US3679102A - Aerosol composition and method for producing same - Google Patents
Aerosol composition and method for producing same Download PDFInfo
- Publication number
- US3679102A US3679102A US8726A US3679102DA US3679102A US 3679102 A US3679102 A US 3679102A US 8726 A US8726 A US 8726A US 3679102D A US3679102D A US 3679102DA US 3679102 A US3679102 A US 3679102A
- Authority
- US
- United States
- Prior art keywords
- microcapsules
- liquefied
- aerosol
- propellant
- dispenser
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000000443 aerosol Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000003094 microcapsule Substances 0.000 claims abstract description 123
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000003380 propellant Substances 0.000 claims abstract description 55
- 239000012530 fluid Substances 0.000 claims abstract description 29
- 239000004479 aerosol dispenser Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims description 45
- 239000002537 cosmetic Substances 0.000 claims description 42
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 16
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 9
- 229940029284 trichlorofluoromethane Drugs 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 8
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 claims description 8
- 229940099364 dichlorofluoromethane Drugs 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000001282 iso-butane Substances 0.000 claims description 8
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000012466 permeate Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001340526 Chrysoclista linneella Species 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/025—Applications of microcapsules not provided for in other subclasses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/203—Exchange of core-forming material by diffusion through the capsule wall
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S206/00—Special receptacle or package
- Y10S206/828—Medicinal content
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2984—Microcapsule with fluid core [includes liposome]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2984—Microcapsule with fluid core [includes liposome]
- Y10T428/2985—Solid-walled microcapsule from synthetic polymer
- Y10T428/2987—Addition polymer from unsaturated monomers only
Definitions
- a sprayable aerosol composltwn 15 prepared ye a q 5s 1 Field of Search ..424/14, 4547; a material in a microcapsule and introduclns Into said 252/305, 316 364; 401/132, 190; 222/192, 394 microcapsule a fluid under a pressure essentially equal to the pressure in the aerosol container from which said composition 56]
- References Cited is dispensed, Also provided is an aerosol dispenser containing UNITED STATES PATENTS 11/1970 Monson ..252/
- microcapsules dispersed in an aerosol propellant.
- This invention relates to a method for producing a sprayable aerosol composition containing a self-releasable encapsulated material and to an aerosol dispenser containing said encapsulated material dispersed in a propellant.
- the present invention relates to the production of an aerosol composition containing an encapsulated material which can be released therefrom without the need of mechanical, chemical or thermal means.
- the present invention has been found to be particularly use ful in the cosmetic and pharmaceutical industry and in the packaging of maintenance products, for projecting active ingredients onto the surface where they are to act, and to obtain automatic liberation of these ingredients on the said support.
- the present invention is a method for producing a sprayable aerosol composition containing a self-releasable encapsulated material which comprises encapsulating the material to be sprayed in the form of an aerosol in a rupturable microcapsule having a size ranging from about 50 to 1000 microns in diameter and introducing into said microcapsule a fluid under sufficient pressure so that when said microcapsule, dispersed in an aerosol propellant, is sprayed into an atmosphere having a pressure less than the pressure of the fluid in said microcap sule, the microcapsule ruptures, thereby releasing the material contained therein.
- the propellant in which the microcapsules are dispersed and stored and the fluid contained in the microcapsules under pressure are essentially the same.
- this fluid and propellant can conveniently be a fluorinated hydrocarbon and particularly a fluorochloroalkane such as trichlorofluoromethane and dichlorofluoromethane or their mixtures.
- the propellant can be a saturated aliphatic hydrocarbon such as propane, isobutane, n-butane or the like.
- the aerosol dispenser in which the propellant and microcapsules are packaged will have a valve provided with a diaphragm, having a diameter greater than the maximum diameter of the microcapsules.
- a fluid having sufficient pressure to rupture the micro-capsule when sprayed into the atmosphere is introduced into the microcapsule in the liquid state in admixture with the material to be released therefrom on rupturing.
- microencapsulation is carried out at a sufficiently low temperature and pressure so that the fluid is in the liquid.
- the material being encapsulated is itself a liquid, it must be miscible with the liquified pressuring medium, especially when the releasable material is an alcohol solution, and the liquified pressuring medium gas is a mixture of fluorochloroalkanes.
- the material to be released is initially microencapsulated in the absence of any pressurizing medium, and the micro-capsules are then placed in an atmosphere of the desired pressurizing medium at a pressure sufficient for the said pressurizing medium to permeate the microcapsule walls in a time ranging from a few minutes to a few days.
- the present invention is also related to an aerosol dispenser containing a suitable propellant and the microcapsules defined above.
- a suitable propellant and the microcapsules defined above.
- microcapsules used in the present invention can be made of any conventionally employed material in the microencapsulation field.
- polymeric materials to produce the microcapsules are such polymers as polyvinyl alcohol, polyethylene, polypropylene, polystyrene, polyacrylamides, polyethers, polyesters, polyamides, polybutadiene, polyisoprene, epoxy resins, polyurethanes, ethylcellulose, carboxymethylcellulose and the like.
