CA1205349A - Nonflammable aerosol propellant microemulsion system - Google Patents

Nonflammable aerosol propellant microemulsion system

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Publication number
CA1205349A
CA1205349A CA000457246A CA457246A CA1205349A CA 1205349 A CA1205349 A CA 1205349A CA 000457246 A CA000457246 A CA 000457246A CA 457246 A CA457246 A CA 457246A CA 1205349 A CA1205349 A CA 1205349A
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Prior art keywords
composition
water
propellant
aerosol
oil
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CA000457246A
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French (fr)
Inventor
Howard R. Stopper
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Bristol Myers Squibb Co
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Bristol Myers Squibb Co
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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/30Materials not provided for elsewhere for aerosols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017Multi-phase liquid compositions
    • C11D17/0021Aqueous microemulsions
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/903Aerosol compositions

Abstract

ABSTRACT OF THE DISCLOSURE

The amount of gaseous flammable propellants such as dimethylether, difluoroethane, propane, butane, and the like can be increased to as high as from 30 to 50% by weight of a propellant composition by dissolving the normally gaseous propellant in the dispersed oil phase of an oil-in-water microemulsion. The aerosol pro-pellant compositions can be simply prepared by metering the ingredients other than the gaseous propellants into an aerosol dispenser, then adding the gaseous pro-pellant, under suitable pressure, into the aerosol dis-penser whereby simply shaking of the dispenser will result in the spontaneous formation of an oil-in-water microemulsion which is clear and stable and which can contain as much as about 50% by weight of the gaseous propellant without causing flaming when the composition is sprayed directly into a candle flame.

Description

3~5~

ACKGRO~ND ~F THE I NV~NT ION

I. FIELD OF 'rHE INVE~I~TION
..
This invention relates to a propellant composition for aerosol dispenser~ which is in the form of an oil-in-water microemulsion. More particularly, this invention relates to a composition and method for rendering highly flammable gaseous aerosol propellants non ~lamma~le by dissolving the gaseous propellants in a water-immiscible solvent which is the dispersed phase of an oil-in-water microemulsion system~

It is known from U.S. Patent 3,207,386 to Presant, et al to suppress the flammability of gaseous propel-lants for aerosol dispensers ~y dissolving the propel-lant in a continuous liquid aqueous phase. However, according to Presant, the maximum concentration of the flammable propellant in the aqueous phase is determined by the limit of its solubility~

On the other hand, the microemulsion techn310gy has also been highly developed, although the primary area of application for both oil-in-water and water-in-oil microemulsions is in the petroleum industry for oil recovery processes. Microemulsions have the advantages of being thermodynamically stable and transparent or clear systems and, therefore, would readily lend them-~selves to commercial application for consumer and indus-trial products. Representative of the patent art relat-ing to the use of microemulsions for oil and petroleum recovery include U.S. Patent Nos. 2,356,205, 3,254,714, 3~301,325, 3,307,628, 3,536,136, 3,540,532, 3,719,606, 3,954,627 and 4,252,657. Water-in-oil microemulsion systems having utility as lubricants for diesel and gasoline engine service and for applying trace elements 34~3 to mineral-de~icient crops are described in U.S. Patent 3,346,494. The use of microelnulsions for separating organic compounds in the liquid state is des- cribed in U.S. Patent 3,641,181. Oil-in-water micro- emulsions for lacquers and paints are described in U.S. Patent ~,122,051. A motor ~uel in the for~n of a microemulsion is taught in U.S. Patent 4,046,519.

U.S. Patents 3,975,294 ana 4,052,331 both describe particular surface-active compositions which can be used as an emulsifier with diorganvpolysiloxanes to form transparent microemulsions or transparent gels or to intro~uce silane cross-lin~iny agents into cataly~ed aqueous polysiloxane emulsions to cross-link the emulsion.

Rosano in U.S. Patent 4,146,499 describes a method for the preparation of oil-in~water microemulsions which are described as useful in a variety of applications including as a reaction venicle for chemical reactions, as a drug deliv~ry system, as an edible food carrier, as a liquid vehicle for water-insoluble dyes and pigments, in cosmetic formulations, and generally for forming stable compositions of hydrGphobic substances.

While it is clear that Rosano discloses oil-in-water microemulsions wi~h various insredients dissolved in the oil phase, this patent does not disclose or suggest dissolving flamnlable propellants in the oil phase to reduce tneir flammability.

SU~MARY OF ~I'HE INVENTION

Accordingly, lt is an object of the present invention to increase the amount of useful flammable gaseous propellant that can be safely stored in an aerosol dispenser without limiting the amount of the flammable gaseous propel~ant by the limit of its solubility in water.

