WO2011107411A1 - Pyranopyranone derivatives as antimicrobial agents - Google Patents

Pyranopyranone derivatives as antimicrobial agents Download PDF

Info

Publication number
WO2011107411A1
WO2011107411A1 PCT/EP2011/052876 EP2011052876W WO2011107411A1 WO 2011107411 A1 WO2011107411 A1 WO 2011107411A1 EP 2011052876 W EP2011052876 W EP 2011052876W WO 2011107411 A1 WO2011107411 A1 WO 2011107411A1
Authority
WO
WIPO (PCT)
Prior art keywords
preservative
biocide
hydrogen
c3oalkyl
pyranopyranone
Prior art date
Application number
PCT/EP2011/052876
Other languages
French (fr)
Inventor
Barbara Wagner
Janina Purschwitz
Karin Bieler
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2011107411A1 publication Critical patent/WO2011107411A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/005—Preparations for sensitive skin
    • 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
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/006—Antidandruff preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • 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

Definitions

  • Pyranopyranone derivatives as antimicrobial agents Description The present invention relates to the use of specific pyranopyranone derivatives for the antimicrobial treatment of surfaces, as antimicrobial active substances against gram- positive and gram-negative bacteria, yeasts and fungi and also for the preservation of cosmetics, household products, textiles and plastics and for use as disinfectants. Therefore, the present invention relates to the use of pyranopyranone derivatives of formula
  • C4-C2oheteroaryl which may be substituted by one or more G, C2-Cisalkenyl, C2-
  • R 4 and R5 together with the carbon atom they are attached to, form a five or six mem- bered ring;
  • R3 and R 4 together with the carbon atoms they are attached to, form a five or six
  • E is -OR 6 ; -SR 6 ; -NR14R15; -NR14COR15; -COR 6 ; -COOR 6 ; -CONR14R15; -CN;
  • G is E; Ci-Ciealkyl, which is optionally interrupted by D; Ci-Ci8perfluoroalkyl; Ci- Ciealkoxy, which is optionally substituted by E and/or interrupted by D; wherein
  • R6 is H; C6-Ci8aryl which is optionally substituted by OH, Ci-C3oalkyl or Ci-C3oalkoxy; or Ci-C3oalkyl which is optionally interrupted by -0-;
  • R7 is H; C6-Ci8aryl which is optionally substituted by OH, Ci-C3oalkyl or Ci-C3oalkoxy; or Ci-C3oalkyl which is optionally interrupted by -0-;
  • R9 and R10 independently of each other are hydrogen; Ci-C3oalkyl; C6-Cisaryl which is optionally substituted by Ci-C3oalkyl; and
  • R11 is hydrogen; C6-Ciearyl, which is optionally substituted by OH, Ci-C3oalkyl or Ci- C3oalkoxy; or Ci-C3oalkyl, which is optionally interrupted by -0-;
  • R12, Ri3, Ri4 and R15 independently of each other are hydrogen; C6-Ci8aryl which is optionally substituted by OH, Ci-C3oalkyl or Ci-C3oalkoxy; Ci-C3oalkyl, which is optionally interrupted by -0-; or
  • Ri4 and R15 together form a five or six membered ring; as antimicrobial and/or preserving agents (collectively named “antimicrobial compound” in the following).
  • Ci-C3oalkyl are straight chain or branched radicals like methyl, ethyl, n-propyl, iso- propyl, n-butyl, sek-butyl, tert-butyl, amyl, isoamyl or tert-amyl, hexyl, 2-ethylhexyl, hep- tyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, undecyl, eicosyl, tetracosyl, pentacosyl, heptacosyl, octacosyl or triacontyl.
  • Ci-C3oalkoxy are straight chain or branched radicals like methoxy, ethoxy, n-propoxy, isopropoxy, n-butyloxy, sek-butyloxy, tert-butyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, 2-ethylhexyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, undecyloxy eicosyloxy tetracosyloxy, pentacosyloxy, heptacosyloxy, octacosyloxy or triacontyloxy.
  • C2-C3oalkenyl are straight chain or branched radicals like allyl, methallyl, isopropenyl, 2- butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n- dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl, n-octadec-4-enyl, eicosenyl,
  • C3-Ci2cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl and preferably cyclohexyl.
  • Each alkyl or cycloalkyl can be saturated or unsaturated.
  • Each alkyl, cycloalkyl or alkoxy can preferably be substituted by one or more E and/or interrupted by one or more D.
  • Each aryl can be preferably substituted by G; adjacent residues G may be intercon- nected to form, for example, C3-C4alkylene, or a residue -O-CH2-O-.
  • Each heteroaryl can be preferably substituted by G, C2-Cisalkenyl, C2-Cisalkynyl, C7- C 25 aralkyl, CN, or -CO-R 6 .
  • Hetero-C3-Ci2aryl is preferably pyridinyl, pyrimidinyl, triazinyl, pyrrolyl, furanyl, thio- phenyl or chinolinyl.
  • C6-C2oaryl is for example naphthyl and preferably phenyl or biphenyl.
  • Ri is Ci-C3oalkyl and even more preferred are compounds wherein Ri is methyl.
  • Ri is d-Cealkyl
  • R2 is hydrogen
  • R3, R 4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, C2-C3oalkenyl, or C3-Ci2cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C6-C2oaryl, which may be substituted by one or more G; C 4 - C2oheteroaryl, which may be substituted by one or more G, C2-Ci8alkenyl, C2- Cisalkynyl, C7-C2saralkyl, or -CO-R6; or
  • R 4 and R5 together form a five or six membered ring
  • E is -OR 6 ; -NR14R15; -NR14COR15; -COR 6 ; -COOR 6 ; -CONR14R15; -CN; halogen; or
  • G is E; Ci-Cisalkyl, which is optionally interrupted by D; C-i-C-isperfluoroalkyl; Ci- Ciealkoxy, which is optionally substituted by E and/or interrupted by D; wherein R6, R7, R11 , R12, Ri3, Ri4 and R15 are defined as in formula (1 ).
  • Ri is d-Cealkyl
  • R2 is hydrogen
  • R3, R 4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, C2-C3oalkenyl, or C3-Ci2cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C6-C2oaryl, which may be substituted by one or more G; C 4 - C2oheteroaryl, which may be substituted by one or more G, C2-Ci8alkenyl, C2- C-isalkynyl, C7-C2saralkyl, or -CO-R6; or
  • R 4 and R5 together form a five or six membered ring
  • E is -OR 6 ; -NR14R15; -NR14COR15; -COR 6 ; -COOR 6 ; -CONR14R15; -CN; halogen; or
  • G is E; Ci-Cisalkyl, which is optionally interrupted by D; C-i-C-isperfluoroalkyl; Ci- Ciealkoxy, which is optionally substituted by E and/or interrupted by D; wherein
  • R6, R7, R11 , R12, Ri3, Ri4 and R15 are defined as in formula (1 ).
  • Ri is Ci-C 4 alkyl
  • R2 is hydrogen
  • R3, R 4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, or C2-C3oal- kenyl, which may be substituted by one or more E and/or interrupted by one or more D; C6-C2oaryl, which may be substituted by one or more G; C 4 -C2oheteroaryl, which may be substituted by one or more G; or
  • R 4 and R5 together form a five or six membered ring
  • E is -OR 6 ; -NR14R15; -NR14COR15; -COR 6 ; -COOR 6 ; or -CONR14R15;
  • G is E; Ci-Cisalkyl, which is optionally interrupted by D; d-dsalkoxy, which is optionally substituted by E and/or interrupted by D; wherein
  • R6, R7, R12, Ri3, Ri4 and R15 are defined as in formula (1 ).
  • Ri is methyl
  • R2 is hydrogen
  • R3, R 4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, or C2-C3oal- kenyl, or
  • R3 and R4 together form a five or six membered ring, which may be interrupted by -0-; or
  • R4 and R5 together form a five or six membered ring.
  • R3 and R4, or R4 and R5, together with the carbon atom(s) they are attached to may form a five or six membered ring as noted above; thus, R3 and R4, or R4 and R5, together may, for example, be C2-C8alkylene, C2-C8alkenylene, C2-C8oxaalkylene, C2- C8oxaalkenylene, C4-C8cycloalkylene, C4-C8cycloalkenylene.
  • the rings formed may be carbocyclic or heterocyclic, and mono- or bicyclic; examples are C5-C6cycloalkyl, C5-C6cycloalkenyl, C6-C7bicycloalkyl, C6-C7bicycloalkenyl, C4- C5oxacycloalkyl, C4-C5oxacycloalkenyl, each of which being unsubstituted or substituted by G, such as in the examples for R3/R4 and R4/R5 listed below.
  • Ri is methyl
  • R2 is hydrogen
  • Ci-Ci2alkyl is hydrogen; Ci-Ci2alkyl; C2-C4alkenyl; or a radical of formula
  • C2-C4alkenyl is hydrogen; Ci-C4alkyl; phenyl; -SiRs R9R10; or a radical of for
  • One of the pyranopyranones defined above is novel and is also a subject of the present invention.
  • the pyranopyranones corresponding to formula (1 ) can be prepared according to stan dard procedures known per se, generally by reacting a pyranone compound corresponding to formula (1 a) with an aldehyde corresponding to formula (1 b) to form the pyranopyranone compound corresponding to formula (1 ) wherein the substituents are as defined above.
  • the compounds of the present invention also exhibit pronounced antimicrobial action, for example against pathogenic gram-positive and gram-negative bacteria and against bacteria of the skin and oral flora, and also against yeasts and molds. They are accordingly suitable for disinfection, deodorisation, and for general and antimicrobial treat- ment of the skin and mucosa and of integumentary appendages (hair), for example, for the disinfection of hands and wounds.
  • Compounds of the invention thus may be used for the preparation of a medicament for skin, mucosal, oral, or wound disinfection.
  • the invention thus includes a method, or a use, for the preparation of a medicament for protecting skin, mucosa and/or integumentary appendages against the action of mi- crobes, including protecting the scalp from dandruff, which method comprises incorporation of an effective amount of a pyranopyranone derivative of formula (1 ) into said medicament.
  • antimicrobial active substances and preservatives are accordingly suitable as antimicrobial active substances and preservatives in personal care preparations, for example shampoos, bath additives, hair care prepara- tions, liquid and solid soaps (based on synthetic surfactants and salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, e.g. cleansing solutions for the skin, moist cleaning cloths, wet wipes, oils or powders.
  • the antimicrobial compounds of the invention are effective as anti- dandruff agents in shampoos or other products used in hair treatment such as oils, sprays, hair gels.
  • the invention accordingly relates also to a personal care preparation comprising at least one antimicrobial compound of the invention and cosmetically tolerable carriers or adjuvants.
  • the personal care preparation according to the invention generally contains from 0.01 to 15 % by weight, for example, from 0.1 to 10 % by weight, based on the total weight of the inventive composition, of the antimicrobial compounds of the invention, and cosmetically tolerable adjuvants and/or carrier.
  • the medicament generally contains from 0.01 to 15 % by weight, for example, from 0.1 to 10 % by weight, based on the total weight of the inventive composition, of the antimicrobial compounds of the invention, and pharmaceutically tolerable adjuvants and/or carrier.
  • Pharmaceutically tolerable adjuvants and/or carriers are usually selected from suitable ingredients, or classes of ingredients, listed below for personal care preparations of the invention.
  • the personal care preparation comprises, in addition to the antimicrobial compounds of the invention, further constituents, for example sequestering agents, colourings, perfume oils, thickening or solidifying agents (consistency regulators), emulsifiers, emollients, UV-absorbers, skin protective agents, anti- oxidants, additives that improve the mechanical properties, such as dicarboxylic acids and/or aluminium, zinc, calcium or magnesium salts of Ci 4 -C22fatty acids, and, optionally, preservatives.
  • further constituents for example sequestering agents, colourings, perfume oils, thickening or solidifying agents (consistency regulators), emulsifiers, emollients, UV-absorbers, skin protective agents, anti- oxidants, additives that improve the mechanical properties, such as dicarboxylic acids and/or aluminium, zinc, calcium or magnesium salts of Ci 4 -C22fatty acids, and, optionally, preservatives.
  • the personal care preparation according to the invention may be in the form of a water- in-oil or oil-in-water emulsion, an alcoholic or alcohol-containing formulation, a vesicular dispersion of an ionic or non-ionic ampiphilic lipid, a gel, a solid stick or an aerosol formulation.
  • the cosmetically tolerable adjuvant contains preferably from 5 to 50 % of an oil phase, from 5 to 20 % of an emulsifier and from 30 to 90 % water.
  • the oil phase may comprise any oil suitable for cosmetic formulations, for example one or more hydrocarbon oils, a wax, a natural oil , a silicone oil, a fatty acid ester or a fatty alcohol.
  • Preferred mono- or poly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
  • Cosmetic formulations according to the invention are used in various fields. There come into consideration, for example, the following preparations:
  • skin-care preparations e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, synthetic detergents or washing pastes,
  • bath preparations e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts;
  • skin-care preparations e.g. skin emulsions, multi-emulsions or skin oils
  • cosmetic personal care preparations e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye- care preparations, e.g. eye shadow preparations, mascaras, eyeliners, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers;
  • intimate hygiene preparations e.g. intimate washing lotions or intimate sprays
  • - foot-care preparations e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations
  • light-protective preparations such as sun milks, lotions, creams or oils, sun-blocks or tropicals, pre-tanning preparations or after-sun preparations
  • skin-tanning preparations e.g. self-tanning creams
  • depigmenting preparations e.g. preparations for bleaching the skin or skin- lightening preparations
  • insect-repellents e.g. insect-repellent oils, lotions, sprays or sticks;
  • deodorants such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons;
  • antiperspirants e.g. antiperspirant sticks, creams or roll-ons
  • - preparations for cleansing and caring for blemished skin e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks;
  • hair-removal preparations in chemical form e.g. hair-removing powders, liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams;
  • - shaving preparations e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions;
  • fragrance preparations e.g. fragrances (eau de Cologne, eau de toilette, eau de perfume, perfume de toilette, perfume), perfume oils or perfume creams;
  • denture-care and mouth-care preparations e.g. toothpastes, gel toothpastes, tooth powders, mouthwash concentrates, anti-plaque mouthwashes, denture cleaners or denture fixatives;
  • cosmetic hair-treatment preparations e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment prepara- tions, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, m ild wave, cold wave) , hai r- straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g.
  • hair-washing preparations in the form of shampoos and conditioners
  • hair-care preparations e.g. pretreatment prepara- tions, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, m ild wave, cold wave) , ha
  • the invention relates also to oral compositions containing from 0.01 to 15 % by weight, based on the total weight of the composition, of the antimicrobial compound, and orally tolerable adjuvants.
  • the oral composition according to the invention may be, for example, in the form of a gel, a paste, a cream or an aqueous preparation (mouthwash).
  • the oral composition according to the invention may also comprise compounds that release fluoride ions which are effective against the formation of caries, for example inorganic fluoride salts, e.g. sodium, potassium, ammonium or calcium fluoride, or organic fluoride salts, e.g. amine fluorides, which are known under the trade name OLAFLUOR.
  • the anti-microbial compounds of this invention are also suitable for treating, especially preserving, textile fibre materials. Such materials are undyed and dyed or printed fibre materials, e.g. of silk, wool, polyamide or polyurethanes, and especially cellulosic fibre materials of all kinds.
  • Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen, jute and hemp, as well as cellulose and regenerated cellulose.
  • the antimicrobial compounds of this invention are suitable also for treating, especially imparting antimicrobial properties to or preserving, plastics, e.g. polyethylene, polypropylene, polyurethane, polyester, polyamide, polycarbonate, latex etc.
  • Fields of use therefore are, for example, floor coverings, plastics coatings, plastics containers and packaging materials; kitchen and bathroom utensils (e.g. brushes, shower curtains, sponges, bathmats), latex, filter materials (air and water filters), plastics articles used in the field of medicine, e.g. dressing materials, syringes, catheters etc., so-called “medical devices", gloves and mattresses.
  • the antimicrobial compounds of this invention are suitable also for treating, especially imparting antimicrobial properties to or preserving industrial formulations such as coatings, lubricants etc.
  • Paper for example papers used for hygiene purposes, may also be provided with anti- microbial properties using the present anti-microbial compounds.
  • nonwovens e.g. nappies/diapers, sanitary towels, panty liners, and cloths for hygiene and household uses
  • nonwovens e.g. nappies/diapers, sanitary towels, panty liners, and cloths for hygiene and household uses
  • the antimicrobial compounds of this invention are also used in washing and cleaning formulations, e.g. in liquid or powder washing agents or softeners.
  • the antimicrobial compounds of this invention can also be used in household and gen- eral-purpose cleaners for cleaning and disinfecting hard surfaces.
  • the preservation of technical products In addition to preserving cosmetic and household products, the preservation of technical products, the provision of technical products with antimicrobial properties and use as a biocide in technical processes are also possible, for example in paper treatment, especially in paper treatment liquors, printing thickeners of starch or cellulose derivatives, surface-coatings and paints.
  • the antimicrobial compounds of the invention are also suitable for the antimicrobial treatment of wood and for the antimicrobial treatment of leather, the preserving of leather and the provision of leather with antimicrobial properties.
  • the compounds according to the invention are also suitable for the protection of cosmetic products, pharmaceutical products and household products from microbial damage.
  • the compounds claimed in the present invention can be combined with biocides used as antimicrobial actives in cosmetic and pharmaceutical products and household products and/or preservatives used in cosmetic and pharmaceutical products or houseold products in order to improve the antimicrobial activity of the cosmetic product, the pharmaceutical product or household product.
  • the compounds are capable of penetrating biofilms on living and non-living surfaces, of preventing the adhesion of bacteria to surfaces and any further build-up of the biofilm, of detaching such biofilm and/or inhibiting the further growth of the biofilm- forming micro-organisms in the biological matrix, or of killing such micro-organisms.
  • Biofilms are understood, very generally, to be aggregations of living and dead microorganisms, especially bacteria, that adhere to living and non-living surfaces, together with their metabolites in the form of extracellular polymeric substances (EPS matrix), e.g. polysaccharides.
  • EPS matrix extracellular polymeric substances
  • the activity of antimicrobial substances that normally exhibit a pronounced growth-inhibiting or lethal action with respect to planktonic cells may be greatly reduced with respect to microorganisms that are organized in biofilms, for example because of inadequate penetration of the active substance into the biological matrix.
  • this may relate to biofilms on human tooth surfaces and oral mucosa, which play a crucial role in the onset of degenerative diseases in the oral cavity, e.g. caries or periodontitis, as a result of the biofilm-forming micro-organisms or their metabolites.
  • Action against bio-films in the present invention also relates to biofilms on non-human surfaces.
  • the antimicrobial compounds of this invention are useful in coatings or films in protecting surfaces from bio-fouling.
  • Such surfaces include surfaces in contact with marine environments (including fresh water, brackish water and salt water environments), for example, the hulls of ships, surfaces of docks or the inside of pipes in circulating or pass-through water systems.
  • Other surfaces are susceptible to similar biofoul- ing, for example walls exposed to rain water, walls of showers, roofs, gutters, pool ar- eas, saunas, floors and walls exposed to damp environs such as basements or garages and even the housing of tools and outdoor furniture.
  • the antimicrobial compounds of this invention are also useful in preventing bio-fouling, or eliminating or controlling microbe accumulation on the surfaces either by incorporating the antimicrobial compounds into the article or surface of the article in question or by applying the antimicrobial to these surfaces as part of a coating or film.
  • the antimicrobial compounds of this invention are part of a composition which also comprises a binder.
  • the binder may be any polymer or oligomer compatible with the present antimicrobials.
  • the binder may be in the form of a polymer or oligomer prior to preparation of the anti- fouling composition, or may form by polymerization during or after preparation, including after application to the substrate. In certain applications, such as certain coating applications, it will be desirable to crosslink the oligomer or polymer of the anti fouling composition after application.
  • binder as used in the present invention also includes materials such as glycols, oils, waxes and surfactants commercially used in the care of wood, plastic, glass and other surfaces. Examples include water proofing materials for wood, vinyl protectants, protective waxes and the like.
  • the composition may be a coating or a film.
  • the binder is the thermoplastic polymer matrix used to prepare the film.
  • the composition when it is a coating, it may be applied as a liquid solution or suspension, a paste, gel, oil or the coating composition may be a solid, for example a powder coating which is subsequently cured by heat, UV light or other method.
  • the binder can be comprised of any polymer used in coating formulations or film preparation.
  • the binder is a thermoset, thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer.
  • Thermoset, thermoplastic, elastomeric, inherently crosslinked or crosslinked polymers include polyolefin, polyamide, polyurethane, polyacrylate, polyacrylamide, polycarbonate, polystyrene, polyvinyl acetates, polyvinyl alcohols, polyester, halogenated vinyl polymers such as PVC, natural and synthetic rubbers, alkyd resins, epoxy resins, unsaturated polyesters, unsaturated polyamides, polyimides, silicon containing and car- bamate polymers, fluorinated polymers, crosslinkable acrylic resins derived from substituted acrylic esters, e.g. from epoxy acrylates, urethane acrylates or polyester acry- lates.
  • the polymers may also be blends and copolymers of the preceding chemistries.
  • Biocompatible coating polymers such as, poly[-alkoxyalkanoate-co-3- hydroxyalkenoate] (PHAE) polyesters, Geiger et. al. Polymer Bulletin 52, 65-70 (2004), can also serve as binders in the present invention.
  • Alkyd resins, polyesters, polyurethanes, epoxy resins, silicone containing polymers, polyacrylates, polyacrylamides, fluorinated polymers and polymers of vinyl acetate, vinyl alcohol and vinyl amine are non-limiting examples of common coating binders useful in the present invention.
  • Other coating binders are part of the present invention.
  • Coatings are frequently crosslinked with, for example, melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates, epoxy resins, anhydrides, poly acids and amines, with or without accelerators.
  • the compositions of present invention are for example a coating applied to a surface which is exposed to conditions favorable for bioaccumulation. The presence of the antimicrobial compounds of this invention in said coating will prevent the adherence of organisms to the surface.
  • the anti-microbial compounds of the present invention may be part of a complete coating or paint formulation, such as a marine gel-coat, shellac, varnish, lacquer or paint, or the anti fouling composition may comprise only a polymer of the instant invention and binder, or a polymer of the instant invention, binder and a carrier substance. It is anticipated that other additives encountered in such coating formulations or applications will find optional use in the present applications as well.
  • the coating may be solvent borne or aqueous.
  • Aqueous coatings are typically considered more environmentally friendly.
  • the coating is, for example, aqueous dispersion of a polymer of the instant invention and a binder or a water based coating or paint.
  • the coating comprises an aqueous dispersion of a polymer of the instant invention and an acrylic, methacrylic or acrylamide polymers or co-polymers or a poly[-alkoxyalkanoate-co-3- hydroxyalkenoate] polyester.
  • the coating may be applied to a surface which has already been coated, such as a protective coating, a clear coat or a protective wax applied over a previously coated article.
  • Coating systems include marine coatings, wood coatings, other coatings for metals and coatings over plastics and ceramics.
  • Exemplary of marine coatings are gel coats comprising an unsaturated polyester, a styrene and a catalyst.
  • the coating is, for example a house paint, or other decorative or protective paint. It may be a paint or other coating that is applied to cement, concrete or other masonry article.
  • the coating may be a water proofer as for a basement or foundation.
  • the coating composition is applied to a surface by any conventional means including spin coating, dip coating, spray coating, draw down, or by brush, roller or other applicator. A drying or curing period will typically be needed.
  • Coating or film thickness will vary depending on application and will become apparent to one skilled in the art after limited testing.
  • the composition may be in the form of a protective laminate film.
  • Such a film typically comprises thermoset, thermoplastic, elastomeric, or crosslinked polymers.
  • polymers include, but are not limited to, polyolefin, poly- amide, polyurethane, polyacrylate, polyacrylamide, polycarbonate, polystyrene, polyvinyl acetates, polyvinyl alcohols, polyester, halogenated vinyl polymers such as PVC, natural and synthetic rubbers, alkyl resins, epoxy resins, unsaturated polyesters, unsaturated polyamides, polyimides, fluorinated polymers, silicon containing and car- bamate polymers.
  • the polymers may also be blends and copolymers of the preceding chemistries.
  • the anti-fouling composition When the anti-fouling composition is a preformed film it is applied to the surface by, for example, the use of an adhesive, or co-extruded onto the surface. It may also be me- chanically affixed via fasteners which may require the use of a sealant or caulk wherein the esters of the instant invention may also be advantageously employed.
  • a plastic film may also be applied with heat which includes calendaring, melt applications and shrink wrapping.
  • the composition may be part of a polish, such a furniture polish, or a dispersant or surfactant formulation such as a glycol or mineral oil dispersion or other formulation as used in for example wood protection.
  • useful surfactants include, but are not limited to, polyoxyethylene-based surface-active substances, including polyoxyethylene sorbitan tetraoleate (PST), poly- oxyethylene sorbitol hexaoleate (PSH), polyoxyethylene 6 tridecyl ether, polyoxyethylene 12 tridecyl ether, polyoxyethylene 18 tridecyl ether, TWEEN RTM surfactants, TRITON RTM surfactants, and the polyoxyethlene-polyoxypropylene copolymers such as the PLURONIC RTM and POLOXAMER RTM product series (from BASF).
  • PST polyoxyethylene sorbitan tetraoleate
  • PSH poly- oxyethylene sorbitol hexaoleate
  • matrix-forming components include dextrans, linear PEG molecules (MW 500 to 5,000,000), star-shaped PEG molecules, comb-shaped and dendrimeric, hyperbrached PEG molecules, as well as the analogous linear, star, and dendrimer polyamine polymers, and various carbonated, perfluorinated (e.g., DUPONT ZONYL RTM fluorosur- factants) and siliconated (e.g, dimethylsiloxane-ethylene oxide block copolymers) surfactants.
  • dextrans linear PEG molecules (MW 500 to 5,000,000)
  • star-shaped PEG molecules comb-shaped and dendrimeric, hyperbrached PEG molecules
  • analogous linear, star, and dendrimer polyamine polymers as well as the analogous linear, star, and dendrimer polyamine polymers
  • various carbonated, perfluorinated e.g., DUPONT ZONYL RTM fluorosur- factants
  • siliconated e.g, dimethylsiloxane
  • the composition may contain other additives such as antioxidants, UV absorbers, hindered amines, phosphites or phosphonites, benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal stearates, nucleating agents, fillers, reinforcing agents, lubricants, emulsifiers, dyes, pigments, dispersants, other optical brighteners, flame retardants, antistatic agents, blowing agents and the like, such as the materials listed below, or mixtures thereof.
  • additives such as antioxidants, UV absorbers, hindered amines, phosphites or phosphonites, benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal stearates, nucleating agents, fillers, reinforcing agents, lubricants, emulsifiers, dyes, pigments, dispersants, other optical brighteners, flame retardants, antistatic agents, blowing agents and the like
  • the substrate can be an inorganic or organic substrate, for example, a metal or metal alloy; a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer as described above; a natural polymer such as wood or rubber; a ceramic material; glass; leather or other textile.
  • a metal or metal alloy for example, a metal or metal alloy; a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer as described above; a natural polymer such as wood or rubber; a ceramic material; glass; leather or other textile.
  • the substrate may be, for example, non-metal inorganic surfaces such as silica, silicon dioxide, titanium oxides, aluminum oxides, iron oxides, carbon, silicon, various silicates and sol-gels, masonry, and composite materials such as fiberglass and plastic lumber (a blend of polymers and wood shavings, wood flour or other wood particles).
  • non-metal inorganic surfaces such as silica, silicon dioxide, titanium oxides, aluminum oxides, iron oxides, carbon, silicon, various silicates and sol-gels, masonry, and composite materials such as fiberglass and plastic lumber (a blend of polymers and wood shavings, wood flour or other wood particles).
  • the inorganic or organic substrate is, for example, a metal or metal alloy, a thermo- plastic, elastomeric, inherently crosslinked or crosslinked polymer, a ceramic material or a glass.
  • the substrate may be a multi-layered article comprised of the same or different components in each layer.
  • the surface coated or laminated may be the exposed surface of an already applied coating or laminate.
  • the inorganic or organic substrate to be coated or laminated can be in any solid form.
  • polymer substrates may be plastics in the form of films, injection-molded articles, extruded workpieces, fibres, felts or woven fabrics.
  • molded or extruded polymeric articles used in construction or the manufacture of durable goods can all benefit from the present method for stabilizer replenishment.
  • Plastics which would benefit from the present method include, but are not limited to, plastics used in construction or the manufacture of durable goods or machine parts, including outdoor furniture, boats, siding, roofing, glazing, protective films, decals, sealants, composites like plastic lumber and fiber reinforced composites, functional films including films used in displays as well as articles constructed from synthetic fibers such as awnings, fabrics such as used in canvas or sails and rubber articles such as outdoor matting and other uses cited in this disclosure.
  • plastics are polypropylene, polyethylene, PVC, POM, polysulfones, styrenics, polyamides, ure- thanes, polyesters, polycarbonate, acrylics, butadiene, thermoplastic polyolefins, iono- mers, unsaturated polyesters and blends of polymer resins including ABS, SAN and PC/ABS.
  • the anti-microbial compounds of the invention are also effective in protecting useful plants, such as plants in agriculture, in horticulture and in forests, plant parts and seeds from disease and spoilage.
  • the present invention also provides a method which comprises applying to useful plants, the locus thereof or propagation material thereof a composition which comprises at least one of the polyglycerol polymers and co-polymers of the invention.
  • Said compositions can be used as foliar, soil and seed treatment fungicides.
  • compositions of the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants.
  • the present compositions are applied by treating the fungi, the useful plants, the locus thereof, the propagation material thereof, the natural substances of plant origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials threatened by fungus attack with the compositions in an effective amount.
  • compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials by the fungi.
  • compositions of the present invention are of particular interest for controlling a large number of fungi in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.
  • field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.
  • the anti-microbial compounds of the invention are applied at rate of 1 to 5000 g a.i./ha, for example 2 to 2000 g a.i./ha, for example, 5 to 2000 g a.i./ha, for example, 10 to 1000 g a.i./ha, e.g. 50, 75, 100, 200, 250, 500, 800, 1000, 1500 g a.i./ha of polymer or co-polymers.
  • the application rates depend on the type of effect desired, and typically range from 20 to 4000 g of total antimicrobials per hectare.
  • rates of 0.001 to 50 g of the present anti-microbial compounds for example 0.01 to 10 g, per kg of seed, are generally sufficient.
  • composition comprising the anti-microbial compounds of the invention may be employed in any conventional form, for example in the form a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emul- sifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil misci- ble liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL
  • compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects).
  • formulation inerts such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, typically contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects.
  • a seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • suitable seed dressing formulation form e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds.
  • seed dressing formulations are known in the art.
  • Seed dressing formulations may contain the single active ingredients or the combination of active in- gredients in encapsulated form, e.g. as slow release capsules or microcapsules.
  • the formulations include from 0.01 to 90% by weight of at least one of the anti-microbial compounds, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), and optionally other active agents, particularly microbiocides or conservatives or the like.
  • Concentrated forms of compositions generally contain in between about 2 and 80%, for example, between about 5 and 70% by weight of total active agent.
  • Application forms of formulation may for example contain from 0.01 to 20% by weight, for example from 0.01 to 5% by weight of active agent.
  • Particular embodiments of the invention therefore relate to methods for protecting plastics, coatings, other materials of construction, home or per- sonal care formulations, plants, agricultural products, industrial formulations or technical process against the action of microbes which comprises adding an effective amount of the anti-microbial compounds of the present invention; a method for protecting skin, mucosa and integumentary appendages against the ac- tion of microbes including protecting the scalp from dandruff, which comprises applying a preparation comprising an effective amount of the anti-microbial compounds of the present invention; a method for protecting paper, wood, leather, synthetic textile materials or natural tex- tile materials such as cotton against the action of microbes comprising incorporating or applying an effective amount of the present polymer or copolymer or a composition comprising an effective amount the anti-microbial compounds of the present invention; a method for cleaning and disinfecting hard surfaces which comprises applying a preparation comprising an effective amount of the anti-microbial compounds of the present invention; a method for preventing bio-fouling of an article comprising
  • materials of construction include, in addition to wood, metals, paper, glass, ceramics, coatings, plastics and textiles, materials such as concrete, cement, adhesives, caulking materials, composites of natural and synthetic materials etc.
  • Table 2 Examples of combinations of biocides and/or preservatives used as antimicro- bial actives in cosmetic products and household products Table 2: A B c D E F G H I K L M N 0 P Q R s T u V w
  • BIOCIDE/PRESERVATIVE 150 X X Table 2: A B C D E F G H I K L M N 0 P Q R s T u V w
  • BIOCIDE/PRESERVATIVE 200 X X Table 2: A B C D E F G H I K L M N 0 P Q R s T u V w
  • BIOCIDE/PRESERVATIVE 250 X X Table 2: A B c D E F G H I K L M N 0 P Q R S T u V w
  • X represents a specific biocide and/or preservative.
  • concentrations of these biocidal/preservative substances in the blends are between 1 % and 99%, preferably between 10% and 90%.
  • concentration of these blends in household and personal care products is typically in the range of 0.1 % to 5% and preferred 0.2% to 2%.
  • biocide combination examples are the following:
  • biocide combinations listed before the weight ratio of the biocides and or preservatives is for combinations of two biocides/preservatives 1 :1 or 1 :2 or 2:1 or 1 :3 or 3:1 .
  • BIO- CIDE/PRESERVATIVE 1 may be (as described in Table 2) BIO- CIDE/PRESERVATIVE 1 , or BIOCIDE/PRESERVATIVE 2, or BIOCIDE/PRESERVATIVE 3, or BIOCIDE/PRESERVATIVE 4, or BIOCIDE/PRESERVATIVE 5, or BIOCIDE/PRESERVATIVE 6, or BIOCIDE/PRESERVATIVE 7, or BIOCIDE/PRESERVATIVE 8, or BIOCIDE/PRESERVATIVE 9, or BIOCIDE/PRESERVATIVE 10, or BIOCIDE/PRESERVATIVE 11 , or BIO- CIDE/PRESERVATIVE 12, or BIOCIDE/PRESERVATIVE 13, or BIOCIDE/PRESERVATIVE 14, or BIOCIDE/PRESERVATIVE 15, or BIOCIDE/PRESERVATIVE 16, or BIOCIDE/PRESERVATIVE 17, or BIOCIDE/PRESERVATIVE 18, or BIOCIDE/PRESERVATIVE 19, or BIOCIDE/PRESERVATIVE 20, or BIOCIDE/PRESERVAT
  • BIOCIDE/PRESERVATIVE 68 or BIOCIDE/PRESERVATIVE 69, or BIOCIDE/PRESERVATIVE 70, or BIOCIDE/PRESERVATIVE 71 , or BIOCIDE/PRESERVATIVE 72, or BIOCIDE/PRESERVATIVE 73, or BIOCIDE/PRESERVATIVE 74, or BIOCIDE/PRESERVATIVE 75, or BIOCIDE/PRESERVATIVE 76, or BIO- CIDE/PRESERVATIVE 77, or BIOCIDE/PRESERVATIVE 78, or BIOCIDE/PRESERVATIVE 79, or BIOCIDE/PRESERVATIVE 80, or BIOCIDE/PRESERVATIVE 81 , or BIOCIDE/PRESERVATIVE 82, or BIOCIDE/PRESERVATIVE 83, or BIOCIDE/PRESERVATIVE 84, or BIOCIDE/PRESERVATIVE 85, or BIOCIDE/PRESERVATIVE 86, or BIOCIDE/PRESERVATIVE
  • Citric Acid (and) Silver Citrate 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10
  • BIOCIDE/PRESERVATIVE (Table 2) 0,00 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
  • BIOCIDE/PRESERVATIVE (Table 2) 0,00 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
  • Triglyceride 9.0 9.0 6.0 - -
  • Vitamins A, C or E (free or derivative forms) 0.80 0.50 1 .00 -
  • Emulsifier free lotion A B C D E F G H I
  • Vitamin E Acetate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
  • Emulsifier free face care A B C D E F G H I
  • Vitamin E Acetate 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20
  • Trisodium EDTA 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30
  • Trisodium EDTA 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10
  • BIOCIDE/PRESERVATIVE (Table 2) 0,00 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
  • Vitamins A, C or E (free or derivative forms) 0.80 0.50 - 1 .00
  • Phenylbenzimidazol Sulfonic Acid 0.50 - - 3.00 -
  • Titanium Dioxide 0.50 - 2.00 3.00 1 .00
  • Zinc Oxide 0.50 1 .00 3.00 - 2.00
  • Vitamins A, C or E (free or as derivative) 0.80 0.50 - 1.00 -
  • PEG/PPG-4/12 Dimethi- 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 cone
  • BIOCIDE/PRESERVATIVE (Table 2) 0,00 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
  • Butane N-Butane 1 .2 Bar
  • Propellant 30.00 30.00 30.00
  • a Luvitol BL (BASF) (benzyl laurate) 2.00 2.00 2.00 2.00 2.00
  • Cremophor GO 32 (BASF) (polyglyceryl-3
  • Vitamin E Acetate C (BASF) (tocopheryl
  • Titanium Dioxide 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50
  • Phenethyl Benzoate 4 00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
  • Sorbitan Sesquioleate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
  • Hydroxyethylcellulose 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30
  • BIOCIDE/PRESERVATIVE 0,30 0,20 0,10 0,00 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30
  • Triclocarban 0 0 0 0 0 0.20 0.40 0.80 1 .50

