-18 Alkyl Sulfate, Sodium C16-20 Alkyl Sulfate, Sodium C9-22 Alkyl Sec Sulfonate,
SUBSTITUTE SHEET (RULE 26) Sodium C14-17 Alkyl Sec Sulfonate, Sodium Caprate, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Caproyl Me- thyltaurate, Sodium Caprylate, Sodium Capryleth-2 Carboxylate, Sodium Capryleth-9 Carbox- ylate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryloamphopropionate, Sodium Capryloyl Glutamate, Sodium Capryloyl Hydrolyzed Wheat Protein, Sodium Caprylyl PG-Sulfonate, Sodium Caprylyl Sulfonate, Sodium Castorate, Sodium Ceteareth-13 Carboxylate, Sodium Cetearyl Sulfate, Sodium Ceteth-13 Carboxylate, Sodium Cetyl Sulfate, Sodium Cocamidopropyl PG-Dimonium Chloride Phosphate, Sodium Cocaminopropionate, Sodium Coceth Sulfate, Sodium Coceth-30 Sulfate, Sodium Cocoabut- teramphoacetate, Sodium Cocoa Butterate, Sodium Cocoamphoacetate, Sodium Cocoam- phohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cocoate, Sodium Co- co/Babassu/Andiroba Sulfate, Sodium Coco/Babassu Sulfate, Sodium Cocoglucosides Hy- droxypropyl Phosphate, Sodium Cocoglucosides Hydroxypropylsulfonate, Sodium Coco- Glucoside Tartrate, Sodium Cocoglyceryl Ether Sulfonate, Sodium Coco/Hydrogenated Tallow Sulfate, Sodium Cocoiminodiacetate, Sodium Cocomonoglyceride Sulfate, Sodium Co- comonoglyceride Sulfonate, Sodium Coco PG-Dimonium Chloride Phosphate, Sodium Coco- Sulfate, Sodium Coco Sulfoacetate, Sodium Cocoyl Alaninate, Sodium Cocoyl Amino Acids, Sodium Cocoyl Collagen Amino Acids, Sodium Cocoyl Glutamate, Sodium Cocoyl Glutami- nate, Sodium Cocoyl Glycinate, Sodium Cocoyl/Hydrogenated Tallow Glutamate, Sodium Cocoyl Hydrolyzed Collagen, Sodium Cocoyl Hydrolyzed Keratin, Sodium Cocoyl Hydrolyzed Rice Protein, Sodium Cocoyl Hydrolyzed Silk, Sodium Cocoyl Hydrolyzed Soy Protein, Sodium Cocoyl Hydrolyzed Sweet Almond Protein, Sodium Cocoyl Hydrolyzed Wheat Protein, Sodi- um Cocoyl Hydrolyzed Wheat Protein Glutamate, Sodium Cocoyl Isethionate, Sodium Cocoyl Methylaminopropionate, Sodium Cocoyl Oat Amino Acids, Sodium Co- coyl/Palmoyl/Sunfloweroyl Glutamate, Sodium Cocoyl Proline, Sodium Cocoyl Sarcosinate, Sodium Cocoyl Taurate, Sodium Cocoyl Threoninate, Sodium Cocoyl Wheat Amino Acids, Sodium C12-14 Olefin Sulfonate, Sodium C14-16 Olefin Sulfonate, Sodium C14- 18 Olefin Sulfonate, Sodium Cl 6-18 Olefin Sulfonate, Sodium Cornamphopropionate, Sodium Cotton- seedamphoacetate, Sodium C13-15 Pareth-8 Butyl Phosphate, Sodium C9-11 Pareth-6 Car- boxylate, Sodium Cl 1 -15 Pareth-7 Carboxylate, Sodium C12-13 Pareth-5 Carboxylate, Sodi- um C12-13 Pareth-8 Carboxylate, Sodium C12-13 Pareth-12 Carboxylate, Sodium C12-15 Pareth-6 Carboxylate, Sodium C12-15 Pareth-7 Carboxylate, Sodium C12-15 Pareth-8 Car- boxylate, Sodium C14-15 Pareth-8 Carboxylate, Sodium C12-14 Sec-Pareth-8 Carboxylate, Sodium C14-15 Pareth-PG Sulfonate, Sodium C12-13 Pareth-2 Phosphate, Sodium C13-15 Pareth-8 Phosphate, Sodium C9-15 Pareth-3 Sulfate, Sodium C10-15 Pareth Sulfate, Sodium CIO-16 Pareth-2 Sulfate, Sodium C12-13 Pareth Sulfate, Sodium C12-15 Pareth Sulfate, Sodi- um C12-15 Pareth-3 Sulfate, Sodium C13-15 Pareth-3 Sulfate, Sodium C12-14 Sec-Pareth-3 Sulfate, Sodium C12-15 Pareth-3 Sulfonate, Sodium Cl 2-15 Pareth-7 Sulfonate, Sodium C12- 15 Pareth-15 Sulfonate, Sodium Deceth-2 Carboxylate, Sodium Deceth Sulfate, Sodium Decylbenzenesulfonate, Sodium Decylglucosides Hydroxypropyl Phosphate, Sodium Decyl- glucosides Hydroxypropylsulfonate, Sodium Dilaureth-7 Citrate, Sodium Dilaureth-10 Phos-
SUBSTITUTE SHEET (RULE 26) phate, Sodium Dilinoleamidopropyl PG-Dimonium Chloride Phosphate, Sodium Dilinoleate, Sodium Dioleth-8 Phosphate, Sodium Dodecylbenzenesulfonate, Sodium Ethyl 2- Sul- folaurate, Sodium Glyceryl Oleate Phosphate, Sodium Grapeseedamidopropyl PG-Dimonium Chloride Phosphate, Sodium Grapeseedamphoacetate, Sodium Grapeseedate, Sodium Hempseedamphoacetate, Sodium Hexeth-4 Carboxylate, Sodium Hydrogenated Cocoate, Sodium Hydrogenated Cocoyl Methyl Isethionate, Sodium Hydrogenated Palmate, Sodium Hydrogenated Tallowate, Sodium Hydrogenated Tallowoyl Glutamate, Sodium Hydroxylau- ryldimonium Ethyl Phosphate, Sodium Hydroxypropyl Palm Kernelate Sulfonate, Sodium Hy- droxypropylphosphate Decylglucoside Crosspolymer, Sodium Hydroxypropylphosphate Lau- rylglucoside Crosspolymer, Sodium Hydroxypropylsulfonate Cocoglucoside Crosspolymer, Sodium Hydroxypropylsulfonate Decylglucoside Crosspolymer, Sodium Hydroxypropyl- sulfonate Laurylglucoside Crosspolymer, Sodium Hydroxystearate, Sodium Isostearate, Sodi- um lsosteareth-6 Carboxylate, Sodium Isosteareth- 11 Carboxylate, Sodium Isostearoampho- acetate, Sodium Isostearoamphopropionate, Sodium N- Isostearoyl Methyltaurate, Sodium Laneth Sulfate, Sodium Lanolate, Sodium Lardate, Sodium Lauramido Diacetate, Sodium Lau- raminopropionate, Sodium Laurate, Sodium Laureth-3 Carboxylate, Sodium Laureth-4 Car- boxylate, Sodium Laureth-5 Carboxylate, Sodium Laureth-6 Carboxylate, Sodium Laureth-8 Carboxylate, Sodium Laureth-11 Carboxylate, Sodium Laureth-12 Carboxylate, Sodium Lau- reth-13 Carboxylate, Sodium Laureth-14 Carboxylate, Sodium Laureth-16 Carboxylate, Sodi- um Laureth-17 Carboxylate, Sodium Laureth Sulfate, Sodium Laureth-5 Sulfate, Sodium Lau- reth- 7 Sulfate, Sodium Laureth-8 Sulfate, Sodium Laureth-12 Sulfate, Sodium Laureth-40 Sulfate, Sodium Laureth-7 Tartrate, Sodium Lauriminodipropionate, Sodium Lauroamphoace- tate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phos- phate, Sodium Lauroamphopropionate, Sodium Lauroyl Aspartate, Sodium Lauroyl Collagen Amino Acids, Sodium Lauroyl Glycine Propionate, Sodium Lauroyl Hydrolyzed Collagen, So- dium Lauroyl Hydrolyzed Silk, Sodium Lauroyl Hydroxypropyl Sulfonate, Sodium Lauroyl Isethionate, Sodium Lauroyl Methylaminopropionate, Sodium Lauroyl Methyl Isethionate, Sodium Lauroyl Millet Amino Acids, Sodium Lauroyl/Myristoyl Aspartate, Sodium Lauroyl Oat Amino Acids, Sodium Lauroyl Sarcosinate, Sodium Lauroyl Silk Amino Acids, Sodium Lauroyl Taurate, Sodium Lauroyl Wheat Amino Acids, Sodium Lauryl Diethylenediaminoglycinate, Sodium Lauryl Glucose Carboxylate, Sodium Laurylglucosides Hydroxypropyl Phosphate, So- dium Laurylglucosides Hydroxypropylsulfonate, Sodium Lauryl Glycol Carboxylate, Sodium Lauryl Hydroxyacetamide Sulfate, Sodium Lauryl Phosphate, Sodium Lauryl Sulfate, Sodium Lauryl Sulfoacetate, Sodium Linoleate, Sodium Macadamiaseedate, Sodium Mangoampho- acetate, Sodium Mangoseedate, Sodium/MEA Laureth-2 Sulfosuccinate, Sodium Methoxy PPG-2 Acetate, Sodium Methyl Cocoyl Taurate, Sodium Methyl Lauroyl Taurate, Sodium Me- thyl Myristoyl Taurate, Sodium Methyl Oleoyl Taurate, Sodium Methyl Palmitoyl Taurate, So- dium Methyl Stearoyl Taurate, Sodium Methyl 2-Sulfolaurate, Sodium Methyl 2- Sulfopalmi- tate, Sodium Methyltaurate Isopalmitamide, Sodium Methyltaurine Cocoyl Methyltaurate, Sodium Myreth Sulfate, Sodium Myristate, Sodium Myristoamphoacetate, Sodium Myristoyl Glutamate, Sodium Myristoyl Hydrolyzed Collagen, Sodium Myristoyl Isethionate, Sodium
SUBSTITUTE SHEET (RULE 26) Myristoyl Sarcosinate, Sodium Myristyl Sulfate, Sodium Nonoxynol-6 Phosphate, Sodium Nonoxynol-9 Phosphate, Sodium Nonoxynol-1 Sulfate, Sodium Nonoxynol-3 Sulfate, Sodium Nonoxynol-4 Sulfate, Sodium Nonoxynol-6 Sulfate, Sodium Nonoxynol-8 Sulfate, Sodium Nonoxynol-10 Sulfate, Sodium Nonoxynol-25 Sulfate, Sodium Octoxynol-2 Ethane Sulfonate, Sodium Octoxynol-2 Sulfate, Sodium Octoxynol-6 Sulfate, Sodium Octoxynol-9 Sulfate, Sodi- um Oleate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Oleoyl Hydrolyzed Collagen, Sodium Oleoyl Isethionate, So- dium Oleth Sulfate, Sodium Oleyl Methyl Isethionate, Sodium Oleyl Sulfate, Sodium Olivam- phoacetate, Sodium Olivate, Sodium Olivoyl Glutamate, Sodium Palmamphoacetate, Sodium Palmate, Sodium Palm Glyceride Sulfonate, Sodium Palmitate, Sodium Palmitoyl Hydrolyzed Collagen, Sodium Palmitoyl Hydrolyzed Wheat Protein, Sodium Palmitoyl Sarcosinate, Sodi- um Palm Kernelate, Sodium Palm Kerneloyl Isethionate, Sodium Palmoyl Glutamate, Sodium Passiflora Edulis Seedate, Sodium Peanutamphoacetate, Sodium Peanutate, Sodium PEG-6 Cocamide Carboxylate, Sodium PEG-8 Cocamide Carboxylate, Sodium PEG-4 Cocamide Sul- fate, Sodium PEG-3 Lauramide Carboxylate, Sodium PEG-4 Lauramide Carboxylate, Sodium PEG-8 Palm Glycerides Carboxylate, Sodium Pentaerythrityl Hydroxypropyl Iminodiacetate Dendrimer, Sodium Propoxy PPG-2 Acetate, Sodium Rapeseedate, Sodium Ricebranampho- acetate, Sodium Ricinoleate, Sodium Ricinoleoamphoacetate, Sodium Rose Hipsamphoace- tate, Sodium Rosinate, Sodium Safflowerate, Sodium Saffloweroyl Hydrolyzed Soy Protein, Sodium Sesameseedate, Sodium Sesamphoacetate, Sodium Sheabutteramphoacetate, Sodi- um Soyate, Sodium Soy Hydrolyzed Collagen, Sodium Stearate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Stearoyl Casein, Sodium Stearoyl Glutamate, Sodium Stearoyl Hyaluronate, Sodium Stearoyl Hydrolyzed Collagen, Sodium Stearoyl Hydrolyzed Corn Protein, Sodium Stearoyl Hydrolyzed Silk, Sodium Stearoyl Hydrolyzed Soy Protein, Sodium Stearoyl Hydrolyzed Wheat Protein, Sodium Stearoyl Lactalbumin, Sodium Stearoyl Methyl Isethionate, Sodium Stearoyl Oat Pro- tein, Sodium Stearoyl Pea Protein, Sodium Stearoyl Soy Protein, Sodium Stearyl Dimethyl Glycine, Sodium Stearyl Sulfate, Sodium Sunflowerseedamphoacetate, Sodium Surfactin, So- dium Sweetalmondamphoacetate, Sodium Sweet Almondate, Sodium Tallamphopropionate, Sodium Tallate, Sodium Tallowamphoacetate, Sodium Tallowate, Sodium Tallow Sulfate, So- dium Tamanuseedate, Sodium Taurate, Sodium Taurine Cocoyl Methyltaurate, Sodium Tau- rine Laurate, Sodium/TEA-Lauroyl Collagen Amino Acids, Sodium/TEA-Lauroyl Hydrolyzed Collagen, Sodium/TEA-Lauroyl Hydrolyzed Keratin, Sodium/TEA- Lauroyl Keratin Amino Ac- ids, Sodium/TEA-Undecylenoyl Collagen Amino Acids, Sodium/TEA- Undecylenoyl Hydro- lyzed Collagen, Sodium/TEA-Undecylenoyl Hydrolyzed Corn Protein, Sodium/TEA- Undecylenoyl Hydrolyzed Soy Protein, Sodium/TEA-Undecylenoyl Hydrolyzed Wheat Protein, Sodium Theobroma Grandiflorum Seedate, Sodium Trideceth-3 Carboxylate, Sodium Tride- ceth-4 Carboxylate, Sodium Trideceth-6 Carboxylate, Sodium Trideceth-7 Carboxylate, Sodi- um Trideceth-8 Carboxylate, Sodium Trideceth-12 Carboxylate, Sodium Trideceth-15 Carbox- ylate, Sodium Trideceth-19 Carboxylate, Sodium Trideceth Sulfate, Sodium Tridecylbenzene- sulfonate, Sodium Tridecyl Sulfate, Sodium Trimethylolpropane Hydroxypropyl Iminodiace-