- the microcapsules are made from a thermoplastic polymer such as low melting polyethylene; the latter is particularly applicable when the pressurizing gas is a mixture of fluorochloroalkanes and when this mixture of fluorochloroalkanes is introduced into the microcapsules by using the permeability characteristics of the wall.
- a thermoplastic polymer such as low melting polyethylene
- the nature of the walls will generally be chosen for its compatibility with the propellant in which the microcapsules are placed.
- the ratio of the weight of the wall to the total weight of the filled microcapsule ranges between 3l0: l 00.
- microcapsule fabrication Any convenient technique of microcapsule fabrication can be used, particularly microencapsulation by mechanical means such as centrifugal microencapsulation.
- droplets of the material to be encapsulated are formed by the centrifugal force of a turntable which then traverse by means of the velocity which they thus acquire, a thin film of fluid product designed to form the wall of the microcapsule.
- a conventional wall-hardening treatment can be employed which, in the case where the wall is prepared from a thermoplastic material, can simply be a sudden cooling of the microcapsules formed.
- Representative suitable microencapsulation operations can be found in the literature, for instance in U.S. Pat. No. 3,015,128.
- the material encapsulated in the microcapsules can be, for instance, such cosmetic preparations as hair dyes, bleaches, dressing composition or the like, pharmaceutical preparations including antiseptics, topical anesthetics, or such products as stain-removing agents, finely divided solid inorganic absorbents such as talc and the like.
- microencapsulated liquid has the following composition:
- microcapsules thus formed are placed in a atmosphere of a fluorochloralkane at a relative pressure of 1.5 kglcm This pressure is maintained for several days, after which the microcapsules are transferred, the external pressure being kept the same, to a liquid medium compatible with the wall, such as, for example, trichlorofluoromethane, dichlorodifluoromethane, or dichlorotetrafluoromethane.
- a liquid medium compatible with the wall such as, for example, trichlorofluoromethane, dichlorodifluoromethane, or dichlorotetrafluoromethane.
- the liquid medium containing the microcapsules is then placed in a pressurized aerosol can type container at a pressure above 1.5 kg/cm by means of a fluorochloroalkane.
- the liquid present in the pressurized container is dispensed directly onto hair to be dyed by the action of the container valve; the diaphragm associated with the valve having an aperture 1 mm in diameter.
- An oxidant is added to the dye thus placed on the hair.
- an oxidant can be included in the propellant. After minutes, a chestnut brown coloration is obtained on 70 percent white hair.
- An aerosol dispenser provided with a valve through which the contents thereof are discharged therefrom and containing a propellant under pressure and sprayable microcapsules dispersed therein, said microcapsules encapsulating a liquid cosmetic or pharmaceutical material and a fluid under pressure to provide a liquefied encapsulated pressuring medium, said microcapsules having walls compatible with and permeable to said aerosol propellant and having a size ranging from about 50 1000 microns in diameter and being less than the diameter of the valve of said aerosol dispenser in which said propellant and microcapsules are packaged; said fluid encapsulated in said microcapsules under pressure and said propellant in which said microcapsules are dispersed and stored being essentially the same and comprising a liquefied gas of a fluorinated hydrocarbon selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane and mixtures thereof or a saturated aliphatic hydrocarbon selected from the group consisting of propane, isobutane, n-
- An aerosol dispenser provided with a valve through which the contents thereof are discharged therefrom and containing a propellant under pressure and sprayable microcapsules dispersed therein, said microcapsules encapsulating a liquid cosmetic or pharmaceutical material and a fluid under pressure to provide a liquefied encapsulated pressuring medium, said microcapsules having walls compatible with said aerosol propellant and having a size ranging from about 50 1000 microns in diameter and being less than the diameter of the valve of said aerosol dispenser in which said propellant and microcapsules are packaged; said fluid encapsulated in said microcapsules under pressure and said propellant in which said microcapsules are dispersed and stored being essentially the same and comprising a liquefied gas of a fluorinated hydrocarbon selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane and mixtures thereof or a saturated aliphatic hydrocarbon selected from the group consisting of propane, isobutane, n-butane and mixture
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Cosmetics (AREA)
- Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
- Medicinal Preparation (AREA)
Abstract
A sprayable aerosol composition is prepared by encapsulating a material in a microcapsule and introducing into said microcapsule a fluid under a pressure essentially equal to the pressure in the aerosol container from which said composition is dispensed. Also provided is an aerosol dispenser containing under pressure said microcapsules dispersed in an aerosol propellant.