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Zoology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Environmental Sciences (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Disclosed is the use of pyranopyranone derivatives of formula (1), wherein R1, R2, R3, R4 and R5 independently of one another are hydrogen; C1-C30alkyl, C2-C30alkenyl, or C3-C12cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C6-C20aryl, which may be substituted by one or more G; C4-C20heteroaryl, which may be substituted by one or more G, C2-C18alkenyl, C2-10 C18alkynyl, C7-C25aralkyl, or -CO-R6; -SiR8 R9R10; or R4 and R5 together form a five or six membered ring; or R3 and R4 together form a five or six membered ring; D is -CO-; -COO-; -S-; -SO-; -SO2-; -O-; -NR7-; -SiR8R9-; -POR10-; -CR12=CR13-; or -C≡C-; and E is OR6; -SR6; -NR14R15; -NR14COR15; -COR6; -COOR6; -CONR14R15; -CN; halogen; or OSO3R11; SO3R11; SO2R11; PO3(R11)2; OPO3(R11)2; G is E; C1-C18alkyl, which is optionally interrupted by D; C1-C18perfluoroalkyl; C1-C18alkoxy, which is optionally substituted by E and/or interrupted by D; wherein R6 is H; C6-C18aryl which is optionally substituted by OH, C1-C30alkyl or C1-C30alkoxy; or C1-C30alkyl which is optionally interrupted by O-; R7 is H; C6-C18aryl which is optionally substituted by OH, C1-C30alkyl or C1-C30alkoxy; or C1-C30alkyl which is optionally interrupted by O-; R8, R9 and R10 independently of each other are hydrogen; C1-C30alkyl; C6-C18aryl which is optionally substituted by C1-C30alkyl; and R11 is hydrogen; C6-C18aryl, which is optionally substituted by OH, C1-C30alkyl or C1- C30alkoxy; or C1-C30alkyl, which is optionally interrupted by O-; R12, R13, R14 and R15 independently of each other are hydrogen; C6-C18aryl which is optionally substituted by OH, C1-C30alkyl or C1-C30alkoxy; C1-C30alkyl, which is optionally interrupted by O-; or R14 and R15 together form a five or six membered ring; as antimicrobial and/or preserving agents.