It is a particular object of the invention to proYide a propellant composition for aerosol dispensers that can ~afely contain up to about 404 to 50% or more by weight of the composition of flammable gaseous pr~pellants without creating a flammability hazard.

These anc other objects of the invention, which will become more apparent from the following detailed description, have been accomplished by a propellant composition for aerosol dispensers which is capable of forming spontaneously an oil-in-water microemulsion upon being introaueed under pressure into an aerosol dis-penser~ The composition includes a water-i~nisci.ble li~uid that is a solvent for the propellant, water, a mixed surfactant system containing at least one primary surfactant and at least one secondary surfactant, wherein the mixed surfactant systems has a hydro-philic-lipophilic balance suficient to cause the water-immiscible liquid to spontaneously disperse as `~
micro-droplets in the -~ater, and at least one normally gaseous flammable aerosol pro~ellant dissolved in the water-immiscible liquid. When the composition is intro-~uced under pressure into an aerosol dispenser, an oil-in-water microemulsion is spontaneously formed, the water-immiscible liguid having the propellantts) dis-solved therein to form the ~ispersed phase of micro-droplets, which micro-droplets are separated from the continuous water phase by the ~ixed surfactant system.
In these compositions, the amount of the propellant can be as high as 40~ to.50~ or more by weight based on the we~ght of the composition. ~or instance, the propellant ~r53~

composition used to form the oil-in-water microemulsion system may preferably contain from about 15 ~o 25% by weight of water, 23 to 35% by weight of the water-immiscible liquid, 3 to 20~ by weight of the mixed surfactant system, and about 30 to about 55% by weight of the flammable gaseous propellant or propellants. The composi-tions of this invention may also be prepared in a pressurizable container, and then transferred to aerosol dispensers.
According to another aspect of the present invention, a method is provided for preparing a non-flammable aerosol pro-pellant composition from normally flammable gaseous aerosol pro-pellant by filling the aerosol dispenser with a spontaneous formable oil-in-water microemulsion system in which the dispersed oil phase i5 a water-immiscible liquid that is a solvent for the propellant or propellants, an~ introducing the gaseous propellant while under pressure into the aerosol dispenser, whereby an oil-in-water microemulsion in which the at least one propellant is present in the dispersed oil phase is spontaneously formed by shaking the contents of the aerosol dispenser.
In certain other aspects the present invention provides a method of preparing a propellant composition suitable for deliver-ing an aerosol from an aerosol dispenser, said aerosol being characterized by its suppressed flammability, the method comprising the steps of filling a con~ainer with a mixture comprising by weight of the total weight of the composition ~rom about 23 to about 35%
of a water-immiscible liquid which is a sol~ent for the propellant, fro~ about 15 to about 25~ water, and ~rom about 3 to about 20% of a mixed surfactant system of at least one primary surfactant and at least one secondary surfactant, and pressurizing the container with at least about 30% by weight of the total weight of the composi-tion of at least one normally gaseous flammable propellant, whereby an oil-in-water microemulsion can be formed by shaking said container.

53~9 - 4a -In a preferred embodiment of such a method the mixed surfactant system comprises a first nonionic surfactant having an HLB of less than about 10.4 and a second nonionic surfactant having an HLB above about 11.0, said first and second surfactants each being selected from the group consisting of isooctyl and isononyl phenol ethoxylates, and alkyl alcohol ethoxylates having from 8 to 24 carbons in the alkyl group, said mixed surfactant system having an HLB between about 11.5 to about 13.0 DETAILED DESCRIPTION OF THE INVEN~ION
AND PREFERRED EM130DI~IENTS
As described in the aforementioned U.S. Patent 4,146,499 to Rosano, a microemulsion is a dispersion of two immiscible liquids (one liquid phase being "dispersed"
and the.other being "continuous") in which the individual droplets of the dispersed phase have an average radius less than about 1/4 of the wavelength of light. Typically, in a microemulsion the dispersed phase droplets are less than about 1,400 A radius, and preferably in the order of 100 A to 500 A. Because the individual droplets or "micro-droplets" of the dispersed ~21~S;~

phase are of a size smaller than the wavelength of light, they appear transparent and, accordingly, micro-emulsions are characterized by being clear or tran-sparent. Still further, the microemulsions o~ the present inVentiQn are further characterized by being ~ubstantially in~initely thermodynamically stable, that is, once formed, the dispersed phase and continuous phase will not separate.