Description
I United States Patent 1151 3,679,102 Charle et al. 1451 July 25, 1972 AEROSOL COMPOSITION AND 3,265,630 8 1966 Jensen ..252/316 METHOD FOR PRODUCING SA 2,959,325 11/1960 Beard ..222/1 3,081,223 3/1963 Gunning et al. 252/305 x 1 Inventors Chris, 7; Gregoire lwonimis, 2,980,941 4/1961 Miller /10493 Pans; C r es i a c n all of 3,196,478 7/1965 Baymiller.... ..401/132 France 3,334,374 8/1967 Watkins ..401/196 3,334,790 8/1967 Baton ..222/107 [73] Ass'gnee' L Pans France 3,441,353 4/1969 Clapp ..401/132 22 Filed: Feb. 4, 1970 3,464,413 9/1969 Goldfarb 131.... ..128/268 3,472,675 10/1969 Gordon et a1 ..117 36.9 [21] APPL 8772 3,516,846 6/1970 Matson ..117/362 Foreign Application Priority um OTHER PQPUCATIONS a 7, n Miles 1. M. et al., J. Soc. Cosmet. Chem 22: 655-666 (Sept. Feb. 4, 1969 Luxembourg ..57.891 17, 1971) Encapsulated Perfumesin Aerosol Producm" """151/17;"161735619275422222#531133 P'immEmmim-shefi-Rose I Y 1 An -Ch ,Db&Csha 206/42, 206/56, 206/84, 264/4, 252/305, 252/316, ar y u m 252/364, 401/132, 401/190, 424/45, 424/47, 57 ABSTRACT 424/62, 424 69, 424/ 51 1 1m. (:1 ..A61j 3/00, A6lk 7/12 A sprayable aerosol composltwn 15 prepared ye a q 5s 1 Field of Search ..424/14, 4547; a material in a microcapsule and introduclns Into said 252/305, 316 364; 401/132, 190; 222/192, 394 microcapsule a fluid under a pressure essentially equal to the pressure in the aerosol container from which said composition 56] References Cited is dispensed, Also provided is an aerosol dispenser containing UNITED STATES PATENTS 11/1970 Monson ..252/
under pressure said microcapsules dispersed in an aerosol propellant.
4 Claims, No Drawings AEROSOL COMPOSITION AND METHOD FOR PRODUCING SAME This invention relates to a method for producing a sprayable aerosol composition containing a self-releasable encapsulated material and to an aerosol dispenser containing said encapsulated material dispersed in a propellant.
More particularly, the present invention relates to the production of an aerosol composition containing an encapsulated material which can be released therefrom without the need of mechanical, chemical or thermal means.
The present invention has been found to be particularly use ful in the cosmetic and pharmaceutical industry and in the packaging of maintenance products, for projecting active ingredients onto the surface where they are to act, and to obtain automatic liberation of these ingredients on the said support.
The present invention is a method for producing a sprayable aerosol composition containing a self-releasable encapsulated material which comprises encapsulating the material to be sprayed in the form of an aerosol in a rupturable microcapsule having a size ranging from about 50 to 1000 microns in diameter and introducing into said microcapsule a fluid under sufficient pressure so that when said microcapsule, dispersed in an aerosol propellant, is sprayed into an atmosphere having a pressure less than the pressure of the fluid in said microcap sule, the microcapsule ruptures, thereby releasing the material contained therein.
Preferably, in the present invention the propellant in which the microcapsules are dispersed and stored and the fluid contained in the microcapsules under pressure are essentially the same. Thus, this fluid and propellant can conveniently be a fluorinated hydrocarbon and particularly a fluorochloroalkane such as trichlorofluoromethane and dichlorofluoromethane or their mixtures. Moreover, the propellant can be a saturated aliphatic hydrocarbon such as propane, isobutane, n-butane or the like. The aerosol dispenser in which the propellant and microcapsules are packaged will have a valve provided with a diaphragm, having a diameter greater than the maximum diameter of the microcapsules.
In one embodiment of the present invention, a fluid having sufficient pressure to rupture the micro-capsule when sprayed into the atmosphere is introduced into the microcapsule in the liquid state in admixture with the material to be released therefrom on rupturing. In this case, microencapsulation is carried out at a sufficiently low temperature and pressure so that the fluid is in the liquid. When the material being encapsulated is itself a liquid, it must be miscible with the liquified pressuring medium, especially when the releasable material is an alcohol solution, and the liquified pressuring medium gas is a mixture of fluorochloroalkanes.
In another embodiment of the present invention, the material to be released is initially microencapsulated in the absence of any pressurizing medium, and the micro-capsules are then placed in an atmosphere of the desired pressurizing medium at a pressure sufficient for the said pressurizing medium to permeate the microcapsule walls in a time ranging from a few minutes to a few days.
The present invention is also related to an aerosol dispenser containing a suitable propellant and the microcapsules defined above. Thus, when these components are sprayed from the pressurized dispenser, it will be evident that when the user depresses the valve of the dispenser, the microcapsules, having dispersed therein the propellant having an internal pressure at least equal to the pressure of the propellant in the dispenser but greater than the atmosphere into which they are sprayed will rupture as soon as they come in contact with the atmosphere. Packaging will thus be achieved in which the microcapsules exist during storage and which do not have to be destroyed by any independent action of the user at the time of dispensing the same onto the desired surface.
