WO1999008721A1 - Air freshener dispenser device with combustible taper strand feature - Google Patents
Air freshener dispenser device with combustible taper strand feature Download PDFInfo
- Publication number
- WO1999008721A1 WO1999008721A1 PCT/US1998/017079 US9817079W WO9908721A1 WO 1999008721 A1 WO1999008721 A1 WO 1999008721A1 US 9817079 W US9817079 W US 9817079W WO 9908721 A1 WO9908721 A1 WO 9908721A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dispenser device
- air freshener
- accordance
- strand
- taper
- Prior art date
Links
- 239000002386 air freshener Substances 0.000 title claims abstract description 65
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- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- IVLCENBZDYVJPA-ARJAWSKDSA-N cis-Jasmone Natural products C\C=C/CC1=C(C)CCC1=O IVLCENBZDYVJPA-ARJAWSKDSA-N 0.000 description 1
- NGHOLYJTSCBCGC-UHFFFAOYSA-N cis-cinnamic acid benzyl ester Natural products C=1C=CC=CC=1C=CC(=O)OCC1=CC=CC=C1 NGHOLYJTSCBCGC-UHFFFAOYSA-N 0.000 description 1
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 description 1
- ZKVZSBSZTMPBQR-UPHRSURJSA-N civetone Chemical compound O=C1CCCCCCC\C=C/CCCCCCC1 ZKVZSBSZTMPBQR-UPHRSURJSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229940043259 farnesol Drugs 0.000 description 1
- 229930002886 farnesol Natural products 0.000 description 1
- 229930006735 fenchone Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229930007503 menthone Natural products 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- ALHUZKCOMYUFRB-UHFFFAOYSA-N muskone Natural products CC1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- MBDOYVRWFFCFHM-UHFFFAOYSA-N trans-2-hexenal Natural products CCCC=CC=O MBDOYVRWFFCFHM-UHFFFAOYSA-N 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
- HRHOWZHRCRZVCU-UHFFFAOYSA-N trans-hex-2-enyl acetate Natural products CCCC=CCOC(C)=O HRHOWZHRCRZVCU-UHFFFAOYSA-N 0.000 description 1
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 description 1
- XMLSXPIVAXONDL-UHFFFAOYSA-N trans-jasmone Natural products CCC=CCC1=C(C)CCC1=O XMLSXPIVAXONDL-UHFFFAOYSA-N 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
- A01M1/00—Stationary means for catching or killing insects
- A01M1/20—Poisoning, narcotising, or burning insects
- A01M1/2022—Poisoning or narcotising insects by vaporising an insecticide
- A01M1/2061—Poisoning or narcotising insects by vaporising an insecticide using a heat source
- A01M1/2066—Poisoning or narcotising insects by vaporising an insecticide using a heat source burning insecticide, e.g. impregnated candles, burning coils
-
- 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
- A61L9/02—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air by heating or combustion
- A61L9/03—Apparatus therefor
Definitions
- This invention generally relates to dispensers of vaporizable media. More specifically, this invention relates to a device for dispensing a fragrance or deodorant in the form of a vapor for air freshening in an enclosed environment.
- a device for dispensing a fragrance or deodorant in the form of a vapor for air freshening in an enclosed environment The need for effectively combating airborne malodors in homes and enclosed public buildings, by odor masking or destruction, is well established.
- Various kinds of vapor-dispensing devices have been employed for this purpose. The most common of such devices is the aerosol container which propels minute droplets of an air freshener composition into the air.
- Another common type of dispensing device is a dish containing or supporting a body of gelatinous matter which when it dries and shrinks releases a vaporized air- treating composition into the atmosphere.
- vapor-dispensing devices utilizes a carrier material such as paperboard impregnated or coated with a vaporizable composition.
- a number of recent developments include a liquid air-treating composition in an enclosure, all or part of which is formed of a polymeric film through which the air-treating composition can migrate to be released as a vapor at an outer surface.
- a liquid air-treating composition in an enclosure, all or part of which is formed of a polymeric film through which the air-treating composition can migrate to be released as a vapor at an outer surface.
- Use of this type of permeable polymeric membrane controls the dispensing of air-treating vapors and tends to eliminate great variations in the rate of dispensing over the life of the product.
- Wicking devices are well known for dispensing volatile liquids into the atmosphere, such as fragrance, deodorant, disinfectant or insecticide active agent.
- a typical wicking device utilizes a combination of a wick and emanating region to dispense a volatile liquid from a liquid reservoir.
- Publications of background interest relative to the present invention include United States Patent Numbers 2,090,297; 2,379,250; 2,818,615; 2,829,51 1 ; 3,332,428; 3,499,452; 3,560,122; 3,705,890; 3,898,039; 4,092,988; 4,568,270; 5,538,018; and 5,569,779; incorporated by reference.
- U.S. 2,818,615 describes a deodorizer device in which a combustible cord is impregnated with an air freshener, and the air freshener is released when the cord is ignited.
- U.S. 2,829,51 1 describes a candle wick structure composed of a core strand of cellulose acetate in combination with an outer web of cotton fibers.
- U.S. 5,538,018 describes a flavorant-release additive which is a cellulose derivative that is incorporated into a cigarette paper wrapper.