The principles of the formation of microemulsions with regard to the requirement~ of the primary and secondary surfactants of the mixed surfactant system~
such as the solubility relationships with respect to the oil and water phases and with respect to each other are suDstantially as described in the previously mentioned patents including the Rosano Patent 4,146,499. However, contrary to the teachings Dy Rosano for forming his oil-in-water microemulsion systems which requires a three-step process in which the primary surfactant is first dissolved in the water-immiscible liquid, and then the solution of the primary surfactant and the water-immiscib~e liq~id is dispersed into ~he aqueous phase to form a lactescent (milky) emulsion, and finally the secondary surfactant is dispersed into the aqueous pha~e to form a lactescent ~milky) emulsion, and finally the secondary surfactant is added to the lactescent emulsion to form the clear microemulsion, the present inventor has found that the stable and clear oil-in-water micro-emulsion will-form spontaneously if all of the ingre-dients, namely the water-immiscible liquid, water, and mixed surfactant system, are added together in the proper proportions. Accordingly, it is a particular advantage of the present invention that the ingredients of the microemulsion need only be metered into the aerosol contain~r followed by pressurization with the se~ected gaseous propellant whereby mere snaking of the 53~

container results in spontaneous formation of the micro-emulsion. ~ccordingly, the requirements for large batching an~ mixing tanks and high shear mixing and homogenizers or other agitation systems normally needed to form an emulsion can be eliminated in the preparation of the pressurized aerosol emulsions according to the present invention.

An additional advantage derived from the present invention is the fact that the compositions are non-flammable in spite of the fact that they may contain as much as 40 to 50% or more of flammable propellants.
In comparison, in most conventional aerosol dispensed products, the amount of flammable propellant must be limited to less than about 15 to 20% to be non-flammable. Even in the systems disclosed in the aforementioned patent 3,207,386 to Presant, et al, the maximum amount of the dimethylether propellant is abGut 25~. -By having larger amounts of the propellant systempresent in the aerosol dispenser, it becomes possible to more readily guarantee that the entire contents of the dispenser can ~e etfectively utilized and, if desired,~
at higher pressures.

The oil-in-water microemulsion of his invention can be used as such as a cleaning composition by taking advantage of the detergent properties of the ~urfactant system as well as the solvating action o~ the water and water-immiscible liquid for most aqueous b~sed and organic based soils and stains, respectively. Moreover~
the microemulsions have broad yeneral utility in sub-stantially al~ applications for which emulsion ~ystems have previously been used including the various utilities disclosed in the Rosano patent and in the other patent refer~nces mentioned aboveO

34~

Tnus, by proper selection of the water-im;niscible liyuid and the aqueous pnase of the microemulsions a Droad variety of oil soluble and water soluble "active"
ingredients can be dispensed ~ith the aer~sol compo-sitions of this invention.

The aerosol microemulsion systems of this invention dre non-flamrnable ~ven tho~gh they may contain up to 50%
or more o~ flammable gaseous propellants. It is be-lieved that tne non-flammability of these compositions result6 from the fact that the flammable propellants are oil solubie and are present in the microemulsion as part of the dispersed oil phase micro-droplets of the elnulsion which are surrounded by a surfactant/water film lthe external phase). Thus~ the flammable propellant is essentially encapsulated by the water. Therefore, when tne aerosol composition is sprayed into a candle fla.~e, it behaves as only water and ~oes not ignite. Con-versely, emulsions which are milky or opaque in which the particle sizes are in tne range of from about 1 to 10 microns (10,000 to 103,000 A) do not exhibit this non-flammability pnenolnenon in an aerosol container.

The flamin3~ility of these emulsions are even '~
fur~her red~ced by USiJlg a non-flammable water-immiscible liguid such as methylene chloride wnich is also a good solvent for the gaseous aerosol pro-pellants. Moveover, the flammability of these micro-emulsions may be further reduced ~y lastly adding to the formed microemulsion a compressed gas such as carbon dioxide, nitrous oxide, nitroyen, or nonflam.~abl-fluorocarbons, for example, dichlorotetrafluoroethane, aichlorodifluoromethane, and trifluoromethane,'''up to the ~ ~'~
saturation limit of the composition. Incorporation of S;~49 such compressed gases intD the microemulsion to further reduce flammability do not suDstantially change the stability of the microemulsion.

A typical composition according to the pres~nt invention includes the following ingredients in the following amounts:

In~redient Part~ by Wei~ht Water 22.0 Methylene Chloride 30.0 Sipon WD - Alcolac Inc. 0.3 Sodium Lauryl Sulfate Igepal C0-430 - G.A.F. Corp. 3.5 Isononyl phenol ethoxylate (4 moles ethylene oxide) HLB 8.8 Neodol 25-9 - Shell Chemical Co~ 3.5 Primary alcohol ethoxylate moles ethylene oxide) HLB 13.3 Difluoroethane ls.?
Dimethy~ether 25.0 `~