The microcapsules used in the present invention can be made of any conventionally employed material in the microencapsulation field. Representative of polymeric materials to produce the microcapsules are such polymers as polyvinyl alcohol, polyethylene, polypropylene, polystyrene, polyacrylamides, polyethers, polyesters, polyamides, polybutadiene, polyisoprene, epoxy resins, polyurethanes, ethylcellulose, carboxymethylcellulose and the like. Preferably, the microcapsules are made from a thermoplastic polymer such as low melting polyethylene; the latter is particularly applicable when the pressurizing gas is a mixture of fluorochloroalkanes and when this mixture of fluorochloroalkanes is introduced into the microcapsules by using the permeability characteristics of the wall. The nature of the walls will generally be chosen for its compatibility with the propellant in which the microcapsules are placed. Generally, the ratio of the weight of the wall to the total weight of the filled microcapsule ranges between 3l0: l 00.
Any convenient technique of microcapsule fabrication can be used, particularly microencapsulation by mechanical means such as centrifugal microencapsulation. In this method droplets of the material to be encapsulated are formed by the centrifugal force of a turntable which then traverse by means of the velocity which they thus acquire, a thin film of fluid product designed to form the wall of the microcapsule. A conventional wall-hardening treatment can be employed which, in the case where the wall is prepared from a thermoplastic material, can simply be a sudden cooling of the microcapsules formed. Representative suitable microencapsulation operations can be found in the literature, for instance in U.S. Pat. No. 3,015,128.
The material encapsulated in the microcapsules can be, for instance, such cosmetic preparations as hair dyes, bleaches, dressing composition or the like, pharmaceutical preparations including antiseptics, topical anesthetics, or such products as stain-removing agents, finely divided solid inorganic absorbents such as talc and the like.
In order to gain a better understanding of the invention, the following example is provided.
EXAMPLE Mechanical centrifuging is used to prepare microcapsules with average dimensions of approximately 400 microns from low melting polyethylene. The microencapsulated liquid has the following composition:
nonylphenol condensed with 4 molecules The microcapsules thus formed are placed in a atmosphere of a fluorochloralkane at a relative pressure of 1.5 kglcm This pressure is maintained for several days, after which the microcapsules are transferred, the external pressure being kept the same, to a liquid medium compatible with the wall, such as, for example, trichlorofluoromethane, dichlorodifluoromethane, or dichlorotetrafluoromethane. The liquid medium containing the microcapsules is then placed in a pressurized aerosol can type container at a pressure above 1.5 kg/cm by means of a fluorochloroalkane. The liquid present in the pressurized container is dispensed directly onto hair to be dyed by the action of the container valve; the diaphragm associated with the valve having an aperture 1 mm in diameter. An oxidant is added to the dye thus placed on the hair. Alternatively, an oxidant can be included in the propellant. After minutes, a chestnut brown coloration is obtained on 70 percent white hair.
What is claimed is:
1. An aerosol dispenser provided with a valve through which the contents thereof are discharged therefrom and containing a propellant under pressure and sprayable microcapsules dispersed therein, said microcapsules encapsulating a liquid cosmetic or pharmaceutical material and a fluid under pressure to provide a liquefied encapsulated pressuring medium, said microcapsules having walls compatible with and permeable to said aerosol propellant and having a size ranging from about 50 1000 microns in diameter and being less than the diameter of the valve of said aerosol dispenser in which said propellant and microcapsules are packaged; said fluid encapsulated in said microcapsules under pressure and said propellant in which said microcapsules are dispersed and stored being essentially the same and comprising a liquefied gas of a fluorinated hydrocarbon selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane and mixtures thereof or a saturated aliphatic hydrocarbon selected from the group consisting of propane, isobutane, n-butane and mixtures thereof, said liquid cosmetic or pharmaceutical material being miscible with said liquefied pressuring medium and the internal pressure of said microcapsules containing said liquid cosmetic or pharmaceutical material and said liquefied pressuring medium being essentially equal to the pressure of said propellant in said dispenser but greater than the atmosphere into which said microcapsules are to be sprayed so that said microcapsules without any independent action of the user upon actuating the valve of the dispenser to discharge said microcapsules into the atmosphere through the valve of the dispenser, rupture as soon as said microcapsules come into contact with the atmosphere thereby releasing said liquid cosmetic or pharmaceutical material therefrom.
