Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L9/00—Disinfection, sterilisation or deodorisation of air
  • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
  • A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
  • A61L9/12—Apparatus, e.g. holders, therefor
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L9/00—Disinfection, sterilisation or deodorisation of air
  • A61L9/01—Deodorant compositions

Definitions

• the invention relates to a fragrance composition for the controlled release of volatile substances into the ambient air, and to air-freshening devices containing the same.
• fragrance release systems which provide a pleasant, natural aroma during a long period of time, e.g. 4 to 6 weeks, without significant changes of the fragrance strength and/or fragrance character during usage.
• Gel compositions to control the degree of fragrance release from air-freshening devices are known.
• One of the first gels has been made from seaweed extracts, e.g. carrageenan.
• these gels can hold only a relatively small concentration of fragrance oils and have poor fragrance-release characteristics.
• the European Patent Application No. 0 631 788 discloses a gel-like fragrance composition which comprises an aqueous gel comprising an aqueous fluid and a gelling agent incorporated in an oil-absorbable resin carrying a fragrant material. It is stated therein that it is possible to achieve a well-balanced volatile emission for a long period, independently of the perfume character.
• These aqueous gel compositions may contain up to 20% by weight of a fragrant material.
• U.S. Patent No. 5 643 866 discloses a crystal clear, self-supporting, highly concentrated gel, comprising fragrance oils, glycols and dibenzylidene sorbitol acetal (DBSA) as gelling agent. Said gels can be loaded up to 80% with fragrance oils.
• US Patent No. 5 780 527 discloses a rigid dry and transparent gel obtained by reacting, in the presence of a fragrance composition, a liquid polymeric material with a cross-linking agent.
• Non-gel like fragrance compositions are widespread in combination with electrical heated vapour dispensing devices, or in combination with other means, e.g. a wick, to control the release of the fragrance.
• a solvent is used to support the controlled release of the fragrance.
• the European Patent Application No. 1 078 640 describes a single- phase aqueous air freshening composition comprising 30% to 60% glycol ethers used in an air freshener device comprising a wick.
• the invention provides an air-freshening device comprising a container having an open end, the container holding a composition comprising an aqueous phase, and a hydrophobic phase comprising a fragrance, and said open end is covered by a breathable film which permits of egress of the fragrance and water-vapour.
• the addition of water to a fragrance not only influences the life- cycle of the air-freshening device but also is important for the essentially continuous release of the fragrance.
• the air-freshener device permits of strong fragrance release and the character of the released fragrance does not substantially alter over a long period of time, e.g. 4 to 6 weeks.
• the present of water influences the impact and quality of the released fragrance and leads to higher evaporation profile measured by the weight lost of the product over a time period of use as is more specifically illustrated in the examples.
• the rate of evaporation and therefore the life-cycle of the air-freshening device may be varied depending on the ratio of water to fragrance.
• the weight ratio between water to fragrance is about 9:1 to about 1 :9, more preferably about 7:3 to about 3:7, most preferably 4:1 to about 2:3.
• the strength of a fragrance can be evaluated by the measurement of the odour value, or by sniffing.
• the odour value of a fragrance material is defined as the ratio of the vapour pressure and its mean odour threshold concentration.
• the odour threshold concentration can be measured by standard methods, for example described by ASTM E679-91. To calculate the odour value of a fragrance composition the vapour pressure and odour threshold concentration of the fragrance has to be determined. Because of the time-consuming and elaborate nature of methods to determine the odour value the analysis of the fragrance strength by sniffing is preferred, as is well known in the perfumery arts.
• the character of a fragrance relies on the contribution of all components of a fragrance through evaporation. Highly volatile fragrance components (so- called «Top Notes») are responsible for the initial impression of a fragrance. Less volatile fragrance components (so-called «Middle Notes», also known as «Heart Notes», and so- called «Bottom Notes», also known as «Base Notes») are responsible for the long-lasting impression of a fragrance.
• a fragrance's character depends on the harmonisation of Top Note, Middle Note, and Bottom Note. Clearly, it is highly desired that the released fragrance character does not significantly change during use of an air-freshening device over a prolonged period of time.
• the air-freshener devices of the present invention may permit substantially the same ease of passage to all fragrance ingredients irrespective of their physicochemical properties such as volatility and thus leads to the balanced nature of the fragrance emitted from the device. Without wishing to be bound by any theory applicant believes that due to the addition of water to the fragrance the developed water-vapour in a headspace of the device acts as a carrier for the fragrance to pass through the breathable film irrespective of their volatility.