Total 100 c, O

The mixed surfactant system in this composition (sodium lauryl sulfate, isononyl phenol ethoxylate and primary alcohol ethoxylate~ has an hydrophilic-lipophilic balance (HLB) of 12.2. However, substantially any other mixed surfactant system utilizing any type of anionic, nonionic or cationic emulsifiers can be used. The only requirement is that there be two or more surfactants, one of which has a low HLB, for example from about 1.0 to~10.4, and the o~her a high HL~, for example from ~L2~i3~
9 _ about 11.0 to 42Ø The average HLB shPuld be such that the mixed sur~actant system has ~uitable solu~ility in the oil and water phases based on the respectI~e compositions. Generally, however, the avexage ~LB of the m~xed surfactant system to form an oil-in-water microemulsion should be from about 10.6 to about 14.5, preferably from about 11.5 to about 13Ø For example, Triton X-100 (trade mark), a product of Rohm and Haas, which is an isooctyl phenyl ethoxylate having 7 moles ethylene oxide with an HLB of 13.5 or Triton N-101 (trade mark) which is an isononyl phenyl ethoxylate with 7 moles ethylene oxide having an HLB of 13.4 can be used in place o~ some or all of the Neodol 25-9 without adversely effecting the properties of the emulsion.
Similarly~ in place of the Igepa~ C0-430 other surfacants having HLB values of from a~out 8 to 9 can be used as a partial or total replacement to maintain the hydrophilic-lipophilic balance of about 12.2 for the mixed surfactant system.
Generally, many different specific mixed surfactant systems capable of providing oil-in-water microemulsions are disclosed in the above mentioned pa*ent art as are the general requirements for HLB values and the methods for determining the HLB values for individual surfactants, as well as for mixed sur-factant systems~ For example, a good discussion of the theory of forming microemulsions and the HLB requirements can be found in the Robins, et al U.S. Patent 3,641,181.
As representative of the nonionic surfactants, mention can be made of polyethoxylates derived from primary and secondary aliphatic alcohols having from 8 to 24 carbon atoms in the alcohol alkyl chain. These preferred ethoxylates frequently contain from 3 to about 14 moles of ethylene oxide per mole of hydrophobic * trade mark.

S3~

moiety. However, there may be as many as 100 moles of ethylene oxide per mole of the hydrophobic moiety. In addition, part or all of the ethylene oxide may be replaced Dy propyler e oxide.

9ther suitable nonionic detergents include the polyoxyalkylene alkyl phenols wherein the hydrophobic group contains a phenolic nucleus having a substituent alkyl group of at least 4 but preferably 8 to 12 carbon atoms and the hydrophilic portion is comprised of at least 3 but preferably 6 to 100 moles of ethylene oxide or propylene oxide per mole of alkyl phenol. Exemplary of this type are the Igepals such as Igepal C0-430, Igepal C0-630 ~ethoxylated nonyl phenol with an average ethylene oxide content of ~.5 moles per mole of nonyl phenol), Igepal C0-880 (ethoxylated nonyl phenol with an average ethylene oxide content of 30 moles per mole of nonyl pnenol), etc.

Still other suitable nonionic surfactants include the polyalkylene esters of the higher organic acids usually having 8 or more carbon atoms in the acid hydropho~e, and 10 or more moles of ethylene oxide as a hydrophilic group; polyalkylene alkyl amines whose hydrophobic group is from a primary, secondary or tertiary amine and whose ethylene oxide content is suf f iciently high to impart both water solubility and nonionic characteristicsJ usually derived from fatty acids with 8 or more carbons; polyalkylene alkyl amides having a hydrophobic gxoup derived from an amide of a fatty acid or ester; fatty acid esters of glycols, polyalkylene oxide block copolymers and the like.
Typical examples of these other classes of nonionic surfactants include thosP commercially available under the designation "Tergitol" ~rom Union Carbide, "Myrj"
from Atlas Chemical Industries, "Ethofat~ from Armac Co., "Priminox" from Rohm and Haas Co., ~Ethomid" from Armac Co., ~Tween" from Atlas Chemical Division of ICI
America, "Pluronic~ from BASF Wyandotte Co., and many others which are well known in the art.

As representative of the anionic surfactants, mention can be made o~, for example, alkyl aryl sulfonates of 6 ts 20 carbon atoms in the alkyl group;
C10-C22 fatty acid soaps; Cl~-C22 f~tty sul-fates; C10-C22 alkyl sulfonates, including the alkali metal salts of he higher alkyl and linear paraffin sulfonic aci~s and salts thereof; alkali metal dialkyl sulfosuccinates~ and the like.

The alkali metal C~ C22 alkyl sulfonates are particularly preferred.

As representative of the cationic surfactants mention can be made of the quaternary ammonium sur-factants and the alkyl amido betaines.