SUBSTITUTE SHEET (RULE 26) tate Dendrimer, Sodium Undeceth-5 Carboxylate, Sodium Undecylenate, Sodium Undecylen- oamphoacetate, Sodium Undecylenoamphopropionate, Sodium Undecylenoyl Glutamate, Sodium Wheat Germamphoacetate, Sorbeth-160 Tristearate, Soy Acid, Soyamidopropyla- mine Oxide, Soyamidopropyl Betaine, Soybean Oil Glycereth-8 Esters, Stearamidopropyla- mine Oxide, Stearamidopropyl Betaine, Stearamine Oxide, Steareth-15, Steareth-16, Steareth- 20, Steareth-21, Steareth-25, Steareth-27, Steareth-30, Steareth- 40, Steareth-50, Steareth- 80, Steareth-100, Steareth-2 Phosphate, Steareth-3 Phosphate, Stearic Acid, Stearoxypro- pyltrimonium Chloride, Stearoyl Glutamic Acid, Stearoyl Sarcosine, Stearyl Betaine, Stearyl- dimoniumhydroxypropyl Butylglucosides Chloride, Stearyldimoniumhydroxypropyl Decylglu- cosides Chloride, Stearyldimoniumhydroxypropyl Laurylglucosides Chloride, Sulfated Castor Oil, Sulfated Coconut Oil, Sulfated Glyceryl Oleate, Sulfated Olive Oil, Sulfated Peanut Oil, Sunfloweramide MEA, Sunflower Seed Acid, Sunflowerseedamidopropyl Hydroxyethyldimo- nium Chloride, Sunflower Seed Oil Glycereth-8 Esters, Tall Oil Acid, Tallow Acid, Tal- lowamidopropylamine Oxide, Tallowamidopropyl Betaine, Tallowamidopropyl Hydroxysul- taine, Tallowamine Oxide, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Tallowoyl Ethyl Glu- coside, TEA-Abietoyl Hydrolyzed Collagen, TEA-C12-14 Alkyl Phosphate, TEA-C10-15 Alkyl Sulfate, TEA-C11-15 Alkyl Sulfate, TEA- C12-13 Alkyl Sulfate, TEA-C12-14 Alkyl Sulfate, TEA- C12-15 Alkyl Sulfate, TEA C14-17 Alkyl Sec Sulfonate, TEA-Canolate, TEA-Cocamide Diace- tate, TEA-Cocoate, TEA-Coco-Sulfate, TEA-Cocoyl Alaninate, TEA-Cocoyl Glutamate, TEA- Cocoyl Glutaminate, TEA-Cocoyl Glycinate, TEA-Cocoyl Hydrolyzed Collagen, TEA-Cocoyl Hydrolyzed Soy Protein, TEA-Cocoyl Sarcosinate, TEA- Dimethicone PEG-7 Phosphate, TEA- Dodecylbenzenesulfonate, TEA-Hydrogenated Cocoate, TEA- Hydrogenated Tallowoyl Glu- tamate, TEA-lsostearate, TEA- Isostearoyl Hydrolyzed Collagen, TEA- Lauraminopropionate, TEA-Laurate, TEA-Laurate/Myristate, TEA-Laureth Sulfate, TEA-Lauroyl Collagen Amino Acids, TEA-Lauroyl Glutamate, TEA-Lauroyl Hydrolyzed Collagen, TEA-Lauroyl Keratin Amino Acids, TEA-Lauroyl Methylaminopropionate, TEA-Lauroyl/Myristoyl Aspartate, TEA- Lauroyl Sar- cosinate, TEA-Lauryl Phosphate, TEA-Lauryl Sulfate, TEA-Myristaminopropionate, TEA- Myristate, TEA-Myristoyl Hydrolyzed Collagen, TEA-Oleate, TEA-Oleoyl Hydrolyzed Collagen, TEA- Oleoyl Sarcosinate, TEA-Oleyl Sulfate, TEA-Palmitate, TEA-Palm Kernel Sarcosinate, TEA- PEG-3 Cocamide Sulfate, TEA-Rosinate, TEA- Stearate, TEA-Tallate, TEA-T ridecylbenzenesul- fonate, TEA- Undecylenate, TEA-Undecylenoyl Hydrolyzed Collagen, Tetramethyl Decynediol, Tetrasodium Dicarboxyethyl Stearyl Sulfosuccinamate, TIPA-Laureth Sulfate, TIPA-Lauryl Sul- fate, TIPA-Myristate, TIPA-Stearate, Tocopheryl Phosphate, Trehalose Undecylenoate, TM- C12-15 Pareth-2 Phosphate, TM-C12-15 Pareth-6 Phosphate, TM-C12-15 Pareth-8 Phos- phate, TM-C12-15 Pareth-10 Phosphate, Trideceth-20, Trideceth-50, Trideceth-3 Carboxylic Acid, Trideceth-4 Carboxylic Acid, Trideceth-7 Carboxylic Acid, Trideceth-8 Carboxylic Acid, Trideceth-15 Carboxylic Acid, Trideceth-19 Carboxylic Acid, Trideceth-10 Phosphate, Tridecylbenzenesulfonic Acid, Trilaureth-9 Citrate, Trimethylolpropane Hydroxypropyl Bis- Hydroxyethylamine Dendrimer, Trisodium Lauroampho PG-Acetate Chloride Phosphate, Un- decanoic Acid, Undeceth-5 Carboxylic Acid, Undecylenamidopropylamine Oxide, Undecyle- namidopropyl Betaine, Undecylenic Acid, Undecylenoyl Collagen Amino Acids, Undecylenoyl
SUBSTITUTE SHEET (RULE 26) Glycine, Undecylenoyl Hydrolyzed Collagen, Undecylenoyl Wheat Amino Acids, Undecyl Glu- coside, Wheat Germ Acid, Wheat Germamidopropylamine Oxide, Wheat Germamidopropyl Betaine, Yucca Schidigera Leaf/Root/Stem Extract, Yucca Schidigera Stem Extract, Zinc Coceth Sulfatea and Zinc Coco-Sulfate.
[0025] Preferred are one or more compounds selected from the group consisting of Sodium Laureth Sulfate, Cocamidopropyl Betaine, Sodium Cocoamphoacetate, CocoGlucoside and Ammonium Lauryl Sulfosuccinate.
[0026] The percentage content of surfactants in the preparations may be from 0.1 to 10% by weight and is preferably from 0.5 to 5% by weight, based on the preparation.
Oil bodies
[0027] Suitable oil bodies, which form constituents of the O/W emulsions, are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6-C 13-carboxylic acids with linear or branched C6-C22 -fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, ce- tyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl be- henate and erucyl erucate. Also suitable are esters of linear C6-C22-fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C18-C38- alkylhydroxy carboxylic acids with linear or branched C6-C 22-fatty alcohols, in particular Dioctyl Malate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C6 -C10-fatty acids, liquid mono-/di-/triglyceride mixtures based on C6-C18-fatty acids, esters of C6- C22-fatty al- cohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, es- ters of C2- C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon at- oms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alco- hol carbonates, such as, for example, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and/or branched C6-C22-alcohols (e.g. Finsolv® TN), linear or branched, sym- metrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid
SUBSTITUTE SH EET ( RULE 26) esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.) and/or aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcy- clohexanes.
Emulsifiers
[0028] Other non-ionic or cationic surfactants may also be added to the preparations as emulsifiers, including for example:
• products of the addition of 2 to 30 mol ethylene oxide and/or 0 to 5 mol propylene oxide onto linear C8-22 fatty alcohols, onto C12-22 fatty acids and onto alkyl phenols con- taining 8 to 15 carbon atoms in the alkyl group;
• C12/18 fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol;
• glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsatu- rated fatty acids containing 6 to 22 carbon atoms and ethylene oxide addition products thereof;
• addition products of 15 to 60 mol ethylene oxide onto castor oil and/or hydrogenated castor oil;
• polyol esters and, in particular, polyglycerol esters such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate isos- tearate. Mixtures of compounds from several of these classes are also suitable;
• addition products of 2 to 15 mol ethylene oxide onto castor oil and/or hydrogenated castor oil;
• partial esters based on linear, branched, unsaturated or saturated C6/22 fatty acids, ricin- oleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, - dipentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose);
• mono-, di and trialkyl phosphates and mono-, di- and/or tri-PEG-alkyl phosphates and salts thereof;
• wool wax alcohols;
• polysiloxane/polyalkyl polyether copolymers and corresponding derivatives;
• mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and/or mixed esters of C6-22 fatty acids, methyl glucose and polyols, preferably glycerol or polyglycer- ol, polyalkylene glycols and
SUBSTITUTE SHEET (RULE 26) • glycerol carbonate.
[0029] The addition products of ethylene oxide and/or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or onto castor oil are known commercially available products. They are homo- logue mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addi- tion reaction is carried out. C12/18 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as lipid layer enhancers for cosmetic formulations. The preferred emulsifiers are described in more detail as follows:
[0030] 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 monoglycer- ide, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyc- eride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quantities of triglyceride from the production process. Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto the partial gly- cerides mentioned are also suitable.
[0031] Sorbitan esters. Suitable sorbitan esters are sorbitan monoisostearate, sorbitan ses- quiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquieru- cate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricino- leate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan tri hydroxystea rate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomale- ate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto the sorbitan esters mentioned are also suitable.
[0032] Polyglycerol esters. Typical examples of suitable polyglycerol esters are Polyglyceryl- 2 Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® Gl 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Poly- glyceryl-3 Beeswax (Cera Beilina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate and mixtures thereof. Examples of other suitable polyolesters are the mono-, di- and triesters of trimethylol propane or pentaerythritol with lauric acid, cocofatty acid, tallow fatty acid, pal-
SUBSTITUTE SHEET (RULE 26) mitic acid, stearic acid, oleic acid, behenic acid and the like optionally reacted with 1 to 30 mol ethylene oxide.
[0033] Tetraalkyl ammonium salts. Cationically active surfactants comprise the hydrophobic high molecular group required for the surface activity in the cation by dissociation in aqueous solution. A group of important representatives of the cationic surfactants are the tetraalkyl ammonium salts of the general formula: (R1R2R3R4N+) X-. Here R1 stands for C1-C8 alk(en)yl, R2, R3 and R4, independently of each other, for alk(en)yl radicals having 1 to 22 carbon atoms. X is a counter ion, preferably selected from the group of the halides, alkyl sulfates and alkyl carbonates. Cationic surfactants, in which the nitrogen group is substituted with two long acyl groups and two short alk(en)yl groups, are particularly preferred.
[0034] Esterquats. A further class of cationic surfactants particularly useful as co-surfactants for the present invention is represented by the so-called esterquats. Esterquats are generally understood to be quaternised fatty acid triethanolamine ester salts. These are known compounds which can be obtained by the relevant methods of preparative organic chemistry. Reference is made in this connection to International patent application WO 91/01295 A1, according to which triethanolamine is partly esterified with fatty acids in the presence of hypophosphorous acid, air is passed through the reaction mixture and the whole is then quaternised with dimethyl sulphate or ethylene oxide. In addition, German patent DE 4308794 C1 describes a process for the production of solid esterquats in which the quaternisation of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.