Description

Pyranopyranone derivatives as antimicrobial agents Description The present invention relates to the use of specific pyranopyranone derivatives for the antimicrobial treatment of surfaces, as antimicrobial active substances against gram- positive and gram-negative bacteria, yeasts and fungi and also for the preservation of cosmetics, household products, textiles and plastics and for use as disinfectants. Therefore, the present invention relates to the use of pyranopyranone derivatives of formula
, wherein
Figure imgf000002_0001
independently of one another are hydrogen; Ci-C3oalkyl, C2-C3oal- kenyl, or C3-Ci2cycloalkyl, which may be substituted by one or more E and/or inter- rupted by one or more D; C6-C2oaryl, which may be substituted by one or more G;
C4-C2oheteroaryl, which may be substituted by one or more G, C2-Cisalkenyl, C2-
Cisalkynyl, C7-C2saralkyl, or -CO-R6; -SiRs R9R10; or
R4 and R5, together with the carbon atom they are attached to, form a five or six mem- bered ring; or
R3 and R4, together with the carbon atoms they are attached to, form a five or six
membered ring;
D is -CO-; -COO-; -S-; -SO-; -SO2-; -0-; -NR7-; -SiR8R9-; -POR10-; -CRi2=CRi3-; or -C≡C-; and
E is -OR6; -SR6; -NR14R15; -NR14COR15; -COR6; -COOR6; -CONR14R15; -CN;
halogen; or OSO3R11 ; SO3R11 ; SO2R11 ; P03(Rn)2; OP03(Rn)2;
G is E; Ci-Ciealkyl, which is optionally interrupted by D; Ci-Ci8perfluoroalkyl; Ci- Ciealkoxy, which is optionally substituted by E and/or interrupted by D; wherein
R6 is H; C6-Ci8aryl which is optionally substituted by OH, Ci-C3oalkyl or Ci-C3oalkoxy; or Ci-C3oalkyl which is optionally interrupted by -0-;
R7 is H; C6-Ci8aryl which is optionally substituted by OH, Ci-C3oalkyl or Ci-C3oalkoxy; or Ci-C3oalkyl which is optionally interrupted by -0-;
Re, R9 and R10 independently of each other are hydrogen; Ci-C3oalkyl; C6-Cisaryl which is optionally substituted by Ci-C3oalkyl; and
R11 is hydrogen; C6-Ciearyl, which is optionally substituted by OH, Ci-C3oalkyl or Ci- C3oalkoxy; or Ci-C3oalkyl, which is optionally interrupted by -0-;
R12, Ri3, Ri4 and R15 independently of each other are hydrogen; C6-Ci8aryl which is optionally substituted by OH, Ci-C3oalkyl or Ci-C3oalkoxy; Ci-C3oalkyl, which is optionally interrupted by -0-; or
Ri4 and R15 together form a five or six membered ring; as antimicrobial and/or preserving agents (collectively named "antimicrobial compound" in the following).
Ci-C3oalkyl are straight chain or branched radicals like methyl, ethyl, n-propyl, iso- propyl, n-butyl, sek-butyl, tert-butyl, amyl, isoamyl or tert-amyl, hexyl, 2-ethylhexyl, hep- tyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, undecyl, eicosyl, tetracosyl, pentacosyl, heptacosyl, octacosyl or triacontyl.
Ci-C3oalkoxy are straight chain or branched radicals like methoxy, ethoxy, n-propoxy, isopropoxy, n-butyloxy, sek-butyloxy, tert-butyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, 2-ethylhexyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, undecyloxy eicosyloxy tetracosyloxy, pentacosyloxy, heptacosyloxy, octacosyloxy or triacontyloxy. C2-C3oalkenyl are straight chain or branched radicals like allyl, methallyl, isopropenyl, 2- butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n- dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl, n-octadec-4-enyl, eicosenyl,
tetracosenyl, pentacoensyl, heptacosenyl, octacosenyl or triacontenyl. C3-Ci2cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl and preferably cyclohexyl.
Each alkyl or cycloalkyl can be saturated or unsaturated.
Each alkyl, cycloalkyl or alkoxy can preferably be substituted by one or more E and/or interrupted by one or more D.
Each aryl can be preferably substituted by G; adjacent residues G may be intercon- nected to form, for example, C3-C4alkylene, or a residue -O-CH2-O-.
Each heteroaryl can be preferably substituted by G, C2-Cisalkenyl, C2-Cisalkynyl, C7- C25aralkyl, CN, or -CO-R6. Hetero-C3-Ci2aryl is preferably pyridinyl, pyrimidinyl, triazinyl, pyrrolyl, furanyl, thio- phenyl or chinolinyl.
C6-C2oaryl is for example naphthyl and preferably phenyl or biphenyl. Preference is given to compounds wherein Ri is Ci-C3oalkyl and even more preferred are compounds wherein Ri is methyl. Further preference is given to compounds of formula (1 ), wherein
Ri is d-Cealkyl;
R2 is hydrogen;
R3, R4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, C2-C3oalkenyl, or C3-Ci2cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C6-C2oaryl, which may be substituted by one or more G; C4- C2oheteroaryl, which may be substituted by one or more G, C2-Ci8alkenyl, C2- Cisalkynyl, C7-C2saralkyl, or -CO-R6; or
R4 and R5 together form a five or six membered ring;
D is -CO-; -COO-; -0-; -IMR7-; -CRi2=CRi3-; or -C≡C-; and
E is -OR6; -NR14R15; -NR14COR15; -COR6; -COOR6; -CONR14R15; -CN; halogen; or
OSO3R11 ; SO3R11 ; SO2R11 ; P03(Rii)2; OP03(Rii)2;
G is E; Ci-Cisalkyl, which is optionally interrupted by D; C-i-C-isperfluoroalkyl; Ci- Ciealkoxy, which is optionally substituted by E and/or interrupted by D; wherein R6, R7, R11 , R12, Ri3, Ri4 and R15 are defined as in formula (1 ).
Further preference is given to compounds of formula (1 ), wherein
Ri is d-Cealkyl;
R2 is hydrogen;
R3, R4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, C2-C3oalkenyl, or C3-Ci2cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C6-C2oaryl, which may be substituted by one or more G; C4- C2oheteroaryl, which may be substituted by one or more G, C2-Ci8alkenyl, C2- C-isalkynyl, C7-C2saralkyl, or -CO-R6; or
R4 and R5 together form a five or six membered ring;
D is -CO-; -COO-; -0-; -IMR7-; -CRi2=CRi3-; or -C≡C-; and
E is -OR6; -NR14R15; -NR14COR15; -COR6; -COOR6; -CONR14R15; -CN; halogen; or
OSO3R11 ; SO3R11 ; SO2R11 ; P03(Rii)2; OP03(Rii)2;
G is E; Ci-Cisalkyl, which is optionally interrupted by D; C-i-C-isperfluoroalkyl; Ci- Ciealkoxy, which is optionally substituted by E and/or interrupted by D; wherein
R6, R7, R11 , R12, Ri3, Ri4 and R15 are defined as in formula (1 ).
More preferred are compounds of formula (1 ), wherein
Ri is Ci-C4alkyl;
R2 is hydrogen;
R3, R4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, or C2-C3oal- kenyl, which may be substituted by one or more E and/or interrupted by one or more D; C6-C2oaryl, which may be substituted by one or more G; C4-C2oheteroaryl, which may be substituted by one or more G; or
R4 and R5 together form a five or six membered ring;
D is -CO-; -COO-; -0-; -IMR7-; -CRi2=CRi3-; or -C≡C-; and
E is -OR6; -NR14R15; -NR14COR15; -COR6; -COOR6; or -CONR14R15; G is E; Ci-Cisalkyl, which is optionally interrupted by D; d-dsalkoxy, which is optionally substituted by E and/or interrupted by D; wherein
R6, R7, R12, Ri3, Ri4 and R15 are defined as in formula (1 ).
Most preferred are compounds of formula (1 ), wherein
Ri is methyl;
R2 is hydrogen;
R3, R4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, or C2-C3oal- kenyl, or
R3 and R4 together form a five or six membered ring, which may be interrupted by -0-; or
R4 and R5 together form a five or six membered ring.
R3 and R4, or R4 and R5, together with the carbon atom(s) they are attached to may form a five or six membered ring as noted above; thus, R3 and R4, or R4 and R5, together may, for example, be C2-C8alkylene, C2-C8alkenylene, C2-C8oxaalkylene, C2- C8oxaalkenylene, C4-C8cycloalkylene, C4-C8cycloalkenylene. In consequence, the rings formed may be carbocyclic or heterocyclic, and mono- or bicyclic; examples are C5-C6cycloalkyl, C5-C6cycloalkenyl, C6-C7bicycloalkyl, C6-C7bicycloalkenyl, C4- C5oxacycloalkyl, C4-C5oxacycloalkenyl, each of which being unsubstituted or substituted by G, such as in the examples for R3/R4 and R4/R5 listed below.
Even more preferred are compounds of formula (1 ), wherein
Ri is methyl
R2 is hydrogen
is hydrogen; Ci-Ci2alkyl; C2-C4alkenyl; or a radical of formula
is hydrogen; C2-C4alkenyl; is hydrogen; Ci-C4alkyl; phenyl; -SiRs R9R10; or a radical of for
Figure imgf000005_0001
or
* * * *
R3 and R4 together form the rings *
R4 and R5 together form the rings
Figure imgf000005_0002
Figure imgf000005_0003
Examples of pyranopyranone compounds according to the present invention are listed in Table 1 below:
Figure imgf000006_0001
Figure imgf000007_0001
Selected compounds are
(P-1 ); (P-2); (P-3); (P-4); (P-6); and (P- 7).
Most preferred compounds are (P-3, (P-4) and (P-6).
One of the pyranopyranones defined above is novel and is also a subject of the present invention.
The no spond to the formula
Figure imgf000008_0001
The pyranopyranones corresponding to formula (1 ) can be prepared according to stan dard procedures known per se, generally by reacting a pyranone compound corresponding to formula (1 a) with an aldehyde corresponding to formula (1 b) to form the pyranopyranone compound corresponding to formula (1 ) wherein the substituents are as defined above.
Figure imgf000008_0002
This con ensat on react on s genera y per orme n su ta e so vents suc as water, ethyl acetate, acetone, acetonitrile, dioxane, chloroform, tetrahydrofurane, dimethyl- formamide, diethylether or tert-butylmethylether, in the presence of an organic or inorganic base, preferably calcium sulfate or potassium carbonate.
Such procedures are described for example in the journals Bioorganic&Medicinal Chemistry Letter, volume 17 (2007) on the pages 978 to 982 or in QSAR & Combinatorial Science, 23(10), (2004), on the pages 895-898; or in Carbohydrate Research, 340(7), (2005), on the pages 1287-1300; or in Organic Letters, volume 8(2), (2006), on the pages 191 -193; or in Journal of Organic Chemistry, volume 68(5), (2003), on the pages 1729-1735; or in Journal of Organic Chemistry, volume 64(3), (1999) on the pages 690-691 ; or in Journal of Organic Chemistry, volume 62(20), (1997) on the pages 6888-6896. The compounds of the present invention also exhibit pronounced antimicrobial action, for example against pathogenic gram-positive and gram-negative bacteria and against bacteria of the skin and oral flora, and also against yeasts and molds. They are accordingly suitable for disinfection, deodorisation, and for general and antimicrobial treat- ment of the skin and mucosa and of integumentary appendages (hair), for example, for the disinfection of hands and wounds. Compounds of the invention thus may be used for the preparation of a medicament for skin, mucosal, oral, or wound disinfection. The invention thus includes a method, or a use, for the preparation of a medicament for protecting skin, mucosa and/or integumentary appendages against the action of mi- crobes, including protecting the scalp from dandruff, which method comprises incorporation of an effective amount of a pyranopyranone derivative of formula (1 ) into said medicament.
Of special interest is the non-therapeutic use of the present compounds as antimicrobial and/or preserving agents.
They are accordingly suitable as antimicrobial active substances and preservatives in personal care preparations, for example shampoos, bath additives, hair care prepara- tions, liquid and solid soaps (based on synthetic surfactants and salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, e.g. cleansing solutions for the skin, moist cleaning cloths, wet wipes, oils or powders. For example, the antimicrobial compounds of the invention are effective as anti- dandruff agents in shampoos or other products used in hair treatment such as oils, sprays, hair gels.
Moreover they can be used as agent against dermatophytes for use in products against seborrheic dermatitis, psoriasis and athlethes foot in formulation types such as creams, lotions, gels, powders, oils, tonics, sprays, wet wipes etc. And as anti-acne agents in facial care producs such as creams, lotions, gels, tonics, powders etc.
The invention accordingly relates also to a personal care preparation comprising at least one antimicrobial compound of the invention and cosmetically tolerable carriers or adjuvants.
The personal care preparation according to the invention, generally contains from 0.01 to 15 % by weight, for example, from 0.1 to 10 % by weight, based on the total weight of the inventive composition, of the antimicrobial compounds of the invention, and cosmetically tolerable adjuvants and/or carrier. Likewise, the medicament generally contains from 0.01 to 15 % by weight, for example, from 0.1 to 10 % by weight, based on the total weight of the inventive composition, of the antimicrobial compounds of the invention, and pharmaceutically tolerable adjuvants and/or carrier. Pharmaceutically tolerable adjuvants and/or carriers are usually selected from suitable ingredients, or classes of ingredients, listed below for personal care preparations of the invention.
Depending upon the form of the personal care preparation, it comprises, in addition to the antimicrobial compounds of the invention, further constituents, for example sequestering agents, colourings, perfume oils, thickening or solidifying agents (consistency regulators), emulsifiers, emollients, UV-absorbers, skin protective agents, anti- oxidants, additives that improve the mechanical properties, such as dicarboxylic acids and/or aluminium, zinc, calcium or magnesium salts of Ci4-C22fatty acids, and, optionally, preservatives.
The personal care preparation according to the invention may be in the form of a water- in-oil or oil-in-water emulsion, an alcoholic or alcohol-containing formulation, a vesicular dispersion of an ionic or non-ionic ampiphilic lipid, a gel, a solid stick or an aerosol formulation.
As a water-in-oil or oil-in-water emulsion, the cosmetically tolerable adjuvant contains preferably from 5 to 50 % of an oil phase, from 5 to 20 % of an emulsifier and from 30 to 90 % water. The oil phase may comprise any oil suitable for cosmetic formulations, for example one or more hydrocarbon oils, a wax, a natural oil , a silicone oil, a fatty acid ester or a fatty alcohol. Preferred mono- or poly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
Cosmetic formulations according to the invention are used in various fields. There come into consideration, for example, the following preparations:
skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, synthetic detergents or washing pastes,
- bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts;
skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils;
cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye- care preparations, e.g. eye shadow preparations, mascaras, eyeliners, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers;
intimate hygiene preparations, e.g. intimate washing lotions or intimate sprays; - foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations; light-protective preparations, such as sun milks, lotions, creams or oils, sun-blocks or tropicals, pre-tanning preparations or after-sun preparations;
skin-tanning preparations, e.g. self-tanning creams;
depigmenting preparations, e.g. preparations for bleaching the skin or skin- lightening preparations;
insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks;
deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons;
antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;
- preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks;
hair-removal preparations in chemical form (depilation), e.g. hair-removing powders, liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams;
- shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions;
fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams;
- dental care, denture-care and mouth-care preparations, e.g. toothpastes, gel toothpastes, tooth powders, mouthwash concentrates, anti-plaque mouthwashes, denture cleaners or denture fixatives;
cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment prepara- tions, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, m ild wave, cold wave) , hai r- straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semipermanent or permanent hair colorants, preparations containing self-oxidising dyes, or natural hair colorants, such as henna or camomile.
The invention relates also to oral compositions containing from 0.01 to 15 % by weight, based on the total weight of the composition, of the antimicrobial compound, and orally tolerable adjuvants.
The oral composition according to the invention may be, for example, in the form of a gel, a paste, a cream or an aqueous preparation (mouthwash).
The oral composition according to the invention may also comprise compounds that release fluoride ions which are effective against the formation of caries, for example inorganic fluoride salts, e.g. sodium, potassium, ammonium or calcium fluoride, or organic fluoride salts, e.g. amine fluorides, which are known under the trade name OLAFLUOR. The anti-microbial compounds of this invention are also suitable for treating, especially preserving, textile fibre materials. Such materials are undyed and dyed or printed fibre materials, e.g. of silk, wool, polyamide or polyurethanes, and especially cellulosic fibre materials of all kinds. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen, jute and hemp, as well as cellulose and regenerated cellulose.
The antimicrobial compounds of this invention are suitable also for treating, especially imparting antimicrobial properties to or preserving, plastics, e.g. polyethylene, polypropylene, polyurethane, polyester, polyamide, polycarbonate, latex etc. Fields of use therefore are, for example, floor coverings, plastics coatings, plastics containers and packaging materials; kitchen and bathroom utensils (e.g. brushes, shower curtains, sponges, bathmats), latex, filter materials (air and water filters), plastics articles used in the field of medicine, e.g. dressing materials, syringes, catheters etc., so-called "medical devices", gloves and mattresses. The antimicrobial compounds of this invention are suitable also for treating, especially imparting antimicrobial properties to or preserving industrial formulations such as coatings, lubricants etc.
Paper, for example papers used for hygiene purposes, may also be provided with anti- microbial properties using the present anti-microbial compounds.
It is also possible for nonwovens, e.g. nappies/diapers, sanitary towels, panty liners, and cloths for hygiene and household uses, to be provided with antimicrobial properties in accordance with the invention.
The antimicrobial compounds of this invention are also used in washing and cleaning formulations, e.g. in liquid or powder washing agents or softeners.
The antimicrobial compounds of this invention can also be used in household and gen- eral-purpose cleaners for cleaning and disinfecting hard surfaces.
In addition to preserving cosmetic and household products, the preservation of technical products, the provision of technical products with antimicrobial properties and use as a biocide in technical processes are also possible, for example in paper treatment, especially in paper treatment liquors, printing thickeners of starch or cellulose derivatives, surface-coatings and paints. The antimicrobial compounds of the invention are also suitable for the antimicrobial treatment of wood and for the antimicrobial treatment of leather, the preserving of leather and the provision of leather with antimicrobial properties. The compounds according to the invention are also suitable for the protection of cosmetic products, pharmaceutical products and household products from microbial damage.
The compounds claimed in the present invention can be combined with biocides used as antimicrobial actives in cosmetic and pharmaceutical products and household products and/or preservatives used in cosmetic and pharmaceutical products or houseold products in order to improve the antimicrobial activity of the cosmetic product, the pharmaceutical product or household product. In addition, the compounds are capable of penetrating biofilms on living and non-living surfaces, of preventing the adhesion of bacteria to surfaces and any further build-up of the biofilm, of detaching such biofilm and/or inhibiting the further growth of the biofilm- forming micro-organisms in the biological matrix, or of killing such micro-organisms. Biofilms are understood, very generally, to be aggregations of living and dead microorganisms, especially bacteria, that adhere to living and non-living surfaces, together with their metabolites in the form of extracellular polymeric substances (EPS matrix), e.g. polysaccharides. The activity of antimicrobial substances that normally exhibit a pronounced growth-inhibiting or lethal action with respect to planktonic cells may be greatly reduced with respect to microorganisms that are organized in biofilms, for example because of inadequate penetration of the active substance into the biological matrix.
In the present invention, this may relate to biofilms on human tooth surfaces and oral mucosa, which play a crucial role in the onset of degenerative diseases in the oral cavity, e.g. caries or periodontitis, as a result of the biofilm-forming micro-organisms or their metabolites.
Action against bio-films in the present invention also relates to biofilms on non-human surfaces. The antimicrobial compounds of this invention are useful in coatings or films in protecting surfaces from bio-fouling. Such surfaces include surfaces in contact with marine environments (including fresh water, brackish water and salt water environments), for example, the hulls of ships, surfaces of docks or the inside of pipes in circulating or pass-through water systems. Other surfaces are susceptible to similar biofoul- ing, for example walls exposed to rain water, walls of showers, roofs, gutters, pool ar- eas, saunas, floors and walls exposed to damp environs such as basements or garages and even the housing of tools and outdoor furniture. The antimicrobial compounds of this invention are also useful in preventing bio-fouling, or eliminating or controlling microbe accumulation on the surfaces either by incorporating the antimicrobial compounds into the article or surface of the article in question or by applying the antimicrobial to these surfaces as part of a coating or film.
When applied as a part of a film or coating, the antimicrobial compounds of this invention are part of a composition which also comprises a binder.
The binder may be any polymer or oligomer compatible with the present antimicrobials. The binder may be in the form of a polymer or oligomer prior to preparation of the anti- fouling composition, or may form by polymerization during or after preparation, including after application to the substrate. In certain applications, such as certain coating applications, it will be desirable to crosslink the oligomer or polymer of the anti fouling composition after application.
The term binder as used in the present invention also includes materials such as glycols, oils, waxes and surfactants commercially used in the care of wood, plastic, glass and other surfaces. Examples include water proofing materials for wood, vinyl protectants, protective waxes and the like.
The composition may be a coating or a film. When the composition is a thermoplastic film which is applied to a surface, for example, by the use of an adhesive or by melt applications including calendaring and co-extrusion, the binder is the thermoplastic polymer matrix used to prepare the film.
When the composition is a coating, it may be applied as a liquid solution or suspension, a paste, gel, oil or the coating composition may be a solid, for example a powder coating which is subsequently cured by heat, UV light or other method. As the composition of the invention may be a coating or a film, the binder can be comprised of any polymer used in coating formulations or film preparation. For example, the binder is a thermoset, thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer. Thermoset, thermoplastic, elastomeric, inherently crosslinked or crosslinked polymers include polyolefin, polyamide, polyurethane, polyacrylate, polyacrylamide, polycarbonate, polystyrene, polyvinyl acetates, polyvinyl alcohols, polyester, halogenated vinyl polymers such as PVC, natural and synthetic rubbers, alkyd resins, epoxy resins, unsaturated polyesters, unsaturated polyamides, polyimides, silicon containing and car- bamate polymers, fluorinated polymers, crosslinkable acrylic resins derived from substituted acrylic esters, e.g. from epoxy acrylates, urethane acrylates or polyester acry- lates. The polymers may also be blends and copolymers of the preceding chemistries. Biocompatible coating polymers, such as, poly[-alkoxyalkanoate-co-3- hydroxyalkenoate] (PHAE) polyesters, Geiger et. al. Polymer Bulletin 52, 65-70 (2004), can also serve as binders in the present invention. Alkyd resins, polyesters, polyurethanes, epoxy resins, silicone containing polymers, polyacrylates, polyacrylamides, fluorinated polymers and polymers of vinyl acetate, vinyl alcohol and vinyl amine are non-limiting examples of common coating binders useful in the present invention. Other coating binders, of course, are part of the present invention.