The amount of the mixed surfactant system is not particularly critical so long as it is sufficient to stably maintain the microemulsion. Generally, the amount of the mixed surfactant system can range from aDout 3 to about 204 by weight, preferably from about 5 to 9~ by weight based on the total composition. Also, the propQrtions of the nonionic and snionic or other surfactants in the mixed surfactant system are not par-ticularly critical so long as the average hydrophobic-lipophobic balance of the mixed s~rfactant system is within the above defined range.
. ... ~ . .. , . . _ .. .., _ -- , _ ... _ ~eferring again to the typical composition according to the present invention as given above, it wi~l be generally appreciated that in addition to the S39~9 mixed surfactant system, there is also present a polar liquid, namely water, and a water-immiscible liquid, namely methylene chl~ride, as well as the gaseous ~ropellants~ However, the present invention is not limited to water as the polar solvent or methylene chloride as the water-immiscible liquid, In addition other gaseous flammable propellants can be used in place of all or part of the difluoroethane and dimethyl ether propellant named above.

~ egarding the water phase, any other water soluble polar solYents or salt additives can be used and the selection of ~he particular polar solvent or polar phase additives can be readily selected depending on the intended end use of the propellant composition.
Naturally, any other water soluble polar solvent should also be non-flammable. In terms of cost, safety to the environmenc, and non flamma~ility, water is the pre-ferred polar solvent to form the continuous external phase o~ the microemulsion systems of the present in-vention.

The amount of the water or other water soluble solvent can range from about 15 to about 25% by weight, preferably from about 18 to 23~ by weight, based on the total compositi~n.

Similarly, ~ubstantially any water-immiscible ~olvent can be used in place of all or part of the me~hylene chlorideO Thus, aliphatic or aromatic hydrocarbons, chlor.inated hydrocarbons or mixtures thereof can be used to form the dispersed oil phase.
Examples of other non-aqueous liquids, which can be used as the oil phase, include, for example, hydr~carbons ~ucb as hexane, benzene, toluene, xylene, mineral sp~rits, petroleum ethers, and other similar hydro-carbons. Other water-immisci~le liquids include the oxygenated hydrocar~ons, such as the higher molecular weignt acids, esters, ke.ones or alcohols. Other chlorinated nydrocar~ons include, for example, carbon tetrachloride, chloro~orm, ethylene dichloride, dichloro~ifluorethane, and the like. ~aturally, the water-immiscihle liq~id muat be one in which the normall gaseous flammable aerosol propellants are soluble to the highe~t possi~le de~ree. ~5ethylene chloride is es-pecially prererred ij~ view of its non-flal~mability, low cost, and ~igh dissolving power for the gaseous pro-pellants.

The arnount of the water-immiscible liquid may range from about 23 to a~out 35~ by weight, preferably from about 25 to 33% by weight, based on the total com-position.

The final essential component of the compositions of tnis invention are the normally flammaole gaseous propellants. Substantially any of the known propellants for aerosol containers can be used in the present in-vention, and include the gaseous hydrocarbons such as n-Dutane, iso-butane and propane, and the halogenated hydrocarbons such as ~ifluoroethalle, l,l,l-chlorodifluoroetharle, and the like.

As previously pointed out, one of the advantages of the compositions of the present invention is that the gaseous propellant can be present in the compositions in amounts much greater than otnerwise possible without becomin~ flammable. Thus, amounts of the gaseous pro-pellants of from about 30 to about 55% by weight of the composltion, preferably from a~out 35 to 45% by weight of the composition can be achieved.

534~

P.nother advantageous feature o$ the compositions of this invention is that the microemulsions can readily be formed simply by metering the ingredients, other than the yaseous propellants, into the aerosol container, under suitable pressure, the gaseous propellant or pro~
pellants and sealing the container. Mere shaking of the container spontaneously forms the microemulsion.
Accordingly, it is pvssible to eliminate the large Datching and mixing tanks, high shear mixers and homo-genizers, heating units and other components nDrmally needed to form emulsions before adding them to an aerosol container.

These hydrocarbon propellants and the aerosol com-positions based thereon can be used in a wide variety of end uses dependin~ on the specific selection of solvents and chemical additives added ko the system. Many such po~ential u~es for delivery of a broad variety of hydro-phobic substances which can also be dissolved in the dispersed oil phase micro-droplets are mentioned in the Rosano Patent 4,146,499. Hence9 by using water soluble chemical additives, a broad array of aerosol com-positions can be formulated. As representative of the type of ~active~ ingredients which can be included in the aerosol propellant compositions of this invention in addition to those cases where the surfactants and/or solvents provide the ~activea role such as in various cleaning compositions, laundry pre-spotter compositions, and the like, mention can be made of active ingredients ~or such applications as, for example, antistatic sprays, aerosol air ~resheners, paint and coating sprays, deicing and defosging compositions~ and a variety of others, which will become apparent to the skilled practitioner.