• breathable film as used herein means a polymeric film that allows water-vapour, but not water in the liquid phase, to pass through it.
• breathable films There are two different classes of breathable films known namely micro-porous films and monolithic films.
• Micro-porous films are such films with small pores that permit passage of water-vapour. Typically, they comprises micropores having pore sizes of e.g. down to about 10 ⁇ m. The small size of the pores prevents the penetration of liquid phase water across the film, but the interconnected pore structure allows the transmission of water-vapour.
• Micro-porous films may be made from, e.g. polyolefins, polytetrafluoroethylenes (PTFE) and precipitated polyurethanes.
• Monolithic films are based on copolymers having so called «hard» and «soft» segments.
• the hard segments may be polyesters, for example glycol, propanediol or butanediol units and dicarboxylic acid units connected by ester functional groups; polyurethanes; or polyamides, for example polyamid 6 (PA-6), polyamid 11 (PA-11 ), or polyamid 12 (PA-12).
• the soft segments, responsible for the water-vapour transmission may be formed by polyether units, for example polyethylene glycol (PEG), polypropylene glycol (PPG) or polytetramethylene glycol (PTMG) or mixtures thereof, and dicarboxylic acids, such as, for example terephtalic acid.
• Monolithic films based on polyester block hard segments are described in US Patents No. 5 800 928, 4 725 481 , and 6 001 464;Monolithic films based on polyurethane hard segments are described in US Patents No. 5 800 928 and 6 001 464; Monolithic films based on polyamide hard segments are described in US Patents No. 5 800 928 and 5506 024; all of which are incorporated herein by reference.
• the molecular weight of the soft segment is preferably between 600 and 4000 g/mol.
• the glass transition temperature is preferably below 0°C.
• the amount of the soft segment may vary widely depending on the particular properties desired. However, in a preferred embodiment the amount of the soft segment may be between 15% and 40% by weight of the film, preferably between 20% and 30% by weight.
• the soft segment formed by polypropylene glycol is preferred. Most preferred are soft segments formed by polyethylene glycol, or a mixture of polyethylene glycol and polypropylene glycol.
• monolithic breathable films examples include poly(ether-co-amide), e.g. PEBAX ® by Atofina and poly(ether-co-ester), e.g. HYTREL ® by DuPont.
• breathability is meant the water-vapour transmission rate (WVT) or water-vapour permeability (WVP). Its measuring unit is g/m 2 /24h and it is calculated by measuring how many grammes of water-vapour pass through one square meter of film in 24 hours.
• WVT water-vapour transmission rate
• WVP water-vapour permeability
• the breathable film according to the present invention preferably may have a thickness from about 10 ⁇ m to about 50 ⁇ m, more preferred from 15 ⁇ m to about 40 ⁇ m.
• the container according to the present invention may be made of any material that is commonly used for air-freshener devices, e.g. glass or plastic. Such materials are preferred, which are stable in the presence of fragrance materials, e.g. essential oils.
• the container may be of any shape or configuration subject to it having an open end and capable of receiving aqueous and oil phases.
• the upper liquid surface does not abut the surface of the breathable film. Rather, in a preferred embodiment there should be a space between the upper surface of the liquid phase and the lower surface of the breathable film in which a head-space of fragrance and water-vapour may develop. This space is preferably not greater than 8cm, more preferably not greater than 3cm, for example between 1cm and 2cm, most preferably not greater than 1cm.
• the breathable film may be attached to the container in a sealed relationship utilising any conventional means, such as an adhesive, heat seal or the like. Such means are preferred which form a strong bond between the film and the container to avoid the leakage of the liquid composition.
• the hydrophobic phase according to the present invention consists of fragrance.
• a fragrance according to the present invention is a mixture of fragrance materials selected from such classes as acids, esters, alcohols, aldehydes, ketones, lactones, nitriles, ethers, acetates, hydrocarbons, sulfur- nitrogen- and oxygen-containing heterocyclic, polycyclic and macrocyclic compounds, as well essential oils of natural or synthetic origin.
• fragrance materials are described, for example, in S. Arctander Perfume Flavors and Chemicals Vols. 1 and 2, Arctander, Montclair, NJ USA 1969.