- Incense burner type devices which are adapted for volatilizing fragrances by means of a slow smoldering combustion.
- Incense burner type devices are described in United States Patent Numbers 4,099,916; 4,155,979; 4,237,097; 4,324,763; 4,334,853; and 5,215,719; incorporated by reference.
- Some air freshener dispensers are expensive to manufacture. Other air freshener dispensers are inexpensive to produce, but tend to have inferior construction and functionality.
- an air freshener dispenser device which comprises:
- a combustible taper strand comprising a cellulosic matrix having a content of chemically-bound air freshener constituent, and which taper strand is disposed within the container storage chamber;
- a closure means which forms a partition across the top section of the container; and (d) a narrow bore tube which is supported by the partition in a vertically extended position, and which has access through the partition to the container storage chamber; wherein the vertical tube is adapted to receive and guide passage of the taper strand from the container storage chamber, and to support an exposed end- section of the strand which extends upward from the tube; and wherein the taper strand is adapted for release of the chemically-bound air freshener constituent into the atmosphere when the taper strand is combusted.
- FIG. 1 is an elevational side view of an invention air freshener dispenser device with a lid cover in place.
- FIG. 2 is a plan top view of a FIG. 1 air freshener dispenser device without a lid cover.
- FIG. 3 is a cross-sectional side view of a FIG. 2 air freshener dispenser device taken along line 3-3.
- FIG. 4 is an enlarged elevational side view of the vertical tube feature of a FIG. 3 air freshener dispenser device.
- FIG. 1 is an elevational side view of invention air freshener dispenser device 10 before it is in an operational mode.
- dispenser device 10 of FIG. 1 is constructed of molded plastic container 12 and dome-shaped lid cover 14.
- Container 12 and lid cover 14 can be injection or thermoform molded from a polymer such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyamide, polymethacrylate, and the like.
- Container 12 and lid cover 14 normally are disposable after the air freshener dispensing function has been completed. If container 12 and lid cover 14 are designed for extended use with air freshener refills, they can be constructed of glass, metal, wood, thermoset resin, or the like.
- Air freshener dispenser device 10 in FIG. 1 typically has an annular cross-section with a height dimension between about 6-12 centimeters and a lateral dimension between about 2-5 centimeters.
- FIG. 2 is a plan top view of FIG. 1 air freshener dispenser device 10 after dome-shaped lid cover 14 has been removed.
- Partition 15 is integrally in combination with vertical tube 18 and ash receptacle means 19. Taper strand
- FIG. 3 is a cross-sectional side view of FIG. 2 air freshener dispenser device 10 taken along line 3-3. Taper strand 16 is guided from the container storage chamber and supported by vertical tube 18.
- Taper strand 16 can have an annular cross-section with a diameter between about 2-8 millimeters, and a length of at least about 20 centimeters. Taper strand 16 typically is comprised of cellulosic fibers which are twisted, plaited, woven, braided, or the like.
- the cellulosic matrix of taper strand 16 can be obtained from sources such as cotton, linen, flax, hemp, wood pulp, and the like.
- the cellulosic matrix also can be in the form of a cellulosic derivative such as rayon, alkylated cellulose or esterified cellulose.
- cellulosic refers to a ⁇ -glucosidic polysaccharide corresponding to the formula:
- n is an integer which provides an average molecular weight between about 100.000-2,000,000.
- Air freshener dispenser device 10 of FIG. 3 illustrates recess 20 for accommodating lid cover 14 when it is in place.
- Lid cover 14 also can be movably secured to container 12 so that it opens without being detached.
- Interior extension rim 22 in FIG. 3 dispenser device 10 secures and supports partition 15.
- partition 15 in combination with vertical tube 18 and ash receptacle means 19 is a retrievable unit. This access means facilitates a refill of the storage chamber with taper strand 16.
- vertical tube 18 and ash receptacle means 19 can be formed of the same or different materials.
- Ash receptacle means 19 is an optional feature, since partition 15 can serve to collect residual ash.
- the combination of partition 15, vertical tube 18 and ash receptacle means 19 can be a unitary structure which is composed of glass, metal or plastic. Because vertical tube 18 has contact with taper strand 16 when it is in a burning phase, vertical tube 18 preferably is a nonflammable or heat- resistant body.
- taper strand 16 After the extended end of taper strand 16 is ignited, it burns with a slow smolder down to the open end of vertical tube 18, where taper strand 16 then self-extinguishes.
- FIG. 4 is an enlarged elevational side view of vertical tube 18 which is shown in FIG. 3.
- the pair of slots 21 permit finger manipulation of taper strand 16 in vertical tube 18.
- a unique aspect of the present invention is the provision of combustible taper strand 16 which is composed of cellulosic fibers which have a content of a chemically-bound air freshener constituent.
- chemically-bound refers to a covalent bond between a cellulose polymer chain and an air freshener molecule, such as an ether or ester linkage.
- the Degree of Substitution (D.S.) can be between about 0.05-3.
- air-freshener as employed herein is meant to include fragrances such as geraniol, insect repellants such as citronellal, and therapeutic agents such as menthol.