[0035] Typical examples of esterquats suitable for use in accordance with the invention are products of which the acyl component derives from monocarboxylic acids corresponding to formula RCOOH in which RCO is an acyl group containing 6 to 10 carbon atoms, and the amine component is triethanolamine (TEA). Examples of such monocarboxylic acids are caproic acid, caprylic acid, capric acid and technical mixtures thereof such as, for example, so- called head-fractionated fatty acid. Esterquats of which the acyl component derives from monocarboxylic acids containing 8 to 10 carbon atoms, are preferably used. Other esterquats are those of which the acyl component derives from dicarboxylic acids like 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 of which the acyl component derives from mixtures of monocarboxylic acids containing 6 to 22 carbon atoms, and adipic acid are preferably used. The molar ratio of mono and dicarboxylic acids in the final esterquat may be in the range from 1 :99 to 99:1 and is preferably in the range from 50:50 to 90:10 and more particularly in the range from 70:30 to 80:20. Besides the quaternised fatty acid triethanolamine ester salts, other suitable esterquats are quaternized ester salts of mono-/dicarboxylic acid mixtures with diethanolalkyamines or 1,2- dihydroxypropyl dialkylamines. The esterquats may be obtained both from fatty acids and
SUBSTITUTE SHEET (RULE 26) from the corresponding triglycerides in admixture with the corresponding dicarboxylic acids. One such process, which is intended to be representative of the relevant prior art, is proposed in European patent EP 0750606 B1. To produce the quaternised esters, the mixtures of mono- and dicarboxylic acids and the triethanolamine - based on the available carboxyl functions - may be used in a molar ratio of 1.1 :1 to 3:1. With the performance properties of the esterquats in mind, a ratio of 1.2:1 to 2.2:1 and preferably 1.5:1 to 1.9:1 has proved to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9.
Superfatting agents and consistency factors
[0036] Superfatting agents may be selected from such substances as, for example, lanolin and lecithin and also polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the fatty acid alkanolamides also serving as foam stabilizers.
[0037] The consistency factors mainly used are fatty alcohols or hydroxyfatty alcohols con- taining 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxyfatty acids. A combination of these substances with alkyl oligoglucosides and/or fatty acid N-methyl glucamides of the same chain length and/or polyglycerol poly-12- hydroxystea rates is preferably used.
Thickening agents and rheology additives
[0038] Suitable thickeners are polymeric thickeners, such as Aerosil® types (hydrophilic sili- cas), polysaccharides, more especially xanthan gum, guar-guar, agar-agar, alginates and tylo- ses, carboxymethyl cellulose and hydroxyethyl cellulose, also relatively high molecular weight polyethylene glycol monoesters and diesters of fatty acids, polyacrylates (for example Carbo- pols® [Goodrich] or Synthalens® [Sigma]), polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, for example pentaerythritol or trimethylol propane, narrow-range fatty alcohol ethoxylates and electrolytes, such as sodium chloride and ammonium chloride.
Polymers
[0039] Suitable cationic polymers are, for example, cationic cellulose derivatives such as, for example, the quaternized hydroxyethyl cellulose obtainable from Amerchol under the name of Polymer JR 400® , cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone/vinyl imidazole 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,
SUBSTITUTE SHEET (RULE 26) Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as, for example, amodimethicone, copolymers of adipic acid and dimethylaminohy- droxypropyl diethylenetriamine (Carta retine®, Sandoz), copolymers of acrylic acid with dime- thyl diallyl ammonium chloride (Merquat® 550, Chemviron), polyaminopolyamides and cross- linked water-soluble polymers thereof, cationic chitin derivatives such as, for example, quaternized chitosan, optionally in microcrystalline distribution, condensation products of dihaloalkyls, for example dibromobutane, with bis-dialkylamines, for example bis- dimethylamino-1,3-propane, cationic guar gum such as, for example, Jaguar®CBS, Jaguar®C- 17, Jaguar®C-16 of Celanese, quaternized ammonium salt polymers such as, for example, Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 of Miranol and the various polyquaternium types (for example 6, 7, 32 or 37) which can be found in the market under the tradenames Rheocare® CC or Ultragel® 300.
[0040] Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl ace- tate/butyl maleate/isobornyl acrylate copolymers, methyl vinylether/maleic anhydride copol- ymers and esters thereof, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamido- propyl trimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacry- late/tert.-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, vinyl pyrroli- done/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and optionally deri- vatized cellulose ethers and silicones.
Pearlizing agents
[0041] Suitable pearlising waxes are, for example, alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially cocofatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polybasic, optionally hydroxy- substituted carboxylic acids with fatty alcohols containing 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; fatty compounds, such as for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates which contain in all at least 24 carbon atoms, especially laurone and distea rylether; fatty acids, such as stearic acid, hy- droxystearic 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 con- taining 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.
Silicones
[0042] Suitable silicones can be chosen from the group consisting of: Acefylline Methylsilanol Mannuronate, Acetylmethionyl Methylsilanol Elastinate Acrylates/Behenyl, Acry- late/Dimethicone Methacrylate Copolymer, Acrylates/Behenyl Methacrylate/Dimethicone
SUBSTITUTE SHEET (RULE 26) Methacrylate Copolymer, Acrylates/Bis-Hydroxypropyl Dimethicone Crosspolymer, Acry- lates/Dimethicone Copolymer, Acrylates/Dimethicone Methacrylate/Ethylhexyl Acrylate Co- polymer, Acrylates/Dimethiconol Acrylate Copolymer, Acrylates/Ethylhexyl Acry- late/Dimethicone Methacrylate Copolymer, Acrylates/Octylacrylamide/Diphenyl Amodimethi- cone Copolymer, Acrylates/Polytrimethylsiloxymethacrylate Copolymer, Acrylates/Propyl Tri- methicone Methacrylate Copolymer, Acrylates/Stearyl Acrylate/Dimethicone Methacrylate Copolymer, Acrylates/Tridecyl Acrylate/Triethoxysilylpropyl Methacrylate/Dimethicone Meth- acrylate Copolymer, Acrylates/Trifluoropropylmethacrylate/Polytrimethyl Siloxymethacrylate Copolymer, Amino Bispropyl Dimethicone, Aminoethylaminopropyl Dimethicone, Aminopro- pyl Dimethicone, Aminopropyl Phenyl Trimethicone, Aminopropyl Triethoxysilane, Ammoni- um Dimethicone PEG-7 Sulfate, Amodimethicone, Amodimethicone Hydroxystearate, Amodimethicone/Silsesquioxane Copolymer, Ascorbyl Carboxydecyl Trisiloxane, Ascorbyl Methylsilanol Pectinate, Behenoxy Dimethicone, Behentrimonium Dimethicone PEG-8 Phthalate, Behenyl Dimethicone, Bisamino PEG/PPG-41/3 Aminoethyl PG-Propyl Dimethi- cone, Bis-Aminopropyl/Ethoxy Aminopropyl Dimethicone, Bis(Butylbenzoate) Diaminotriazine Aminopropyltrisiloxane, Bis-Butyldimethicone Polyglyceryl-3, Bis-
Butyloxyamodimethicone/PEG-60 Copolymer, Bis(C13-15 Alkoxy) Hydroxybutamidoamodi- methicone, Bis(C13-15 Alkoxy) PG- Amodimethicone, Bis-(C1 -8 Alkyl Lauroyl Lysine Decyl- carboxamide) Dimethicone, Bis-Cetyl Cetyl Dimethicone, Bis-Cetyl/PEG-8 Cetyl PEG-8 Dime- thicone, Bis-Diphenylethyl Disiloxane, Bis-Ethyl Ethyl Methicone, Bis- Gluconamidoethylaminopropyl Dimethicone, Bis-Hydrogen Dimethicone, Bis- Hydroxyethox- ypropyl Dimethicone Bis-Hydroxylauryl, Dimethicone/IPDI Copolymer, Bis- Hydroxy/Methoxy Amodimethicone, Bis-Hydroxypropyl Dimethicone Behenate, Bis-Hydroxypropyl Dimethi- cone/SMDI Copolymer, Bis-lsobutyl PEG-14/Amodimethicone Copolymer, Bis-lsobutyl PEG- 15/Amodimethicone Copolymer, Bis-lsobutyl PEG/PPG-20/35/Amodimethicone Copolymer, Bis- Isobutyl PEG/PPG-10/7/Dimethicone Copolymer, Bis-lsobutyl PEG-24/PPG- 7/Dimethicone Copolymer, Bis-PEG-1 Dimethicone, Bis-PEG-4 Dimethicone, Bis-PEG-8 Dime- thicone, Bis-PEG-12 Dimethicone, Bis-PEG-20 Dimethicone, Bis-PEG-12 Dimethicone Beeswax, Bis-PEG-12 Dimethicone Candelillate, Bis-PEG-15 Dimethicone/IPDI Copolymer, Bis-PEG-15 Methyl Ether Dimethicone, Bis- PEG-18 Methyl Ether Dimethyl Silane, Bis-PEG/PPG-14/14 Dimethicone, Bis-PEG/PPG-15/5 Dimethicone, Bis-PEG/PPG-18/6 Dimethicone, Bis-PEG/PPG- 20/20 Dimethicone, Bis-PEG/PPG- 16/16 PEG/PPG-16/16 Dimethicone, Bis-PEG/PPG-20/5 PEG/PPG-20/5 Dimethicone, Bisphenylhexamethicone, Bis-Phenylpropyl Dimethicone, Bispol- yethylene Dimethicone, Bis- (Polyglyceryl-3 Oxyphenylpropyl) Dimethicone, Bis-(Polyglyceryl- 7 Oxyphenylpropyl) Dimethicone, Bis-PPG-15 Dimethicone/IPDI Copolymer, Bis(PPG-7 Unde- ceneth-21) Dimethicone, Bis-Stearyl Dimethicone, Bis-Trimethoxysilylethyl Tetramethyl- disiloxyethyl Dimethicone, Bis-Vinyldimethicone, Bis-Vinyl Dimethicone/Dimethicone Copol- ymer, Borage Seed Oil PEG-7 Dimethicone Esters, Butyl Acrylate/C6-14 Perfluoroalkylethyl Acrylate/Mercaptopropyl Dimethicone Copolymer, Butyl Acrylate/Hydroxypropyl Dimethi- cone Acrylate Copolymer, Butyl Dimethicone Acrylate/Cyclohexylmethacrylate/Ethylhexyl Acrylate Copolymer, Butyldimethicone Methacrylate/Methyl Methacrylate Crosspolymer, t-