Coatings are frequently crosslinked with, for example, melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates, epoxy resins, anhydrides, poly acids and amines, with or without accelerators. The compositions of present invention are for example a coating applied to a surface which is exposed to conditions favorable for bioaccumulation. The presence of the antimicrobial compounds of this invention in said coating will prevent the adherence of organisms to the surface. The anti-microbial compounds of the present invention may be part of a complete coating or paint formulation, such as a marine gel-coat, shellac, varnish, lacquer or paint, or the anti fouling composition may comprise only a polymer of the instant invention and binder, or a polymer of the instant invention, binder and a carrier substance. It is anticipated that other additives encountered in such coating formulations or applications will find optional use in the present applications as well.
The coating may be solvent borne or aqueous. Aqueous coatings are typically considered more environmentally friendly. The coating is, for example, aqueous dispersion of a polymer of the instant invention and a binder or a water based coating or paint. For example, the coating comprises an aqueous dispersion of a polymer of the instant invention and an acrylic, methacrylic or acrylamide polymers or co-polymers or a poly[-alkoxyalkanoate-co-3- hydroxyalkenoate] polyester.
The coating may be applied to a surface which has already been coated, such as a protective coating, a clear coat or a protective wax applied over a previously coated article. Coating systems include marine coatings, wood coatings, other coatings for metals and coatings over plastics and ceramics. Exemplary of marine coatings are gel coats comprising an unsaturated polyester, a styrene and a catalyst. The coating is, for example a house paint, or other decorative or protective paint. It may be a paint or other coating that is applied to cement, concrete or other masonry article. The coating may be a water proofer as for a basement or foundation. The coating composition is applied to a surface by any conventional means including spin coating, dip coating, spray coating, draw down, or by brush, roller or other applicator. A drying or curing period will typically be needed.
Coating or film thickness will vary depending on application and will become apparent to one skilled in the art after limited testing.
The composition may be in the form of a protective laminate film.
Such a film typically comprises thermoset, thermoplastic, elastomeric, or crosslinked polymers. Examples of such polymers include, but are not limited to, polyolefin, poly- amide, polyurethane, polyacrylate, polyacrylamide, polycarbonate, polystyrene, polyvinyl acetates, polyvinyl alcohols, polyester, halogenated vinyl polymers such as PVC, natural and synthetic rubbers, alkyl resins, epoxy resins, unsaturated polyesters, unsaturated polyamides, polyimides, fluorinated polymers, silicon containing and car- bamate polymers. The polymers may also be blends and copolymers of the preceding chemistries.
When the anti-fouling composition is a preformed film it is applied to the surface by, for example, the use of an adhesive, or co-extruded onto the surface. It may also be me- chanically affixed via fasteners which may require the use of a sealant or caulk wherein the esters of the instant invention may also be advantageously employed.
A plastic film may also be applied with heat which includes calendaring, melt applications and shrink wrapping.
The composition may be part of a polish, such a furniture polish, or a dispersant or surfactant formulation such as a glycol or mineral oil dispersion or other formulation as used in for example wood protection. Examples of useful surfactants include, but are not limited to, polyoxyethylene-based surface-active substances, including polyoxyethylene sorbitan tetraoleate (PST), poly- oxyethylene sorbitol hexaoleate (PSH), polyoxyethylene 6 tridecyl ether, polyoxyethylene 12 tridecyl ether, polyoxyethylene 18 tridecyl ether, TWEEN RTM surfactants, TRITON RTM surfactants, and the polyoxyethlene-polyoxypropylene copolymers such as the PLURONIC RTM and POLOXAMER RTM product series (from BASF). Other matrix-forming components include dextrans, linear PEG molecules (MW 500 to 5,000,000), star-shaped PEG molecules, comb-shaped and dendrimeric, hyperbrached PEG molecules, as well as the analogous linear, star, and dendrimer polyamine polymers, and various carbonated, perfluorinated (e.g., DUPONT ZONYL RTM fluorosur- factants) and siliconated (e.g, dimethylsiloxane-ethylene oxide block copolymers) surfactants.
Given the wide array of applications for the present anti-microbial compositions, the composition may contain other additives such as antioxidants, UV absorbers, hindered amines, phosphites or phosphonites, benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal stearates, nucleating agents, fillers, reinforcing agents, lubricants, emulsifiers, dyes, pigments, dispersants, other optical brighteners, flame retardants, antistatic agents, blowing agents and the like, such as the materials listed below, or mixtures thereof.
The substrate can be an inorganic or organic substrate, for example, a metal or metal alloy; a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer as described above; a natural polymer such as wood or rubber; a ceramic material; glass; leather or other textile.
The substrate may be, for example, non-metal inorganic surfaces such as silica, silicon dioxide, titanium oxides, aluminum oxides, iron oxides, carbon, silicon, various silicates and sol-gels, masonry, and composite materials such as fiberglass and plastic lumber (a blend of polymers and wood shavings, wood flour or other wood particles).
The inorganic or organic substrate is, for example, a metal or metal alloy, a thermo- plastic, elastomeric, inherently crosslinked or crosslinked polymer, a ceramic material or a glass.
The substrate may be a multi-layered article comprised of the same or different components in each layer. The surface coated or laminated may be the exposed surface of an already applied coating or laminate.
The inorganic or organic substrate to be coated or laminated can be in any solid form.
For example, polymer substrates may be plastics in the form of films, injection-molded articles, extruded workpieces, fibres, felts or woven fabrics.
For example molded or extruded polymeric articles used in construction or the manufacture of durable goods such as siding, fascia and mailboxes can all benefit from the present method for stabilizer replenishment.
Plastics which would benefit from the present method include, but are not limited to, plastics used in construction or the manufacture of durable goods or machine parts, including outdoor furniture, boats, siding, roofing, glazing, protective films, decals, sealants, composites like plastic lumber and fiber reinforced composites, functional films including films used in displays as well as articles constructed from synthetic fibers such as awnings, fabrics such as used in canvas or sails and rubber articles such as outdoor matting and other uses cited in this disclosure. Exemplary of such plastics are polypropylene, polyethylene, PVC, POM, polysulfones, styrenics, polyamides, ure- thanes, polyesters, polycarbonate, acrylics, butadiene, thermoplastic polyolefins, iono- mers, unsaturated polyesters and blends of polymer resins including ABS, SAN and PC/ABS.
The anti-microbial compounds of the invention are also effective in protecting useful plants, such as plants in agriculture, in horticulture and in forests, plant parts and seeds from disease and spoilage. For example, the present invention also provides a method which comprises applying to useful plants, the locus thereof or propagation material thereof a composition which comprises at least one of the polyglycerol polymers and co-polymers of the invention. Said compositions can be used as foliar, soil and seed treatment fungicides.
The compositions of the invention it is possible to inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants. The present compositions are applied by treating the fungi, the useful plants, the locus thereof, the propagation material thereof, the natural substances of plant origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials threatened by fungus attack with the compositions in an effective amount.
The compositions according to the invention may be applied before or after infection of the useful plants, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials by the fungi.
The compositions of the present invention are of particular interest for controlling a large number of fungi in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.
When applied to plants, the anti-microbial compounds of the invention are applied at rate of 1 to 5000 g a.i./ha, for example 2 to 2000 g a.i./ha, for example, 5 to 2000 g a.i./ha, for example, 10 to 1000 g a.i./ha, e.g. 50, 75, 100, 200, 250, 500, 800, 1000, 1500 g a.i./ha of polymer or co-polymers. In agricultural practice the application rates depend on the type of effect desired, and typically range from 20 to 4000 g of total antimicrobials per hectare.
When treating seed, rates of 0.001 to 50 g of the present anti-microbial compounds, for example 0.01 to 10 g, per kg of seed, are generally sufficient.
The composition comprising the anti-microbial compounds of the invention may be employed in any conventional form, for example in the form a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emul- sifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil misci- ble liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.
Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). For example, formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, typically contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects. A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active in- gredients in encapsulated form, e.g. as slow release capsules or microcapsules.
In general, the formulations include from 0.01 to 90% by weight of at least one of the anti-microbial compounds, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), and optionally other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 and 80%, for example, between about 5 and 70% by weight of total active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, for example from 0.01 to 5% by weight of active agent.
Methods of preparing the above plant protection formulations are well known, for ex- ample, in US 20070265267, already incorporated by reference.
Particular embodiments of the invention therefore relate to methods for protecting plastics, coatings, other materials of construction, home or per- sonal care formulations, plants, agricultural products, industrial formulations or technical process against the action of microbes which comprises adding an effective amount of the anti-microbial compounds of the present invention; a method for protecting skin, mucosa and integumentary appendages against the ac- tion of microbes including protecting the scalp from dandruff, which comprises applying a preparation comprising an effective amount of the anti-microbial compounds of the present invention; a method for protecting paper, wood, leather, synthetic textile materials or natural tex- tile materials such as cotton against the action of microbes comprising incorporating or applying an effective amount of the present polymer or copolymer or a composition comprising an effective amount the anti-microbial compounds of the present invention; a method for cleaning and disinfecting hard surfaces which comprises applying a preparation comprising an effective amount of the anti-microbial compounds of the present invention; a method for preventing bio-fouling of an article comprising incorporating anti-microbial compounds of the present invention into the article or surface of the article or by apply- ing the anti-microbial compounds of the present invention to these surfaces either directly or as part of a coating or film.
Other materials of construction include, in addition to wood, metals, paper, glass, ceramics, coatings, plastics and textiles, materials such as concrete, cement, adhesives, caulking materials, composites of natural and synthetic materials etc.
In the following examples for combinations of the compounds claimed in the present invention and biocides and/or preservatives are shown:
Table 2: Examples of combinations of biocides and/or preservatives used as antimicro- bial actives in cosmetic products and household products Table 2: A B c D E F G H I K L M N 0 P Q R s T u V w
Combination name
BIOCIDE/PRESERVATIVE 1 X
BIOCIDE/PRESERVATIVE 2 X
BIOCIDE/PRESERVATIVE 3 X
BIOCIDE/PRESERVATIVE 4 X
BIOCIDE/PRESERVATIVE 5 X
BIOCIDE/PRESERVATIVE 6 X
BIOCIDE/PRESERVATIVE 7 X
BIOCIDE/PRESERVATIVE 8 X
BIOCIDE/PRESERVATIVE 9 X
BIOCIDE/PRESERVATIVE 10 X
BIOCIDE/PRESERVATIVE 11 X
BIOCIDE/PRESERVATIVE 12 X
BIOCIDE/PRESERVATIVE 13 X
BIOCIDE/PRESERVATIVE 14 X
BIOCIDE/PRESERVATIVE 15 X
BIOCIDE/PRESERVATIVE 16 X
BIOCIDE/PRESERVATIVE 17 X
BIOCIDE/PRESERVATIVE 18 X
BIOCIDE/PRESERVATIVE 19 X
BIOCIDE/PRESERVATIVE 20 X
BIOCIDE/PRESERVATIVE 21 X
BIOCIDE/PRESERVATIVE 22 X
BIOCIDE/PRESERVATIVE 23 X X
BIOCIDE/PRESERVATIVE 24 X X
BIOCIDE/PRESERVATIVE 25 X X
BIOCIDE/PRESERVATIVE 26 X X
BIOCIDE/PRESERVATIVE 27 X X
BIOCIDE/PRESERVATIVE 28 X X
BIOCIDE/PRESERVATIVE 29 X X
BIOCIDE/PRESERVATIVE 30 X X
BIOCIDE/PRESERVATIVE 31 X X
BIOCIDE/PRESERVATIVE 32 X X
BIOCIDE/PRESERVATIVE 33 X X
BIOCIDE/PRESERVATIVE 34 X X
BIOCIDE/PRESERVATIVE 35 X X
BIOCIDE/PRESERVATIVE 36 X X
BIOCIDE/PRESERVATIVE 37 X X
BIOCIDE/PRESERVATIVE 38 X X
BIOCIDE/PRESERVATIVE 39 X X
BIOCIDE/PRESERVATIVE 40 X X
BIOCIDE/PRESERVATIVE 41 X X
BIOCIDE/PRESERVATIVE 42 X X
BIOCIDE/PRESERVATIVE 43 X X
BIOCIDE/PRESERVATIVE 44 X X
BIOCIDE/PRESERVATIVE 45 X X
BIOCIDE/PRESERVATIVE 46 X X
BIOCIDE/PRESERVATIVE 47 X X
BIOCIDE/PRESERVATIVE 48 X X
BIOCIDE/PRESERVATIVE 49 X X
BIOCIDE/PRESERVATIVE 50 X X Table 2: A B c D E F G H I K L M N 0 P Q R s T u V w
Combination name
BIOCIDE/PRESERVATIVE 51 X X
BIOCIDE/PRESERVATIVE 52 X X
BIOCIDE/PRESERVATIVE 53 X X
BIOCIDE/PRESERVATIVE 54 X X
BIOCIDE/PRESERVATIVE 55 X X
BIOCIDE/PRESERVATIVE 56 X X
BIOCIDE/PRESERVATIVE 57 X X
BIOCIDE/PRESERVATIVE 58 X X
BIOCIDE/PRESERVATIVE 59 X X
BIOCIDE/PRESERVATIVE 60 X X
BIOCIDE/PRESERVATIVE 61 X X
BIOCIDE/PRESERVATIVE 62 X X
BIOCIDE/PRESERVATIVE 63 X X
BIOCIDE/PRESERVATIVE 64 X X
BIOCIDE/PRESERVATIVE 65 X X
BIOCIDE/PRESERVATIVE 66 X X
BIOCIDE/PRESERVATIVE 67 X X
BIOCIDE/PRESERVATIVE 68 X X
BIOCIDE/PRESERVATIVE 69 X X
BIOCIDE/PRESERVATIVE 70 X X
BIOCIDE/PRESERVATIVE 71 X X
BIOCIDE/PRESERVATIVE 72 X X
BIOCIDE/PRESERVATIVE 73 X X
BIOCIDE/PRESERVATIVE 74 X X
BIOCIDE/PRESERVATIVE 75 X X
BIOCIDE/PRESERVATIVE 76 X X
BIOCIDE/PRESERVATIVE 77 X X
BIOCIDE/PRESERVATIVE 78 X X
BIOCIDE/PRESERVATIVE 79 X X
BIOCIDE/PRESERVATIVE 80 X X
BIOCIDE/PRESERVATIVE 81 X X
BIOCIDE/PRESERVATIVE 82 X X
BIOCIDE/PRESERVATIVE 83 X X
BIOCIDE/PRESERVATIVE 84 X X
BIOCIDE/PRESERVATIVE 85 X X
BIOCIDE/PRESERVATIVE 86 X X
BIOCIDE/PRESERVATIVE 87 X X
BIOCIDE/PRESERVATIVE 88 X X
BIOCIDE/PRESERVATIVE 89 X X
BIOCIDE/PRESERVATIVE 90 X X
BIOCIDE/PRESERVATIVE 91 X X
BIOCIDE/PRESERVATIVE 92 X X
BIOCIDE/PRESERVATIVE 93 X X
BIOCIDE/PRESERVATIVE 94 X X
BIOCIDE/PRESERVATIVE 95 X X
BIOCIDE/PRESERVATIVE 96 X X
BIOCIDE/PRESERVATIVE 97 X X
BIOCIDE/PRESERVATIVE 98 X X
BIOCIDE/PRESERVATIVE 99 X X
BIOCIDE/PRESERVATIVE 100 X X Table 2: A B C D E F G H I K L M N 0 P Q R s T u V w
Combination name
BIOCIDE/PRESERVATIVE 101 X X
BIOCIDE/PRESERVATIVE 102 X X
BIOCIDE/PRESERVATIVE 103 X X
BIOCIDE/PRESERVATIVE 104 X X
BIOCIDE/PRESERVATIVE 105 X X
BIOCIDE/PRESERVATIVE 106 X X
BIOCIDE/PRESERVATIVE 107 X X
BIOCIDE/PRESERVATIVE 108 X X
BIOCIDE/PRESERVATIVE 109 X X
BIOCIDE/PRESERVATIVE 110 X X
BIOCIDE/PRESERVATIVE 111 X X
BIOCIDE/PRESERVATIVE 112 X X
BIOCIDE/PRESERVATIVE 113 X X
BIOCIDE/PRESERVATIVE 114 X X
BIOCIDE/PRESERVATIVE 115 X X
BIOCIDE/PRESERVATIVE 116 X X
BIOCIDE/PRESERVATIVE 117 X X
BIOCIDE/PRESERVATIVE 118 X X
BIOCIDE/PRESERVATIVE 119 X X
BIOCIDE/PRESERVATIVE 120 X X
BIOCIDE/PRESERVATIVE 121 X X
BIOCIDE/PRESERVATIVE 122 X X
BIOCIDE/PRESERVATIVE 123 X X
BIOCIDE/PRESERVATIVE 124 X X
BIOCIDE/PRESERVATIVE 125 X X
BIOCIDE/PRESERVATIVE 126 X X
BIOCIDE/PRESERVATIVE 127 X X
BIOCIDE/PRESERVATIVE 128 X X
BIOCIDE/PRESERVATIVE 129 X X
BIOCIDE/PRESERVATIVE 130 X X
BIOCIDE/PRESERVATIVE 131 X X
BIOCIDE/PRESERVATIVE 132 X X
BIOCIDE/PRESERVATIVE 133 X X
BIOCIDE/PRESERVATIVE 134 X X
BIOCIDE/PRESERVATIVE 135 X X
BIOCIDE/PRESERVATIVE 136 X X
BIOCIDE/PRESERVATIVE 137 X X
BIOCIDE/PRESERVATIVE 138 X X
BIOCIDE/PRESERVATIVE 139 X X
BIOCIDE/PRESERVATIVE 140 X X
BIOCIDE/PRESERVATIVE 141 X X
BIOCIDE/PRESERVATIVE 142 X X
BIOCIDE/PRESERVATIVE 143 X X
BIOCIDE/PRESERVATIVE 144 X X
BIOCIDE/PRESERVATIVE 145 X X
BIOCIDE/PRESERVATIVE 146 X X
BIOCIDE/PRESERVATIVE 147 X X
BIOCIDE/PRESERVATIVE 148 X X
BIOCIDE/PRESERVATIVE 149 X X
BIOCIDE/PRESERVATIVE 150 X X Table 2: A B C D E F G H I K L M N 0 P Q R s T u V w
Combination name
BIOCIDE/PRESERVATIVE 151 X X
BIOCIDE/PRESERVATIVE 152 X X
BIOCIDE/PRESERVATIVE 153 X X
BIOCIDE/PRESERVATIVE 154 X X
BIOCIDE/PRESERVATIVE 155 X X
BIOCIDE/PRESERVATIVE 156 X X
BIOCIDE/PRESERVATIVE 157 X X
BIOCIDE/PRESERVATIVE 158 X X
BIOCIDE/PRESERVATIVE 159 X X
BIOCIDE/PRESERVATIVE 160 X X
BIOCIDE/PRESERVATIVE 161 X X
BIOCIDE/PRESERVATIVE 162 X X
BIOCIDE/PRESERVATIVE 163 X X
BIOCIDE/PRESERVATIVE 164 X X
BIOCIDE/PRESERVATIVE 165 X X
BIOCIDE/PRESERVATIVE 166 X X
BIOCIDE/PRESERVATIVE 167 X X
BIOCIDE/PRESERVATIVE 168 X X
BIOCIDE/PRESERVATIVE 169 X X
BIOCIDE/PRESERVATIVE 170 X X
BIOCIDE/PRESERVATIVE 171 X X
BIOCIDE/PRESERVATIVE 172 X X
BIOCIDE/PRESERVATIVE 173 X X
BIOCIDE/PRESERVATIVE 174 X X
BIOCIDE/PRESERVATIVE 175 X X
BIOCIDE/PRESERVATIVE 176 X X
BIOCIDE/PRESERVATIVE 177 X X
BIOCIDE/PRESERVATIVE 178 X X
BIOCIDE/PRESERVATIVE 179 X X
BIOCIDE/PRESERVATIVE 180 X X
BIOCIDE/PRESERVATIVE 181 X X
BIOCIDE/PRESERVATIVE 182 X X
BIOCIDE/PRESERVATIVE 183 X X
BIOCIDE/PRESERVATIVE 184 X X
BIOCIDE/PRESERVATIVE 185 X X
BIOCIDE/PRESERVATIVE 186 X X
BIOCIDE/PRESERVATIVE 187 X X
BIOCIDE/PRESERVATIVE 188 X X
BIOCIDE/PRESERVATIVE 189 X X
BIOCIDE/PRESERVATIVE 190 X X
BIOCIDE/PRESERVATIVE 191 X X
BIOCIDE/PRESERVATIVE 192 X X
BIOCIDE/PRESERVATIVE 193 X X
BIOCIDE/PRESERVATIVE 194 X X
BIOCIDE/PRESERVATIVE 195 X X
BIOCIDE/PRESERVATIVE 196 X X
BIOCIDE/PRESERVATIVE 197 X X
BIOCIDE/PRESERVATIVE 198 X X
BIOCIDE/PRESERVATIVE 199 X X
BIOCIDE/PRESERVATIVE 200 X X Table 2: A B C D E F G H I K L M N 0 P Q R s T u V w
Combination name
BIOCIDE/PRESERVATIVE 201 X X
BIOCIDE/PRESERVATIVE 202 X X
BIOCIDE/PRESERVATIVE 203 X X
BIOCIDE/PRESERVATIVE 204 X X
BIOCIDE/PRESERVATIVE 205 X X
BIOCIDE/PRESERVATIVE 206 X X
BIOCIDE/PRESERVATIVE 207 X X
BIOCIDE/PRESERVATIVE 208 X X
BIOCIDE/PRESERVATIVE 209 X X
BIOCIDE/PRESERVATIVE 210 X X
BIOCIDE/PRESERVATIVE 211 X X
BIOCIDE/PRESERVATIVE 212 X X
BIOCIDE/PRESERVATIVE 213 X X
BIOCIDE/PRESERVATIVE 214 X X
BIOCIDE/PRESERVATIVE 215 X X
BIOCIDE/PRESERVATIVE 216 X X
BIOCIDE/PRESERVATIVE 217 X X
BIOCIDE/PRESERVATIVE 218 X X
BIOCIDE/PRESERVATIVE 219 X X
BIOCIDE/PRESERVATIVE 220 X X
BIOCIDE/PRESERVATIVE 221 X X
BIOCIDE/PRESERVATIVE 222 X X
BIOCIDE/PRESERVATIVE 223 X X
BIOCIDE/PRESERVATIVE 224 X X
BIOCIDE/PRESERVATIVE 225 X X
BIOCIDE/PRESERVATIVE 226 X X
BIOCIDE/PRESERVATIVE 227 X X
BIOCIDE/PRESERVATIVE 228 X X
BIOCIDE/PRESERVATIVE 229 X X
BIOCIDE/PRESERVATIVE 230 X X
BIOCIDE/PRESERVATIVE 231 X X
BIOCIDE/PRESERVATIVE 232 X X
BIOCIDE/PRESERVATIVE 233 X X
BIOCIDE/PRESERVATIVE 234 X X
BIOCIDE/PRESERVATIVE 235 X X
BIOCIDE/PRESERVATIVE 236 X X
BIOCIDE/PRESERVATIVE 237 X X
BIOCIDE/PRESERVATIVE 238 X X
BIOCIDE/PRESERVATIVE 239 X X
BIOCIDE/PRESERVATIVE 240 X X
BIOCIDE/PRESERVATIVE 241 X X
BIOCIDE/PRESERVATIVE 242 X X
BIOCIDE/PRESERVATIVE 243 X X
BIOCIDE/PRESERVATIVE 244 X X
BIOCIDE/PRESERVATIVE 245 X X
BIOCIDE/PRESERVATIVE 246 X X
BIOCIDE/PRESERVATIVE 247 X X
BIOCIDE/PRESERVATIVE 248 X X
BIOCIDE/PRESERVATIVE 249 X X
BIOCIDE/PRESERVATIVE 250 X X Table 2: A B c D E F G H I K L M N 0 P Q R S T u V w
Combination name
BIOCIDE/PRESERVATIVE 251 X X
BIOCIDE/PRESERVATIVE 252 X X
BIOCIDE/PRESERVATIVE 253 X X
Figure imgf000026_0001
In all of the biocide combinations listed before in Table 2, "X" represents a specific biocide and/or preservative. The concentrations of these biocidal/preservative substances in the blends are between 1 % and 99%, preferably between 10% and 90%. The use concentration of these blends in household and personal care products is typically in the range of 0.1 % to 5% and preferred 0.2% to 2%.
Further biocide combination examples are the following:
In all the biocide combinations listed before the weight ratio of the biocides and or preservatives (based on the weight of all biocides/preservatives in the combination) is for combinations of two biocides/preservatives 1 :1 or 1 :2 or 2:1 or 1 :3 or 3:1 .
Formulation examples The compounds of the present invention from table 1 can be componed with the BIO- CIDES/PRESERVARTIVES from Table 2 as shown in the following formulation examples:
„BIOCIDE/PRESERVATIVE" may be (as described in Table 2) BIO- CIDE/PRESERVATIVE 1 , or BIOCIDE/PRESERVATIVE 2, or BIOCIDE/PRESERVATIVE 3, or BIOCIDE/PRESERVATIVE 4, or BIOCIDE/PRESERVATIVE 5, or BIOCIDE/PRESERVATIVE 6, or BIOCIDE/PRESERVATIVE 7, or BIOCIDE/PRESERVATIVE 8, or BIOCIDE/PRESERVATIVE 9, or BIOCIDE/PRESERVATIVE 10, or BIOCIDE/PRESERVATIVE 11 , or BIO- CIDE/PRESERVATIVE 12, or BIOCIDE/PRESERVATIVE 13, or BIOCIDE/PRESERVATIVE 14, or BIOCIDE/PRESERVATIVE 15, or BIOCIDE/PRESERVATIVE 16, or BIOCIDE/PRESERVATIVE 17, or BIOCIDE/PRESERVATIVE 18, or BIOCIDE/PRESERVATIVE 19, or BIOCIDE/PRESERVATIVE 20, or BIOCIDE/PRESERVATIVE 21 , or BIOCIDE/PRESERVATIVE 22, or BIOCIDE/PRESERVATIVE 23, or BIOCIDE/PRESERVATIVE 24, or BIOCIDE/PRESERVATIVE 25, or BIOCIDE/PRESERVATIVE 26, or BIOCIDE/PRESERVATIVE 27, or BIOCIDE/PRESERVATIVE 28, or BIOCIDE/PRESERVATIVE 29, or BIOCIDE/PRESERVATIVE 30, or BIOCIDE/PRESERVATIVE 31 , or BIOCIDE/PRESERVATIVE 32, or BIOCIDE/PRESERVATIVE 33, or BIOCIDE/PRESERVATIVE 34, or BIOCIDE/PRESERVATIVE 35, or BIO- CIDE/PRESERVA-TIVE 36, or BIOCIDE/PRESERVATIVE 37, or BIOCIDE/PRESERVATIVE 38, or BIOCIDE/PRESERVATIVE 39, or BIOCIDE/PRESERVATIVE 40, or BIOCIDE/PRESERVATIVE 41 , or BIOCIDE/PRESERVATIVE 42, or BIOCIDE/PRESERVATIVE 43, or BIOCIDE/-PRESER- VATIVE 44, or BIOCIDE/PRESERVATIVE 45, or BIOCIDE/PRESERVATIVE 46, or BIOCIDE/PRESERVATIVE 47, or BIOCIDE/PRESERVATIVE 48, or BIOCIDE/PRESERVATIVE 49, or BIOCIDE/PRESERVATIVE 50, or BIOCIDE/PRESERVATIVE 51 , or BIOCIDE/PRESERVATIVE 52, or BIOCIDE/PRESERVATIVE 53, or BIOCIDE/PRESERVATIVE 54, or BIO- CIDE/PRESERVATIVE 55, or BIOCIDE/PRESERVATIVE 56, or BIOCIDE/PRESERVATIVE 57, or BIOCIDE/PRESERVATIVE 58, or BIOCIDE/PRESERVATIVE 59, or BIOCIDE/PRESERVATIVE 60, or BIOCIDE/PRESERVATIVE 61 , or BIOCIDE/PRESERVATIVE 62, or BIOCIDE/PRESERVATIVE 63, or BIOCIDE/PRESERVATIVE 64, or BIOCIDE/PRESERVATIVE 65, or BIO- CIDE/PRESERVATIVE 66, or BIOCIDE/PRESERVATIVE 67, or BIOCIDE/-