- An air freshener constituent of a present invention taper strand can be any inherently volatile organic compound which is capable of being covalently linked to a cellulosic matrix by chemical reaction.
- Suitable volatile air freshener compounds include alcohols such as undecanol, 4-isopropyl-cyclohexanol, geraniol. linalool, citronellol. farnesol. menthol. 3-trans-isocamphylcyclohexanol. benzyl alcohol, 2-phenylethyl alcohol. 3-phenyl-propanol. 3-methyl-5-phenylpentanol. cinnamic alcohol, isoborneol, thymol, eugenol.
- air freshener compounds include aldehydes and ketones such as hexanal, decanal, 2-methyldecanal, trans-2-hexenal, acetoin, diacetyl, geranial, citronellal, methoxydihydro-citronellal, menthone, carvone, camphor, fcnchone, ionone, irone, damascone, cedryl methyl ketone, muscone, civetone, 2,4-dimethyl-3-cyclohexene carboxaldehyde, 2-heptylcyclopentanone, cis- jasmone, dihydrojasmone, cyclopentadecanone, benzaldehyde, phenylacetaldehyde, dihydrocinnamaldehyde, cinnamaldehyde, ⁇ -amy
- acetophenone benzylacetone. benzophenone, piperonal, and the like.
- Other suitable air freshener compounds include esters such as trans-2- hexenyl acetate, allyl 3-cyclohexylpropionate, methyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, and the like.
- the reaction proceeds readih in the presence of a basic reagent such as sodium hydroxide or an organic amine.
- a basic reagent such as sodium hydroxide or an organic amine.
- the production of cellulose carbonates are described in publications such as U.S. 3.705,890 and U.S. 5,068.321 ; incorporated by reference.
- Another chemical means for forming a linkage between an alcohol air freshener and a cellulose polymer is by the use of an alcohol epichlorohydrin derivative under alkaline reaction conditions.
- the chemical-bonding of an aldehyde such as citronellal or a ketone such as fenchone to a cellulose polymer can be accomplished by the formation of a hemiacetal (ketal) and/or acetal (ketal) linkage under acidic conditions:
- RO 2 C-CH CH-R + cellulose — -
- the air freshener constituent is released only when the taper strand is being combusted.
- the air freshener is released by pyrolysis at a sustained constant rate.
- the amount of air freshener constituent which is chemically-bound can be predetermined within a D.S. range between about 0.05-3 by selected synthesis conditions.
- a present invention air freshener dispenser device is easily assembled from inexpensive materials, and it is safely disposable after usage.
- a present invention air freshener dispenser device is less hazardous than a candle in home use, since the taper strand smolders rather than burn with an open flame, and there is no pool of spillable melted wax.
- the storage supply of taper strand in a present invention air freshener device can serve for an extended period of frequent use.
- Geraniol 100 g is added dropwise to a stirred mixture of 50% aqueous sodium hydroxide (300 mL), epichlorohydrin (300 g), and tetrabutylammonium hydrogen sulfate (60 g) with cooling to maintain a temperature of 20EC.
- a reactor equipped with a reflux condenser and stirrer is charged with hexane (one liter), caustic solution (20 g of 50% aqueous sodium hydroxide), and a strand of braided cotton (30 g). The mixture is stirred for 30 minutes at 25EC under a nitrogen atmosphere. Geraniol glycidyl ether (50 g) is added to the slurry, and the resulting reaction mixture is heated at 80EC for 8 hours. The mixture then is cooled to room temperature, neutralized with glacial acetic acid, and filtered.
- the recovered cotton strand is washed with acetone and then with water. After drying, solid state NMR indicates that the cellulosic matrix of the cotton strand has a D.S. of 0.36. An end of the cotton strand is ignited, and it smolders with a flameless glow. The combustion of the strand releases a flowery-rose note which is characteristic of geraniol.
- This Example illustrates the preparation of a present invention taper strand which is substituted with a fragrance mixture.
- a strand of braided cotton is treated with the glycidyl ether mixture to chemically bind the fragrance constituents to the cellulosic matrix of the braided cotton (a D.S. of 0.6).
- This Example illustrates the preparation of a present invention taper strand which is substituted with a fragrance mixture.
- glycidyl ethers are formed with the constituents of a perfume oil: Parts hydroxycitronellal 50.00 benzyl alcohol 4.0 geraniol 3.0 citronellol 3.0 linalool 3.0
- a strand of braided cotton is treated with the glycidyl ether mixture to chemically bind the fragrance constituents to the cellulose matrix of the braided cotton (D.S. of 1.8).
- Dimethylformamide and lithium chloride are employed as additional ingredients in the reaction process to increase the D.S. in the cellulose matrix. Ignition of the cotton strand releases a lily-of-the-valley note.
- This Example illustrates the preparation of menthyl chloro formate.
- a reactor in a dry-ice/acetone bath (-75EC) is charged with liquid phosgene (1 17 g).
- Menthol (130 g) dissolved in 120 mL of cyclopentane, is added dropwise to the phosgene with stirring.
- the reaction medium is refluxed for six hours at room temperature.
- the excess phosgene and cyclopentane are removed under reduced pressure.