SUBSTITUTE SHEET (RULE 26) Butyl Dimethyl Silyl Grape Seed Extract, Butyl Polydimethylsiloxyl Eth- ylene/Propylene/Vinylnorbornene Copolymer, C6-8 Alkyl C3-6 Alkyl Glucoside Dimethicone, C20-24 Alkyl Dimethicone, C24-28 Alkyl Dimethicone, C26-28 Alkyl Dimethicone, C30-45 Al- kyl Dimethicone, C30-60 Alkyl Dimethicone, C32 Alkyl Dimethicone, C30-45 Alkyl Dimethi- cone/Polycyclohexene Oxide Crosspolymer, C26-28 Alkyldimethylsilyl Polypropylsilsesquiox- ane, C30-45 Alkyldimethylsilyl Polypropylsilsesquioxane, C20-24 Alkyl Methicone, C24-28 Alkyl Methicone, C26-28 Alkyl Methicone, C30-45 Alkyl Methicone, C20-28 Alkyl Per- fluorodecylethoxy Dimethicone, C26-54 Alkyl Tetradecyl Dimethicone, Capryl Dimethicone, Caprylyl Dimethicone Ethoxy Glucoside, Caprylyl Methicone, Caprylyl Trimethicone, Carboxy- decyl Trisiloxane, Castor Oil Bis-Hydroxypropyl Dimethicone Esters Cerotyl Dimethicone, Ce- tearyl Dimethicone Crosspolymer, Cetearyl Dimethicone/Vinyl Dimethicone Crosspolymer, Cetearyl Methicone, Cetrimonium Carboxydecyl PEG-8 Dimethicone, Cetrimonium Dimethi- cone PEG-7 Phthalate, Cetyl Behenyl Dimethicone, Cetyl Dimethicone, Cetyl Dimethicone/Bis- Vinyldimethicone Crosspolymer, Cetyl Hexacosyl Dimethicone, Cetyloxy Dimethicone, Cetyl PEG-8 Dimethicone, Cetyl PEG/PPG-15/15 Butyl Ether Dimethicone, Cetyl PEG/PPG-7/3 Di- methicone, Cetyl PEG/PPG-10/1 Dimethicone, Cetyl Triethylmonium Dimethicone PEG-8 Phthalate, Cetyl Triethylmonium Dimethicone PEG-8 Succinate, Copper Acetyl Tyrosinate Me- thylsilanol, Copper PCA Methylsilanol, C4-14 Perfluoroalkylethoxy Dimethicone, Cycloethox- ymethicone, Cycloheptasiloxane, Cyclohexasiloxane, Cyclomethicone, Cyclopentasiloxane, Cyclophenylmethicone, Cyclotetrasiloxane, mCyclovinylmethicone, Cystine Bis-PG-Propyl Silanetriol, DEA PG-Propyl PEG/PPG-18/21 Dimethicone, Diisostearoyl Trimethylolpropane Siloxy Silicate, Dilauroyl Trimethylolpropane Siloxy Silicate, Dilinoleamidopropyl Dimethyla- mine Dimethicone PEG-7 Phosphate, Dimethicone, Dimethicone Crosspolymer, Dimethicone Crosspolymer-3, Dimethicone/Divinyldimethicone/Silsesquioxane Crosspolymer, Dimethicone Ethoxy Glucoside, Dimethicone Hydroxypropyl Trimonium Chloride, Dimethi- cone/Mercaptopropyl Methicone Copolymer, Dimethicone PEG-15 Acetate Dimethicone PEG-8 Adipate, Dimethicone PEG-7 Avocadoate, Dimethicone PEG-8 Avocadoate, Dimethi- cone PEG-8 Beeswax, Dimethicone PEG-8 Benzoate, Dimethicone PEG-8 Borageate, Dimethi- cone PEG-7 Cocoate, Dimethicone/PEG-10 Crosspolymer, Dimethicone/PEG-10/15 Crosspol- ymer, Dimethicone/PEG-15 Crosspolymer, Dimethicone PEG-7 Isostearate, Dimethicone PEG- 8 Isostearate, Dimethicone PEG-7 Lactate, Dimethicone PEG-8 Lanolate, Dimethicone PEG-8 Laurate, Dimethicone PEG-8 Meadowfoamate, Dimethicone PEG-7 Octyldodecyl Citrate, Di- methicone PEG-7 Olivate, Dimethicone PEG-8 Olivate, Dimethicone PEG-7 Phosphate, Dime- thicone PEG-8 Phosphate, Dimethicone PEG-10 Phosphate, Dimethicone PEG-7 Phthalate, Dimethicone PEG-8 Phthalate, Dimethicone PEG-8 Polyacrylate, Dimethicone PEG/PPG- 20/23 Benzoate, Dimethicone PEG/PPG-7/4 Phosphate, Dimethicone PEG/PPG-12/4 Phos- phate, Dimethicone PEG-7 Succinate, Dimethicone PEG-8 Succinate, Dimethicone PEG-7 Sul- fate, Dimethicone PEG-7 Undecylenate, Dimethicone PG-Diethylmonium Chloride, Dimethi- cone/Phenyl Vinyl Dimethicone Crosspolymer, Dimethicone/Polyglycerin-3 Crosspolymer, Dimethicone/PPG-20 Crosspolymer, Dimethicone Propylethylenediamine Behenate, Dimethi- cone Propyl PG-Betaine, Dimethicone/Silsesquioxane Copolymer, Dimethicone Silylate, Di-
SUBSTITUTE SHEET (RULE 26) methicone?/inyl Dimethicone Crosspolymer, Dimethicone/Vinyltrimethylsiloxysilicate Cross- polymer, Dimethiconol, Dimethiconol Arginine, Dimethiconol Beeswax, Dimethiconol Be- henate, Dimethiconol Borageate, Dimethiconol Candelillate, Dimethiconol Carnaubate, Dime- thiconol Cysteine, Dimethiconol Dhupa Butterate, Dimethiconol Fluoroalcohol Dilinoleic Acid, Dimethiconol Hydroxystearate, Dimethiconol lllipe Butterate, Dimethiconol/IPDI Copolymer, Dimethiconol Isostearate, Dimethiconol Kokum Butterate, Dimethiconol Lactate, Dimethi- conol Meadowfoamate, Dimethiconol Methionine, Dimethiconol/Methylsilanol/Silicate Crosspolymer, Dimethiconol Mohwa Butterate, Dimethiconol Panthenol, Dimethiconol Sal Butterate, Dimethiconol/Silica Crosspolymer, Dimethiconol/Silsesquioxane Copolymer, Dime- thiconol Stearate, Dimethiconol/Stearyl, Methicone/Phenyl Trimethicone Copolymer, Di- methoxysilyl Ethylenediaminopropyl Dimethicone, Dimethylaminopropylamido PCA Dimethi- cone, Dimethyl Oxobenzo Dioxasilane, Dimethylsilanol Hyaluronate, Dioleyl Tocopheryl Me- thylsilanol, Diphenyl Amodimethicone, Diphenyl Dimethicone, Diphenyl Dimethicone Cross- polymer Diphenyl Dimethicone?/inyl Diphenyl Dimethicone/Silsesquioxane Crosspolymer, Diphenylethyl Benzyloxy Dilsiloxane, Diphenylisopropyl Dimethicone, Diphenylsiloxy Phe- nyl/Propyl Trimethicone, Diphenylsiloxy Phenyl Trimethicone Disiloxane, Disodium Amodime- thicone Disuccinamide, Disodium PEG-12 Dimethicone Sulfosuccinate, Disodium PEG-8 Lau- ryl Dimethicone Sulfosuccinate, Divinyldimethicone/Dimethicone Copolymer, Divinyldimethi- cone/Dimethicone Crosspolymer, Drometrizole Trisiloxane, Ethylhexyl Acry- late/VP/Dimethicone Methacrylate Copolymer, Ethyl Methicone, Ethyl Trisiloxane, Fluoro C2- 8 Alkyldimethicone, Gluconamidopropyl Aminopropyl Dimethicone, 4-(2-Beta- Glucopyranosiloxy) Propoxy-2-Hydroxybenzophenone, Glyceryl Undecyl Dimethicone, Glycidoxy Dimethicone, Hexadecyl Methicone, Hexyl Dimethicone, Hexyl Methicone, Hex- yltrimethoxysilane, Hydrogen Dimethicone, Hydrogen Dimethicone/Octyl Silsesquioxane Co- polymer, Hydrolyzed Collagen PG-Propyl Dimethiconol, Hydrolyzed Collagen PG-Propyl Me- thylsilanediol, Hydrolyzed Collagen PG-Propyl Silanetriol, Hydrolyzed Keratin PG-Propyl Me- thylsilanediol, Hydrolyzed Sesame Protein PG-Propyl Methylsilanediol, Hydrolyzed Silk PG- Propyl Methylsilanediol, Hydrolyzed Silk PG-Propyl Methylsilanediol Crosspolymer, Hydro- lyzed Soy Protein/Dimethicone PEG-7 Acetate, Hydrolyzed Soy Protein PG-Propyl Me- thylsilanediol, Hydrolyzed Vegetable Protein PG-Propyl Silanetriol, Hydrolyzed Wheat Pro- tein/Cystine Bis-PG-Propyl Silanetriol Copolymer, Hydrolyzed Wheat Protein/Dimethicone PEG-7 Acetate, Hydrolyzed Wheat Protein/Dimethicone PEG-7 Phosphate Copolymer, Hydro- lyzed Wheat Protein PG-Propyl Methylsilanediol, Hydrolyzed Wheat Protein PG-Propyl Silan- etriol, Hydroxyethyl Acetomonium PG-Dimethicone, Hydroxypropyldimethicone, Hydroxy- propyl Dimethicone Behenate, Hydroxypropyl Dimethicone Isostearate, Hydroxypropyl Dime- thicone Stearate, Isobutylmethacrylate/Bis-Hydroxypropyl Dimethicone Acrylate Copolymer, Isobutylmethacrylate/T rifluoroethylmethacrylate/Bis-Hydroxypropyl Dimethicone Acrylate Copolymer, Isopentyl Trimethoxycinnamate Trisiloxane, lsopolyglyceryl-3 Dimethicone, lsopolyglyceryl-3 Dimethiconol, Isopropyl Titanium Triisostearate/Triethoxysilylethyl, Polydi- methylsiloxyethyl Dimethicone Crosspolymer, Isostearyl Carboxydecyl PEG-8 Dimethicone, Lactoyl Methylsilanol Elastinate, Lauryl Dimethicone, Lauryl Dimethicone PEG-15 Crosspoly-
SUBSTITUTE SHEET (RULE 26) mer, Lauryl Dimethicone PEG- 10 Phosphate, Lauryl Dimethicone/Polyglycerin-3 Crosspoly- mer, Lauryl Methicone, Lauryl PEG-8 Dimethicone, Lauryl PEG-10 Methyl Ether Dimethicone, Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone, Lauryl PEG/PPG-18/18 Methicone, Lauryl Phenylisopropyl Methicone, Lauryl Phenylpropyl Methicone, Lauryl Polydimethylsiloxyethyl Dimethicone/Bis-Vinyldimethicone Crosspolymer, Lauryl Polyglyceryl-3 Polydimethylsiloxy- ethyl Dimethicone, Lauryl Trimethicone, Linoleamidopropyl PG-Dimonium Chloride Phos- phate Dimethicone, Methacryloyl Propyltrimethoxysilane, Methicone, Methoxy Amodimethi- cone/Silsesquioxane Copolymer, Methoxycinnamidopropyl Polysilsesquioxane, Methox- ycinnamoylpropyl Silsesquioxane Silicate, Methoxy PEG-13 Ethyl Polysilsesquioxane, Methoxy PEG/PPG-7/3 Aminopropyl Dimethicone, Methoxy PEG/PPG-25/4 Dimethicone, Methoxy PEG-10 Propyltrimethoxysilane, Methyleugenyl PEG- 8 Dimethicone, Methylpolysiloxane Emulsion, Methylsilanol Acetylmethionate, Methylsilanol Acetyltyrosine, Methylsilanol Ascor- bate, Methylsilanol Carboxymethyl Theophylline, Methylsilanol Carboxymethyl Theophylline Alginate, Methylsilanol Elastinate, Methylsilanol Glycyrrhizinate, Methylsilanol Hydroxypro- line, Methylsilanol Hydroxyproline Aspartate, Methylsilanol Mannuronate, Methylsilanol PCA, Methylsilanol PEG-7 Glyceryl Cocoate, Methylsilanol/Silicate Crosspolymer, Methylsilanol Spirulinate, Methylsilanol Tri-PEG-8 Glyceryl Cocoate, Methyl Trimethicone, Methyltrimethox- ysilane, Myristylamidopropyl Dimethylamine Dimethicone PEG-7 Phosphate, Myristyl Methi- cone, Myristyl Trisiloxane, Nylon-611/Dimethicone Copolymer, PCA Dimethicone, PEG-7 Amodimethicone, PEG-8 Amodimethicone, PEG-8 Cetyl Dimethicone, PEG-3 Dimethicone, PEG-6 Dimethicone, PEG-7 Dimethicone, PEG-8 Dimethicone, PEG-9 Dimethicone, PEG-10 Dimethicone, PEG-12 Dimethicone, PEG-14 Dimethicone, PEG-17 Dimethicone, PEG-10 Di- methicone Crosspolymer, PEG-12 Dimethicone Crosspolymer, PEG-8 Dimethicone Dimer Dilinoleate, PEG-8 Dimethicone/Dimer Dilinoleic Acid Copolymer, PEG-10 Dimethicone/Vinyl Dimethicone Crosspolymer, PEG-8 Distearmonium Chloride PG-Dimethicone, PEG-10/Lauryl Dimethicone Crosspolymer, PEG- 15/Lauryl Dimethicone Crosspolymer, PEG-15/Lauryl Poly- dimethylsiloxyethyl Dimethicone Crosspolymer, PEG-8 Methicone, PEG-6 Methicone Acetate, PEG-6 Methyl Ether Dimethicone, PEG- 7 Methyl Ether Dimethicone, PEG-8 Methyl Ether Di- methicone, PEG-9 Methyl Ether Dimethicone, PEG-10 Methyl Ether Dimethicone, PEG-11 Me- thyl Ether Dimethicone, PEG-32 Methyl Ether Dimethicone, PEG-8 Methyl Ether Triethox- ysilane, PEG-10 Nonafluorohexyl Dimethicone Copolymer, PEG-4 PEG-12 Dimethicone, PEG-8 PG-Coco-Glucoside Dimethicone, PEG-9 Polydimethylsiloxyethyl Dimethicone, PEG/PPG- 20/22 Butyl Ether Dimethicone, PEG/PPG-22/22 Butyl Ether Dimethicone, PEG/PPG-23/23 Butyl Ether Dimethicone, PEG/PPG-24/18 Butyl Ether Dimethicone, PEG/PPG-27/9 Butyl Ether Dimethicone, PEG/PPG-3/10 Dimethicone, PEG/PPG-4/12 Dimethicone, PEG/PPG-6/4 Dime- thicone, PEG/PPG-6/11 Dimethicone, PEG/PPG-8/14 Dimethicone, PEG/PPG-8/26 Dimethi- cone, PEG/PPG-10/2 Dimethicone, PEG/PPG-12/16 Dimethicone, PEG/PPG- 12/18 Dimethi- cone, PEG/PPG-14/4 Dimethicone, PEG/PPG-15/5 Dimethicone, PEG/PPG- 15/15 Dimethicone, PEG/PPG-16/2 Dimethicone, PEG/PPG-16/8 Dimethicone, PEG/PPG- 17/18 Dimethicone, PEG/PPG-18/6 Dimethicone, PEG/PPG-18/12 Dimethicone, PEG/PPG- 18/18 Dimethicone, PEG/PPG-19/19 Dimethicone, PEG/PPG-20/6 Dimethicone, PEG/PPG-