2. An aerosol dispenser provided with a valve through which the contents thereof are discharged therefrom and containing a propellant under pressure and sprayable microcapsules dispersed therein, said microcapsules encapsulating a liquid cosmetic or pharmaceutical material and a fluid under pressure to provide a liquefied encapsulated pressuring medium, said microcapsules having walls compatible with said aerosol propellant and having a size ranging from about 50 1000 microns in diameter and being less than the diameter of the valve of said aerosol dispenser in which said propellant and microcapsules are packaged; said fluid encapsulated in said microcapsules under pressure and said propellant in which said microcapsules are dispersed and stored being essentially the same and comprising a liquefied gas of a fluorinated hydrocarbon selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane and mixtures thereof or a saturated aliphatic hydrocarbon selected from the group consisting of propane, isobutane, n-butane and mixtures thereof, said liquid cosmetic or pharmaceutical material being miscible with said liquefied pressuring medium and the internal pressure of said microcapsules containing said liquid cosmetic or pharmaceutical material and said liquefied pressuring medium being essentially equal to the pressure of said propellant in said dispenser but greater than the atmosphere into which said microcapsules are to be sprayed so that said microcapsules without any independent action of the user upon actuating the valve of the dispenser to discharge said microcapsules into the atmosphere through the valve of the dispenser, rupture as soon as said microcapsules come into contact with the atmosphere thereby releasing said liquid cosmetic or pharmaceutical material therefrom.
3. A method for producing and dispensing a sprayable aerosol composition contained under pressure in an aerosol dispenser provided with a valve through which the contents thereof are discharged therefrom into an atmosphere having a pressure less than the pressure in said aerosol dispenser, said composition comprising an aerosol propellant and sprayable microcapsules dispersed therein, said microcapsules encapsulating a liquid cosmetic or pharmaceutical material and a fluid under pressure to provide a liquefied encapsulated pressuring medium, said microcapsules having walls compatible with and permeable to said aerosol propellant and having a size ranging from about 50 1000 microns in diameter and being less than the diameter of the valve of said aerosol dispenser in which said propellant and microcapsules are contained, the steps comprising microencapsulating said liquid cosmetic or pharmaceutical material in said microcapsules; placing said microcapsules in an atmosphere containing said fluid at a pressure sufficient for said fluid to permeate the microcapsule walls so that fluid is contained within said microcapsules as a liquid to provide a liquefied encapsulated pressuring medium; dispersing at said pressure the resulting microcapsules containing said liquid cosmetic or pharmaceutical material and liquefied pressuring medium in an aerosol propellant, liquefied pressuring medium and said aerosol propellant in which said microcapsules are dispersed and stored being essentially the same and comprising a liquefied gas of a fluorinated hydrocarbon selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane and mixtures thereof or a saturated aliphatic hydrocarbon selected from the group consisting of propane, isobutane, n-butane and mixtures thereof, said liquid cosmetic or pharmaceutical material being miscible with said liquefied pressuring medium; and confining under pressure said microcapsules, containing said liquefied cosmetic or pharmaceutical material and liquefied pressuring medium, dispersed in said aerosol propellant in said aerosol dispenser, the internal pressure of said microcapsules containing said liquefied cosmetic or pharmaceutical material and said liquefied pressuring medium being essentially equal to the pressure of said aerosol propellant in said dispenser but greater than the atmosphere into which said microcapsules are to be sprayed so that said microcapsules without any independent action of the user upon actuating the valve of the dispenser rupture as soon as said microcapsules come into contact with the atmosphere thereby releasing said liquid cosmetic or pharmaceutical material therefrom.
4. A method for producing and dispensing a sprayable aerosol composition contained under pressure in an aerosol dispenser provided with a valve through which the contents thereof are discharged therefrom into an atmosphere having a pressure less than the pressure in said aerosol dispenser, said composition comprising an aerosol propellant and sprayable microcapsules dispersed therein, said microcapsules encapsulating a liquid cosmetic or pharmaceutical material and a fluid under pressure to provide a liquefied encapsulated pressuring medium, said microcapsules having walls compatible with said aerosol propellant and having a size ranging from about 50 1000 microns in diameter and being less than the diameter of the valve of said aerosol dispenser in which said propellant and microcapsules are contained, the steps comprising microencapsulating said liquid cosmetic or pharmaceutical material in admixture with said fluid in said microcapsules at a sufiiciently low temperature and at a pressure so that said fluid provides a liquefied pressuring medium encapsulated therein; dispersing the resulting microcapsules, containing said liquid cosmetic or pharmaceutical material and liquefied pressuring medium, in an aerosol propellant, said liquefied pressuring medium and said aerosol propellant in which said microcapsules are dispersed and stored being essentially the same and comprising a liquefied gas of a fluorinated hydrocarbon selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane and mixtures thereof or a saturated aliphatic hydrocarbon selected from the group consisting of propane, isobutane, n-butane and mixtures thereof, said liquid cosmetic or pharmaceutical material being miscible with said liquefied pressuring medium; and confining, under pressure, said microcapsules, containing said liquid cosmetic or pharmaceutical material and liquefied pressuring medium, dispersed in said aerosol propellant in said aerosol dispenser, the internal pressure of said microcapsules containing said liquid cosmetic or pharmaceutical material and said liquefied said microcapsules into the atmosphere through the valve of the dispenser, rupture as soon as said microcapsules come into contact with the atmosphere thereby releasing said liquid cosmetic or pharmaceutical material therefrom.