- the recovered menthyl chloroformate is dissolved in diethyl ether (60 mL), and the solution is washed with aqueous sodium bicarbonate, and then with distilled water. The liquid medium is dried over sodium sulfate, and the solvent is removed under reduced pressure to yield a purified menthyl chloroformate.
- EXAMPLE VI This Example illustrates the preparation of a menthyl carbonate ester- substituted taper strand in accordance with the present invention.
- a 400 g strand of multi-filament rayon (North American Rayon, yarn 4321) is suspended in a blend of pyridine (1800 g) and benzene (3 liters), and the admixture is stirred for 20 hours at room temperature.
- a 1200 g quantity of menthyl chloroformate is added dropwise to the stirred reaction medium at room temperature. The stirring is continued for 10 hours at a reaction medium temperature of 80EC. After cooling and filtering, the recovered strand product is washed with benzene, then with isopropanol and with water. The strand product has a menthyl carbonate D.S. of 0.9. Smolder combustion of the taper strand releases a readily detectable menthol scent into the atmosphere.
- EXAMPLE VII This Example illustrates the preparation of a citronellal acetal- substituted taper strand in accordance with the present invention.
- a reactor is equipped with a stirrer and a reflux condenser having a water-removal unit.
- the reactor is charged with benzene (500 mL), p-toluenesulfonic acid (50 mg), citronellal (50 g) and a strand of braided cotton (30 g).
- the admixture is heated at reflux with stirring, and continued until no more water is entrained as an azeotrope.
- the acid catalyst is neutralized with ammonium hydroxide.
- the mixture is filtered, and the recovered cotton strand is washed with water.
- solid state NMR indicates that the cellulosic matrix of the cotton strand has a D.S. of about 0.2. Smolder combustion of the taper strand releases a mild citronellal scent into the atmosphere.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Engineering & Computer Science (AREA)
- Insects & Arthropods (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
This invention provides an air freshener dispenser device which as a combustible taper strand feature. The taper strand consists of a cellulosic matrix, such as cotton or rayon yarn, which has a content of a chemically-bond air freshener constituent such as geraniol, citronellal or menthol. The linkage between the air freshener and cellulosic matrix can be an ether or carbonate ester covalent bond. When the taper strand is ignited, it burns with a slow smolder-type combustion, and there is a controlled release of the air freshener constituent into the atmosphere.
Description
AIR FRESHENER DISPENSER DEVICE WITH COMBUSTIBLE TAPER STRAND FEATURE
BACKGROUND OF THE INVENTION
This invention generally relates to dispensers of vaporizable media. More specifically, this invention relates to a device for dispensing a fragrance or deodorant in the form of a vapor for air freshening in an enclosed environment. The need for effectively combating airborne malodors in homes and enclosed public buildings, by odor masking or destruction, is well established. Various kinds of vapor-dispensing devices have been employed for this purpose. The most common of such devices is the aerosol container which propels minute droplets of an air freshener composition into the air. Another common type of dispensing device is a dish containing or supporting a body of gelatinous matter which when it dries and shrinks releases a vaporized air- treating composition into the atmosphere. Other products such as deodorant blocks are also used for dispensing air-treating vapors into the atmosphere by evaporation. Another group of vapor-dispensing devices utilizes a carrier material such as paperboard impregnated or coated with a vaporizable composition.
A number of recent developments include a liquid air-treating composition in an enclosure, all or part of which is formed of a polymeric film through which the air-treating composition can migrate to be released as a vapor at an outer surface. Use of this type of permeable polymeric membrane controls the dispensing of air-treating vapors and tends to eliminate great variations in the rate of dispensing over the life of the product.
Wicking devices are well known for dispensing volatile liquids into the atmosphere, such as fragrance, deodorant, disinfectant or insecticide active
agent. A typical wicking device utilizes a combination of a wick and emanating region to dispense a volatile liquid from a liquid reservoir.
Publications of background interest relative to the present invention include United States Patent Numbers 2,090,297; 2,379,250; 2,818,615; 2,829,51 1 ; 3,332,428; 3,499,452; 3,560,122; 3,705,890; 3,898,039; 4,092,988; 4,568,270; 5,538,018; and 5,569,779; incorporated by reference.
U.S. 2,818,615 describes a deodorizer device in which a combustible cord is impregnated with an air freshener, and the air freshener is released when the cord is ignited. U.S. 2,829,51 1 describes a candle wick structure composed of a core strand of cellulose acetate in combination with an outer web of cotton fibers.
U.S. 5,538,018 describes a flavorant-release additive which is a cellulose derivative that is incorporated into a cigarette paper wrapper.
Of special interest with respect to the present invention are incense burner type devices which are adapted for volatilizing fragrances by means of a slow smoldering combustion. Incense burner type devices are described in United States Patent Numbers 4,099,916; 4,155,979; 4,237,097; 4,324,763; 4,334,853; and 5,215,719; incorporated by reference.
Some air freshener dispensers are expensive to manufacture. Other air freshener dispensers are inexpensive to produce, but tend to have inferior construction and functionality.