SUBSTITUTE SHEET (RULE 26) 20/15 Dimethicone, PEG/PPG-20/20 Dimethicone, PEG/PPG-20/23 Dimethicone, PEG/PPG- 20/29 Dimethicone, PEG/PPG-22/23 Dimethicone, PEG/PPG-22/24 Dimethicone, PEG/PPG- 23/6 Dimethicone, PEG/PPG-25/25 Dimethicone, PEG/PPG-27/27 Dimethicone, PEG/PPG- 30/10 Dimethicone, PEG/PPG-25/25 Dimethicone/ Acrylates Copolymer, PEG/PPG-20/22 Me- thyl Ether Dimethicone, PEG/PPG-24/24 Methyl Ether Glycidoxy Dimethicone, PEG/PPG-10/3 Oleyl Ether Dimethicone, PEG/PPG-5/3 Trisiloxane, PEG-4 Trifluoropropyl Dimethicone Co- polymer, PEG-8 Trifluoropropyl Dimethicone Copolymer, PEG-10 Trifluoropropyl Dimethi- cone Copolymer, PEG-8 Trisiloxane, Perfluorocaprylyl riethoxysilylethyl Methicone, Perfluoro- nonyl Dimethicone, Perfluorononyl Dimethicone/Methicone/Amodimethicone Crosspolymer, Perfluorononylethyl Carboxydecyl Behenyl Dimethicone, Perfluorononylethyl Carboxydecyl Hexacosyl Dimethicone, Perfluorononylethyl Carboxydecyl Lauryl/Behenyl Dimethicone, Per- fluorononylethyl Carboxydecyl Lauryl Dimethicone, Perfluorononylethyl Carboxydecyl PEG-8 Dimethicone, Perfluorononylethyl Carboxydecyl PEG-10 Dimethicone, Perfluorononylethyl Dimethicone/Methicone Copolymer, Perfluorononylethyl PEG-8 Dimethicone, Perfluorono- nylethyl Stearyl Dimethicone, Perfluorooctylethyl/Diphenyl Dimethicone Copolymer, Perfluo- rooctylethyl Triethoxysilane, Perfluorooctylethyl Trimethoxysilane, Perfluorooctylethyl Trisiloxane, Perfluorooctyl Triethoxysilane, PG-Amodimethicone, Phenethyl Dimethicone, Phenethyl Disiloxane, Phenyl Dimethicone, Phenylisopropyl Dimethicone, Phenyl Methicone, Phenyl Methiconol, Phenylpropyldimethylsiloxysilicate, Phenylpropyl Ethyl Methicone, Phenyl Propyl Trimethicone, Phenyl Propyl Trimethicone/Diphenylmethicone, Phenyl Trimethicone, Platinum Divinyldisiloxane, Polyacrylate-6, Polydiethylsiloxane, Polydimethylsiloxyethyl Dime- thicone/Bis-Vinyldimethicone Crosspolymer, Polydimethylsiloxyethyl Dimethicone/Methicone Copolymer, Polydimethylsiloxy PEG/PPG-24/19 Butyl Ether Silsesquioxane, Polydimethylsiloxy PPG- 13 Butyl Ether Silsesquioxane, Polyglyceryl-3 Disiloxane Dimethicone, Polyglyceryl- 3/Lauryl Polydimethylsiloxyethyl Dimethicone Crosspolymer, Polyglyceryl-3 Polydime- thylsiloxyethyl Dimethicone, Poly(Glycol Adipate)/Bis-Hydroxyethoxypropyl Dimethicone Co- polymer, Polymethylsilsesquioxane, Polymethylsilsesquioxane/Trimethylsiloxysilicate, Poly- phenylsilsesquioxane, Polypropylsilsesquioxane, Polysilicone-1, Polysilicone-2, Polysilicone-3, Polysilicone-4, Polysilicone-5, Polysilicone-6, Polysilicone-7, Polysilicone-8, Polysilicone-9, Polysilicone-10, Polysilicone-11, Polysilicone-12, Polysilicone-13, Polysilicone-14, Polysili- cone-15, Polysilicone-16, Polysilicone-17, Polysilicone-18, Polysilicone-19, Polysilicone-20, Polysilicone-21, Polysilicone-18 Cetyl Phosphate, Polysilicone-1 Crosspolymer, Polysilicone- 18 Stearate, Polyurethane-10, Potassium Dimethicone PEG-7 Panthenyl Phosphate, Potassi- um Dimethicone PEG- 7 Phosphate, PPG-12 Butyl Ether Dimethicone, PPG-2 Dimethicone, PPG-12 Dimethicone, PPG-27 Dimethicone, PPG-4 Oleth-10 Dimethicone, Propoxytetrame- thyl Piperidinyl Dimethicone, Propyl Trimethicone, Quaternium-80, Retinoxytrimethylsilane, Silanediol Salicylate, Silanetriol, Silanetriol Arginate, Silanetriol Glutamate, Silanetriol Lysinate, Silanetriol Melaninate, Silanetriol Trehalose Ether, Silica, Silica Dimethicone Silylate, Silica Di- methyl Silylate, Silica Silylate, Silicon Carbide, Silicone Quaternium-1, Silicone Quaternium-2, Silicone Quaternium-2 Panthenol Succinate, Silicone Quaternium-3, Silicone Quaternium-4, Silicone Quaternium-5, Silicone Quaternium-6, Silicone Quaternium-7, Silicone Quaternium-
SUBSTITUTE SHEET (RULE 26) 8, Silicone Quaternium-9, Silicone Quaternium-10, Silicone Quaternium-11, Silicone Quater- nium-12, Silicone Quaternium-15, SiliconeQuaternium-16, Silicone Quaternium-16/Glycidoxy Dimethicone Crosspolymer, Silicone Quaternium-17, Silicone Quaternium- 18, Silicone Qua- ternium-19, Silicone Quaternium-20, Silicone Quaternium-21, Silicone Quaternium- 22, Sili- cone Quaternium-24, Silicone Quaternium-25, Siloxanetriol Alginate, Siloxanetriol Phytate, Simethicone, Sodium Carboxydecyl PEG-8 Dimethicone, Sodium Dimethicone PEG-7 Acetyl Methyltaurate, Sodium Hyaluronate Dimethylsilanol, Sodium Lactate Methylsilanol, Sodium Mannuronate Methylsilanol, Sodium PCA Methylsilanol, Sodium PG-Propyldimethicone Thio- sulfate Copolymer, Sodium PG-Propyl Thiosulfate Dimethicone, Sodium Propoxyhydroxypro- pyl Thiosulfate Silica, Sorbityl Silanediol, Soy Triethoxysilylpropyldimonium Chloride, Stea- ralkonium Dimethicone PEG-8 Phthalate, Stearamidopropyl Dimethicone, Steardimonium Hydroxypropyl Panthenyl PEG-7 Dimethicone Phosphate Chloride, Steardimonium Hydroxy- propyl PEG-7 Dimethicone Phosphate Chloride, Stearoxy Dimethicone, Stearoxymethi- cone/Dimethicone Copolymer, Stearoxytrimethylsilane, Stearyl Aminopropyl Methicone, Stearyl Dimethicone, Stearyl/Lauryl Methacrylate Crosspolymer, Stearyl Methicone, Stearyl Triethoxysilanek, Stearyl Trimethicone, Styrene/Acrylates/Dimethicone Acrylate Crosspolymer, Styrene/Acrylates/Dimethicone Copolymer, TEA-Dimethicone PEG-7 Phosphate, Tetrabutox- ypropyl Trisiloxane, Tetramethyl Hexaphenyl Tetrasiloxane, Tetramethyl Tetraphenyl Trisilox- ane, Tocopheryloxypropyl Trisiloxane, Trideceth-9 PG-Amodimethicone, Triethoxycapry- lylsilane, Triethoxysilylethyl Dimethicone/Methicone Copolymer, Triethoxysilylethyl Polydime- thylsiloxyethyl Dimethicone, Triethoxysilylethyl Polydimethylsiloxyethyl Hexyl Dimethicone, Triethoxysilylpropylcarbamoyl Ethoxypropyl Butyl Dimethicone, Trifluoromethyl C1 -4 Alkyl Dimethicone, Trifluoropropyl Cyclopentasiloxane, Trifluoropropyl Cyclotetrasiloxane, Tri- fluoropropyl Dimethicone, Trifluoropropyl Dimethicone/PEG-10 Crosspolymer, Trifluoropro- pyl Dimethicone/Trifluoropropyl Divinyldimethicone Crosspolymer, Trifluoropropyl Dimethi- cone/Vinyl Trifluoropropyl, Dimethicone/Silsesquioxane Crosspolymer, Trifluoropropyl Dime- thiconol, Trifluoropropyldimethyl/trimethylsiloxysilicate, Trifluoropropyl Methicone, Tri- methoxycaprylylsilane, Trimethoxysilyl Dimethicone, Trimethyl Pentaphenyl Trisiloxane, Tri- methylsiloxyamodimethicone, Trimethylsiloxyphenyl Dimethicone, Trimethylsiloxysilicate, Trimethylsiloxysilicate/Dimethicone Crosspolymer, Trimethylsiloxysilicate/Dimethiconol Crosspolymer, Trimethylsiloxysilylcarbamoyl Pullulan, Trimethylsilyl Hydrolyzed Conchiolin Protein PG-Propyl Methylsilanediol Crosspolymer, Trimethylsilyl Hydrolyzed Silk PG-Propyl Methylsilanediol Crosspolymer, Trimethylsilyl Hydrolyzed Wheat Protein PG-Propyl Me- thylsilanediol Crosspolymer, Trimethylsilyl Pullulan, Trimethylsilyl Trimethylsiloxy Glycolate, Trimethylsilyl Trimethylsiloxy Lactate, Trimethylsilyl Trimethylsiloxy Salicylate, Triphenyl Tri- methicone, Trisiloxane, Tris-Tributoxysiloxymethylsilane, Undecylcrylene Dimethicone, Vinyl Dimethicone, Vinyl Dimethicone/Lauryl Dimethicone Crosspolymer, Vinyl Dimethi- cone/Methicone Silsesquioxane Crosspolymer, Vinyldimethyl/Trimethylsiloxysilicate Stearyl Dimethicone Crosspolymer, VP/Dimethiconylacrylate/Polycarbamyl/Polyglycol Ester, Zinc Carboxydecyl Trisiloxane and Zinc Dimethicone PEG-8 Succinate and mixtures thereof.
SUBSTITUTE SHEET (RULE 26) [0043] More preferably the silicones to be contained in the mixture according to the inven- tions are Dimethicone, Cyclomethicone, Phenyl Trimethicone, Cyclohexasiloxane and Cyclo- pentasiloxane. A detailed overview of suitable volatile silicones can be found in Todd et al. in Cosm. Toil. 91. 27 (1976).
Waxes and stabilizers
[0044] Besides natural oils used, waxes may also be present in the preparations, more espe- cially natural waxes such as, for example, candelilla wax, carnauba wax, Japan wax, espar- tograss wax, cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffin waxes and microwaxes; chemically modified waxes (hard waxes) such as, for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxes and syn- thetic waxes such as, for example, polyalkylene waxes and polyethylene glycol waxes.
[0045] Metal salts of fatty acids such as, for example, magnesium, aluminium and/or zinc stearate or ricinoleate may be used as stabilizers.
Primary sun protection filters
[0046] Primary sun protection factors in the context of the invention are, for example, organ- ic substances (light filters) which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet radiation and of releasing the energy absorbed in the form of longer-wave radiation, for example heat.
[0047] The formulations according to the invention advantageously contain 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. Formulations according to the invention preferably contain at least one UV-B filter or a broadband filter, more particularly preferably at least one UV-A filter and at least one UV-B filter.
[0048] Preferred cosmetic compositions, preferably topical formulations according to the present invention comprise one, two, three or more sun protection factors selected from the group consistiung of 4-aminobenzoic acid and derivatives, salicylic acid derivatives, benzo- phenone derivatives, dibenzoylmethane derivatives, diphenyl acrylates, 3-imidazol-4-yl acryl- ic acid and esters thereof, benzofuran derivatives, benzylidene malonate derivatives, poly- meric UV absorbers containing one or more organosilicon radicals, cinnamic acid derivatives, camphor derivatives, trianilino-s-triazine derivatives, 2-hydroxyphenylbenzotriazole deriva- tives, phenylbenzimidazole sulfonic acid derivatives and salts thereof, anthranilic acid menthyl esters, benzotriazole derivativesand indole derivatives.