PRESERVATIVE 68, or BIOCIDE/PRESERVATIVE 69, or BIOCIDE/PRESERVATIVE 70, or BIOCIDE/PRESERVATIVE 71 , or BIOCIDE/PRESERVATIVE 72, or BIOCIDE/PRESERVATIVE 73, or BIOCIDE/PRESERVATIVE 74, or BIOCIDE/PRESERVATIVE 75, or BIOCIDE/PRESERVATIVE 76, or BIO- CIDE/PRESERVATIVE 77, or BIOCIDE/PRESERVATIVE 78, or BIOCIDE/PRESERVATIVE 79, or BIOCIDE/PRESERVATIVE 80, or BIOCIDE/PRESERVATIVE 81 , or BIOCIDE/PRESERVATIVE 82, or BIOCIDE/PRESERVATIVE 83, or BIOCIDE/PRESERVATIVE 84, or BIOCIDE/PRESERVATIVE 85, or BIOCIDE/PRESERVATIVE 86, or BIOCIDE/PRESERVATIVE 87, or BIOCIDE/PRESERVATIVE 88, or BIOCIDE/PRESERVATIVE 89, or BIOCIDE/PRESERVATIVE 90, or BIOCIDE/PRESERVATIVE 91 , or BIOCIDE/PRESERVATIVE 92, or BIO- CIDE/PRESERVATIVE 93, or BIOCIDE/PRESERVATIVE 94, or BIOCIDE/PRESERVATIVE 95, or BIOCIDE/PRESERVATIVE 96, or BIOCIDE/PRESERVATIVE 97, or BIOCIDE/PRESERVATIVE 98, or BIOCIDE/PRESERVATIVE 99, or BIOCIDE/PRESERVATIVE 100, or BIOCIDE/PRESERVATIVE 101 , or BIOCIDE/PRESERVATIVE 102, or BIOCIDE/PRESERVATIVE 103, or BIO- CIDE/PRESERVATIVE 104, or BIOCIDE/PRESERVATIVE 105, or BIOCIDE/PRESERVATIVE 106, or BIOCIDE/PRESERVATIVE 107, or BIOCIDE/PRESERVATIVE 108, or BIOCIDE/PRESERVATIVE 109, or BIOCIDE/PRESERVATIVE 1 10, or BIOCIDE/PRESERVATIVE 1 1 1 , or BIOCIDE/PRESERVATIVE 1 12, or BIOCIDE/PRESERVATIVE 1 13, or BIOCIDE/PRE- SERVATIVE 1 14, or BIOCIDE/PRESERVATIVE 1 15, or BIOCIDE/PRESERVATIVE 1 16, or BIOCIDE/PRESERVATIVE 1 17, or BIOCIDE/PRESERVATIVE 1 18, or BIOCIDE/PRESERVATIVE 1 19, or BIOCIDE/PRESERVATIVE 120, or BIOCIDE/PRESERVATIVE 121 , or BIOCIDE/PRESERVATIVE 122, or BIOCIDE/PRESERVATIVE 123, or BIOCIDE/PRESERVATIVE 124, or BIO- CIDE/PRESERVATIVE 125, or BIOCIDE/PRESERVATIVE 126, or BIO-CIDE/PRE- SERVATIVE 127, or BIOCIDE/PRESERVATIVE 128, or BIOCIDE/PRESERVA-TIVE 129, or BIOCIDE/PRESERVATIVE 130, or BIOCIDE/PRESERVATIVE 131 , or BIOCIDE/PRESERVATIVE 132, or BIOCIDE/PRESERVATIVE 133, or BIOCIDE/PRESERVATIVE 134, or BIOCIDE/PRESERVATIVE 135, or BIOCIDE/PRESERVATIVE 136, or BIOCIDE/PRESERVATIVE 137, or BIOCIDE/PRESERVATIVE 138, or BIOCIDE/PRESERVATIVE 139, or BIOCIDE/PRESERVATIVE 140, or BIOCIDE/PRESERVATIVE 141 , or BIOCIDE/PRESERVATIVE 142, or BIOCIDE/PRESERVATIVE 143, or BIOCIDE/PRESERVATIVE 144, or BIOCIDE/PRESERVATIVE 145, or BIOCIDE/PRESERVATIVE 146, or BIO- CIDE/PRESERVATIVE 147, or BIOCIDE/PRESERVATIVE 148, or BIOCIDE/PRESERVATIVE 149, or BIOCIDE/PRESERVATIVE 150, or BIOCIDE/PRESERVATIVE 151 , or BIOCIDE/PRESERVATIVE 152, or BIOCIDE/PRESERVATIVE 153, or BIOCIDE/PRESERVATIVE 154, or BIOCIDE/PRESERVATIVE 155, or BIOCIDE/PRESERVATIVE 156, or BIOCIDE/PRESERVATIVE 157, or BIO- CIDE/PRESERVATIVE 158, or BIOCIDE/PRESERVATIVE 159, or BIOCIDE/PRESERVATIVE 160, or BIOCIDE/PRESERVATIVE 161 , or BIOCIDE/PRESERVATIVE 162, or BIOCIDE/PRESERVATIVE 163, or BIOCIDE/PRESERVATIVE 164, or BIOCIDE/PRESERVATIVE 165, or BIOCIDE/PRESERVATIVE 166, or BIOCIDE/PRESERVATIVE 167, or BIO- CIDE/PRESERVATIVE 168, or BIOCIDE/PRESERVATIVE 169, or BIOCIDE/PRESERVATIVE 170, or BIOCIDE/PRESERVATIVE 171 , or BIOCIDE/- PRESERVATIVE 172, or BIOCIDE/PRESERVATIVE 173, or BIOCIDE/PRESERVA- TIVE 174, or BIOCIDE/PRESERVATIVE 175, or BIOCIDE/PRESERVATIVE 176, or BIOCIDE/PRESERVATIVE 177, or BIOCIDE/PRESERVATIVE 178, or BIOCIDE/PRESERVATIVE 179, or BIOCIDE/PRESERVATIVE 180, or BIOCIDE/PRESERVATIVE 181 , or BIOCIDE/PRESERVATIVE 182, or BIO- CIDE/PRESERVATIVE 183, or BIOCIDE/PRESERVATIVE 184, or BIOCIDE/PRESERVATIVE 185, or BIOCIDE/PRESERVATIVE 186, or BIO-CIDE/- PRESERVATIVE 187, or BIOCIDE/PRESERVATIVE 188, or BIOCIDE/PRESERVATIVE 189, or BIOCIDE/PRESERVATIVE 190, or BIOCIDE/PRESERVATIVE 191 , or BIOCIDE/PRESERVATIVE 192, or BIOCIDE/PRESERVATIVE 193, or BIO- CIDE/PRESERVA-TIVE 194, or BIOCIDE/PRESERVATIVE 195, or BIOCIDE/PRESERVATIVE 196, or BIOCIDE/PRESERVATIVE 197, or BIOCIDE/PRESERVATIVE 198, or BIOCIDE/PRESERVATIVE 199, or BIOCIDE/PRESERVATIVE 200, or BIOCIDE/PRESERVATIVE 201 , or BIOCIDE/- PRESERVATIVE 202, or BIOCIDE/PRESERVATIVE 203, or BIOCIDE/PRESERVA- TIVE 204, or BIOCIDE/PRESERVATIVE 205, or BIOCIDE/PRESERVATIVE 206, or BIOCIDE/PRESERVATIVE 207, or BIOCIDE/PRESERVATIVE 208, or BIOCIDE/PRESERVATIVE 209, or BIOCIDE/PRESERVATIVE 210, or BIOCIDE/PRESERVATIVE 21 1 , or BIOCIDE/PRESERVATIVE 212, or BIOCIDE/PRESERVATIVE 213, or BIOCIDE/PRESERVATIVE 214, or BIO- CIDE/PRESERVATIVE 215, or BIOCIDE/PRESERVATIVE 216, or BIOCIDE/PRESERVATIVE 217, or BIOCIDE/PRESERVATIVE 218, or BIOCIDE/PRESERVATIVE 219, or BIOCIDE/PRESERVATIVE 220, or BIOCIDE/PRESERVATIVE 221 , or BIOCIDE/PRESERVATIVE 222, or BIOCIDE/PRESERVATIVE 223, or BIOCIDE/PRESERVATIVE 224, or BIO- CIDE/PRESERVATIVE 225, or BIOCIDE/PRESERVATIVE 226, or BIOCIDE/PRESERVATIVE 227, or BIOCIDE/PRESERVATIVE 228, or BIOCIDE/PRESERVATIVE 229, or BIOCIDE/PRESERVATIVE 230, or BIOCIDE/PRESERVATIVE 231 , or BIOCIDE/PRESERVATIVE 232, or BIOCIDE/PRESERVATIVE 233, or BIOCIDE/PRESERVATIVE 234, or BIO- CIDE/PRESERVATIVE 235, or BIOCIDE/PRESERVATIVE 236, or BIOCIDE/PRESERVATIVE 237, or BIOCIDE/PRESERVATIVE 238, or BIOCIDE/PRESERVATIVE 239, or BIOCIDE/PRESERVATIVE 240, or BIOCIDE/PRESERVATIVE 241 , or BIOCIDE/PRESERVATIVE 242, or BIOCIDE/PRESERVATIVE 243, or BIOCIDE/PRESERVATIVE 244, or BIO- CIDE/PRESERVATIVE 245, or BIOCIDE/PRESERVATIVE 246, or BIOCIDE/PRESERVATIVE 247, or BIOCIDE/PRESERVATIVE 248, or BIOCIDE/PRESERVATIVE 249, or BIOCIDE/PRESERVATIVE 250, or BIOCIDE/PRESERVATIVE 251 , or BIOCIDE/PRESERVATIVE 252, or BIOCIDE/PRESERVATIVE 253.
In the following some examples of formulations combining the compounds of the present invention with other cosmetic and household product ingredients including the BIOCIDES/PRESERVATIVES of table 2 are shown:
Figure imgf000030_0002
Figure imgf000030_0001
Figure imgf000031_0001
Every Day Lotion A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Stearyl Phosphate 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00
Phenethyl Benzoate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 Every Day Lotion A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Triisodecyl Trimellitate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00
Dimethyl Capramide 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Tricontanyl PVP 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Ethoxydiglycol Oleate 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50
Squalane 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00
C12-15 Alkyl Benzoate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Glyceryl Stearate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Cetyl Alcohol 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Bis-Ethylhexyloxyphenol Methoxy- 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00 phenyl Triazine (Tinosorb S)
Diethylhexyl Butamido Triazone 0,00 5,00 0,00 0,00 5,00 0,00 0,00 5,00 0,00
Methylene Bis-Benzotriazolyl 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 Tetramethylbutylphenol (and) water
(and) decyl glucoside (and) propylene glycol (and) xanthan gum (Tinosorb M)
Water qs qs qs qs qs qs qs qs qs to to to to to to to to to 100 100 100 100 100 100 100 100 100
Steareth-10 Allyl Ether/Acrylates 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 Copolymer
Glycerin 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50
Diazolidinyl Urea (and) lodopropynyl 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 Butylcarbamate
Sodium Lauroyl Glutamate 0,70 0,70 0,70 0,70 0,70 0,70 0,70 0,70 0,70
Cyclopentasiloxane (and) Dimethi- 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 conol
Triethanolamine 1,85 1,85 1,85 1,85 1,85 1,85 1,85 1,85 1,85
Citric Acid (and) Silver Citrate 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10
Sclerotium Gum 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 pyranopyranone derivative (Table 1) 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50
BIOCIDE/PRESERVATIVE (Table 2) 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
Everyday Moisturizing Cream A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Water qs. qs. qs. qs. qs. qs. qs. qs. qs.
100 100 100 100 100 100 100 100 100 Everyday Moisturizing Cream A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Hydroxyethylcellulose 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Panthenol 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Preservative 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20
Tocopheryl acetate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Grape seed oil 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Almond 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00
Caprilyc/Capric triglyceride 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00
Caprylyl methicone 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Dimethicone 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Glyceryl stearate (and) cetearyl al5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 cohol (and) sodium stearoyi lactylate
Evening primrose oil 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
Sodium hyaluronate, 1 % aq.soln 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Hydrocotyl extract 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 pyranopyranone derivative (Table 1 ) 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50
BIOCIDE/PRESERVATIVE (Table 2) 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
Figure imgf000033_0001
O/W Lotion A B C D E F G H I
Figure imgf000034_0001
Solid-stabilizing O/W Emulsions
Component [% b.w.] Examples
a b c d e
Mineral Oil - - 16.0 16.0 -
Octyldodecanol 9.0 9.0 5.0 - -
Caprylic/Capric. Triglyceride 9.0 9.0 6.0 - -
C12-15- Alkyl Benzoate - - - 5.0 8.0
Butylen Glycol Dicaprylate/Dicaprate - - - - 8.0
Figure imgf000035_0001
Component [% b.w.] Examples
a b c d e
Vitamins A, C or E (free or derivative forms) 0.80 0.50 1 .00 -
Fragrance qs qs qs qs qs
Pickering O/W Emulsions
Figure imgf000036_0001
Emulsifier free lotion A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w Emulsifier free lotion A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Ceteareth-20 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
Xanthan Gum 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Bis-Ethylhexyloxyphenol 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00
Methoxyphenyl Triazine (Ti- nosorb S)
Homosalate 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00
Methylene Bis- 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00
Benzotriazolyl Tetramethyl- butylphenol (and) water
(and) decyl glucoside (and)
propylene glycol (and) xanthan gum (Tinosorb M)
Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Triisodecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Tridecyl Trimellitate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
Dimethyl Capramide 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
C12-15 Alkyl Benzoate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
Butylenglycol Dicapry- 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 lat/Dicaprate
Cyclomethicone 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00
PVP Hexadecene Copoly0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 mer
Glycerin 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00
Vitamin E Acetate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Polyethylene Terephthalate 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40
Ethanol 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00
Parfume 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50
(Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
(Table 2)
Water ad. ad. ad. ad. ad. ad. ad. ad. ad.
100 100 100 100 100 100 100 100 100
Emulsifier free face care A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Sodium Carbomer 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20
Xanthan Gum 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30
Bis-Ethylhexyloxyphenol 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00 Methoxyphenyl Triazine (Tinosorb S) Emulsifier free face care A B C D E F G H I
INCI-Name % % % % % % % % %
w/w w/w w/w w/w w/w w/w w/w w/w w/w
Isoamyl p-Methoxycinnamate 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00
Methylene Bis-Benzotriazolyl 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 Tetramethylbutylphenol (and)
water (and) decyl glucoside
(and) propylene glycol (and)
xanthan gum (Tinosorb M)
Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Dimethyl Capramide 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
C12-15 Alkyl Benzoate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Dicaprylyl Carbonate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Dimethicone 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Shea Butter 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Ethylhexylglycerine 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Glycerin 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50
Glycine Soja 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50
Vitamin E Acetate 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20
□-Glycosil Rutin 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30
Polyethylene Terephthalate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Trisodium EDTA 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30
Ethanol 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1)
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Water ad.100 ad.100 ad.100 ad.100 ad.100 ad.100 ad.100 ad.100 ad.100
Skin care spray A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Butylene Glycol Dicapry- 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 late/Dicaprate
C18-36 Acid Triglyceride 0,70 0,70 0,70 0,70 0,70 0,70 0,70 0,70 0,70
Ceteareth-20 0,60 0,60 0,60 0,60 0,60 0,60 0,60 0,60 0,60
Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Triisodecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Dimethyl Capramide 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
C12-15 Alkyl Benzoate 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00
Taurine 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40
PVP/Hexadecene Copolymer 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 Skin care spray A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Bis-Ethylhexyloxyphenol Methoxy- 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00 phenyl Triazine (Tinosorb S)
Polysilicone-15 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00
Methylene Bis-Benzotriazolyl Tetra- 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 methylbutylphenol (and) water (and)
decyl glucoside (and) propylene glycol (and) xanthan gum (Tinosorb M)
Water qs. qs. qs. qs. qs. qs. qs. qs. qs.
To To To To To To To To To 100 100 100 100 100 100 100 100 100
Glycerin 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00
Methylpropanediol 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
Acrylates/C 10-30 Alkyl Acrylate 0,18 0,18 0,18 0,18 0,18 0,18 0,18 0,18 0,18 Crosspolymer
Trisodium EDTA 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10
Alcohol Denatured 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Tocopheryl Acetate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Pyranopyranone derivative (Table 1 ) 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50
BIOCIDE/PRESERVATIVE (Table 2) 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
Figure imgf000039_0001
SPRAY EMULSION WATER-RESISTANT Ex.1 Ex.2 Ex.3 Ex.4
Wt. %
Figure imgf000040_0001
Sclerotium Gum 0.50 2.50 5.00 10.00
Figure imgf000040_0002
O/W Spray without Emulsifier a b c d
Ingredient
Pyranopyranone derivative (Table 1 ) 0,10 0,20 0,30 0,40
BIOCIDE/PRESERVATIVE (Table 2) 0,40 0,30 0,20 0,10
Vitamins A, C or E (free or derivative forms) 0.80 0.50 - 1 .00
Fragrance qs qs qs qs
Hydrodispersions
Component [% b.w.] Examples
a b c d e
Polyoxyethylene(20)cetylstearylether 1 .00 - - 0.5 -
Cetylalcohol - - 1 .00 - -
Natriumpolyacrylate - 0.20 - 0.30 -
Acrylate /C10-30-Alkyl-Acrylate Crosspolymer 0.50 0.40 0.10 0.10
Xanthan Gum - 0.30 0.15 - 0.50
2-Ethylhexyl Methoxycinnamate - - - 5.00 8.00
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]- 1 .50 2.00 2.50 phenyl}-6-(4-methoxyphenyl)-(1 ,3,5)-triazine
(Tinosorb S)
Dimethicodiethylbenzalmalonate - 3.50 - - -
Butyl-dimethoxy-dibenzoylmethane 1 .00 - 2.00 - -
Diethylhexyl Butamidotriazone - 2.00 - 2.00 1 .00
Ethylhexyl Tdazone 4.00 - 3.00 4.00 -
4-Methylbenzylidene Camphor - - - - 2.00
Methylene bis-benzotriazolyl tetramethylbutyl- 2.00 1 .40 0.50 4.60 5.20 phenol (TinosorbM)
Octocrylene - 4.00 4.00 - 2.50
Phenylen-1 ,4-bis-(monosodium-2- 1 .00 0.50 2.00 benzimidazyl-5,7-disulfonic Acid)
Phenylbenzimidazol Sulfonic Acid 0.50 - - 3.00 -
Titanium Dioxide 0.50 - 2.00 3.00 1 .00
Zinc Oxide 0.50 1 .00 3.00 - 2.00
C12-15 Alkyl Benzoate 2.00 2.50 - - -
Diethylhexyl-2.6-naphthalate 4.00 - - - -
Dicaprylylether - 4.00 - - -
Butylenglycol-Dicaprylate/-Dicaprate 4.00 - 2.00 6.00 -
Dicaprylylcarbonate - 2.00 6.00 - -
Dimethicone Polydimethylsiloxane - 0.50 1 .00 - -
Phenylmethylpolysiloxane 2.00 - - 0.50 2.00
Shea Butter - 2.00 - - -
PVP Hexadecenecopolymer 0.50 - - 0.50 1 .00
Octoxyglycerine - - 1 .00 - 0.50 Hydrodispersions
Component [% b.w.] Examples
a b c d e
Glycerine 3.00 7.50 - 7.50 2.50
Glycinesoja - - 1.50 - -
Dioic Acid 0.3 0.10 0.50 1.00 0.20
DMDM Hydantoine - 0.25 - 0.60 0.45
Parabene 0.15 - 0.50 0.30 -
Trisodium EDTA - - 0.70 - 1.00
Ethanol 3.00 2.00 1.50 - 1.00
Water Ad 100 Ad 100 Ad 100 Ad 100 ad 100
Pyranopyranone derivative (Table 1) 0,10 0,20 0,30 0,40 0,50
BIOCIDE/PRESERVATIVE (Table 2) 0,40 0,30 0,20 0,10 0,50
Vitamins A, C or E (free or as derivative) 0.80 0.50 - 1.00 -
Fragrance qs qs qs qs qs
Gel A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Alcohol Denatured Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100
Phenethyl Benzoate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Triisodecyl Trimellitate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Dimethyl Capramide 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Hydroxypropyl Cellulose 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Acrylates/Octylacrylamide 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 Copolymer
C12-15 Alkyl Benzoate 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00
Cyclotetrasiloxane (and) 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 Cyclopentasiloxane
PEG/PPG-4/12 Dimethi- 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 cone
Bis-Ethylhexyloxyphenol 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00 Methoxyphenyl Triazine
(Tinosorb S)
Ethylhexyl Salicylate 0,00 5,00 2,50 0,00 5,00 2,50 0,00 5,00 2,50
Methylene Bis-Benzotria- 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 zolyl Tetramethylbutylphe- nol (and) water (and) decyl
glucoside (and) propylene
glycol (and) xanthan gum
(Tinosorb M)
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1) Gel A B c D E F G H 1
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Figure imgf000043_0001
Waterproofed Gel Ex.1 Ex.2 Ex.3 Ex.4
Wt. %
Anhydrous Ethanol Qsp 100 Qsp 100 Qsp 100 Qsp 100
Hydroxypropyl Cellulose /Klucel MF 1.00 1.00 1.00 1.00
Acrylates/Octylacrylamide Copolymer
1.00 1.00 1.00 1.00 /Dermacryl-79
Figure imgf000044_0001
Sclerotium Gum 0.50 2.50 5.00 10.00
Nourishing Gel Ex.1 Ex.2 Ex.3 Ex.4
Ingredient Wt. %
Acritamer 940 (Carbomer 940)/Gelling Agent 1 .00 1 .00 1 .00 1 .00
Deionized Water Qsp 100 Qsp 100 Qsp 100 Qsp 100
Ritapan D (d-Panthenol)/Conditioner 0.20 0.20 0.20 0.20
SD Alcohol (Ethanol @ 95%)/Solvent, Solubi-
10.00 10.00 10.00 10.00 lizer
Ritachol (Mineral Oil and Lanolin Alco¬
8.00 8.00 8.00 8.00 hol/Emollient
Pationic ISL (Sodium IsostearoyI Lactylate)/
0.50 0.50 0.50 0.50 Solubilizer
Fragrance/Odor q.s. q.s. q.s. q.s.
NaOH (18% Soln.)/Neutralizer 2.40 2.40 2.40 2.40
Pyranopyranone derivative (Table 1 ) 0,10 0,20 0,30 0,40
BIOCIDE/PRESERVATIVE (Table 2) 0,40 0,30 0,20 0,10
Sclerotium Gum 0.50 2.50 5.00 10.00
Figure imgf000044_0002
(and) decyl glucoside (and) propyl- O/W Foaming Lotion A B c D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w ene glycol (and) xanthan gum (Ti- nosorb M)
Glycerin 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
EDTA 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10
Water Qsp Qsp Qsp Qsp Qsp Qsp Qsp Qsp Qsp
100 100 100 100 100 100 100 100 100
Carbomer 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05
Acrylates/C 10-30 Alkyl Acrylates 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 Crosspolymer
Sodium Hydroxide (10% in water) q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.
Pyranopyranone derivative (Table 1 ) 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50
BIOCIDE/PRESERVATIVE (Table 2) 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
Undecylenamidopropyl Betain 6,70 6,70 6,70 6,70 6,70 6,70 6,70 6,70 6,70
Sclerotium Gum 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10
Figure imgf000045_0001
Crackling Foam UV Protection A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w Crackling Foam UV Protection A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Behenyl Alcohol (and) Glyceryl Ste- 1 .00 1 .50 2.00 1 .00 2.00 1 .50 2.00 2.50 2.00 arate (and) Glyceryl Stearate Citrate (and) Sodium Dicocoylethyl- enediamine PEG-15 Sulfate
Dibutyl Adipate 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00
Homosalate 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Ethylhexyl Salicylate 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Butyl Methoxydibenzoylmethane 3.00 2.00 1 .00 4.00 3.00 2.00 1 .00 4.00 3.00
Bis-Ethylhexyloxyphenol Methoxy- 2.00 3.00 3.00 2.00 2.00 3.00 3.00 2.00 3.00 phenyl Triazine
Ethylhexyl Triazone 2.00 1 .00 2.00 2.00 2.00 1 .00 2.00 2.00 3.00
Water qsp qsp qsp qsp qsp qsp qsp qsp qsp
100 100 100 100 100 100 100 100 100
Disodium EDTA 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Pentylene Glycol (and) Sclerotium 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Gum
Xanthane gum 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Sodium Dicocoylethylenediamine 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 PEG-15 Sulfate (and) Sodium
Lauroyl Lactylate
Cyclopentasiloxane (and) Cyclo- 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 hexasiloxane
Alcohol 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Methylene Bis-Benzotriazolyl 6.00 4.00 3.50 5.00 2.50 6.00 4.00 3.50 5.00 Tetramethylbutylphenol (and) Aqua
(and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum
Figure imgf000046_0001
Continuous Spray UV protection
INCI-Name % w/w (as supplied)
Part Diethylhexyl Adipate 15.00 20.00 10.00 15.00 A Continuous Spray UV protection
INCI-Name % w/w (as supplied)
Dicaprylyl Carbonate 5.00 5.00 5.00 5.00
Homosalate 10.00 8.00 10.00 8.00
Octocrylene 9.00 5.00 8.00 6.00
Ethylhexyl Salicylate 5.00 5.00 5.00 5.00
Butyl Methoxydibenzoylmethane 4.00 2.00 2.00 3.00
Bis-Ethylhexyloxyphenol Methoxyphenyl Tri- 1 .50 2.00 3.00 2.00 azine
Part Cyclomethicone 5.00 5.00 5.00 5.00 B
Pyranopyranone derivative (Table 1 ) 0,10 0,20 0,30 0,40
BIOCIDE/PRESERVATIVE (Table 2) 0,40 0,30 0,20 0,10
Part Alcohol (Ethanol 96%) Qsp Qsp Qsp Qsp C 100 100 100 100
Butane (N-Butane 1 .2 Bar) (Propellant) 30.00 30.00 30.00 30.00
Manufacturing Instruction
Mix part A and heat up to 80°C to melt TINOSORB® S.
Cool down to 40°C, then add part B, then C under stirring.
Fill cans with the formulation (70%) and charge with propellant (30%)
W/O Emulsion A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Butylen Glycol Dicapry- 5,50 5,50 5,50 5,50 5,50 5,50 5,50 5,50 5,50 late/Dicaprate
Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Dimethyl Capramide 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
C18-36 Acid Triglyceride 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Isopropyl Stearate 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50
C12-15 Alkyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Polyglyceryl-2 Dipolyhydroxys- 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 tearate
Diethylhexyl Butamido Triazone 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Cetyl Dimethicone 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Bis-Ethylhexyloxyphenol Methoxy0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00 phenyl Triazine (Tinosorb S)
Ethylhexyl Methoxycinnamate 0,00 5,00 10,00 0,00 5,00 10,0C 0,00 5,00 10,0C
Tris-Biphenyl Triazine 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00
Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
Figure imgf000048_0001
Figure imgf000048_0003
Figure imgf000048_0002
Figure imgf000049_0001
Figure imgf000049_0003
Figure imgf000049_0002
Figure imgf000050_0001
Figure imgf000050_0002
Light W/O Lotion Ex.1 Ex.2 Ex.3 Ex.4
Part Ingredient
ABIL® EM 90 (Cetyl PEG/PPG-10/1 Di¬
A 2.0 2.0 2.0 2.0 methicone) Light W/O Lotion Ex.1 Ex.2 Ex.3 Ex.4
Part Ingredient
TEGOSOFT® DEC (Diethylhexyl Car¬
A 1 1 .5 1 1 .5 1 1 .5 1 1 .5 bonate)
A Beeswax 0.5 0.5 0.5 0.5
A Hydrogenated Castor Oil 0.5 0.5 0.5 0.5
A Tocopheryl Acetate 0.5 0.5 0.5 0.5
GluCare® S (Sodium Carboxymethyl Be-
B 0.2 0.2 0.2 0.2 taglucan)
B Allantoin 0.1 0.1 0.1 0.1
B Glycerin 1 .0 1 .0 1 .0 1 .0
B Sodium Chloride 0.5 0.5 0.5 0.5
Qsp Qsp 100 Qsp 100 Qsp 100
B Water
100
B Pyranopyranone derivative (Table 1 ) 0,10 0,20 0,30 0,40
B BIOCIDE/PRESERVATIVE (Table 2) 0,40 0,30 0,20 0,10
B Sclerotium Gum 0.50 2.50 5.00 10.00
C Fragrance q.s. q.s. q.s. q.s.
W/ Si emulsion Ex.1 Ex.2 Ex.3 Ex.4
Part Ingredient Wt. %
Masil 756 CG (BASF) (tetrabutoxypropyl
A 0.90 0.90 0.90 0.90 methicone)
A Luvitol BL (BASF) (benzyl laurate) 2.00 2.00 2.00 2.00
A Cetyl dimethicone 2.00 2.00 2.00 2.00
Polyglyceryl-4, isostearate, cetyl dimethi¬
A 6.00 6.00 6.00 6.00 cone copolyol and hexyl laurate
Cremophor GO 32 (BASF) (polyglyceryl-3
A 0.60 0.60 0.60 0.60 dioleate)
A Glyceryl tribehenate 3.00 3.00 3.00 3.00
B Masil SF V5 CG (BASF) (cyclomethicone) 8.85 8.85 8.85 8.85
B Microfine zinc oxide 2.00 2.00 2.00 2.00
C Deionized water Qsp 100 Qsp 100 Qsp 100 Qsp 100
C Xanthan gum NF 0.10 0.10 0.10 0.10
C Disodium EDTA 0.10 0.10 0.10 0.10
C Sodium chloride 1 .00 1 .00 1 .00 1 .00
C Glycerin 3.00 3.00 3.00 3.00
C Pyranopyranone derivative (Table 1 ) 0,10 0,20 0,30 0,40
BIOCIDE/PRESERVATIVE (Table 2) 0,40 0,30 0,20 0,10 W/ Si emulsion Ex.1 Ex.2 Ex.3 Ex.4
Part Ingredient Wt. %
C Sclerotium Gum 0.50 2.50 5.00 10.00
D Panthenol USP (BASF) (panthenol) 0.10 0.10 0.10 0.10
D Sodium ascorbyl phosphate 0.20 0.20 0.20 0.20
Vitamin E Acetate C (BASF) (tocopheryl
E 0.50 0.50 0.50 0.50 acetate)
E Phytantriol 0.30 0.30 0.30 0.30
E Fragrance q.s. q.s. q.s. q.s.
Figure imgf000052_0001
W/O/W Multiple EmulA B C D E F G H I sion
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w W/O/W Multiple EmulA B C D E F G H I sion
INCI-Name % % % % % % % % %
w/w w/w w/w w/w w/w w/w w/w w/w w/w
1. Primary emulsion
W/O:
Isohexadecane 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00
Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Triisodecyl Trimelli2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 tate
Dimethyl Capramide 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
Caprylic/capric 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 triglycerides
PPG-15 stearyl ether 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50
PEG-30 Dipolyhy- 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 droxystearate
Bis- 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00
Ethylhexyloxyphenol
Methoxyphenyl Triaz- ine (Tinosorb S)
Octocrylene 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00
Methylene Bis- 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 Benzotriazolyl
Tetramethylbutylphe- nol (and) water (and)
decyl glucoside (and)
propylene glycol
(and) xanthan gum
(Tinosorb M)
Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100
Sodium chloride 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40
Preservative q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.
II. Secondary emulsion
W/O/W:
Primary emulsion (W/O) 70,00 70,00 70,00 70,00 70,00 70,00 70,00 70,00 70,00
Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100
Poloxamer 407 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
(2-{4-[2-(4-Diethylamino-2- 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 hydroxy-benzoyl)-benzoyl]- piperazine-1 -carbonyl}- phenyl)-(4-diethylamino-2- II. Secondary emulsion
W/O/W:
hydroxy-phenyl)- methanone
Carbomer 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Sodium chloride 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20
Triethanolamine 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
W/O/W Multiple EmulA B c D E F G H I sion
INCI-Name % % % % % % % % %
w/w w/w w/w w/w w/w w/w w/w w/w w/w
I. Primary emulsion
W/O:
Isohexadecane 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00
Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Triisodecyl Trimelli2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 tate
Dimethyl Capramide 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
Caprylic/capric 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 triglycerides
PPG-15 stearyl 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50 ether
PEG-30 Dipolyhy- 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 droxystearate
Ethylhexyl Triazone 2,50 2,50 2,50 2,50 2,50 5,00 5,00 5,00 5,00
Methylene Bis- 4,00 6,00 8,00 10,00 12,00 4,00 6,00 8,00 10,00 Benzotriazolyl
Tetramethylbutyl- phenol (and) water
(and) decyl gluco- side (and) propylene
glycol (and) xanthan
gum (Tinosorb M)
Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100
Sodium chloride 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 II. Secondary emulsion
W/O/W:
Primary emulsion (W/O) 70,00 70,00 70,00 70,00 70,00 70,00 70,00 70,00 70,00
Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100
Poloxamer 407 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Titanium Dioxide 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50
Carbomer 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Sodium chloride 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20
Triethanolamine 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Figure imgf000055_0001
Lipstick A B c D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
(Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Lipstick A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Octyldodecanol 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00
Phenethyl Benzoate 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00
Triisodecyl Trimellitate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Dimethyl Capramide 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Butylene Glycol Dicapry- 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 late/ Dicaprate
Pentaerythrityl Tetrai- 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 sostearate
Bis-Diglyceryl Polyacyladi- 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00 pate-2
Cetearyl Alcohol 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00
Myristyl Myristate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00
Beeswax 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00
Copernicia Cerifera (Car- 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 nauba) Wax
Cera Alba 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
C20-40 Alkyl Stearate 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50
Tocopheryl Acetate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Tocopherol; Ascorbyl 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05
Palmitate
Simmondsia Chinensis 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
(Jojoba) Seed Extract
Parfum. BHT q.s q.s q.s q.s q.s q.s q.s q.s q.s
Ricinus Communis QS to QS to QS to QS to QS to QS to QS to QS to QS to
100 100 100 100 100 100 100 100 100
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50
(Table 1)
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
(Table 2)
Lip balm SPF 15 A B C D E F G H I
INCI-Name % % % % % % % % %
w/w w/w w/w w/w w/w w/w w/w w/w w/w
Petrolatum 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00
Beeswax 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00
Candelilla wax 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00
Cocoa seed butter 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Benzophenone-3 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1)
Figure imgf000058_0001
Figure imgf000058_0002
Foundations: Anhydrous A B C D E F G H I forms
INCI-Name % % % % % % % % %
- w/w w/w w/w w/w w/w w/w w/w w/w w/w
Isononyl Isononanoate qsp qsp qsp qsp qsp qsp qsp qsp qsp
Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Triisodecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Dimethyl Capramide 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Sorbitan Sesquioleate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Cyclopentasiloxane 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00
Cylopentasiloxane (and) 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 Quaternium-18 Hectorite
Talc 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00
Iron oxides 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50
PVP / eicosane copolymer 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Tocopherol Acetate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1)
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Figure imgf000059_0001
Full Length Lush Mascara A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
PVP 1.80 1.80 1.80 1.80 1.80 1.80 1.80 1.80 1.80
Hydroxyethylcellulose 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30
40% Black iron oxide dis20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 persed in propylene glycol
Triethanolamine 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Water 53.10 53.10 53.10 53.10 53.10 53.10 53.10 53.10 53.10 Full Length Lush Mascara A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Stearic Acid 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50
Glyceryl Monostearate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Carnauba Wax 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Lanolin Alcohol 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
Beeswax 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Polyquaternium-7 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
Figure imgf000060_0001
Eye Make-up Remover
Part Ingredient Wt. % Wt. % Wt. % Wt. %
REWOTERIC® AM KSF 40 (Sodium Cocoampho-
A 5.00 5.00 5.00 5.00 propionate)
A Propylene Glycol Qs Qs Qs Qs 100 100 100 100
A Glycerin 30.00 30.00 30.00 30.00
A Lipoxol 400 Med (PEG-8, Sasol) 15.00 8.00 6.00 10.00
A Cetearyl Octanoate 2.00 4.00 6.00 3.00
Tridecyl Trimellitate 4.00 2.00 1 .00 6.00
Pyranopyranone derivative (Table 1 ) 0,10 0,20 0,30 0,40
BIOCIDE/PRESERVATIVE (Table 2) 0,40 0,30 0,20 0,10
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000062_0003
Figure imgf000062_0002
Figure imgf000063_0001
Deodorant shower gel A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
A BIOCIDE/PRESERVATIVE 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 (Table 2)
B Sodium laureth sulfate 28,60 28,60 28,60 28,60 28,60 28,60 28,60 28,60 28,60
Decyl glucoside 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00
Cocamidopropyl betaine 7,90 7,90 7,90 7,90 7,90 7,90 7,90 7,90 7,90
C Water qs qs qs qs qs qs qs qs qs
100 100 100 100 100 100 100 100 100
D Glycerin 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Polyquaternium-7 1,25 1,25 1,25 1,25 1,25 1,25 1,25 1,25 1,25
Panthenol 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30
Color 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05
Figure imgf000064_0001
Figure imgf000064_0002
Skin Liquid A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Sodium Lauryl Sulfate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
PPG-2 Methyl Ether 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Propylene Glycol 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Color and Perfume qs qs qs qs qs qs qs qs qs
Pyranopyranone deriva- 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 tive(Table 1 ) Skin Liquid A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
BIOCIDE/PRESERVATIVE 0,30 0,20 0,10 0,00 0,30 0,30 0,30 0,30 0,30
(Table 2)
Ethanolamine ad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH
5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7
Figure imgf000065_0002
Figure imgf000065_0001
Hand Scrub A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Triclocarban 0 0 0 0 0 0.20 0.40 0.80 1 .50
D&C Red No. 33 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Ethanolamine ad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH
5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5
Figure imgf000066_0001
Moisturizing Antibacterial liqA B C D E F G H I uid Hand Soap
INCI-Name % % % % % % % % %
- w/w w/w w/w w/w w/w w/w w/w w/w w/w
Water 18.20 18.20 18.20 18.20 18.20 18.20 18.20 18.20 18.20
Sodium C14-16 Olefin Sul30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 fonate (and) Sodium Laueth
Sulfate (and) Lauramide
DEA
Cocamidopropyl Betaine 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Glycerin 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Aloe Vera 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Moisturizing Antibacterial liqA B C D E F G H I uid Hand Soap
INCI-Name % % % % % % % % %
- w/w w/w w/w w/w w/w w/w w/w w/w w/w
Lauramide DEA 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Water 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00
Acrylamidopropyltrimonium 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Chloride/Acrylamide Copo- ymer
Polysorbate 20 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
Sodium Chloride 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
Citric Acid 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65
Figure imgf000067_0001
Figure imgf000068_0001
Shampoo Shower gel A B c D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Decyl Glucoside 15,00 10,00 8,00 5,00 10,00 12,00 15,00 20,00 8,00
Cocamidopropyl Betaine 7,00 5,00 4,00 6,00 4,00 8,00 6,00 4,00 8,00
Water Qsp Qsp Qsp Qsp Qsp Qsp Qsp Qsp Qsp
100 100 100 100 100 100 100 100 100
Piroctone Olamine - 0.3 1.00 - 0.5 - - 0.75 -
Climbazole - 0.5 - - 0.75 - - - -
Zinc Pyrithion, 48% - 2,00 - 2,00 2,00 - 2,00 2,00 -
Glycerin 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Sodium Chloride 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00
Pyranopyranone derivative 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 1,00 (Table 1)
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Citric Acid Qs to Qs to Qs Qs Qs to Qs to Qs to Qs to Qs to pH 6 pH 6 to to pH 6 pH 6 pH 6 pH 6 pH 6 pH 6 pH 6
Clear shampoo A B c D E F G H I
NCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Sodium Lauryl Sulfate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 Clear shampoo A B c D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Sodium Polyoxyethylene 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 lauryl sulfate
Lauroamidopropyl betaine 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
POE(16) lauryl ether 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
Glyceryl monoisodecyl 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 ether
Cationized cellulose 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Polyvinyl Alcohol 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20
Glycerin 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00
Tocopherol Acetate 0,24 0,24 0,24 0,24 0,24 0,24 0,24 0,24 0,24
Sodium Sulfate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00
Perfume 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10
Sodium Hydroxide q.s q.s q.s q.s q.s q.s q.s q.s q.s pH=7 pH=7 pH=7 pH=7 pH=7 pH=7 pH=7 pH=7 pH=7
Piroctone Olamine 1 .00 0.3 1 .00 - 0.5 - - 0.75 -
Climbazole - 0.5 - 0.3 0.75 1 .00 - - 1 .00
Water Qsp Qsp Qsp Qsp Qsp Qsp Qsp Qsp Qsp
100 100 100 100 100 100 100 100 100
Pyranopyranone derivative 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 1 ,00
(Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
(Table 2)
Sclerotium Gum 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10
Anti-Dandruff shampoo A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Water Qs. Qs. Qs. Qs. Qs. Qs. Qs. Qs. Qs.
100 100 100 100 100 100 100 100 100
Magnesium Aluminium 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00
Silicate
Ammonium Lauryl Sulfate 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00
Ammonium Laureth Sul10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 fate
Cocamidopropyl hydroxy- 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 sultaine
Sodium Lauryol Sarcosi- 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 nate
Di-PPG-2 Myreth-10 Adi- 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 pate Anti-Dandruff shampoo A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
PEG-150 Pentaerythrityl 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 Tetrastearate and PEG-6
Capriliy/Capric Glycerides
and water
Dimethicone 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20
DMDM Hydantoin 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30
Zinc Pyrithion, 48% 2,00 2,00 - 2,00 2,00 2,00 - 2,00 2,00
Piroctone Olamine - 0.3 1 .00 - 0.5 - - 0.75 -
Climbazole - 0.5 - - 0.75 - 0.80 - -
Citric Acid, 30% qs. qs. qs. qs. qs. qs. qs. qs. qs.
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Figure imgf000070_0001
Conditioning Shampoo A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Xanthan Gum qs qs qs qs qs qs qs qs qs
Starch/acrylates/acrylamide co0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 polymer
Figure imgf000071_0001
Pearlized Mild Body Wash
Ingredients Ex. 1 Ex. 2 Ex. 3 Ex. 4
Sodium Laureth Sulfate 15% 15% 15% 15%
Cocoyl Isethionate 4% 5% 3% 6%
Sodium Lauroamphoacetate 6% 4% 6% 4%
Sodium Xylene Sulfonate 1 % 2% 4% 5%
Sodium Methyl Cocoyl Taurate 5% 3% 4% 5%
Acrylates Crosspolymer 1 .5% 1 .5% 1 .5% 1 .5%
Dimethiconol and TEA- 4% 4% 4% 4%
Dodecylbenzenesulfonate
Sodium Cocoamphoacetate 2% 2% 2% 2%
Polyquaternium-7 2% 2% 2% 2%
Sodium Hydroxide (18% solution) 0.05% 0.05% 0.05% 0.05%
Guar Hydroxypropyl trimonium Chlo0.15% 0.15% 0.15% 0.15% ride
Citric acid (50% solution) 0.05 0.05 0.05 0.05
Mica and Titanium Dioxide 0.2% 0.2% 0.2% 0.2%
Perfume 0.5% 0.5% 0.5% 0.5%
Citric acid (50% solution) 0.6% 0.6% 0.6% 0.6%
Pyranopyranone derivative (Table 1 ) 0,10% 0,20% 0,30% 0,40%
BIOCIDE/PRESERVATIVE (Table 2) 0,40% 0,30% 0,20% 0,10%
Sclerotium Gum 0.50% 2.50% 5.00% 10.00%
Water deionized qs 100 qs 100 qs 100 qs 100 Clear bath gel with suspended beads
Ingredients Ex. 1 Ex. 2 Ex. 3 Ex. 4
Sodium Laureth Sulfate (28% solution) 30% 30% 30% 30%
Acrylates Crosspolymer (30% solution) 10% 10% 10% 10%
Propylene Glycol 2% 2% 2% 2%
Sodium Hydroxide (18% solution) 1 .9% 1 .9% 1 .9% 1 .9%
Disodium EDTA 0.1 % 0.1 % 0.1 % 0.1 %
Benzophenone-4 0.02% 0.02% 0.02% 0.02%
Cocamidopropyl Betaine (35% solution) 4% 4% 4% 4%
Polysorbate 20 0.8% 0.8% 0.8% 0.8%
White beads 1 % 1 % 1 % 1 %
Perfume 0.6% 0.6% 0.6% 0.6%
Citric acid (50% solution) 0.6% 0.6% 0.6% 0.6%
Preservative 1 % 1 % 1 % 1 %
Water deionized Qsp 100 Qsp 100 Qsp 100 Qsp 100
Pyranopyranone derivative (Table 1 ) 0,10% 0,20% 0,30% 0,40%
BIOCIDE/PRESERVATIVE (Table 2) 0,40% 0,30% 0,20% 0,10%
Figure imgf000072_0001
Feminine Hygiene Wash A B C D E F G H I
INCI-Name % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Pyranopyranone deriva0,10 0,20 0,30 0,40 0,50 0,50 0,50 0,50 0,50 tive (Table 1 )
BIOCIDE/PRESERVATIVE 0.50 0.50 0.50 0.50 0.50 0,10 0,20 0 0
(Table 2) Feminine Hygiene Wash A B C D E F G H I
INCI-Name % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w % w/w
Triclosan 0.10 0.30 0 0 0.10 0 0 0 0
Fragrance qs qs qs qs qs qs qs qs qs
Sodium Laureth Sulfate 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00
Cocamidopropyl Betaine 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 (and) Glyceryl Laurate
Lactic Acid 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
Sodium Chloride 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
Allantoin 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
Water (and) Sodium Hyad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH droxide 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
Figure imgf000073_0001
Personal Lubricant
Ingredients Ex. 1 Ex. 2 Ex. 3 Ex. 4
Lubricating agents 5% 10% 8% 15%
Lanolin anhydrous 8% 8% 8% 8%
Sweet almond oil 5% 5% 5% 5%
Coconut oil 10.75% 10.75% 10.75% 10.75%
Cetyl alcohol 0.5% 0.5% 0.5% 0.5%
Mineral oil 1 % 1 % 1 % 1 %
Preservative 0.3% 0.3% 0.3% 0.3% Personal Lubricant
Ingredients Ex. 1 Ex. 2 Ex. 3 Ex. 4
Water deioniz. Qsp Qsp Qsp Qsp
Sodium lauryl sulfate 1 .5% 1 .5% 1 .5% 1 .5%
Propylene glycol 3% 3% 3% 3%
Aloe vera gel 9% 9% 9% 9%
Sorbitol 1 % 1 % 1 % 1 %
Allantoin 2.5% 2.5% 2.5% 2.5%
Polyethylene oxides of MW< 100 000 10% 13% 12% 15%
Xanthan gum 0.5% 0.5% 0.5% 0.5%
Coconut flavor 0.9% 0.9% 0.9% 0.9%
Pyranopyranone derivative (Table 1 ) 0,10% 0,20% 0,30% 0,40%
BIOCIDE/PRESERVATIVE (Table 2) 0,40% 0,30% 0,20% 0,10%
Sclerotium Gum 0.50% 2.50% 5.00% 10.00%
Figure imgf000074_0001
Mouth Rinse formulation A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Sodium Lauryl Sulfate 0,60 0,60 0,60 0,60 0,60 0,60 0,60 0,60 0,60
Ethanol 15,0 15,0 15,0 15,0 15,0 15,0 15,0 15,0 15,0
0 0 0 0 0 0 0 0 0
Pyranopyranone derivative (Ta0,01 0,02 0,05 0,08 0,10 0,15 0,20 0,30 0,50 ble 1 ) Mouth Rinse formulation A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Triclosan 0.05 0 0 0 0.10 0 0.05 0 0
Benzalkonium chloride (or bro0 0.05 0.10 0 0 0 0 0 0.01 mide)
Cetrimonium chloride (or bro0.05 0 0 0.05 0.05 0.10 0 0 0 mide)
Propylene Glycol 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00
Glycerin 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70
Sorbitol 70% 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00
Sodium Saccharine 0,03 0,03 0,03 0,03 0,03 0,03 0,03 0,03 0,03
BIOCIDE/PRESERVATIVE (Ta0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,10 0,15 ble 2)
Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100
Mouthwash A B c D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone derivative (Ta0.05 0.05 0.05 0.05 0.05 0.05 0.10 0.05 0.20 ble 1 )
Glycerin 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Triclosan 0.10 0 0 0 0 0 0 0 0
SD Alcohol 39-C 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Flavour qs qs qs qs qs qs qs qs qs
Poloxamer 407 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Sodium Saccharin 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Sodium Fluoride 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
Sodium Benzoate 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
BIOCIDE/PRESERVATIVE (Ta0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,10 0,15 ble 2)
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Mild transparent Toothgel A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Sorbitol 23.50 23.50 23.50 23.50 23.50 23.50 23.50 23.50 23.50
Sodium Saccharin 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Sodium Citrate 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Betaine 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Triclosan 0.05 0.10 0 0 0 0 0 0 0 Mild transparent Toothgel A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Glycerin 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00
Water qs qs qs qs qs qs qs qs qs to to to to to to to to to 100 100 100 100 100 100 100 100 100
PEG-8 1 .75 1 .75 1 .75 1 .75 1 .75 1 .75 1 .75 1 .75 1 .75
Gellan Gum 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25
Xanthan Gum 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25
Hydrated Silica 15,0 15,0 15,0 15,0 15,0 15,0 15,0 15,0 15,0
0 0 0 0 0 0 0 0 0
FD&C Blue No.1 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
Propylene Glycol (and) Olaflur 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Aroma 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75
Pyranopyranone derivative (Ta0,05 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 ble 1 )
BIOCIDE/PRESERVATIVE (Ta0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,10 0,15 ble 2)
Sodium Lauroyl Sarcosinate 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00
Opaque silica-based dentifrice
Ingredients a b c d
Sodium Lauryl Sulfate 1 .50 % 2,00 % 1 ,00 % 2.50 %
Sodium Carboxymethyl cellulose or Xan0.70 % 1 .00% 0.90% 0.80% than gum
Sorbitol (70%) 45% 45% 45% 45%
Abrasive silica 10% 10% 10% 10%
Thickening silica 8 - 10% 8 - 10% 8 - 10% 8 - 10%
PEG 1500 5% 5% 5% 5%
Titanium Dioxide (opacifier) 1 % 1 % 1 % 1 %
Sodium Saccharinate qs qs qs qs
Flavouring agents < 1 .5% < 1 .5% < 1 .5% < 1 .5%
Colorants qs qs qs qs
Pyranopyranone derivative (Table 1 ) 0,10 0,20 0,30 0,40
BIOCIDE/PRESERVATIVE (Table 2) 0,40 0,30 0,20 0,10
Triclosan 0 0.05 0 0
Water deionized Qsp 100 Qsp 100 Qsp 100 Qsp 100
Vitamins A, C or E (free or as derivative) 0.80% 0.50% - 1 .00% Deodorant Stick A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Propylene Glycol 18,10 18,10 18,10 18,10 18,10 18,10 18,10 18,10 18,10
PPG-3 Myristyl Ether Q 46,70 46,70 46,70 46,70 46,70 46,70 46,70 46,70
Cyclomethicone 28,90 28,90 28,90 28,90 28,90 28,90 28,90 28,90 28,90
Sodium Stearate 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Deodorant Pump spray A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
PEG-40 Hydrogenated 4,50 4,50 4,50 4,50 4,50 4,50 4,50 4,50 4,50 castor Oil
PEG-08 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00
Glyceryl Laurate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
Cetearyl Octanoate (and) 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 Isopropyl Myristate
Alcohol 30,00 30,00 30,00 30,00 30,00 30,00 30,00 30,00 30,00
Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 101 102 103 104 105 106 107 108
Aluminum Chlorohydrate 30,00 31 ,00 32,00 33,00 34,00 35,00 36,00 37,00 38,00
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
O/W-Deodorant A B c D E F G H I
INCI-Name % % % % % % % % %
w/w w/w w/w w/w w/w w/w w/w w/w w/w
Gylceryl Stearate (and) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Ceteth-20
Cetearyl Ethylhexanoate 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Stearyl Alcohol 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
Dicaprylyl Ether 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00
Dimethicone 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
Water Qsp tc Qsp tc Qsp tc 3sp tc Qsp tc Qsp tc Qsp tc Qsp tc Qsp tc
100 100 100 100 100 100 100 100 100 Farnesol 0.05 0.10 0 0 0 0 0.25 0 0
Sodium Polyacrylate 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50
(Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
(Table 2)
Figure imgf000078_0001
Alcohol-free Deodorant roll-on A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
PEG 60 Hydrogenated Cas3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 tor Oil
PEG-6 Caprylic Capric 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 Glyceride
Propylene Glycol 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
Steareth-10 allyl 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 ether/acrylates copolymer
Ethanolamine qs qs qs qs qs qs qs qs qs
Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100 Formulation for Tissues, A B C D E F G H I
Moisturizing Face Mask
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Sclerotium Gum 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
Glycerin 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Butylene Glycol 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Allantoin 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
Xanthan Gum 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
Aqua (and) Tocopheryl 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Acetate (and) Caprylic/Ca- ric Triglyceride (and) Poly- sorbate 80 (and) Lecithin
Aqua (and) Retinyl Palmi- 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 tate (and) Caprylic/Capric
Triglyceride (and) Polysor- bate 80 (and) Lecithin
(and) Benzalkonium Chloride
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Antibacterial Shaving Foam A B c D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Stearic Acid 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00
Laurie Acid 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Triethanolamine 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00
Glycerin 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00
PEG-14 Dimethicone 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Perfume qs qs qs qs qs qs qs qs qs
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100 Foot Cream A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Polyglyceryl-3 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Diisostearate
Beeswax 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Glyceryl Oleate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Zinc Stearate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Hexyldecanol 10.0 10.0 10.00 10.0 10.00 10.00 10.0 10.0 10.0
0 0 0 0 0 0
C12-15 Alkyl Benzoate 10.0 10.0 10.00 10.0 10.00 10.00 10.0 10.0 10.0
0 0 0 0 0 0
Glycerin 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Magnesium Sulfate 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Sodium Hydroxide qs qs qs qs qs qs qs qs qs
Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100
Deodorant and Antiseptic A B c D E F G H I
Foot Cream
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Polyglyceryl-3 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Diisostearate