There remains a need for a well-constructed air freshener dispenser device which can be mass-produced economically and which can deliver a vapor medium at a controlled uniform rate over an extended period of time. Accordingly, it is an object of this invention to provide an improved air freshener dispenser device for delivering an odorant and/or deodorant vapor in an enclosed environment.
It is another object of this invention to provide an air freshener dispenser device with a primary structure which is a plastic assembly that can be produced economically by a thermoforming means.
It is another object of this invention to provide an air freshener dispenser device which features a combustible taper strand which has a content of air freshener constituent.
It is a further object of this invention to provide a freshener dispenser device which volatilizes an air freshener by means of a slow smoldering combustion.
Other objects and advantages of the present invention shall become apparent from the accompanying drawings and examples.
SUMMARY OF THE INVENTION
One or more objects of the present invention are accomplished by the provision of an air freshener dispenser device which comprises:
(a) a container with an interior storage chamber;
(b) a combustible taper strand comprising a cellulosic matrix having a content of chemically-bound air freshener constituent, and which taper strand is disposed within the container storage chamber;
(c) a closure means which forms a partition across the top section of the container; and (d) a narrow bore tube which is supported by the partition in a vertically extended position, and which has access through the partition to the container storage chamber; wherein the vertical tube is adapted to receive and guide passage of the taper strand from the container storage chamber, and to support an exposed end- section of the strand which extends upward from the tube; and wherein the taper strand is adapted for release of the chemically-bound air freshener constituent into the atmosphere when the taper strand is combusted.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational side view of an invention air freshener dispenser device with a lid cover in place.
FIG. 2 is a plan top view of a FIG. 1 air freshener dispenser device without a lid cover.
FIG. 3 is a cross-sectional side view of a FIG. 2 air freshener dispenser device taken along line 3-3.
FIG. 4 is an enlarged elevational side view of the vertical tube feature of a FIG. 3 air freshener dispenser device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is an elevational side view of invention air freshener dispenser device 10 before it is in an operational mode.
As illustrated, dispenser device 10 of FIG. 1 is constructed of molded plastic container 12 and dome-shaped lid cover 14. Container 12 and lid cover 14 can be injection or thermoform molded from a polymer such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyamide, polymethacrylate, and the like.
Container 12 and lid cover 14 normally are disposable after the air freshener dispensing function has been completed. If container 12 and lid cover 14 are designed for extended use with air freshener refills, they can be constructed of glass, metal, wood, thermoset resin, or the like.
Air freshener dispenser device 10 in FIG. 1 typically has an annular cross-section with a height dimension between about 6-12 centimeters and a lateral dimension between about 2-5 centimeters.
FIG. 2 is a plan top view of FIG. 1 air freshener dispenser device 10 after dome-shaped lid cover 14 has been removed. Partition 15 is integrally in combination with vertical tube 18 and ash receptacle means 19. Taper strand
16 is disposed within vertical tube 18.
FIG. 3 is a cross-sectional side view of FIG. 2 air freshener dispenser device 10 taken along line 3-3. Taper strand 16 is guided from the container storage chamber and supported by vertical tube 18.
Taper strand 16 can have an annular cross-section with a diameter between about 2-8 millimeters, and a length of at least about 20 centimeters. Taper strand 16 typically is comprised of cellulosic fibers which are twisted, plaited, woven, braided, or the like.
The cellulosic matrix of taper strand 16 can be obtained from sources such as cotton, linen, flax, hemp, wood pulp, and the like. The cellulosic matrix also can be in the form of a cellulosic derivative such as rayon, alkylated cellulose or esterified cellulose.
The term "cellulosic" as employed herein refers to a β-glucosidic polysaccharide corresponding to the formula:
where n is an integer which provides an average molecular weight between about 100.000-2,000,000.
Air freshener dispenser device 10 of FIG. 3 illustrates recess 20 for accommodating lid cover 14 when it is in place. Lid cover 14 also can be movably secured to container 12 so that it opens without being detached.
Interior extension rim 22 in FIG. 3 dispenser device 10 secures and supports partition 15. As illustrated in FIG. 3, partition 15 in combination with vertical tube 18 and ash receptacle means 19 is a retrievable unit. This access means facilitates a refill of the storage chamber with taper strand 16. Partition 15. vertical tube 18 and ash receptacle means 19 can be formed of the same or different materials. Ash receptacle means 19 is an optional feature, since partition 15 can serve to collect residual ash.
The combination of partition 15, vertical tube 18 and ash receptacle means 19 can be a unitary structure which is composed of glass, metal or
plastic. Because vertical tube 18 has contact with taper strand 16 when it is in a burning phase, vertical tube 18 preferably is a nonflammable or heat- resistant body.
After the extended end of taper strand 16 is ignited, it burns with a slow smolder down to the open end of vertical tube 18, where taper strand 16 then self-extinguishes.
FIG. 4 is an enlarged elevational side view of vertical tube 18 which is shown in FIG. 3. Slot 21 in FIG. 4, and another slot 21 on the back side (not shown), together provide a taper strand 16 advancing means from the storage chamber of container 10 up through vertical tube 18. The pair of slots 21 permit finger manipulation of taper strand 16 in vertical tube 18.