[0049] In addition, it is advantageous to combine compounds of formula (I) with active in- gredients which penetrate into the skin and protect the skin cells from inside against sun-
SUBSTITUTE SHEET (RULE 26) light-induced damage and reduce the level of cutaneous matrix metalloproteases. Preferred respective ingredients, so called arylhydrocarbon receptor antagonists, are described in WO 2007/128723, incorporated herein by reference. Preferred is 2-benzylidene-5,6-dimethoxy- 3,3-dimethylindan-1 -one.
[0050] The UV filters cited below which can be used within the context of the present inven- tion are preferred but naturally are not limiting.
[0051] UV filters which are preferably used 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 (homosalates) (Neo Heliopan®HMS)
• salicylic acid-2-ethylhexyl ester (Neo Heliopan®OS)
• triethanolamine salicylate
• 4-isopropyl benzyl salicylate
• anthranilic acid menthyl ester (Neo Heliopan®MA)
• diisopropyl cinnamic acid ethyl ester
• p-methoxycinnamic acid-2-ethylhexyl ester (Neo Heliopan®AV)
• diisopropyl cinnamic acid methyl ester
• p-methoxycinnamic acid isoamyl ester (Neo Heliopan®E 1000)
• p-methoxycinnamic acid diethanolamine salt
• p-methoxycinnamic acid isopropyl ester
• 2-phenylbenzimidazole sulfonic acid and salts (Neo Heliopan®Hydro)
• 3-(4'-trimethylammonium) benzylidene bornan-2-one methyl sulfate
• beta-imidazole-4(5)-acrylic acid (urocanic acid)
• 3-(4'-sulfo)benzylidene bornan-2-one and salts
• 3-(4'-methyl benzylidene)-D,L-camphor (Neo Heliopan®MBC)
• 3-benzylidene-D,L-camphor
• N-[(2 and 4)-[2-(oxoborn-3-ylidene) methyl] benzyl] acrylamide polymer
SUBSTITUTE SHEET (RULE 26) • 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)
• benzylidene malonate 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).
[0052] Broadband filters which are preferably combined with one or more compounds of formula (I) in a preparation according to the present invention are selected from the group consisting of
• 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (Neo Heliopan®303)
• ethyl-2-cyano-3,3'-diphenyl acrylate
• 2-hydroxy-4-methoxybenzophenone (Neo Heliopan®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'-methyl benzophenone
• sodium hydroxymethoxybenzophenone 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 -(trime- thylsilyl)oxy)disiloxyanyl) propyl) (Mexoryl®XL)
• 2,2'-methylene bis-(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-hydroxy}phenyl]-6-(4- methoxyphenyl)-1,3,5-triazine sodium salt
SUBSTITUTE SHEET (RULE 26) • 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-methoxyethyl carbonyl) 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.
[0053] The compositions can comprise further typical detergent and cleansing composition ingredients such as UV-A filters filters which are preferably combined with one or more com- pounds of formula (I) in a preparation according to the present invention are selected from the group consisting of
• 4-isopropyl dibenzoyl methane
• terephthalylidene dibornane sulfonic acid and salts (Mexoryl®SX)
• 4-t-butyl-4'-methoxydibenzoyl methane (avobenzone) I (Neo Heliopan®357)
• phenylene bis-benzimidazyl tetrasulfonic acid disodium salt (Neo Heliopan®AP)
• 2,2'-(1,4-phenylene)-bis-(1 H-benzimidazole-4,6-disulfonic acid), monosodium salt
• 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester (Uvinul® A Plus)
• indanylidene compounds in accordance with DE 100 55 940 A1 (= WO 2002 038537 A1)
[0054] The compositions can comprise further typical detergent and cleansing composition ingredients such as UV filters which are more preferably combined with one or more com- pounds of formula (I) in a preparation according to the present invention are selected from the group consisting of
• p-aminobenzoic acid
• 3-(4'-trimethylammonium) benzylidene bornan-2-one methyl sulfate
• salicylic acid homomenthyl ester (Neo Heliopan®HMS)
• 2-hydroxy-4-methoxybenzophenone (Neo Heliopan®BB)
SUBSTITUTE SHEET (RULE 26) • 2-phenylbenzimidazole sulfonic acid (Neo Heliopan®Hydro)
• terephthalylidene dibornane sulfonic acid and salts (Mexoryl®SX)
• 4-tert-butyl-4'-methoxydibenzoyl methane (Neo Heliopan®357)
• 3-(4'-sulfo)benzylidene bornan-2-one and salts
• 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (Neo Heliopan®303)
• N-[(2 and 4)-[2-(oxoborn-3-ylidene) methyl] benzyl] acrylamide polymer
• p-methoxycinnamic acid-2-ethylhexyl ester (Neo Heliopan®AV)
• p-aminobenzoic acid ethyl ester (25 mol) ethoxylated (INCI name: PEG-25 PABA)
• p-methoxycinnamic acid isoamyl ester (Neo Heliopan®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 -(trime- thylsilyl)oxy)disiloxyanyl) propyl) (Mexoryl®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'-methyl benzylidene)-D,L-camphor (Neo Heliopan®MBC)
• 3-benzylidene camphor
• salicylic acid-2-ethylhexyl ester (Neo Heliopan®OS)
• 4-dimethylaminobenzoic acid-2-ethylhexyl ester (Padimate O)
• hydroxy-4-methoxybenzophenone-5-sulfonic acid and Na salt
• 2,2'-methylene bis-(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl) phenol) (Tinosorb®M)
• phenylene bis-benzimidazyl tetrasulfonic acid disodium salt (Neo Heliopan®AP)
• 2,4-bis-[{(4-(2-ethylhexyloxy)-2-hydroxy}phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (Tinosorb®S)
• benzylidene malonate polysiloxane (Parsol®SLX)
• menthyl anthranilate (Neo Heliopan®MA)
• 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester (Uvinul® A Plus)
• indanylidene compounds in accordance with DE 100 55 940 (= WO 02/38537).
[0055] Advantageous primary and also secondary sun protection factors are mentioned in WO 2005 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 such as are conventionally used for sun protection prepara-
SUBSTITUTE SHEET (RULE 26) tions. Thus, they may be in form of a solution, an emulsion of the water-in-oil type (W/O) or of the oil-in-water type (O/W) or a multiple emulsion, for example of the water-in-oil-in- water type (W/O/W), a gel, a hydrodispersion, a solid stick or else an aerosol.
[0056] In a further preferred embodiment a formulation according to the invention contains a total amount of sunscreen agents, i.e. in particular UV filters and/or inorganic pigments (UV filtering pigments) so that the formulation according to the invention has a light protection factor of greater than or equal to 2 (preferably greater than or equal to 5). Such formulations according to the invention are particularly suitable for protecting the skin and hair.
Secondary sun protection filters
[0057] Besides the groups of primary sun protection factors mentioned above, secondary sun protection factors of the antioxidant type may also be used. Secondary sun protection factors of the antioxidant type interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin. Typical examples are amino acids (for example glycine, histidine, tyrosine, tryptophane) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (for example anserine), carotinoids, carotenes (for example alpha- carotene, beta-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, liponic acid and derivatives thereof (for example dihydroliponic acid), aurothioglu- cose, propylthiouracil and other thiols (for example thioredoxine, glutathione, cysteine, cys- tine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, alpha-linoleyl, cholesteryl and glyceryl esters thereof) and their salts, dilaurylthiodi- propionate, distearylthiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (for example butionine sulfoximines, homocysteine sulfoximine, butionine sulfones, penta-, hexa- and hepta-thionine sulfoximine) in very small compatible dosages, also (metal) chelators (for example alpha-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrine), alpha-hydroxy ac- ids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (for example linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiq- uinol and derivatives thereof, vitamin C and derivatives thereof (for example ascorbyl palmi- tate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vit- amin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, man- nose and derivatives thereof, superoxide dismutase, titanium dioxide (for example disper- sions in ethanol), zinc and derivatives thereof (for example ZnO, ZnSCU), selenium and deriva- tives thereof (for example selenium methionine), stilbenes and derivatives thereof (for exam-
SUBSTITUTE SHEET (RULE 26) pie stilbene oxide, trans-stilbene oxide) and derivatives of these active substances suitable for the purposes of the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids).
[0058] Advantageous inorganic secondary light protection pigments are finely dispersed metal oxides and metal salts which are also mentioned in WO 2005 123101 A1. The total quantity of inorganic pigments, in particular hydrophobic inorganic micro-pigments in the finished cosmetic preparation according to the present invention is advantageously from 0.1 to 30% by weight, preferably 0.5 to 10.0% by weight, in each case based on the total weight of the preparation.
[0059] Also preferred are particulate UV filters or inorganic pigments, which can optionally be hydrophobed, can be used, such as the oxides of titanium (TiO2), zinc (ZnO), iron (Fe2O3), zirconium (ZrO2), silicon (SiO2), manganese (e.g. MnO), aluminium (AI2O3), cerium (e.g. Ce2O3) and/or mixtures thereof.
Anti-inflammatory agents
[0060] Suitable anti-inflammatory agent encompass in particular steroidal substances of the corticosteroid type selected from the group consisting of hydrocortisone, dexamethasone, dexamethasone phosphate, methyl prednisolone or cortisone, are advantageously used as anti-inflammatory active ingredients or active ingredients to relieve reddening and itching, the list of which can be extended by the addition of other steroidal anti-inflammatories. Non- steroidal anti-inflammatories can also be used. More particularly:
(i) steroidal anti-inflammatory substances of the corticosteroid type, in particular hydro- cortisone, hydrocortisone derivatives such as hydrocortisone 17-butyrate, dexame- thasone, dexamethasone phosphate, methylprednisolone or cortisone,
(ii) non-steroidal anti-inflammatory substances, in particular oxicams such as piroxicam or tenoxicam, salicylates such as aspirin, disalcid, solprin or fendosal, acetic acid deriv- atives such as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or clindanac, fenamates such as mefenamic, meclofenamic, flufenamic or niflumic, propionic acid derivatives such as ibuprofen, naproxen or benoxaprofen, pyrazoles such as phenyl- butazone, oxyphenylbutazone, febrazone or azapropazone,
(iii) natural or naturally occuring anti-inflammatory substances or substances that allevi- ate reddening and/or itching, in particular extracts or fractions from camomile, Aloe vera, Commiphora species, Rubia species, willow, willow-herb, oats, calendula, arnica, St John's wort, honeysuckle, rosemary, Passiflora incarnata, witch hazel, ginger or Echinacea, or single active compounds thereof,
(iv) histamine receptor antagonists, serine protease inhibitors (e.g. of Soy extracts), TRPV1 antagonists (e.g. 4-t-Butylcyclohexanol), NK1 antagonists (e.g. Aprepitant, Hydroxy-
SUBSTITUTE SHEET (RULE 26) phenyl Propamidobenzoic Acid), cannabinoid receptor agonists (e.g. Palmitoyl Ethan- olamine) and TRPV3 antagonists.
[0061] Examples which can be cited here are oxicams such as piroxicam or tenoxicam; salicy- lates such as aspirin, disalcid, solprin or fendosal; acetic acid derivatives such as diclofenac, fenclofenac, indomethacin, sulindac, tolmetin or clindanac; fenamates such as mefenamic, meclofenamic, flufenamic or niflumic; propionic acid derivatives such as ibuprofen, naproxen, benoxaprofen or pyrazoles such as phenylbutazone, oxyphenylbutazone, febrazone or azapropazone. Anthranilic acid derivatives, in particular avenanthramides described in WO 2004 047833 A1, are also preferred in a composition according to the present invention.
[0062] Also useful are natural or naturally occurring anti-inflammatory mixtures of substanc- es or mixtures of substances such as for example alpha-bisabolol, apigenin, apigenin-7- glucoside, gingerols, shogaols, gingerdiols, dehydrogingerdiones, paradols, natural or natu- rally occuring avenanthramides, preferably tranilast, avenanthramide A, avenanthramide B, avenanthramide C, non-natural or non-naturally occuring avenanthramides, preferably dihy- droavenanthramide D, dihydroavenanthramide E, avenanthramide D, avenanthramide E, av- enanthramide F, boswellic acid, phytosterols, glycyrrhizin, glabridin and licochalcone A; pref- erably selected from the group consisting of alpha-bisabolol, natural avenanthramides, non- natural avenanthramides, preferably dihydroavenanthramide D (as described in WO 2004 047833 A1), and/or allantoin, panthenol, lanolin, (pseudo-)ceramides [preferably Ceramide 2, hydroxypropyl bispalmitamide MEA, cetyloxypropyl glyceryl methoxypropyl myristamide, N- (1-hexadecanoyl)-4-hydroxy-L-proline (1 -hexadecyl) ester, hydroxyethyl palmityl oxyhydrox- ypropyl palmitamide], glycosphingolipids, phytosterols, chitosan, mannose, lactose and beta- glucans, in particular 1,3-1,4-beta-glucan from oats.