Claims (3)
- 2. An aerosol dispenser provided with a valve through which the contents thereof are discharged therefrom and containing a propellant under pressure and sprayable microcapsules dispersed therein, said microcapsules encapsulating a liquid cosmetic or pharmaceutical material and a fluid under pressure to provide a liquefied encapsulated pressuring medium, said microcapsules having walls compatible with said aerosol propellant and having a size ranging from about 50 - 1000 microns in diameter and being less than the diameter of the valve of said aerosol dispenser in which said propellant and microcapsules are packaged; said fluid encapsulated in said microcapsules under pressure and said propellant in which said microcapsules are dispersed and stored being essentially the same and comprising a liquefied gas of a fluorinated hydrocarbon selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane and mixtures thereof or a saturated aliphatic hydrocarbon selected from the group consisting of propane, isobutane, n-butane and mixtures thereof, said liquid cosmetic or pharmaceutical material being miscible with said liquefied pressuring medium and the internal pressure of said microcapsules containing said liquid cosmetic or pharmaceutical material and said liquefied pressuring medium being essentially equal to the pressure of said propellant in said dispenser but greater than the atmosphere into which said microcapsules are to be sprayed so that said microcapsules without any independent action of the user upon actuating the valve of the dispenser to discharge said microcapsules into the atmosphere through the valve of the dispenser, rupture as soon as said microcapsules come into contact with the atmosphere thereby releasing said liquid cosmetic or pharmaceutical material therefrom.
- 3. A method for producing and dispensing a sprayable aerosol composition contained under pressure in an aerosol dispenser provided with a valve through which the contents thereof are discharged therefrom into an atmosphere having a pressure less than the pressure in said aerosol dispenser, said composition comprising an aerosol propellant and sprayable microcapsules dispersed therein, said microcapsules encapsulating a liquid cosmetic or pharmaceutical material and a fluid under pressure to provide a liquefied encapsulated pressuring medium, said microcapsules having walls compatible with and permeable to said aerosol propellant and having a size ranging from about 50 - 1000 microns in diameter and being less than the diameter of the valve of said aerosol dispenser in which said propellant and microcapsules are contained, the steps comprising microencapsulating said liquid cosmetic or pharmaceutical material in said microcapsules; placing said microcapsules in an atmosphere containing said fluid at a pressure sufficient for said fluid to permeate the microcapsule walls so that fluid is contained within said microcapsules as a liquid to provide a liquefied encapsulated pressuring medium; dispersing at said pressure the resulting microcapsules containing said liquid cosmetic or pharmaceutical material and liquefied pressuring medium in an aerosol propellant, liquefied pressuring medium and said aerosol propellant in which said microcapsules are dispersed and stored being essentially the same and comprising a liquefied gas of a fluorinated hydrocarbon selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane and mixtures thereof or a saturated aliphatic hydrocarbon selected from the group consisting of propane, isobutane, n-butane and mixtures thereof, said liquid cosmetic or pharmaceutical material being miscible with said liquefied pressuring medium; and confining under pressure said microcapsules, containing said liquefied cosmetic or pharmaceutical material and liquefied pressuring medium, dispersed in said aerosol propellant in said aerosol dispenser, the internal pressure of said microcapsules containing said liquefied cosmetic or pharmaceutical material and said liquefied pressuring medium being essentially equal to the pressure of said aerosol propellant in said dispenser but greater than the atmosphere into which said microcapsules are to be sprayed so that said microcapsules without any independent action of the useR upon actuating the valve of the dispenser rupture as soon as said microcapsules come into contact with the atmosphere thereby releasing said liquid cosmetic or pharmaceutical material therefrom.