Glyceryl Oleate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Zinc Stearate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Caprylic/Capric Triglyc10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 eride
Hexyldecanol 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Beeswax 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Pyranopyranone derivative 0,30 0,30 0,30 0,30 0,10 0,25 0,20 0,30 0,30 (Table 1 )
BIOCIDE/PRESERVATIVE 0,10 0,25 0,20 0,30 0,30 0,30 0,30 0,30 0,00 (Table 2)
Glycerin 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Magnesium Sulfate 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 Deodorant Foot Powder A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone derivative 0,1 0,2 0,3 0,4 0,5 0,6 0,75 1 1 ,5 (Table 1 )
Talc qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Magnesium Carbonate 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Rice Starch 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Zinc Undecylinate 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Potassium Sulfate 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Allantoin 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
Pinus Palustris Oil 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
BIOCIDE/PRESERVATIVE 0,10 0,25 0,20 0,30 0,30 0,30 0,30 0,30 0.00 (Table 2)
Deodorant Footspray A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone derivative 0,1 0,2 0,3 0,4 0,5 0,6 0,75 1 1 ,5
(Table 1 )
PEG-40 Hydrogenated 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50
Castor Oil
PEG-8 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
Glyceryl Laurate 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
Cetearyl Ethylhexanoate 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
(and) Isopropyl Myristate
SD Alcohol 39-C 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00
Perfume qs qs qs qs qs qs qs qs qs
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
BIOCIDE/PRESERVATIVE 0,10 0,25 0,20 0,30 0,30 0,30 0,30 0,30 0,40
(Table 2)
Non-aqueous antiperspi- A B C D E F G H I rant spray
% % % % % % % % %
Silicone oil DC® 245 28 28 23 23 23 38 42 47 31
Eutanol®G 16 10 - - 15 10 - 10 - 10
Cetiol® OE - 10 15 - - - - - -
Ucon Fluid® AP 5 5 5 5 5 5 5 5 5
Cutina® HR 6 6 6 6 6 6 2 5 6
Lorol®C 18 20 20 20 - 20 20 - - 20
Lanette® 0 - - - 20 - - 10 12 -
Eumulgin® B 3 3 3 3 3 3 3 3 3 -
Cutina® E 24 PF - - - - 5 - - - -
Aluminium chlorohydrate 20 20 20 20 20 20 20 - -
Talcum 7.995 7.9 7.9 7.9 7.5 7.5 7.995 27.9 27.5
Pyranopyranone derivative 0.005 0.01 0.01 0.005 0.10 0.01 0.05 0.50 0.25 (Table 1)
BIOCIDE/PRESERVATIVE 0.10 0.25 0.50 1.00 0.10 0 0 0 0 (Table 2)
Deodorant Microemulsion A B C D E F G H I Spray
% % % % % % % % %
Plantaren® 1200 1.71 1.71 - 1.71 1.71 - 1.71 1.71 1.71
Plantaren® 2000 1.14 1.39 2.40 1.14 1.39 2.40 1.14 1.39 1.39
Glycerol monooleate 0.71 0.71 - 0.71 0.71 - 0.71 0.71 0.71
Dioctyl ether 4.00 4.00 0.09 4.00 4.00 0.09 4.00 4.00 4.00
Octyl dodecanol 1.00 1.00 0.02 1.00 1.00 0.02 1.00 1.00 1.00
Perfume oil 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Aluminium chlorohydrate 8.00 5.00 5.00 - - - 8.00 5.00 5.00
1 ,2-Propylene glycol 5.00 5.00 - 5.00 5.00 - 5.00 5.00 5.00
Glycerol - - 5.00 - - 5.00 - - -
Tocopheryl acetate 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6
Pyranopyranone derivative 0.05 0.01 0.10 0.20 0.30 0.50 0.15 0.25 1.00 (Table 1)
BIOCIDE/PRESERVATIVE 0.10 0.25 0.50 1.00 0 0 0.10 0.05 0 (Table 2)
Water ad ad ad ad ad ad ad ad ad
100 100 100 100 100 100 100 100 100 Soap-containing deodorant stick A B C D E F G H
% % % % % % % %
Ethanol 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5
Cutina® FS 45 4.4 4.4 4.4 4.4 4.4 4.4 4.4 4.4
1 ,3-Butanediol 31.7 31.7 31.7 31.7 31.7 31.7 31.7 31.7
1 ,2-Propylene glycol 21.0 21.0 21.0 21.0 21.0 21.0 21.0 21.0
Eutanol® G 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Aethoxal® B 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
Cremophor® RH 455 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
NaOH 45 % 1.44 1.44 1.44 1.44 1.44 1.44 1.44 1.44
Phenoxyethanol 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Sensiva® SC 50 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Perfume oil 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Pyranopyranone derivative (Ta0.05 0.10 0.20 0.25 0.50 1.00 0.10 0.30 ble 1)
BIOCIDE/PRESERVATIVE (Ta0.50 0.30 0.10 0.05 0.50 0 0 0.25 ble 2)
Water dist. ad ad ad 100 ad ad ad ad ad
100 100 100 100 100 100 100
Figure imgf000083_0001
Non-aqueous doedorant spray 5.1 5.2 5.3
% % %
2-Octyl dodecanol 0.5 0.5 0.5
Ethanol 99 % (DEP denatured) 38.1 39.495 38.85
Pyranopyranone derivative (Table 1) 0.05 0.10 0.30
BIOCIDE/PRESERVATIVE (Table 2) 0.50 0.10 0 n-Butane 60 60 60 Antiperspirant Roll-on A B C D E F
% % % % % %
Ethanol 96 % (DEP denatured) 30.0 30.0 30.0 30.0 30.0 30.0
Mergital® CS 1 1 2.0 2.0 2.0 2.0 2.0 2.0
Eumulgin® B 3 2.0 2.0 2.0 2.0 2.0 2.0
Aluminium chlorohydrate 20.0 20.0 20.0 20.0 20.0 20.0
Hydroxyethylcellulose 0.5 0.5 0.5 0.5 0.5 0.5
Pyranopyranone derivative (Table 1 ) 0.05 0.10 0.25 0.50 0.10 0.50
BIOCIDE/PRESERVATIVE (Table 2) 1 .00 0.50 0.25 0.10 0 0
Perfume oil 0.8 0.8 0.8 0.8 0.8 0.8
Water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100
Figure imgf000084_0001
Figure imgf000084_0002
List of raw materials used
Aerosil R 972 Silica dimethyl silylate Degussa
Aethoxal® B PPG-5 laureth-5 Cognis
Cetiol® OE Dicaprylyl ether Cognis
Chlorhydrol® 50 % Aluminium chlorohydrate, 50 % water Reheis
Cremophor13 RH 455 Hydrogenated castor oil with 40 EO, conBASF
taining propylene glycol
Cutina13 FS 45 Fatty acid mixture of palmitic and stearic Cognis
acid
Cutina® E 24 PF PEG-20 glyceryl stearate Cognis List of raw materials used
Cutina® HR Hydrogenated castor oil Cognis
DC® 245 Cyclopentasiloxane Dow Corning
DC® 3225 Cyclomethicone/dimethicone copolyol Dow Corning
Eumulgin® B 3 Ceteareth-30 Cognis
Eutanol® G 2-Octyl dodecanol Cognis
Eutanol® G 16 2-Hexyl decanol Cognis
Lanette® 0 Cetyl/stearyl alcohol in a ratio of 1 :1 Cognis
Lorol® C 18 Stearyl alcohol Cognis
Mergital® CS 1 1 Ceteareth-1 1 Cognis
PlantarerT 1200 Lauryl glucoside, about 50 % active subCognis
stance
Plantaren® 2000 Decyl glucoside, about 50 % active subst. Cognis
Sensiva® SC 50 2-Ethylhexylglycerol ether Schulke & Mayr
Ucon Fluid® AP PPG-14 butyl ether Amerchol (Union
Carbide)
Anti-bacterial Fabric Softener A B C D E F G H I
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50
(Table 1 )
C12-15 Pareth-7 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
Quaternium 18 (and) Iso- 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 propyl Alcohol
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)
Perfume qs qs qs qs qs qs qs qs qs
Concentrated Fabric SofA B C D E F G H I tener
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone derivative 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 (Table 1 )
Dihydrogenated Tal- 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 lowethyl Hydroxyethylamo- 0 0 0 0 0 0 0 0 0 nium
Oleth-10 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Simethicone 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
Isopropyl Alcohol 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Magnesium Chloride 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Perfume qs qs qs qs qs qs qs qs qs
BIOCIDE/PRESERVATIVE 0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80
(Table 2)
Figure imgf000086_0001
Liquid Laundry Detergent A B C D E F G H I
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone derivative 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 1,00 (Table 1)
Sodium Dodecylbenzene- 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 sulfonate
Trideceth-12 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50
Penta Sodium Triphos24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 24.0 phate 0 0 0 0 0 0 0 0 0
Sodium Sulfate 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20
Water (and) Sodium Hy1.60 1.60 1.60 1.60 1.60 1.60 1.60 1.60 1.60 droxide
Glycerin 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Oleic Acid 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90 0.90
Sodium Borate 1.80 1.80 1.80 1.80 1.80 1.80 1.80 1.80 1.80
Cellulose Gum 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2) Heavy Duty Liquid Detergent A B C D E F G H I
INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone derivative 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 1 ,00
(Table 1 )
Sodium Dodecylbenzenesul- 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 fonate
C14-15 Pareth-7 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0 14.0
0 0 0 0 0 0 0 0 0
SD Alcohol 39-C 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00
Sodium Tallowate (and) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Sodium Cocoate
Trisodium Citrate Dihydrate 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Triethanolamine 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Fluorescent Whitening 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
Agent (FWA)
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
BIOCIDE/PRESERVATIVE 0,50 0.20 0,00 0,25 0,25 0,25 0,50 0 0
(Table 2)
Liquid Laundry Detergent A B c D E F G H I
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Lauryl-myristyl sulfate 25.0 ~ 25.0 ~ 25.0 ~ 25.0 ~ 25.0 Na-salt (Texapon LS35) 0 0 0 0 0
Alkyl Ether Sulfate So~ 8.00 ~ 5.00 ~ 10.0 ~ 15.0 ~ dium salt 0 0
Coconut Fatty Acid 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 (Edenor K12-18)
C-14,15 alcohol ethoxy- 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 late 7 EO (Neodol 45-7)
Part Isopropyl Alcohol 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 B
Pyranopyranone deriva0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 tive (Table 1 )
BIOCIDE/PRESERVATIVE 0.25 0,00 0.05 0,25 0,25 0,25 0,50 0.00 0,00 (Table 2)
Propylene Glycol 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Ethanolamine 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Triethanolamine 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Citric acid (sol. 50%) 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00
Potassium Hydroxide 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 (sol. 45%)
Fluorescent Whitening 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Agent (FWA)
Acid blue 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Anionic acrylic polymer 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 (Rheovis ATA)
Deionized Water Qs Qs Qs Qs Qs Qs Qs Qs Qs to to to to to to to to to 100 100 100 100 100 100 100 100 100
Manufacturing instruction
Mix 2-Propanol and Propylene glycol. Then add successively while stirring Edenor
(melted at 40°C), Texapon, Triethanolamine, Ethanolamine, Neodol, potassium hydroxide and citric acid.
Finally add deionized water to the former solution while powerful stirring. Incorporate TINOPAL, IRAGON Blue, followed by RHEOVIS ATA slowly while stirring Powdery Laundry DeA B c D E F G H I tergent
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Alkyl benzene sulfona7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 te, sodium salt (Marlon
A 375)
Alkyl Ether Sulfate So4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 dium salt (Empicol ESC
70)
Coconut Fatty Acid 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 (Edenor K12-18)
C14-15 Pareth-7 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 (Neodol 45-7 E)
Part Sodium Aluminium Sili30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 B cate (zeolithe 4 A) 0 0 0 0 0 0 0 0 0
Sodium Carbonate 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00
Sodium Sulfate 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Acrylic acid based 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 polymer (Antiprex
A100)
Sodium Silicate 12.00 12.00 12.00 12.00 12.00 12.00 12.00 12.00 12.00 (Britesil C20)
Pyranopyranone deriva0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 tive (Table 1 )
BIO- 0,20 0.10 0,00 0,00 0,00 0,00 0,00 0,00 0,00
CIDE/PRESERVATIVE
(Table 2)
TINOFIX CL SOLID 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
Deionized Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100
Manufacturing instruction:
Make two premixes:
A 30% solution of Marlon in deionized water is mixed with 50% of the amount of Zeo- lith, dried in oven and crushed to small pieces.
A 30% solution of Empicol in deionized water is mixed with 50% of the amount of Zeo- lith, dried in oven and crushed to small pieces.
The dried premixes are mixed with Antiprex, Britesil and Sodium carbonate. The
melted Neodol and Edenor are added step by step, then Sodium sulfate and finally
TINOFIX CL solid. Laundry Sanitizer A B C D E F G H I
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Sodium Lauryl Sulfate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00
Sodium Cumene Sul5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 fonate
Water deioniz Qs Qs Qs Qs Qs Qs Qs Qs Qs to10 to10 to10 to10 to10 to10 to10 to10 to10 0 0 0 0 0 0 0 0 0
Part PPG-2 Methyl Ether 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 B (Dowanol DPM)
Propylene Glycol 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00
Color and Perfume qs qs qs qs qs qs qs qs qs
§ Citric Acid 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Pyranopyranone deriva0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 tive (Table 1 )
BIO0,00 0,00 0,00 0,25 0,25 0,25 0,50 0.00 0.00 CIDE/PRESERVATIVE
(Table 2)
Sodium Hydroxide Qs Qs Qs Qs Qs Qs Qs Qs Qs (10% solution) to to to to to to to to to pH 5 pH 5 pH 5 pH 5 pH 5 pH 5 pH 5 pH 5 pH 5
Figure imgf000090_0001
Antibacterial Dishwashing A B C D E F G H I
Paste
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Water 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00
Sodium Carbonate 16.00 16.00 16.00 16.00 16.00 16.00 16.00 16.00 16.00
Calcium Carbonate 28.00 28.00 28.00 28.00 28.00 28.00 28.00 28.00 28.00
Sodium Silicate 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Nonoxynol-10 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
Fragrance 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
Figure imgf000091_0001
Bactericidal Dishwashing A B C D E F G H I Liquid
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone derivative 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 (Table 1 )
BIO- 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50
CIDE/PRESERVATIVE
(Table 2)
Sodium Laureth Sulfate 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00 50.00
Sodium Dodecylbenzene- 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 sulfonate
Sodium Cumene Sulfonate 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Citric Acid 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
Benzoic Acid 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
Sodium Chloride 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
Sodium Sulfate 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50
Water (and) Sodium Hyad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH droxide 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Dishwashing liquid and AntiA B C D E F G H I bacterial Hand Soap
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone deriva0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 tive (Table 1 )
Lauryl-myristyl sulfate Na- 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 salt Dishwashing liquid and AntiA B C D E F G H I bacterial Hand Soap
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Sodium Myreth Sulfate 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00
Lauryl Glucoside 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
Coco Betaine 1 .1 1 .1 1 .1 1 .1 1 .1 1 .1 1 .1 1 .1 1 .1
SD Alcohol 39-C 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Sodium Chloride 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00
Citric Acid ad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH ad pH
6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5
BIO- 0,10 0,10 0,10 0,25 0,25 0,25 0.00 0.00 0.00
CIDE/PRESERVATIVE
(Table 2)
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Figure imgf000092_0001
Milky acidic Cleaner A B C D E F G H I
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
C- 12, 15 alcohol ethoxylate 7 EO 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50
(Neodol 25-7E)
C-12,13 alcohol ethoxylate 6.5 EO 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
(Neodol 23-6.5E)
Citric acid sol. 50% 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Figure imgf000093_0001
Manufacturing Instructions
Firstly add Neodol 25-7 to the water at 40°C while stirring (100rpm) and wait until the formulation is homogeneous, then add Neodol 23-6.5 and wait until the formulation is homogeneous. Stop heating.
Finally add citric acid and after 5 minutes incorporate VIBRACOLOR Green and RHEO- VIS CDP slowly while stirring.
Desinfectant Toilet Cleaner A B C D E F G H I
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Alkyl Polyglycoside 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50 3.50
C9-11 pareth-8 1.70 1.70 1.70 1.70 1.70 1.70 1.70 1.70 1.70 (Neodol 91-8E)
Cationic Polymer 11.30 11.30 11.30 11.30 11.30 11.30 11.30 11.30 11.30 Rheovis® CSP
Acetic Acid 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40 2.40
Citric Acid 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00
Pyranopyranone derivative (Table 1) 0,05 0,1 0,2 0,3 0,4 0,5 0,75 0,85 1
BIOCIDE/PRESERVATIVE 0.25 1.00 0.00 0.00 0.00 0.00 0.00 0.00 0.05 (Table 2)
Deionized Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to
100 100 100 100 100 100 100 100 100
Acid blue 80 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
(IRAGON®Blue ABL80 sol.1 %)
Figure imgf000094_0001
Figure imgf000094_0003
Figure imgf000094_0002
Figure imgf000095_0001
Wet wipes A B C D E F G H I
% % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w
Pyranopyranone derivative (Table 1) 0.01 0.05 0.10 0.50 0.01 0.05 0.10 0.50 1.00
PEG-5 Glyceryl Stearate 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Steareth-20 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Steareth-21 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Mineral Oil 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Isopropyl Myristate 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Perfume qs qs qs qs qs qs qs qs qs
Propylene Glycol 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Glycerin 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50
BIOCIDE/PRESERVATIVE (Table 2) 2.00 1.00 0.50 0.20 0 0 0 0 0
Water qs to qs to qs to qs to qs to qs to qs to qs to qs to
100 100 100 100 100 100 100 100 100
Examples
Example 1 :
Preparation of P-7
Figure imgf000096_0001
5.66 g (60.0 mmol) 4-hydroxy-6-methyl-2/-/-pyran-2-one, 6.36 g 2-propyl-2-heptenal, 1 .80 g of D-alanine and 2.75 g (90.0 mmol) calcium sulfate suspended in 200 ml of ethylacetate are heated under reflux for 24 hours. After cooling to room temperature the mixture is extracted with 100 mL of a saturated aqueous sodium hydrogen carbon- ate solution. The aqueous phase is extracted twice with 100 mL of ethyl acetate. The combined organic phases are washed with 200 mL brine and finally dried over sodium sulfate. The solvent is removed in vacuum. Purification was achieved by column chromatography (silica gel, toluene/ethyl acetate 9:1 as eluent). Yellow oil, yield 3.95 g. UV-Vis (ethanol): Dmax = 341 nm,□ = 4039.
1 H-NMR (CDCIs, [ppm]): 6.19 (s,1 H), 5.80 (m,1 H), 4.79 (dd,1 H), 2.21 (d,3H), 1 .92-2.04 (m,2H), 1 .72-1 .82 (m,1 H), 1 .42-1.62 (m,4H), 1 .28-1 .42 (m,3H), 0.95 (t,3H), 0.91 (t,3H).
Example 2:
Tests for antimicrobial efficacy
The bactericidal activity of the compounds of the present invention is measured in a suspension test according to trivial modifications of the European Standard method EN
1040.
Substances listed in Table 1 are tested against gram positive and gram negative bacteria, yeasts and moulds. A selection of the results is shown in the following.
Suspension Test
The pyrano pyranone derivatives are dissolved in ethanol or DMSO resulting in 1 % stock solutions of the compounds.
The cell densities of the bacterial suspensions used as inoculums for the suspension test are as follows (cfu = colony forming units):
Staphylococcus aureus ATCC 6538 1 .8 x 108 cfu/ml
Escherichia coli ATCC 10536 1 .4 x 108 cfu/ml
Pseudomonas aeruginosa ATCC15442 2.2 x 108 cfu/ml
For the suspension tests, an appropriate concentration of the test compound is mixed with a bacterial suspension resulting in a final cell count in the mixture of about 105 cfu/ml. These test mixtures are incubated at room temperature (22°C +/- 2°C) and ali- quots of 1 ml test mixture containing the test bacteria were taken after set contact times for determination of the residual cell count of test bacteria. For inactivation of the antimicrobial compounds, the 1 ml aliquots are diluted in 1 :10 steps in a solution with 10 % Tween, 3 % lecithin, 0.1 % histidine and 0.5 % sodium thiosulfate.
The results of the determination of residual cell counts are given in the table below. The fungicidal activity of the compounds of the present invention is measured in a suspension test according to trivial modifications of the European Standard method EN 1275.
The pyrano pyranone derivatives are dissolved in ethanol or DMSO resulting in 1 % stock solutions of the compounds.
The cell density of Candida albicans ATCC 10231 used as inoculum for the suspension test was 2.4 x 108 cfu/ml and of A niger ATCC 6275 3.8 x 108 cfu/ml. For the suspension tests, an appropriate concentration of the test compound is mixed with a Candida albicans suspension resulting in a final cell count of about 105 cfu/ml. These test mixtures are incubated at room temperature (22°C +/- 2°C) and aliquots of 1 ml test mixture containing Candida albicans were taken after set contact times for determination of the residual cell count.
For inactivation of the antimicrobial compounds, the 1 ml aliquots are diluted in 1 :10 steps in a solution with 10 % Tween, 3 % lecithin, 0.1 % histidine and 0.5 % sodium thiosulfate. Aliquots of 1 ml were taken of the A. niger containing test mixtures after set contact times for determination of the residual cell count. For inactivation of the antimicrobial compounds, the 1 ml aliquots werde diluted in 1 :10 steps in a solution of the following composition:
10 % preformulation preformulation: 30 % Tween 80
6.5 % Sabouraudagar 3 % lecithin
0.1 % Histidine
The results of the determination of residual cell counts are given in the below table.
Figure imgf000098_0001
The results show a strong microbicidal activity of the tested pyrano pyranone derivatives.
For determination of the microbistatic activity, the Minimum Inhibitory Concentrations (MIC) of the test compounds is determined.
The pyrano pyranone derivatives are also tested in an agar incorporation test in order to determine their minimum inhibitory concentrations (MIC) against various tests organisms. A selection of the results is shown in the following.
For this compound, a 1 % stock solutions i9s prepared in ethanol. A dilution series of the test compound in 15 ml still liquid agar media are prepared with 400 ppm, 200 ppm, 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, 6,25 ppm, 3.125 ppm and 1 .56 pmm of active.
The media used for the agar plates are Muller-Hinton (Merck) for the determination of the MIC against bacteria and C. albicans and Sabouraud Agar (Merck) for the determination of the MIC against A. niger. For the determination of the MIC against
Malassezia furfur DSM 6171 , CIP 1636-86 Medium 472 (DSMZ - Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH) was used.
After solidification of the agar, all agar plates containing the test compounds were stored over night in the laboratory (at about 22°C) for drying.
The test bacteria Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 10536, Pseudomonas aeruiginosa ATCC 15442 and the yeast Candida albicans ATCC 10231 are grown in liquid nutrient media at 37°C for 24 hours. The test fungi Aspergillus niger ATCC 6275 is grown in Sabouraud media for 3 days at 28°C. In case of Malassezia furfur DSM 6171 , CIP 1636-86 an agarpetridish grown for 8 days at 30 °C is washed with 10 ml sterile water and the suspension is stirred for 30 minutes.
The cell suspensions of the test organisms are diluted in 0.85% sodium chloride as follows:
100 dilution of Staphylococcus aureus ATCC 6538
1000 dilution of Escherichia coli ATCC 10536
1000 dilution of Pseudomonas aeruginosa ATCC 15442
10 dilution of Candida albicans ATCC 10231
10 dilution of Aspergillus niger ATCC 6275
10 dilution of Malassezia furfur DSM 6171 , CIP 1636-86 10 μΙ of these cell dilutions are then dotted onto the surface of the agar media. The so inoculated agar plates are then incubated for 24 hours at 37°C (for bacteria and the yeast) or 3 days at 28°C (for Aspergillus niger), 4 days at 30 °C and then the highest dilution of the test compound at which no more growth was observed (corresponds to the MIC) ios determined.
Growth controls are conducted for all strains with the pure growth medium (Muller- Hinton for S. aureus, E. coli, Ps. aeruginosa, C. albicans; Sabouraud for A niger and Medium 472 for M. furfur) as well as with ethanol.
Table B: MIC- values in ppm] conducted to determine the microstatic activities:
M.fufur
Compound P-5
50