• the fragrance optionally may comprise odourless liquids such as dipropylene glycol, propylene glycol, diethylphtalate, benzyl benzoate, triethylcitrate, isopropylmyristate, carbitol, and hexylene glycol, or mixtures thereof.
• odourless liquids such as dipropylene glycol, propylene glycol, diethylphtalate, benzyl benzoate, triethylcitrate, isopropylmyristate, carbitol, and hexylene glycol, or mixtures thereof.
• the fragrance comprises not more than 20% by weight of these liquids.
• a fragrance may contain residual water either due to the presence of a solvent or due to the production process.
• composition according to the present invention comprises more than 10% by weight of water, more preferably more than 25% by weight, most preferably between 50% and 90%by weight of water.
• a composition comprising 95% by weight of water or even more, e.g. 98%, may also be used to form a composition according to the present invention.
• the hydrophobic phase may comprise a lipophilic dye, for example Puricolor ® blue FBL5, Puricolor ® blue ABL9, Puricolor ® green U3 or Puricolor ® yellow AYE23 from Ciba.
• a lipophilic dye for example Puricolor ® blue FBL5, Puricolor ® blue ABL9, Puricolor ® green U3 or Puricolor ® yellow AYE23 from Ciba.
• fragrances are preferred comprising a high amount of fragrance material having a vapour pressure greater than 1000 ⁇ g/l.
• These fragrance materials are classified as «Top Notes» and may be selected from acetate C6 hexylic, acetophenone, alcohol C6 hexylic, aldehyde C7 heptylic, aldehyde C9 isononylic, allyl caproate, allyl oenanthate, amyl butyrate, amyl vinyl carbinol, anapear, benzaldehyde, benzyl formate, benzyl methyl ether, bornyl acetate liquid, butyl acetate, camphene, carbitol, citronellal, cresyl methyl ether para, cyclal C, cymene para, decenal-4-trans, delta-3 carene, diethyl malonate, dihydro anethole, dihydro myrcenol
• Fragrance materials having a vapour pressure between 10 ⁇ g/I and 1000 ⁇ g/l are classified as «Middle Notes» and may be selected from acetal E, acetal R, acetanisole, adoxal, agrumex, alcohol C10 decylic, alcohol C11 undecylenic, alcohol C12 lauric, alcohol C8 octylic, alcohol C9 nonylic, aldehyde C11 undecylenic, aldehyde C11 undecylic, aldehyde C12 lauric, aldehy, aldehyde iso C11 , allyl amyl glycolate, allyl cyclohexyl propionate, ambrinol, amyl benzoate, amyl caproate, amyl cinnamic aldehyde, amyl phenyl acetate, amyl salicylate, anethole synthetic, anisyl acetate, anisyl alcohol,
• Fragrance materials having a vapour pressure below 10 ⁇ g/I are classified as «Bottom Notes» and may be selected from 2-benzyl-4-methanol-1,3-dioxolane, aldrone, ambrettolide, ambroxan, benzophenone, benzyl benzoate, benzyl cinnamate, benzyl phenyl acetate, cepionate, cetalox, citronellyl ethoxalate, civettone, cresyl caprylate para, cresyl phenyl acetate para, cyclohexal, diethyl phthalate, dione, dodecalactone delta, dodecalactone gamma, ethyl maltol, ethyl vanillin, ethylene brassylate, eugenyl phenyl acetate, evernyl, fixolide, florhydral, galaxolide, geranyl phenyl a
• fragrances are preferred comprising from about 15% to about 80% by weight «Top Notes», more preferably from about 25% to about 60% by weight.
• the aqueous phase according to the present invention may be water, for example distilled water.
• Other excipients optionally present in the aqueous phase are salts, for example sodium chloride and magnesium sulfate to minimize the migration of water soluble fragrance materials.
• Other excipients, e.g. water soluble dyes may also be present in the aqueous phase.
• the device may have fitted over the container and the breathable film, a non-breathable material, such as an aluminium foil, polyolefine films, ethylene acrylic acid copolymer films, polyethylene terephtalate films, or ethylen vinyl acetate films, which may be easily removed prior to use.
• a non-breathable material such as an aluminium foil, polyolefine films, ethylene acrylic acid copolymer films, polyethylene terephtalate films, or ethylen vinyl acetate films, which may be easily removed prior to use.