A unique aspect of the present invention is the provision of combustible taper strand 16 which is composed of cellulosic fibers which have a content of a chemically-bound air freshener constituent. The term "chemically-bound" as employed herein refers to a covalent bond between a cellulose polymer chain and an air freshener molecule, such as an ether or ester linkage. The Degree of Substitution (D.S.) can be between about 0.05-3.
The term "air-freshener" as employed herein is meant to include fragrances such as geraniol, insect repellants such as citronellal, and therapeutic agents such as menthol.
An air freshener constituent of a present invention taper strand can be any inherently volatile organic compound which is capable of being covalently linked to a cellulosic matrix by chemical reaction. Suitable volatile air freshener compounds include alcohols such as undecanol, 4-isopropyl-cyclohexanol, geraniol. linalool, citronellol. farnesol. menthol. 3-trans-isocamphylcyclohexanol. benzyl alcohol, 2-phenylethyl alcohol. 3-phenyl-propanol. 3-methyl-5-phenylpentanol. cinnamic alcohol, isoborneol, thymol, eugenol. isoeugenol. anise alcohol, methyl salicylate. and the like.
Other suitable air freshener compounds include aldehydes and ketones such as hexanal, decanal, 2-methyldecanal, trans-2-hexenal, acetoin, diacetyl, geranial, citronellal, methoxydihydro-citronellal, menthone, carvone, camphor, fcnchone, ionone, irone, damascone, cedryl methyl ketone, muscone, civetone, 2,4-dimethyl-3-cyclohexene carboxaldehyde, 2-heptylcyclopentanone, cis- jasmone, dihydrojasmone, cyclopentadecanone, benzaldehyde, phenylacetaldehyde, dihydrocinnamaldehyde, cinnamaldehyde, α-amylcinnamaldehyde. acetophenone. benzylacetone. benzophenone, piperonal, and the like. Other suitable air freshener compounds include esters such as trans-2- hexenyl acetate, allyl 3-cyclohexylpropionate, methyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, and the like.
The chemical-bonding of an alcohol air freshener such as geraniol or menthol to a cellulose polymer can be accomplished by the formation of a carbonate ester linkage:
O O
II II
R-OCC1 + cellulose- OCO-cellulose
The reaction proceeds readih in the presence of a basic reagent such as sodium hydroxide or an organic amine. The production of cellulose carbonates are described in publications such as U.S. 3.705,890 and U.S. 5,068.321 ; incorporated by reference.
Another chemical means for forming a linkage between an alcohol air freshener and a cellulose polymer is by the use of an alcohol epichlorohydrin derivative under alkaline reaction conditions.
O
/ \
R-O-CH2-CH — CH2 + cellulose — -.
OH"
OH
R-0-CH2-CH-CH2-O-cellulose
The chemical-bonding of an aldehyde such as citronellal or a ketone such as fenchone to a cellulose polymer can be accomplished by the formation of a hemiacetal (ketal) and/or acetal (ketal) linkage under acidic conditions:
OH
R-CHO + cellulose — -yR --CCHH--0-cellulose H+
R' O
R'-CO-R2 + cellulose C -cellulose
H^
Rz 0
The chemical bonding of an ester such as phenylethyl cinnamate air freshener to a cellulose polymer can be accomplished by a Michael addition reaction under alkaline conditions:
RO2C-CH=CH-R + cellulose — -
OH"
R
( RO2C-CH CH-0-cellulose
The Michael addition reaction is described in publications such as U.S. 2,415,040 and U.S. 5,569,779; incorporated by reference.
The chemical-bonding of an air freshener constituent to a cellulosic matrix in a present invention taper strand provides significant advantages not previously contemplated by the prior art.
The air freshener constituent is released only when the taper strand is being combusted. The air freshener is released by pyrolysis at a sustained constant rate.
The amount of air freshener constituent which is chemically-bound can be predetermined within a D.S. range between about 0.05-3 by selected synthesis conditions.
Because the air freshener constituent is chemically-bound, there is no premature loss of air freshener by migration and evaporation.
A present invention air freshener dispenser device is easily assembled from inexpensive materials, and it is safely disposable after usage.
A present invention air freshener dispenser device is less hazardous than a candle in home use, since the taper strand smolders rather than burn with an open flame, and there is no pool of spillable melted wax.
Because of the slow burn nature of the taper strand combustion, the storage supply of taper strand in a present invention air freshener device can serve for an extended period of frequent use.
The following examples are further illustrative of the present invention. The components and specific ingredients are presented as being typical, and various modifications can be derived in view of the foregoing disclosure within the scope of the invention.
EXAMPLE I This Example illustrates the preparation of geraniol glycidyl ether.
Geraniol (100 g) is added dropwise to a stirred mixture of 50% aqueous sodium hydroxide (300 mL), epichlorohydrin (300 g), and tetrabutylammonium hydrogen sulfate (60 g) with cooling to maintain a temperature of 20EC.
After a reaction period of 18 hours, the mixture is poured into water (one liter), and the aqueous medium is extracted with chlorofomi. The extract layer is washed with water, dried over sodium sulfate and filtered, and an oil product is recovered after solvent evaporation. NMR and IR confirm the structure.