,~

~IL~1S39~9 Additional representative examples of compositions within the scope of the invention are shown in the followiny examples which are provided merely by way of illu~tration an~ are not intended to be compr~hensive of the scope ~f the invention.

_ _ In~redient eight %
A B C D EF
Water 18.4 18.918.717.9 22.0 21.6 ~ethylene Chloride 25.125.825.6 24.4 30.0 29.3 Sipon WD 0.25 0.430.34 0.3 0.3 0.34 Igepal C0-~30 2.9 3.0 3.0 2.9 3.5 3.5 Neodol 25-9 2.9 3.0 3.5 rritOn N-101 3.0 2.9 3.5 ~ifluoroethane 13.4 13.713.612.9 15.5 ~imethylether 36.9 35.235.838.7 23.3 Propane 16.0 Butane 25.0 Carbon dioxide ~3.0 . . .
HLB 12.2 13.012.712.5 12.2 12.4 Each of the above ~ormulatlons A-F provide clear, stable oil-in-water microemulsions. These compositions are prepared 3~y metering the suractants, water and methylene chloride into an aerosol dispenser and separately filling the dispenser with the gaseous pro-pellants under suitable pressure, for example, about 50 to 60 pounds per square inch. The mere shaking of the container results in spontaneous formation of the micro-jj34~

emulsi~n, which is quite stable. Compressed 9ases, suchas carbon dioxide shown in formulation F, may then be added if further suppression of the flammability of the composition is desired.

Claims (24)

II. CLAIMS
1. A propellant composition for aerosol dis-pensers that is capable of spontaneously forming an oil-in-water microemulsion upon being introduced under pressure into an aerosol dispenser, said composition comprising a water-immiscible liquid which is a solvent for said propellant, water, a mixed surfactant system of at least one primary surfactant and at least one secondary surfactant wherein said mixed surfactant system has a hydrophilic-lipophilic balance sufficient to cause said water-immiscible liquid to spontaneously disperse as micro-droplets in said water, and at least one normally gaseous flammable aerosol propellant dis-solved in the water-immiscible liquid, whereby, when said composition is introduced under pressure into an aerosol dispenser, an oil-in-water microemulsion is spontaneously formed, the water-immiscible liquid having the at least one propellant dissolved therein to form a dispersed phase of micro-droplets, which micro- droplets are separated from the continuous water phase by the mixed surfactant system.
2. The composition of claim 1 wherein the total amount of propellant is in the range of from about 30%
to about 55% by weight based on the weight of the com-position.
3. The composition of claim 1 which comprises
4. The composition of claim 3 wherein the water-immiscible liquid is methylene chloride.
5. The composition of claim 3 wherein the mixed surfactant system comprises a first nonionic surfactant emulsifier having a HLB in the range of from about 1.0 to about 10.4 and a second nonionic surfactant emul-sifier having an HLB in the range of from about 11.0 to about 42.0, the HLB of the mixed surfactant system being between 10.6 to 14.5.
6. The composition of claim 5 wherein the mixed surfactant system further comprises an alkali metal salt of an alkyl sulfate anionic surfactant.
7. The composition of claim 5 wherein the HLB of the mixed surfactant system is from about 11.5 to about 13Ø
8. The composition of claim 1 further comprising a compressed gas to further suppress flammability of the composition.
9. The composition of claim 8 wherein the com-pressed gas is selected from the group consisting of carbon dioxide, nitrous oxide, nitrogen, and nonflam-mable fluorocarbons.
10. The composition of claim 8 wherein the com-pressed gas is carbon dioxide.
11. The composition of claim 3 wherein the normally gaseous flammable propellant is selected from the group consisting of propane, butane, isobutane, di-methylether, and difluoroethane, or mixtures thereof.
12. The composition of claim 1 which comprises
13. The composition of Claim 12 further com-prising a compressed gas up to the saturation limit of the composition therefore, the gas selected from the group consisting of carbon dioxide, nitrous oxide, nitrogen, and nonflammable fluorocarbons.
14. The composition of Claim 13 wherein the gas is carbon dioxide.
15. A non flammable aerosol propellant com-position comprising an oil-in-water microemulsion system comprising a continuous aqueous phase, a dispersed oil phase in the form of micro-droplets, said micro-droplets comprising a water-immiscible solvent having dissolved therein at least an equal amount, by weight, of a mix-ture of normally gaseous flammable aerosol propellants, and a mixed surfactant system stably separating the micro-droplets from the aqueous phase.
16. A method for preparing a non-flammable aerosol propellant composition in an aerosol dispenser from at least one normally flammable gaseous aerosol propellant which comprises filling the aerosol dispenser with a spontaneously formable oil-in-water microemulsion system in which the dispersed oil phase is a water-immiscible liquid that is a solvent for the at least one propellant, and introducing the gaseous propellant while, under pressure, into the aerosol dis-penser, whereby an oil-in-water microemulsion in which the at least one propellant is present in the dispersed oil phase is spontaneously formed by shaking the contents of the aerosol dispenser.
17. The method of claim 16 further comprising injecting a compressed gas into said composition, the gas being selected from the group consisting of carbon dioxide, nitrogen, nitrous oxide and nonflammable fluorocarbons.
18. A method for preparing a propellant composition suitable for delivering an aerosol from an aerosol dispenser, said aerosol being characterized by its suppressed flammability, the method comprising the steps of filling a container with a mixture comprising by weight of the total weight of the composition from about 23 to about 35% of a water-immiscible liquid which is a solvent for the propellant, from about 15 to about 25% water, and from about 3 to about 20% of a mixed surfactant system of at least one primary surfactant and at least one secondary surfactant, and pressurizing the container with at least about 30% by weight of the total weight of the composition of at least one normally gaseous flammable propellant, whereby an oil-in-water micro-emulsion can be formed by shaking said container.
19. The method of claim 18 further comprising the step of transferring the composition from the container to an aerosol dispenser.
20. The method of claim 18 wherein the container is an aerosol dispenser.
21. The method of claim 18 wherein the normally gaseous flammable propellant is selected from the group consisting of propane, butane, isobutane, dimethylether, and difluoroethane, and mixtures thereof, and wherein the total amount of said pro-pellant is in the range of from about 30% to about 55% by weight based on the weight of the composition.
22. The method of claim 21 wherein the mixed surfactant system has an HLB of from about 10.6 to about 14.5.
23. The method of claim 22 wherein the mixed sur-factant is present in an amount of from 5 to 9% by weight of the total composition.
24. The method of claim 19, 20 or 23 wherein the mixed surfactant system comprises a first nonionic surfactant having an HLB of less than about 10.4 and a second nonionic surfactant having an HLB above about 11.0, said first and second surfactants each being selected from the group consisting of isooctyl and isononyl phenol ethoxylates, and alkyl alcohol ethoxylates having from 8 to 24 carbons in the alkyl group, said mixed surfactant system having an HLB between about 11.5 to about 13.0
CA000457246A 1983-06-28 1984-06-22 Nonflammable aerosol propellant microemulsion system Expired CA1205349A (en)