[0063] When bisabolol is used in the context of the present invention it can be of natural or synthetic origin, and is preferably "alpha-bisabolol". Preferably, the bisabolol used is syn- thetically prepared or natural (-)-alpha-bisabolol and/or synthetic mixed-isomer alpha- bisabolol. If natural (-)-alpha-bisabolol is used, this can also be employed as a constituent of an essential oil or of a plant extract or of a fraction thereof, for example as a constituent of (fractions of) oil or extracts of camomile or of Vanillosmopsis (in particular Vanillosmopsis erythropappa or Vanillosmopsis arborea). Synthetic alpha-bisabolol is obtainable, for exam- ple, under the name "Dragosantol" from Symrise.
[0064] In case ginger extract is used in the context of the present invention, preferably ex- tracts of the fresh or dried ginger root are used which are prepared by extraction with meth- anol, ethanol, iso-propanol, acetone, ethyl acetate, carbon dioxide (CO2), hexane, methylene chloride, chloroform or other solvents or solvent mixtures of comparable polarity. The ex- tracts are characterized by the presence of active skin irritation-reducing amounts of constit- uents such as e.g. gingerols, shogaols, gingerdiols, dehydrogingerdiones and/or paradols.
SUBSTITUTE SHEET (RULE 26) Physiological cooling agents
[0065] The compositions may also contain one or more substances with a physiological cool- ing effect (cooling agents), which are preferably selected here from the following list: men- thol and menthol derivatives (for example L-menthol, D-menthol, racemic menthol, isomen- thol, neoisomenthol, neomenthol) menthylethers (for example (l-menthoxy)-1,2-propandiol, (l-menthoxy)-2-methyl-1,2-propandiol, l-menthyl-methylether), menthylesters (for example menthylformiate, menthylacetate, menthylisobutyrate, menthyllactates, L-menthyl-L-lactate, L-menthyl-D-lactate, menthyl-(2-methoxy)acetate, menthyl-(2-methoxyethoxy)acetate, menthylpyroglutamate), menthylcarbonates (for example menthylpropyleneglycolcarbonate, menthylethyleneglycolcarbonate, menthylglycerolcarbonate or mixtures thereof), the semi- esters of menthols with a dicarboxylic acid or derivatives thereof (for example mono- menthylsuccinate, mono-menthylglutarate, mono-menthylmalonate, O-menthyl succinic acid ester-N,N-(dimethyl)amide, O-menthyl succinic acid ester amide), menthanecarboxylic acid amides (in this case preferably menthanecarboxylic acid-N-ethylamide [WS3] or Na- (menthanecarbonyl)glycinethylester [WS5], as described in US 4,150,052, menthanecarbox- ylic acid-N-(4-cyanophenyl)amide or menthanecarboxylic acid-N-(4-cyanomethylphenyl)- amide as described in WO 2005 049553 A1, methanecarboxylic acid-N-(alkoxyalkyl)amides), menthone and menthone derivatives (for example L-menthone glycerol ketal), 2,3-dimethyl-
2-(2-propyl)-butyric acid derivatives (for example 2,3-dimethyl-2-(2-propyl)-butyric acid-N- methylamide [WS23]), isopulegol or its esters (l-(-)-isopulegol, l-(-)-isopulegolacetate), men- thane derivatives (for example p-menthane-3,8-diol), cubebol or synthetic or natural mix- tures, containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (for example
3-methyl-2(1-pyrrolidinyl)-2-cyclopentene-1-one) or tetrahydropyrimidine-2-one (for exam- ple iciline or related compounds, as described in WO 2004/026840), further carboxamides (for example N-(2-(pyridin-2-yl)ethyl)-3-p-menthanecarboxamide or related compounds), (1R,2S,5R)-N-(4-Methoxyphenyl)-5-methyl-2-(1-isopropyl)cyclohexane-carboxamide [WS12], oxamates (preferably those described in EP 2033688 A2).
Anti-microbial agents
[0066] Suitable anti-microbial agents are, in principle, all substances effective against Gram- positive bacteria, such as, 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 (triclo- san), 4-chloro-3,5-dimethyl-phenol, 2,2'-methylenebis(6-bromo-4- chlorophenol), 3-methyl-
4-(1-methylethyl)phenol, 2-benzyl-4-chloro-phenol, 3-(4-chlorophenoxy)-1,2-propanediol, 3- iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, oil of cloves, menthol, mint oil, farnesol, phenoxy- ethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglyc- erol monocaprate (DMC), salicylic acid N-alkylamides, such as, for example, n- octylsalicylamide or n- decylsalicylamide.
SUBSTITUTE SHEET (RULE 26) Preservatives
[0067] Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of compounds listed in Appendix 6, Parts A and B of the Kosmetikverordnung ("Cosmetics Directive").
Preparations
[0068] Preferred compositions according to the present inventions are selected from the group of products for treatment, protecting, care and cleansing of the skin and/or hair or as a make-up product, preferably as a leave-on product (meaning that the one or more com- pounds of formula (I) stay on the skin and/or hair for a longer period of time, compared to rinse-off products, so that the moisturizing and/or anti-ageing and/or wound healing pro- moting action thereof is more pronounced).
[0069] The formulations according to the invention are preferably in the form of an emul- sion, e.g. 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) emulsion, PIT emulsion, Pickering emulsion, emulsion with a low oil content, micro- or nanoemulsion, a solution, e.g. in oil (fatty oils or fatty acid esters, in particular C&- C32 fatty acid C2-C30 esters) or silicone oil, dispersion, suspension, creme, lotion or milk, de- pending on the production method and ingredients, a gel (including hydrogel, hydrodisper- sion gel, oleogel), spray (e.g. pump spray or spray with propellant) or a foam or an impreg- nating solution for cosmetic wipes, a detergent, e.g. soap, synthetic detergent, liquid wash- ing, shower and bath preparation, bath product (capsule, oil, tablet, salt, bath salt, soap, etc.), effervescent preparation, a skin care product such as e.g. an emulsion (as described above), ointment, paste, gel (as described above), oil, balsam, serum, powder (e.g. face powder, body powder), eau de perfume, eau de toilette, after-shave, a mask, a pencil, stick, roll-on, pump, aerosol (foaming, non-foaming or post-foaming), a deodorant and/or antiperspirant, mouthwash and mouth rinse, a foot care product (including keratolytic, deodorant), an insect repellent, a sunscreen, aftersun preparation, a shaving product, aftershave balm, pre- and aftershave lotion, a depilatory agent, a hair care product such as e.g. shampoo (including 2- in-1 shampoo, anti-dandruff shampoo, baby shampoo, shampoo for dry scalps, concentrated shampoo), conditioner, hair tonic, hair water, hair rinse, styling creme, pomade, perm and setting lotion, hair spray, styling aid (e.g. gel or wax), hair smoothing agent (detangling agent, relaxer), hair dye such as e.g. temporary direct-dyeing hair dye, semi-permanent hair dye, permanent hair dye, hair conditioner, hair mousse, eye care product, make-up, make-up remover or baby product.
[0070] The formulations according to the invention are particularly preferably in the form of an emulsion, in particular in the form of a W/O, O/W, W/O/W, O/W/O emulsion, PIT emul- sion, Pickering emulsion, emulsion with a low oil content, micro- or nanoemulsion, a gel (in- cluding hydrogel, hydrodispersion gel, oleogel), a solution e.g. in oil (fatty oils or fatty acid
SUBSTITUTE SHEET (RULE 26) esters, in particular C6-C32 fatty acid C2-C30 esters)) or silicone oil, or a spray (e.g. pump spray or spray with propellant).
[0071] Auxiliary substances and additives can be included in quantities of 5 to 99 % b.w., preferably 10 to 80 % b.w., based on the total weight of the formulation. The amounts of cosmetic or dermatological auxiliary agents and additives and perfume to be used in each case can easily be determined by the person skilled in the art by simple trial and error, de- pending on the nature of the particular product.
[0072] The preparations can also contain water in a quantity of up to 99 % b.w., preferably 5 to 80 % b.w., based on the total weight of the preparation
INDUSTRIAL APPLICATION
[0073] Another object of the present invention concerns a non-therapeutical method for strengthening human connective tissue comprising or consisting of the following steps:
(a) providing the agonists as defined above optionally dissolved in a pharmaceutically ac- ceptable carrier,
(b) applying the agonists or a composition comprising them topically to the skin of an in- dividual.
[0074] Finally, the present invention covers the use of agonists as defined above for strengthening human tissue, particular female skin.
[0075] Finally, the present invention also refers to the use of said agonists of olfactory recep- tors as cosmetic ingredients. For the sake of good order it is emphasized that all preferred embodiments, ranges, combinations and compositions as described above are also valid with respective to the claimed industrial applications. Any repretition is therefor superfluous.
SUBSTITUTE SHEET (RULE 26) EXAMPLES
Examples 1 to 268 For determination of MMPs and TIMPs expression HaCat keratinocytes were seeded in 24 well plates incubated with PolylC (10 pg/ml) in absence and presence of the test samples (3 doses, n=2) for 24 hours. Unstimulated cells served as negative control. 24 h after cell stimu- lation, supernatants were removed, centrifuged and investigated for MMP1, MMP9 and TIMP1 concentrations by ELISAs (from Biotechne). The results are compiled in Table 1:
Table 1
Effects of samples on inhibition of TMP1, MMP1 and MMP9 expression versus Polyl C control [%] - results are limited to those tests showing reduction in expression for at least 10 % compared to control
Figure imgf000048_0001
0 Control 100 100 100
1 (-) CBD (Cannabidiol) 1 90
2 (-) CBG (Cannabigerol) 0.1 90
3 (-) CBG 0.5 96 90
4 (-) CBG 1 86
5 (+) CBDV (Cannabidivarin) 2.5 90
6 Acetophenone 500 75
7 Aldehyde C8 10 75 80
8 Aldehyde C1 1 0.5 90
9 Aldehyde C12 0.1 88
10 Aldehyde C16 50 60
11 Aldehyde C16 100 50
12 Aldehyde C18 5 - 75
13 Aldehyde C18 10 - 75 80
14 Amber Core 100 86
15 Anethole 10 84
16 Agrunitrile 5 - 83 81
SUBSTITUTE SHEET (RULE 26) Agrunitrile 10 85 70 85
Allyl caproate 1 - 80
Allyl cyclohexyl propionate 2.5 78
Allyl heptoate 2.5 85 70
Allyl phenoxyacetate 81
Allyl phenoxyacetate 10 81
Allyl phenoxyacetate 50 88 78
Amalia oil 10 80
Amalia oil 50 81 81
Amarocit 0.1 75
Amarocit 1 60
Amarocit 5 75
Ambrocenide 0.1 75
Ambrocenide 1 70
Ambrocenide 10 60
Am brostar 10 70
Ambroxide 10 90
Amyl butyrate 25 70
Anisic aldehyde 100 80
Anisic aldehyde 250 60
Benzaldehyde 500 60 90
Benzophenone 10 84 85 87
Benzyl acetone 100 85
Benzyl cinnamate 0.1 80
Benzyl isobutyrate 1 88
Benzyl isobutyrate 25 86
Benzyl propionate 25 82
Borneol/lsoborneol 5 70