EXAMPLE II This Example illustrates the preparation of an air freshener-substituted taper strand in accordance with the present invention.
A reactor equipped with a reflux condenser and stirrer is charged with hexane (one liter), caustic solution (20 g of 50% aqueous sodium hydroxide), and a strand of braided cotton (30 g). The mixture is stirred for 30 minutes at 25EC under a nitrogen atmosphere. Geraniol glycidyl ether (50 g) is added to the slurry, and the resulting reaction mixture is heated at 80EC for 8 hours. The mixture then is cooled to room temperature, neutralized with glacial acetic acid, and filtered.
The recovered cotton strand is washed with acetone and then with water. After drying, solid state NMR indicates that the cellulosic matrix of the cotton strand has a D.S. of 0.36.
An end of the cotton strand is ignited, and it smolders with a flameless glow. The combustion of the strand releases a flowery-rose note which is characteristic of geraniol.
EXAMPLE III
This Example illustrates the preparation of a present invention taper strand which is substituted with a fragrance mixture.
Following the general procedure of Example I, glycidyl ethers are formed with the constituents of a perfume oil:
Parts hydroxycitronellal 18.0 cinnamyl alcohol 1.7 terpineol 8.0 benzyl alcohol 18.0 phenethyl alcohol 20.0 linalool 2.0
In a manner similar to that described in Example II, a strand of braided cotton is treated with the glycidyl ether mixture to chemically bind the fragrance constituents to the cellulosic matrix of the braided cotton (a D.S. of 0.6).
Ignition of the cotton strand releases a flower,' lilac note.
EXAMPLE IV
This Example illustrates the preparation of a present invention taper strand which is substituted with a fragrance mixture.
Following the general procedure of Example I, glycidyl ethers are formed with the constituents of a perfume oil:
Parts hydroxycitronellal 50.00 benzyl alcohol 4.0 geraniol 3.0 citronellol 3.0 linalool 3.0
In a mamier similar to that described in Example II, a strand of braided cotton is treated with the glycidyl ether mixture to chemically bind the fragrance constituents to the cellulose matrix of the braided cotton (D.S. of 1.8). Dimethylformamide and lithium chloride are employed as additional ingredients in the reaction process to increase the D.S. in the cellulose matrix. Ignition of the cotton strand releases a lily-of-the-valley note.
EXAMPLE V
This Example illustrates the preparation of menthyl chloro formate. A reactor in a dry-ice/acetone bath (-75EC) is charged with liquid phosgene (1 17 g). Menthol (130 g), dissolved in 120 mL of cyclopentane, is added dropwise to the phosgene with stirring. The reaction medium is refluxed for six hours at room temperature.
The excess phosgene and cyclopentane are removed under reduced pressure. The recovered menthyl chloroformate is dissolved in diethyl ether (60 mL), and the solution is washed with aqueous sodium bicarbonate, and then with distilled water. The liquid medium is dried over sodium sulfate, and the solvent is removed under reduced pressure to yield a purified menthyl chloroformate.
EXAMPLE VI This Example illustrates the preparation of a menthyl carbonate ester- substituted taper strand in accordance with the present invention.
A 400 g strand of multi-filament rayon (North American Rayon, yarn 4321) is suspended in a blend of pyridine (1800 g) and benzene (3 liters), and the admixture is stirred for 20 hours at room temperature.
A 1200 g quantity of menthyl chloroformate is added dropwise to the stirred reaction medium at room temperature. The stirring is continued for 10 hours at a reaction medium temperature of 80EC. After cooling and filtering, the recovered strand product is washed with benzene, then with isopropanol and with water. The strand product has a menthyl carbonate D.S. of 0.9. Smolder combustion of the taper strand releases a readily detectable menthol scent into the atmosphere.
EXAMPLE VII This Example illustrates the preparation of a citronellal acetal- substituted taper strand in accordance with the present invention.
A reactor is equipped with a stirrer and a reflux condenser having a water-removal unit. The reactor is charged with benzene (500 mL), p-toluenesulfonic acid (50 mg), citronellal (50 g) and a strand of braided cotton (30 g). The admixture is heated at reflux with stirring, and continued until no more water is entrained as an azeotrope. After cooling, the acid catalyst is neutralized with ammonium hydroxide. The mixture is filtered, and the recovered cotton strand is washed with water. After drying, solid state NMR indicates that the cellulosic matrix of the cotton strand has a D.S. of about 0.2. Smolder combustion of the taper strand releases a mild citronellal scent into the atmosphere.
Claims
1. An air freshener dispenser device which comprises:
(a) a container with an interior storage chamber;
(b) a combustible taper strand comprising a cellulosic matrix having a content of chemically- bound air freshener constituent, and which taper strand is disposed within the container storage chamber;
(c) a closure means which forms a partition across the top section of the container; and
(d) a narrow bore tube which is supported by the partition in a vertically extended position, and which has access through the partition to the container storage chamber; wherein the vertical tube is adapted to receive and guide passage of the taper strand from the container storage chamber, and to support an exposed end- section of the strand which extends upward from the tube; and wherein the taper strand is adapted for release of the chemically-bound air freshener constituent into the atmosphere when the taper strand is combusted.