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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4655959A (en) * 1983-06-28 1987-04-07 The Drackett Company Preparation of non-flammable aerosol propellant microemulsion system
CA2028811C (en) * 1989-03-17 1998-12-29 Toshimitsu Seki Aerosol preparation for external use
US5091111A (en) * 1990-09-19 1992-02-25 S. C. Johnson & Son, Inc. Aqueous emulsion and aersol delivery system using same
US5145604A (en) * 1990-09-19 1992-09-08 S. C. Johnson & Son, Inc. Aqueous emulsion and aerosol delivery system using same
WO1992020767A1 (en) * 1991-05-20 1992-11-26 Dorsey Industries, Inc. Method of applying invert dispersions of non-miscible solutions
US5639441A (en) * 1992-03-06 1997-06-17 Board Of Regents Of University Of Colorado Methods for fine particle formation
US5269958A (en) * 1993-01-13 1993-12-14 S. C. Johnson & Son, Inc. Self-pressurized aerosol spot dry cleaning compositions
AU7320694A (en) * 1994-06-30 1996-01-25 Precision Valve Corporation Four-component aerosol composition
WO1996017898A1 (en) * 1994-12-09 1996-06-13 Engine Fog, Inc. Tire inflating and puncture sealing composition
US5603942A (en) * 1995-05-19 1997-02-18 Isp Investments Inc. Stable, single phase w/o microemulsion matrix formulation for forming sprayable, aerosol agriculturally active compositions
FR2745716B1 (en) * 1996-03-07 1998-04-17 Oreal ULTRAFINE PRESSURIZABLE FOAMING OIL-IN-WATER EMULSIONS
US5792465A (en) * 1996-06-28 1998-08-11 S. C. Johnson & Son, Inc. Microemulsion insect control compositions containing phenol
US6238646B1 (en) 1999-05-28 2001-05-29 Global Technology Transfer, L.L.C. Aqueous aerosol compositions for delivery of atomized oil
GB9921037D0 (en) * 1999-09-07 1999-11-10 Reckitt & Colmann Prod Ltd Compositions
WO2007125460A1 (en) * 2006-05-03 2007-11-08 Firmenich Sa Microemulsion composition for air freshener
US9393336B2 (en) 2011-07-08 2016-07-19 S. C. Johnson & Son, Inc. Insert for dispensing a compressed gas product, system with such an insert, and method of dispensing a compressed gas product
EP3491093A4 (en) 2016-07-28 2020-04-15 Honeywell International Inc. Propellants and emulsification compositions