- 4. A method for producing and dispensing a sprayable aerosol composition contained under pressure in an aerosol dispenser provided with a valve through which the contents thereof are discharged therefrom into an atmosphere having a pressure less than the pressure in said aerosol dispenser, said composition comprising an aerosol propellant and sprayable microcapsules dispersed therein, said microcapsules encapsulating a liquid cosmetic or pharmaceutical material and a fluid under pressure to provide a liquefied encapsulated pressuring medium, said microcapsules having walls compatible with said aerosol propellant and having a size ranging from about 50 - 1000 microns in diameter and being less than the diameter of the valve of said aerosol dispenser in which said propellant and microcapsules are contained, the steps comprising microencapsulating said liquid cosmetic or pharmaceutical material in admixture with said fluid in said microcapsules at a sufficiently low temperature and at a pressure so that said fluid provides a liquefied pressuring medium encapsulated therein; dispersing the resulting microcapsules, containing said liquid cosmetic or pharmaceutical material and liquefied pressuring medium, in an aerosol propellant, said liquefied pressuring medium and said aerosol propellant in which said microcapsules are dispersed and stored being essentially the same and comprising a liquefied gas of a fluorinated hydrocarbon selected from the group consisting of trichlorofluoromethane, dichlorofluoromethane and mixtures thereof or a saturated aliphatic hydrocarbon selected from the group consisting of propane, isobutane, n-butane and mixtures thereof, said liquid cosmetic or pharmaceutical material being miscible with said liquefied pressuring medium; and confining, under pressure, said microcapsules, containing said liquid cosmetic or pharmaceutical material and liquefied pressuring medium, dispersed in said aerosol propellant in said aerosol dispenser, the internal pressure of said microcapsules containing said liquid cosmetic or pharmaceutical material and said liquefied pressuring medium being essentially equal to the pressure of said aerosol propellant in said dispenser but greater than the atmosphere into which said microcapsules are to be sprayed so that said microcapsules without any independent action of the user upon actuating the valve of the dispenser to discharge said microcapsules into the atmosphere through the valve of the dispenser, rupture as soon as said microcapsules come into contact with the atmosphere thereby releasing said liquid cosmetic or pharmaceutical material therefrom.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
LU57891 | 1969-02-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3679102A true US3679102A (en) | 1972-07-25 |
Family
ID=19725896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US8726A Expired - Lifetime US3679102A (en) | 1969-02-04 | 1970-02-04 | Aerosol composition and method for producing same |
Country Status (7)
Country | Link |
---|---|
US (1) | US3679102A (en) |
BE (1) | BE744920A (en) |
CH (1) | CH520529A (en) |
DE (1) | DE2005075A1 (en) |
FR (1) | FR2033287A1 (en) |
GB (1) | GB1295036A (en) |
LU (1) | LU57891A1 (en) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3839220A (en) * | 1968-10-23 | 1974-10-01 | Mennen Co | Microcapsules for use in pressurized systems |
US3918452A (en) * | 1974-08-01 | 1975-11-11 | Edward Cornfeld | Tampons impregnated with contraceptive compositions |
US4147766A (en) * | 1976-06-09 | 1979-04-03 | Armour Pharmaceutical Company | Macrospherical particles of anti-perspirants |
US4149551A (en) * | 1977-03-28 | 1979-04-17 | The Procter & Gamble Company | Method of conditioning hair using a flexible substrate |
US4183911A (en) * | 1973-09-18 | 1980-01-15 | Colgate-Palmolive Company | Antiperspirant compositions |
US4220447A (en) * | 1971-07-29 | 1980-09-02 | L'oreal | Solid, frozen stabilized hair dye |
US4247537A (en) * | 1977-11-09 | 1981-01-27 | Lunn Peter F R | Bleaching systems comprising percarbonate, persulfate, and pyrogenic silica |
US4439343A (en) * | 1979-07-23 | 1984-03-27 | United Industries Corporation | Aerosol preparation |
US4439342A (en) * | 1979-07-23 | 1984-03-27 | United Industries Corporation | Aerosol preparation |
US4608211A (en) * | 1983-03-22 | 1986-08-26 | L'oreal | Process for preparing lipid vesicles by vaporisation of solvents |
US4635651A (en) * | 1980-08-29 | 1987-01-13 | Jacobs Allen W | Process for the inclusion of a solid particulate component into aerosol formulations of inhalable nicotine |
US4941615A (en) * | 1988-10-03 | 1990-07-17 | Bolduc Lee R | Aerosol dispenser |
US4979638A (en) * | 1987-05-14 | 1990-12-25 | Bolduc Lee R | Aerosol dispenser with sealed actuator |
US5012978A (en) * | 1988-10-03 | 1991-05-07 | Bolduc Lee R | Aerosol dispenser and method |
US5018643A (en) * | 1987-05-14 | 1991-05-28 | Bolduc Lee R | Aerosol dispenser with sealed actuator and aerosol dispensing method |
US5052585A (en) * | 1988-10-24 | 1991-10-01 | Bolduc Lee R | Dispenser |