Borneol/lsoborneol 10 30
Bourg eonal 1 84 82
Bourg eonal 10 82
SUBSTITUTE SHEET (RULE 26) Bows bioactive bullet 1 0.5 90
Brahmanol 2.5 85 85 85
Butyl acetate 100 84 80 84
Butyl acetate 500 80 75 80
Butyl butyrate 1 80
Butyl butyrate 10 80
Butyl cyclohexanol, p-tert. 5 80
Butyl cyclohexanol, p-tert. 10 75
Camphor 5 88
Camphor 10 68
Cedar wood oil 1 90
Cedar wood oil 10 90 90
Cedar wood oil 25 58 90
Cedryl acetate -I 82
Ceylanil 10 90 85
Ceylanil 25 82 75
Cinnamic alcohol 100 62
Cinnamic alcohol 250 42
Citral diethyl acetal 2.5 90
Citronellyl acetate 0.1 75 48
Citronellyl acetate 0.5 78 38
Citronellyl acetate 1 70 26
Citronellyl isobutyrate 0.25 86
Citronellyl isobutyrate 2.5 90 90
Citronellyl tiglate -I 90
Citronitril 1 - 90
Citronitril 10 90 90
Citronitril 50 67
Clove bud oil 50 61
Cresyl methyl ether 5 - 75
Cyclabute 1 90 85
SUBSTITUTE SHEET (RULE 26) Cyclamen aldehyde 5 85 85
Cyclamen aldehyde 10 75 90
Cyclohexylmagnol 10 85
Cyclohexyl salicylate 5 76
Decalactone, gamma 85
Decalactone, gamma 5 - 85
Decalactone, gamma 10 85
Decyl acetate 5 90
Diethyl malonate 100 78
Diethyl malonate 500 78 63 78
Di hydro myrcenyl acetate 1 - 90
Dimethyl anthranilate 1 84
Dimethyl anthranilate 10 84
Dimethyl anthranilate 25 80 80
Ethyl acetoacetate 100 64 54
Ethyl acetoacetate 500 40
Ethyl butyl butyrate 1 - 70
Ethyl butyl butyrate 10 - 75
Ethyl butyl butyrate 50 - 75
Ethyl butyrate 100 90 90 80
Ethyl butyrate 500 90 90 80
Ethyl cinnamate 10 90
Ethyl cinnamate 25 82
Ethyl linalool 10 80
Ethyl linalyl acetate 2.5 82
Eucalyptus oil 5 85
Eucalyptus oil 10 85
Eugenol 10 70
Fenchol 10 - 90
Fenchol 25 90
Florazon 2.5 85
SUBSTITUTE SHEET (RULE 26) 0 Fragolan 100 861 Frambionon 500 80 90 302 Frambinon methyl ether 1 - 84 783 Frambinon methyl ether 10 90 82 704 Frambinon methyl ether 100 685 Fresiol 25 88 786 Frutinat 2.5 - 75 7 Geranyl acetate 0.1 - 75 658 Geranyl acetate 0.5 - 70 739 Geranyl acetate 1 - 75 0 Geranyl butyrate 0.5 901 Geranyl butyrate 902 Geranyl butyrate 5 903 Geranyl tiglate 1 90 4 Geranyl tiglate 5 88 5 Globalide 0.1 - 85 6 Globalide 1 - 85 7 Globalide 2.5 82 8 Globanone 2.5 78 789 Guaiac wood oil 0.1 900 Guaiac wood oil 901 Guaiac wood oil 2.5 80 752 Heliotropin 100 78 70 683 Heliotropin 500 45 40 484 Herbarome 1 855 Hexyl acetate 25 75 6 Hexenyl acetate 25 807 Hydrocitronitrile 10 908 Hydrocitronitrile 25 - 90 909 Indole 1 - 83 0 Indole 10 - 83
SUBSTITUTE SHEET (RULE 26) Indole 25 - 83
Intreleven aldehyde 1 82
Ionone 0.1 80
Ionone 1 82
Ionone 5 76
Isoamyl acetate 50 58
Isoamyl acetate 100 - 55 55
Isoamyl butyrate 5 - 75
Isoamyl salicylate 0.1 90
Isoamyl salicylate 0.5 80
Isoamyl salicylate 1 70 50
Isoborneol 1 - 90 80
Isoborneol 5 - 90 70
Isoborneol 10 - 80 50
Isoeugenol 1 - 70
Isoeugenol 10 - 78 58
Isoeugenol 25 - 65 56
Isoeugenyl methyl ether 10 90 90 90
Isoeugenyl methyl ether 25 70 70
Isotridecyl acetate 1 - 75
Isotridecyl acetate 10 - 60
Jasmol 5 78 90
Jasmopyrane 25 82
Jessemal 10 84 82
Jessemal 25 62 62
Koavone 10 - 60
Labdanum extract 10 85
Lavandine Espieur 10 75 80 75
Lavender oil ! 70
Lavender oil 5 - 72 65
Lavender oil 10 68 65 65
SUBSTITUTE SHEET (RULE 26) Leovovert 1 - 82
Limoneal 1 90
Limonene ! (" (%
Macrolide supra 2.5 85
Magnolan 1 - 82
Magnolan 10 - 82 82
Magnolan 25 82 80 82
Majantol 10 82
Majantol 25 55 65 80
Mandaril 0.1 - 90 72
Mandaril 0.5 - 80
Mandaril 1 - 76
Melonal 1 - 82
Melonal 10 - 72
Melonal 25 - 62
Menthanyl acetate 5 70 82
Menthol 10 82 90
Menthol 25 60 60 85
Menthone/lsomenthone 0.1 - 59
Menthone/lsomenthone 1 - 63
Menthone/lsomenthone 10 - 61
Menthyl acetate 1 65
Methyl anthranilate 50 70
Methyl anthranilate 100 58 58
Methyl benzoate 100 - 75
Methyl naphthyl ketone 25 75 78
Methyl phenylacetate 10 86 88
Methyl phenylacetate 100 82
Mintonat 1 88
Mintonat 5 75
Mugetanol 0.1 90 90
SUBSTITUTE SHEET (RULE 26) 3 Mugetanol 1 90 - 90 Mugetanol 5 70 75 805 Neononyl acetate 5 65 6 Nerol 25 70 84 7 Nerolin 1 858 Nopyl acetate 0.1 75 78 9 Nopyl acetate 0.5 70 68 0 Nopyl acetate 1 66 66 1 Octahydrocoumarin 100 82 2 Octahydrocoumarin 500 78 88 3 Octalactone, gamma 500 78 82 4 Orange Oil 5 88 5 Palisandal 0.1 906 Palisandal 1 867 Pearadise 250 70 - 588 Phenoxyethyl alcohol 500 82 80 9 Phenyl acetaldehyde dimethyl acetal 100 70 0 Phenyl acetaldehyde dimethyl acetal 250 50 65 1 Phenylethyl acetate 10 70 2 Phenylethyl acetate 100 55 55 553 Phenylethyl dimethyl carbinol 100 80 4 Phenylethyl isobutyrate 25 60 55 705 Phenylethyl isovalerate 1 806 Phenylethyl isovalerate 2.5 827 Phenylethyl phenylacetate 5 78 708 Phenylethyl phenylacetate 25 90 72 709 Phenylethyl phenylacetate 50 85 70 700 Phenoxanol 1 751 Phenoxanol 5 702 Phenoxanol 10 75 - 753 Pinene, alpha 1 62 90
SUBSTITUTE SHEET (RULE 26) Pinene, alpha 82
Prenyl acetate 55
Prenyl acetate 10 50
Prenyl acetate 50 40
Poivrol 90
Profarnesal 0.1 82
Resedafol 0.1 78
Resedafol 85
Resedafol 82 84
Resedylacetal 70
Resedylacetal 1 - 70
Resedylacetal 5 - 75
Rosaphen 10 78
Rosaphen 25 55 65
Rose oxide L 25 75
Sandalwood oil 2.5 73
Sandalore 0.25 82 84
Sandalore 0.5 - 84
Symrose 5 75 80 -
Symrose 10 48 75 82
Tagetes oil 78
Tagetes oil 81
Tonka lactone 82
Tonka lactone 85
Thyme oil 90 58
Thyme oil 82 58
Thyme oil 82 55
Thymol 0.1 90
Timberol 0.5 50
Timberol 1 50
Vanillin 250 60 62 35
SUBSTITUTE SHEET (RULE 26) Verdolea 25 73 70 Ylang Ylang oil 5 85 Ylang Ylang oil 10 70 85 Ysamber K 0.1 - 64 Ysamber K 0.5 62
SUBSTITUTE SHEET (RULE 26)

Claims

WHAT CLAIMED IS
1. Agonists of olfactory receptors, particularly OR2AT4, showing
(i) a molecular weight ranging from about 50 to about 300 Dalton and (ii) an evaporation rate versus butyl acetate of about 3 to about 15 for use as a medicament for preventing and/or treating collagen degradation in human connective tissue.
2. Agonists according to Claim 1 showing a molecular weight of from about 75 to about 200.
3. Agonists according to Claim 1 showing n evaporation rate of from about 5 to about 10.
4. Agonists according to Claim 1 selected from the group consisting of
• (-) CBD
• (-) CBG
• (+) CBDV
• Acetophenone
• Agrunitrile
• Aldehyde C8
• Aldehyde C11
• Aldehyde C12
• Aldehyde C16
• Aldehyde C18
• Allyl caproate
• Allyl cyclohexylpropionate
• Allyl heptoate
• Allyl phenoxyacetate
• Amalia oil
• Amarocit
• Amber Core
• Ambrocenide
• Ambrostar
• Ambroxide
SUBSTITUTE SHEET (RULE 26) • Amyl butyrate
• Anethole
• Anisic aldehyde
• Benzaldehyde
• Benzophenone
• Benzyl acetone
• Benzyl cinnamate
• Benzyl isobutyrate
• Benzyl isobutyrate
• Benzyl propionate
• Borneol/lsoborneol
• Bourgeonal
• Bows bioactive bullet 1
• Brahmanol
• Butyl acetate
• Butyl butyrate
• Butyl cyclohexanol, p-tert.
• Camphor
• Cedar wood oil
• Cedryl acetate
• Ceylanil
• Cinnamic alcohol
• Citral diethyl acetal
• Citronellyl acetate
• Citronellyl isobutyrate
• Citronellyl tiglate
• Citronitril
• Clove bud oil
• Cresyl methyl ether
• Cyclabute
• Cyclamen aldehyde
• Cyclohexyl magnol
SUBSTITUTE SHEET (RULE 26) • Cyclohexyl salicylate
• Decalactone, gamma
• Decyl acetate
• Diethyl malonate
• Dihydro myrcenyl acetate
• Dimethyl anthranilate
• Dimethyl benzyl carbonyl butyrate
• Ethyl acetoacetate
• Ethyl butyl butyrate
• Ethyl butyrate
• Ethyl cinnamate
• Ethyl linalool
• Eucalyptus oil
• Eugenol
• Fenchol
• Florazon
• Fragolan
• Frambionon
• Frambinon methyl ether
• Fresiol
• Frutinat
• Geranyl acetate
• Geranyl butyrate
• Geranyl tiglate
• Geranyl tiglate
• Globalide
• Globanone
• Guaiac wood oil
• Heliotropin
• Herbarome
• Hexyl acetate
• Hexenyl acetate
SUBSTITUTE SHEET (RULE 26) Hydrocitronitrile
Indole
Intreleven aldehyde
Ionone
Isoborneol
Isoamyl acetate
Isoamyl butyrate
Isoamyl salicylate
Isoeugenol
Isoeugenyl methyl ether Isotridecyl acetate Jasmol
Jasmopyrane
Jessemal
Koavone
Labdanum extract
Lavandine Espieur
Lavender oil
Lemonile
Leovovert
Limonene
Limoneal
Macrolide supra
Magnolan
Majantol
Mandaril
Manzanate
Melonal
Menthol
Menthone/lsomenthone
Menthyl acetate Menthanyl acetate
SUBSTITUTE SHEET (RULE 26) • Methyl anthranilate
• Methyl benzoate
• Methyl naphthyl ketone
• Methyl phenylacetate
• Mintonat
• Mugetanol
• Neononyl acetate
• Nerol
• Nerolin
• Nopyl acetate
• Octahydrocoumarin
• Octalactone, gamma
• Orange Oil
• Palisandal
• Pearadise
• Peonile
• Phenoxanol
• Phenoxyethyl alcohol
• Phenyl acetaldehyde dime- thyl acetal
• Phenylethyl acetate
• Phenylethyl acetate
• Phenylethyl dimethyl carbinol
• Phenylethyl isobutyrate
• Phenylethyl isovalerate
• Phenylethyl phenylacetate
• Pinene
• Poivrol
• Prenyl acetate
• Profarnesal
• Projasmone
• Resedafol
• Resedylacetal
SUBSTITUTE SHEET (RULE 26) • Rosaphen
• Rose oxide L
• Sandalore
• Sandalwood oil
• Symrose
• Symrose
• Tagetes oil
• Terpineol
• Tetrahydrogeraniol
• Tonka lactone
• Thyme oil
• Thymol
• Timberol
• Timberol
• Undecavertrol
• Vanillin
• Verdolea
• Vertomugal
• Ylang Ylang oil
• Ysamber K and mixtures thereof.
5. Agonists according to Claim 1, wherein they are applied in a concentration of from 0.1 to 100 pg/ml.
6. agonists according to Claim 1, wherein they are applied in a concentration of from 0.5 to 10 pg/ml.
7. A cosmetic or pharmaceutical composition comprising the agonists of Claim 1.
8. The composition of Claim 7 representing a lotion, a cream, an emulsion, or an ointment
9. The composition of Claim 7 further comprising a cosmetically or pharmaceutically ac- ceptable carrier.
10. The composition of Claim 9, wherein said carrier is selected from the group consisting of water, ethanol, isopropyl alcohol, butanol, glycerol, ethylene glycol, propylene glycol and diethylene glycol or mixtures thereof.
SUBSTITUTE SHEET (RULE 26) The composition of claim 7 further comprising at least one biogenic agent or antioxi- dant. The composition of Claim 11, wherein said biogenic agents or antioxidants are selected from the group consisting of tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and its fragmentation products, |3-glucans, reti- nol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, vitamin complexes, amino acids, pep- tides and mixtures thereof. A non-therapeutical method for improving strength of human connective tissue com- prising or consisting of the following steps:
(a) providing the agonists according to Claim 1 optionally dissolved in a pharmaceu- tically acceptable carrier,
(b) applying the agonists or a composition comprising them topically to the skin. The use of agonists of Claim 1 for improving strength of human connective tissue, par- ticularly female skin. The use of agonists of Claim 1 as cosmetic ingredients.
SUBSTITUTE SHEET (RULE 26)
PCT/EP2020/085972 2020-12-14 2020-12-14 Medicament for prevention and treatment of collagen degradation in human connecting tissue WO2022128057A1 (en)

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