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2356205A (en) * 1942-10-21 1944-08-22 Petrolite Corp Process for increasing productivity of subterranean oil-bearing strata
US2655480A (en) * 1949-11-02 1953-10-13 Spitzer Lather producing composition
US3207386A (en) * 1962-06-01 1965-09-21 Aerosol Tech Inc Aerosol dispenser producing non-flammable spray with fluid system having a flammable propellant
NL300468A (en) * 1962-11-24
US3346494A (en) * 1964-04-29 1967-10-10 Exxon Research Engineering Co Microemulsions in liquid hydrocarbons
FR1439361A (en) * 1964-05-13 1966-05-20 Exxon Research Engineering Co Emulsifiable lubricants for use in glass molding
US3387425A (en) * 1964-12-08 1968-06-11 Allied Chem Process for preparing aerosol packages
US3275075A (en) * 1965-04-27 1966-09-27 Marathon Oil Co Viscosity control in petroleum recovery
US3254714A (en) * 1965-11-05 1966-06-07 Marathon Oil Co Use of microemulsions in miscible-type oil recovery procedure
US3301325A (en) * 1965-11-05 1967-01-31 Marathon Oil Co Petroleum recovery materials and process
US3307628A (en) * 1966-04-06 1967-03-07 Marathon Oil Co Process for secondary recovery of petroleum using stabilized microemulsions
US3505236A (en) * 1966-06-07 1970-04-07 Colgate Palmolive Co Water-based aerosol composition
US3630951A (en) * 1967-12-15 1971-12-28 Minnesota Mining & Mfg Bubble compositions
US3506070A (en) * 1967-12-26 1970-04-14 Marathon Oil Co Use of water-external micellar dispersions in oil recovery
US3495988A (en) * 1968-03-06 1970-02-17 Leslie L Balassa Encapsulation of aromas and flavors
US3467194A (en) * 1968-03-12 1969-09-16 Marathon Oil Co Stimulation of producing wells with water-external micellar dispersions
US3493048A (en) * 1968-07-22 1970-02-03 Marathon Oil Co Cosurfactant influencing the thermostability of micellar dispersions
US3536106A (en) * 1968-08-29 1970-10-27 Atomic Energy Commission Method for measurement and transfer of small fluid volumes
US3839220A (en) * 1968-10-23 1974-10-01 Mennen Co Microcapsules for use in pressurized systems
BE744162A (en) * 1969-01-16 1970-06-15 Fuji Photo Film Co Ltd ENCAPSULATION PROCESS
US3719606A (en) * 1969-08-08 1973-03-06 Pan American Petroleum Corp Microemulsion of increased viscosity for improved oil recovery
US3641181A (en) * 1969-09-10 1972-02-08 Exxon Research Engineering Co Microemulsion separation of organic compounds in liquid state
US3540532A (en) * 1969-09-30 1970-11-17 Marathon Oil Co Hydrophobicity of surfactant influencing the thermostability of micellar dispersions used in oil recovery
DE2010115A1 (en) * 1970-03-04 1971-09-16 Farbenfabriken Bayer Ag, 5090 Leverkusen Process for the production of micro-granules
US3813345A (en) * 1971-08-05 1974-05-28 Vanguard Chem Co Inc Method of producing microcolloidal aqueous emulsions of unsaturated organic compounds
US3778381A (en) * 1972-04-24 1973-12-11 Allied Chem Fluorocarbon microemulsions
FR2205358B1 (en) * 1972-11-03 1976-04-23 Rhone Poulenc Ind
US4052331A (en) * 1972-11-03 1977-10-04 Rhone-Poulenc S.A. Surface active composition
US3928215A (en) * 1973-06-29 1975-12-23 Marathon Oil Co High fluidity cutting oils which exhibit retro-viscous properties
FR2249657B1 (en) * 1973-11-07 1977-04-15 Ugine Kuhlmann
SE402305B (en) * 1975-04-04 1978-06-26 Perstorp Ab WATERPREDABLE PAINTER IN THE FORM OF MICROEMULSIONS
US4046519A (en) * 1975-10-31 1977-09-06 Mobil Oil Corporation Novel microemulsions
US4146499A (en) * 1976-09-18 1979-03-27 Rosano Henri L Method for preparing microemulsions
DK532877A (en) * 1976-12-10 1978-06-11 Elf Aquitaine CONCENTRATE FOR THE PRODUCTION OF MICRO-EMISSION MICRO-EMISSIONS OF OIL AND WATER

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