US5061106A (en) * | 1988-03-08 | 1991-10-29 | Colgate-Palmolive Company | Toothbrush with slow release of disinfectant and antibacterial agents and method of manufacturing the same |
US5064121A (en) * | 1988-10-03 | 1991-11-12 | Bolduc Lee R | Dispenser |
US5858343A (en) * | 1997-01-31 | 1999-01-12 | S. C. Johnson & Son, Inc. | Post-foaming shaving gel including poly(ethylene oxide) and polyvinylpyrrolidone in a preferred range of weight ratios |
US6102036A (en) * | 1994-04-12 | 2000-08-15 | Smoke-Stop | Breath activated inhaler |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2335818A1 (en) * | 2009-07-09 | 2011-06-22 | Altachem Holdings NV | Leach-proof microcapsules, the method for preparation and use of leach-proof microcapsules |
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US3541581A (en) * | 1967-11-13 | 1970-11-17 | Johnson & Son Inc S C | Package containing a post-foaming gel |
-
1969
- 1969-02-04 LU LU57891D patent/LU57891A1/xx unknown
-
1970
- 1970-01-26 BE BE744920D patent/BE744920A/xx unknown
- 1970-01-30 FR FR7003329A patent/FR2033287A1/fr not_active Withdrawn
- 1970-02-02 CH CH152770A patent/CH520529A/en not_active IP Right Cessation
- 1970-02-04 DE DE19702005075 patent/DE2005075A1/en active Pending
- 1970-02-04 US US8726A patent/US3679102A/en not_active Expired - Lifetime
- 1970-02-04 GB GB1295036D patent/GB1295036A/en not_active Expired
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US2980941A (en) * | 1958-12-08 | 1961-04-25 | Ncr Co | Cleaning sheet |
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US3081223A (en) * | 1961-07-19 | 1963-03-12 | Union Carbide Corp | Self-propelled powder aerosol system |
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US3472675A (en) * | 1966-01-27 | 1969-10-14 | Ncr Co | Pressure-sensitive capsule-containing foraminated sheet material |
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US3441353A (en) * | 1967-01-31 | 1969-04-29 | Claff Clarence L | Perfume dispenser |
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US3516846A (en) * | 1969-11-18 | 1970-06-23 | Minnesota Mining & Mfg | Microcapsule-containing paper |
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Title |
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Miles J. M. et al., J. Soc. Cosmet. Chem. 22: 655 666 (Sept. 17, 1971) Encapsulated Perfumes in Aerosol Products. * |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3839220A (en) * | 1968-10-23 | 1974-10-01 | Mennen Co | Microcapsules for use in pressurized systems |
US4220447A (en) * | 1971-07-29 | 1980-09-02 | L'oreal | Solid, frozen stabilized hair dye |
US4183911A (en) * | 1973-09-18 | 1980-01-15 | Colgate-Palmolive Company | Antiperspirant compositions |
US3918452A (en) * | 1974-08-01 | 1975-11-11 | Edward Cornfeld | Tampons impregnated with contraceptive compositions |
US4147766A (en) * | 1976-06-09 | 1979-04-03 | Armour Pharmaceutical Company | Macrospherical particles of anti-perspirants |
US4149551A (en) * | 1977-03-28 | 1979-04-17 | The Procter & Gamble Company | Method of conditioning hair using a flexible substrate |
US4247537A (en) * | 1977-11-09 | 1981-01-27 | Lunn Peter F R | Bleaching systems comprising percarbonate, persulfate, and pyrogenic silica |
US4439343A (en) * | 1979-07-23 | 1984-03-27 | United Industries Corporation | Aerosol preparation |
US4439342A (en) * | 1979-07-23 | 1984-03-27 | United Industries Corporation | Aerosol preparation |
US4635651A (en) * | 1980-08-29 | 1987-01-13 | Jacobs Allen W | Process for the inclusion of a solid particulate component into aerosol formulations of inhalable nicotine |
US4608211A (en) * | 1983-03-22 | 1986-08-26 | L'oreal | Process for preparing lipid vesicles by vaporisation of solvents |
US4979638A (en) * | 1987-05-14 | 1990-12-25 | Bolduc Lee R | Aerosol dispenser with sealed actuator |
US5018643A (en) * | 1987-05-14 | 1991-05-28 | Bolduc Lee R | Aerosol dispenser with sealed actuator and aerosol dispensing method |
US5061106A (en) * | 1988-03-08 | 1991-10-29 | Colgate-Palmolive Company | Toothbrush with slow release of disinfectant and antibacterial agents and method of manufacturing the same |
US4941615A (en) * | 1988-10-03 | 1990-07-17 | Bolduc Lee R | Aerosol dispenser |
US5012978A (en) * | 1988-10-03 | 1991-05-07 | Bolduc Lee R | Aerosol dispenser and method |
US5064121A (en) * | 1988-10-03 | 1991-11-12 | Bolduc Lee R | Dispenser |
US5052585A (en) * | 1988-10-24 | 1991-10-01 | Bolduc Lee R | Dispenser |
US6102036A (en) * | 1994-04-12 | 2000-08-15 | Smoke-Stop | Breath activated inhaler |
US5858343A (en) * | 1997-01-31 | 1999-01-12 | S. C. Johnson & Son, Inc. | Post-foaming shaving gel including poly(ethylene oxide) and polyvinylpyrrolidone in a preferred range of weight ratios |
US6352689B1 (en) | 1997-01-31 | 2002-03-05 | S. C. Johnson & Son, Inc. | Post-foaming shaving gel including poly (ethylene oxide) and polyvinylpyrrolidone in a preferred range of weight ratios |
Also Published As
Publication number | Publication date |
---|---|
FR2033287A1 (en) | 1970-12-04 |
GB1295036A (en) | 1972-11-01 |
DE2005075A1 (en) | 1970-08-06 |
CH520529A (en) | 1972-03-31 |
BE744920A (en) | 1970-07-27 |
LU57891A1 (en) | 1970-08-04 |
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