• the composition held in the container comprises an upper hydrophobic phase comprising a fragrance, and a lower aqueous phase.
• composition comprising the hydrophobic phase and the aqueous phase is provided as an emulsion.
• the emulsion may optionally comprise a surfactant such as for example non-ionic surfactants, e.g. Neodol 91-8 from Shell Chemicals and Cremophor RH40 from BASF.
• a surfactant such as for example non-ionic surfactants, e.g. Neodol 91-8 from Shell Chemicals and Cremophor RH40 from BASF.
• fragrance compositions may comprise excipients such as dyes and UV-absorbers.
• the container may be filled in a first step with the aqueous phase followed by adding on top of the aqueous phase the hydrophobic phase. If the hydrophobic phase and the aqueous phase is provided as an emulsion, in a first step both phases may be prepared separately and then mixed together to form an emulsion, according to a process well known in the art, followed by filling the resulting emulsion into the container. After filling the container the open end of the container is covered by the breathable film, which itself might be covered by a removable impermeable film for storage.
• a fragrance composition having citrus and spicy top notes with floral and middle notes and ambery and musky bottom notes was used in all examples.
• Comparative Product A Liquid fragrance composition comprising a cellulose wick
• Blend under stirring at room temperature 8.0g fragrance and 8.0 g of Neodol (manufactured by Shell). Then, add 34g water, 25g dipropyleneglycolmethyleter, and 25g ethyl alcohol. Stir until the solution becomes clear. Pour 70 g of the solution into a glass container and insert a wick, made of cellulose in the middle of the container. The one end of the wick is in contact with the solution and the other end of it is in contact with the ambient air to supply the ambient air with fragrance.
• Comparative Product B Solid gel fragrance composition comprising a gelling agent
• Blend at room temperature 1.735g Lithene N4-9000-10MAfrom Revertex Ltd with 8.0g fragrance together.
• Add under stirring 0.265g of Crodamet O2 from Revertex Ltd. Stir for about 10 minutes and pour 7g of the composition into a glass container.
• Pebax ® MV 6100 film from Atofina was evaluated in booths.
• the fragrance strength of each of the products was evaluated by an expert panel of 20 members by sniffing. The result was entered on a scale from 1 to 5, wherein 5 is very strong,
• the fragrance strength of Product C is at all stages better than the fragrance strength of the comparison products, i.e. the wick system (Comp. Product A) permits at each age of the product only a weak egress of the fragrance and the gel system (Comp. Product B) releases a strong fragrance up to one week but the strength of the fragrance decreases over the period of time and was described to be weak after 4 weeks.
• Example 2 Evaluation of the fragrance character by headspace.
• the concentration of the «Top Notes» decreases markedly for the comparative products, i.e. the wick system (Product A) and the gel system (Product B), whereas the concentration of the «Top Notes» remains very high for Product C during the evaluation period of 4 weeks.
• Mixture A, B, C and D were evaluated by an expert panel in terms of strength and quality and resulted in the following ranking: Mixture D was better than Mixture C and Mixture C was better than Mixture B. The weakest was mixture A. If no water is added, Mixture A, the fragrance performance is very weak.

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• Public Health (AREA)
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• Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
• Fats And Perfumes (AREA)
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• Treatment Of Sludge (AREA)
• Treating Waste Gases (AREA)
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• Packaging Of Annular Or Rod-Shaped Articles, Wearing Apparel, Cassettes, Or The Like (AREA)

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• 2002
  • 2002-02-28 EP EP02004584A patent/EP1340513A1/en not_active Withdrawn
• 2003
  • 2003-01-30 EP EP03700300A patent/EP1478410B1/en not_active Expired - Lifetime
  • 2003-01-30 JP JP2003570894A patent/JP2005518840A/ja active Pending
  • 2003-01-30 DE DE60310204T patent/DE60310204D1/de not_active Expired - Lifetime
  • 2003-01-30 WO PCT/CH2003/000076 patent/WO2003072151A1/en not_active Ceased
  • 2003-01-30 US US10/505,819 patent/US20050145711A1/en not_active Abandoned
  • 2003-01-30 AU AU2003201603A patent/AU2003201603A1/en not_active Abandoned
  • 2003-01-30 AT AT03700300T patent/ATE347384T1/de not_active IP Right Cessation
  • 2003-01-30 KR KR10-2004-7013326A patent/KR20040088553A/ko not_active Withdrawn

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