Claims

Claims
1 . Use of a pyranopyranone of the formula
, wherein
Figure imgf000100_0001
Ri , R2, R3, R4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, C2-C3oal- kenyl, or C3-Ci2cycloalkyl, each of which may be substituted by one or more E and/or interrupted by one or more D; C6-C2oaryl, which may be substituted by one or more G; C4-C2oheteroaryl, which may be substituted by one or more G, C2- Cisalkenyl, C2-Ci8alkynyl, C7-C2saralkyl, or -CO-R6; -S1R8R9R10; or
R4 and R5 together form a five or six membered ring; or
R3 and R4 together form a five or six membered ring;
D is -CO-; -COO-; -S-; -SO-; -SO2-; -0-; -NR7-; -SiR8R9-; -POR10-; -CRi2=CRi3-; or -C≡C-; and
E is -OR6; -SR6; -NR14R15; -NRi4CORi5; -COR6; -COOR6; -CONR14R15; -CN;
halogen; or OSO3R11 ; SO3R11 ; SO2R11 ; P03(Rn)2; OP03(Rn)2;
G is E; Ci-Cisalkyl, which is optionally interrupted by D; d-dsperfluoroalkyl; Ci- Ciealkoxy, which is optionally substituted by E and/or interrupted by D; wherein R6 is H; C6-Cisaryl which is optionally substituted by OH, Ci-C3oalkyl or Ci-C3oalkoxy; or Ci-C3oalkyl which is optionally interrupted by -0-;
R7 is H; C6-Ci8aryl which is optionally substituted by OH, Ci-C3oalkyl or Ci-C3oalkoxy; or Ci-C3oalkyl which is optionally interrupted by -0-;
Rs, R9 and R10 independently of each other are hydrogen; Ci-C3oalkyl; C6-Ci8aryl which is optionally substituted by Ci-C3oalkyl; and
R11 is hydrogen; C6-Ci8aryl, which is optionally substituted by OH, Ci-C3oalkyl or Ci- C3oalkoxy; or Ci-C3oalkyl, which is optionally interrupted by -0-;
R12, Ri3, Ri4 and R15 independently of each other are hydrogen; C6-Cisaryl which is optionally substituted by OH, Ci-C3oalkyl or Ci-C3oalkoxy; Ci-C3oalkyl, which is optionally interrupted by -0-; or
Ri4 and R15 together form a five or six membered ring;
as an antimicrobial and/or preserving agent.
2. Use according to claim 1 , wherein
Ri is d-Cealkyl;
R2 is hydrogen;
R3, R4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, C2-C3oalkenyl, or C3-Ci2cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C6-C2oaryl, which may be substituted by one or more G; C4- C2oheteroaryl, which may be substituted by one or more G, C2-Ci8alkenyl, C2-
Cisalkynyl, C7-C2saralkyl, or -CO-R6; or
R4 and R5 together form a five or six membered ring;
D is -CO-; -COO-; -0-; -IMR7-; -CRi2=CRi3-; or -C≡C-; and
E is -OR6; -NR14R15; -NR14COR15; -COR6; -COOR6; -CONR14R15; -CN; halogen; or
OSO3R11 ; SO3R11 ; SO2R11 ; P03(Rii)2; OP03(Rii)2;
G is E; Ci-Cisalkyl, which is optionally interrupted by D; Ci-Ci8perfluoroalkyl; Ci-
Ciealkoxy, which is optionally substituted by E and/or interrupted by D; wherein R6, R7, R11 , R12, Ri3, Ri4 and R15 are defined as in formula (1 ).
3. Use according to claim 1 or 2, wherein
Ri is methyl;
R2 is hydrogen;
R3, R4 and R5 independently of one another are hydrogen; or Ci-C3oalkyl, C2-C3oal- kenyl, phenyl, pyridinyl, pyrimidinyl, triazinyl, pyrrolyl, furanyl, thiophenyl or chino- linyl, each of which is unsubstituted or substituted by G; or Si(Ci-C4alkyl)3; and R3 and R4 together, or R4 and R5 together, may be C2-Csalkylene, C2-Csalkenylene, C2-Csoxaalkylene, C2-Csoxaalkenylene, C4-C8cycloalkylene, C4-C8cycloalkenylene, each of which is unsubstituted or substituted by G;
G is C-i-Csalkyl, d-Csalkoxy, OH, where two adjacent residues G may be interconnected to form C3-C4alkylene or a residue -O-CH2-O-.
4. Use according to any of claims 1 to 3, wherein
Ri is methyl;
R2 is hydrogen;
R3, R4 and R5 independently of one another are hydrogen; Ci-C3oalkyl, or C2-C3oal- kenyl, or
R3 and R4 together form a five or six membered ring, which may be interrupted by -0-; or
R4 and R5 together form a five or six membered ring.
5. Use according to any of claims 1 to 4, wherein
Ri is methyl
R2 is hydrogen
R3 is hydrogen; Ci-Ci2alkyl; C2-C4alkenyl; or a radical of formula //
O'
R4 is hydrogen; C2-C4alkenyl;
R5 is hydrogen; Ci-C4alkyl; phenyl; -SiRs R9R10; or a radical of formula
Figure imgf000101_0001
R3 and R4 together form the rings ; *^ * ; or |^ ; or
Figure imgf000102_0001
6. A method for protecting skin, mucosa and integumentary appendages against the action of microbes including protecting the scalp from dandruff, which comprises applying an effective amount of pyranopyranone derivatives of formula (1 ) according to any of claims 1 to 5.
7. A method for protecting paper, wood, leather, synthetic textile materials or natural textile materials against the action of microbes comprising incorporating or applying an effective amount of pyranopyranone derivatives of formula (1 ) according to any of claims 1 to 5.
8. A method for cleaning and disinfecting hard surfaces which comprises applying a preparation comprising an effective amount of pyranopyranone derivatives of formula (1 ) according to any of claims 1 to 5.
9. A method for preventing bio-fouling of an article comprising incorporating the pyranopyranone derivatives of formula (1 ) according to claim 1 into the article or sur- face of the article or by applying the pyranopyranone derivative of formula (1 ) according to any of claims 1 to 5 to these surfaces either directly or as part of a coating or film.
10. Non-therapeutic use or method according to any of claims 1 to 9.
1 1 . Personal care preparations comprising
0.01 to 15 weight % of the pyranopyranone derivative of formula (1 ) according to any of claims 1 to 5 and
cosmetically compatible ingredients such as carrier and/or adjuvants.
12. The compound of formula
Figure imgf000102_0002
PCT/EP2011/052876 2010-03-02 2011-02-28 Pyranopyranone derivatives as antimicrobial agents WO2011107411A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10155147.1 2010-03-02
EP10155147 2010-03-02

Publications (1)

Publication Number Publication Date
WO2011107411A1 true WO2011107411A1 (en) 2011-09-09

Family

ID=42762621

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/052876 WO2011107411A1 (en) 2010-03-02 2011-02-28 Pyranopyranone derivatives as antimicrobial agents

Country Status (1)

Country Link
WO (1) WO2011107411A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106032383A (en) * 2015-03-19 2016-10-19 中国科学院上海药物研究所 Tricyclic analogues, preparation method and applications thereof
EP3030214B1 (en) 2013-08-09 2021-02-24 Beiersdorf AG Alcoholic sunscreen gel
CN113150006A (en) * 2021-02-02 2021-07-23 五邑大学 Pyran compound and synthetic method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558658A (en) * 1967-03-03 1971-01-26 Dow Chemical Co 2h,5h-pyrano(3,2-e)(1)benzo-pyran-4(3h),5-diones
US20070265267A1 (en) 2004-10-08 2007-11-15 Syngenta Crop Protection, Inc. Fungicidal compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558658A (en) * 1967-03-03 1971-01-26 Dow Chemical Co 2h,5h-pyrano(3,2-e)(1)benzo-pyran-4(3h),5-diones
US20070265267A1 (en) 2004-10-08 2007-11-15 Syngenta Crop Protection, Inc. Fungicidal compositions

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
BIOORGANIC&MEDICINAL CHEMISTRY LETTER, vol. 17, 2007, pages 978 - 982
CARBOHYDRATE RESEARCH, vol. 340, no. 7, 2005, pages 1287 - 1300
GEIGER, POLYMER BULLETIN, vol. 52, 2004, pages 65 - 70
H.LEUTBECHER ET.AL.: "Microwave assisted domino Knoevenagel Condensation/6p-electron electrocyclization reactions for the rapir and efficient synthesis of substituted 2H,5H-pyrano[4,3-b]pyran-5-ones and related heterocycles", QSAR COMBINATORIAL SCIENCE, vol. 23, no. 10, 2004, Weinheim, DE, pages 895 - 898, XP002602996, DOI: 10.1002/qsar.200420048 *
JOURNAL OF ORGANIC CHEMISTRY, vol. 62, no. 20, 1997, pages 6888 - 6896
JOURNAL OF ORGANIC CHEMISTRY, vol. 64, no. 3, 1999, pages 690 - 691
JOURNAL OF ORGANIC CHEMISTRY, vol. 68, no. 5, 2003, pages 1729 - 1735
LEUTBECHER ET AL: "Efficient synthesis of substituted 7-methyl-2H,5H-pyrano[4,3-b]pyran- 5-ones and evaluation of their in vitro antiproliferative/cytotoxic activities", BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, PERGAMON, ELSEVIER SCIENCE, GB LNKD- DOI:10.1016/J.BMCL.2006.11.045, vol. 17, no. 4, 1 February 2007 (2007-02-01), pages 978 - 982, XP005868822, ISSN: 0960-894X *
ORGANIC LETTERS, vol. 8, no. 2, 2006, pages 191 - 193
QSAR & COMBINATORIAL SCIENCE, vol. 23, no. 10, 2004, pages 895 - 898
SAGAR R ET AL: "Diastereoselective annulation of 4-hydroxypyran-2H-ones with enantiopure 2,3-dideoxy-alpha,beta-unsaturated sugar aldehydes derived from respective glycals", CARBOHYDRATE RESEARCH, PERGAMON, GB LNKD- DOI:10.1016/J.CARRES.2005.02.018, vol. 340, no. 7, 23 May 2005 (2005-05-23), pages 1287 - 1300, XP004861527, ISSN: 0008-6215 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3030214B1 (en) 2013-08-09 2021-02-24 Beiersdorf AG Alcoholic sunscreen gel
CN106032383A (en) * 2015-03-19 2016-10-19 中国科学院上海药物研究所 Tricyclic analogues, preparation method and applications thereof
JP2018508560A (en) * 2015-03-19 2018-03-29 中国科学院上海薬物研究所Ｓｈａｎｇｈａｉ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｍａｔｅｒｉａ Ｍｅｄｉｃａ， Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ Tricyclic analogues, methods for their production and use
CN106032383B (en) * 2015-03-19 2019-08-13 中国科学院上海药物研究所 A kind of tricyclic analog, preparation method and use
CN113150006A (en) * 2021-02-02 2021-07-23 五邑大学 Pyran compound and synthetic method thereof

Similar Documents

Publication Publication Date Title
US20110224170A1 (en) Pyranopyranone derivatives as antimicrobial agents
JP2015515997A (en) Use of cyclohexanol ether with antimicrobial properties
US20090068138A1 (en) Polyglycerol anti-microbial agents and compositions
US20090286878A1 (en) Polyol derived anti-microbial agents and compositions
US6814960B1 (en) Hydroxystilbene compounds used as microbicidal active substances
ES2260202T3 (en) EMPLOYMENT OF PHENYLETHYLAMINE DERIVATIVES FOR ANTIMICROBIAL SURFACE TREATMENT.
WO2011107411A1 (en) Pyranopyranone derivatives as antimicrobial agents
WO2011048011A2 (en) Benzotropolone derivatives as antimicrobial agents
US7015228B2 (en) 4-amino-2-(2-pyridyl)pyrimidines as microbicidal active substances
US20050124579A1 (en) Benzyl alcohol derivatives
US9644175B2 (en) Antimicrobial amino-salicylic acid derivatives
US6689372B1 (en) Microbicidal active substances
US6346260B1 (en) Microbicidal active ingredients
US6624182B1 (en) Hydroxyphenylvinylthiazoles
US20070196407A1 (en) Alkoxyphenylcarboxylic acid derivatives
US7476753B2 (en) 3-aryl-2-cyano-3-hydroxy-acrylic acid derivatives
EP1074179B1 (en) Microbicidal active ingredients
US6743940B2 (en) 4-aminobut-2-ynecarboxylic acid derivatives
WO2004035012A1 (en) The use of biomimic polymers in personal care compositions
MXPA06001069A (en) 3-aryl-2-cyano-3-hydroxy-acrylic acid derivatives
EP1215198A1 (en) 4-Aminobut-2-yne carboxylic acid derivatives and their use as antimicrobial agents

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11704804

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11704804

Country of ref document: EP

Kind code of ref document: A1