2. A dispenser device in accordance with claim 1 which is in combination with a lid cover means that is movably secured to the container as an enclosure for the vertical tube and partition section.
3. A dispenser device in accordance with claim 1 which is in combination with means for advancing the taper strand upward through the vertical tube.
4. A dispenser device in accordance with claim 1 wherein the vertical tube and partition section are in combination with an ash receptacle means.
5. A dispenser device in accordance with claim 1 wherein the dispenser device has an annular cross-section with a height dimension between about 6-12 centimeters and a lateral dimension between about 2-5 centimeters.
6. A dispenser device in accordance with claim 1 wherein the taper strand has an annular cross-section with a diameter between about 2-8 millimeters.
7. A dispenser device in accordance with claim 1 wherein the taper strand has a length of at least about 20 centimeters.
8. A dispenser device in accordance with claim 1 wherein the degree of air freshener substitution (D.S.) in the cellulosic matrix of the taper strand is between about 0.05-3.
9. A dispenser device in accordance with claim 1 wherein the air freshener constituent is chemically-bound to the cellulosic matrix of the taper strand by an ether linkage.
10. A dispenser device in accordance with claim 1 wherein the air freshener constituent is chemically-bound to the cellulosic matrix of the taper strand by an ester linkage.
1 1. A dispenser device in accordance with claim 1 wherein the air freshener constituent after release from the cellulosic matrix has a reconstituted alcohol group.
12. A dispenser device in accordance with claim 1 wherein the air freshener constituent after release from the cellulosic matrix has a reconstituted carbonyl group.
13. A dispenser device in accordance with claim 1 wherein the air freshener constituent after release from the cellulosic matrix has a reconstituted olefin group.
14. A dispenser device in accordance with claim 1 wherein the air freshener constituent after release from the cellulosic matrix is a fragrance composition.
15. A dispenser device in accordance with claim 1 wherein the air freshener constituent after release from the cellulosic matrix is an insect repellant composition.
16. A dispenser device in accordance with claim 1 wherein the air freshener constituent after release from the cellulosic matrix is a therapeutic composition.
17. A dispenser device in accordance with claim 1 wherein the released air freshener comprises geraniol.
18. A dispenser device in accordance with claim 1 wherein the released air freshener comprises citronellal.
19. A dispenser device in accordance with claim 1 wherein the released air freshener comprises menthol.
20. A dispenser device in accordance with claim 1 wherein the cellulosic matrix is cotton or rayon yarn.
21. A dispenser device in accordance with claim 1 wherein the taper strand after ignition burns with a slow smolder-type combustion.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU89121/98A AU8912198A (en) | 1997-08-19 | 1998-08-18 | Air freshener dispenser device with combustible taper strand feature |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US91285297A | 1997-08-19 | 1997-08-19 | |
US08/912,852 | 1997-08-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999008721A1 true WO1999008721A1 (en) | 1999-02-25 |
Family
ID=25432560
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/017079 WO1999008721A1 (en) | 1997-08-19 | 1998-08-18 | Air freshener dispenser device with combustible taper strand feature |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU8912198A (en) |
TW (1) | TW400237B (en) |
WO (1) | WO1999008721A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1774982A1 (en) * | 2005-10-14 | 2007-04-18 | Fritz Altmann | A phial for a perfuming and/or deodorising device |
WO2012025899A1 (en) | 2010-08-26 | 2012-03-01 | Dominó - Indústrias Cerâmicas Sa | Fragrance slow-release silica-based layer, ceramic tile and production process thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR732458A (en) * | 1932-02-29 | 1932-09-21 | Device for the evaporation of a liquid and the absorption of bad odors, fumes, etc. | |
GB2199246A (en) * | 1987-12-07 | 1988-07-06 | Ki Yip Chemical Works Limited | Wax air freshener |
WO1997027424A1 (en) * | 1996-01-26 | 1997-07-31 | S.C. Johnson & Son, Inc. | Candle wick holder |
-
1998
- 1998-08-18 AU AU89121/98A patent/AU8912198A/en not_active Abandoned
- 1998-08-18 WO PCT/US1998/017079 patent/WO1999008721A1/en active Application Filing
- 1998-09-18 TW TW87113504A patent/TW400237B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR732458A (en) * | 1932-02-29 | 1932-09-21 | Device for the evaporation of a liquid and the absorption of bad odors, fumes, etc. | |
GB2199246A (en) * | 1987-12-07 | 1988-07-06 | Ki Yip Chemical Works Limited | Wax air freshener |
WO1997027424A1 (en) * | 1996-01-26 | 1997-07-31 | S.C. Johnson & Son, Inc. | Candle wick holder |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1774982A1 (en) * | 2005-10-14 | 2007-04-18 | Fritz Altmann | A phial for a perfuming and/or deodorising device |
WO2012025899A1 (en) | 2010-08-26 | 2012-03-01 | Dominó - Indústrias Cerâmicas Sa | Fragrance slow-release silica-based layer, ceramic tile and production process thereof |
Also Published As
Publication number | Publication date |
---|---|
TW400237B (en) | 2000-08-01 |
AU8912198A (en) | 1999-03-08 |
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