Aerosol concentrates containing a sta-

  • Inventors:
  • Assignees:
  • Publication Date: March 10, 1964
  • Publication Number: US-3124505-A

Abstract

Claims

1. AN AEROSOL CONCENTRATE SUITABLE FOR PREPARING AEROSOL COMPOSITIONS WHICH COMPRISES A SUSPENSION MEDIUM SELECTED FROM THE GROUP CONSISTING OF 1,1,1-TRICHLOROETHANE, SOLVENT NAPHTHA AND MIXTURES THEREOF; AN EFFECTIVE AMOUNT OF A LOW MOLECULAR WEIGHT SUSPENSION STABILIZATION AGENT SELECTED FROM THE GROUP CONSISTING OF ALCOHOLS AND KETONES, SAID ALCOHOLS AND KETONES CONTAINING NO MORE THAN 10 CARBON ATOMS AND FROM ABOUT 10 TO ABOUT 20 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF THE TOTAL CONCENTRATE, OF FINELY DIVIDED SILICA.
United States Patent Ofiice 3,124,505 Patented Mar. 10, 1964 AERGSOL CONCENTRATES CONTAMING A STA- BHJZED SUSPENSION F FINELY mvmun SILICA Carroll F. Doyle, Ellicott City, and Luther 0. Young and Joseph Albert Chatard, Jr., Baltimore, Md, assignors to W. R. Grace & Co., New York, N.Y., a corporation of Connecticut N0 Drawing. Filed Aug. 15, 1961, Ser. No. 131,485 27 Claims. (Cl. 161-39) This invention relates to insecticidal compositions suitable for use in preparing sprayable compositions, to the sprayable compositions so produced, and to aerosol bombs containing the said sprayable compositions. More specifically, this invention relates to insecticidal compositions comprising insecticidal silica which are suitable for the uses described. It has been discovered in recent years that fine particle size silica, having an average particle size of from about 1 to about 10 microns, preferably less than about 5 microns with a typical particle size distribution ranging from about 2 to about 6 microns is excellently adapted for use as an insecticidal agent. Fine particle size silica is not toxic to animals unless its dust is persistently breathed over a long period of time. Such silica can also be removed from plants and shrubs by simple Washing and will leave no toxic residue. Fine particle size silica has been found to be extremely lethal to many inserts such as roaches, fleas, termites, various mites, mosquitoes and the like. Specific results of some tests made in this regard are found in the literature, e.g., Tarshis, UCLA Tests With Desiccant Dusts for Roach Control; Pest Control, vol. 27, No. 6 at pp. 14 et seq. (1959); Tarshis, Use of Sorptive Dusts on Fleas; California Agriculture, col. 13, N0. 3, pp. 13, 14 (1959); and Ebeling et al., Rapid Desiccation of Drywood Termites With Inert Sorptive Dusts; Journal of Economic Entymology, vol. 52, No. 2, pp. 190-207 (1959). Despite this highly attractive use for fine particle size silicas, it has not been possible to make economical aerosol bombs containing this material. In preparing such aerosol bombs, the silica is first mixed with a suitable suspending medium to prepare an aerosol concentrate, the concentrate is then blended with about one-half to about one and one-half parts by weight of propellant per part of concentrate and the aerosol composition is placed into a pressure container having a hand operated dispensing valve. Since the propellant thus dilutes the silica concentration in the final aerosol composition it is obvious that in order to obtain a satisfactory product, the amount of silica in the aerosol concentrate should be as high as possible. It has been observed, however, that when any economically feasible concentration of finely divided silica is mixed with the suspending media used in preparing the aerosol concentrate, the dispersions exhibit a great variety of colloidal phenomena, among which are high false body visabout 12 percent by weight in the concentrate, the concentration in the aerosol composition is reduced to a maximum of about 5 or 6 percent which is undesirably low and highly uneconomical. It is an object of this invention to avoid the problems enumerated above. It is another object of this invention to provide aerosol concentrates which contain up to about 20 percent by weight of finely divided silica and which nevertheless can be used to prepare aerosol compositions and moreover possess long time storage stability. It is another object of this invention to provide aerosol compositions having a much higher concentration of finely divided silica than previously possible which at the same time remain sprayable for months, thus permitting intermittent use of the aerosol bomb without clogging the valve or the nozzle. Other objects of the invention will be obvious to those skilled in the art in view of the following description. It has been found that a particular choice of suspending media together with a suspension stabilizer in certain critical proportions permits the incorporation of a much higher proportion of silica, in the range of from about 10 to 20 percent by weight, in the aerosol concentrate without detracting from the usefulness of the said concentrate in an aerosol composition. The suspending media which have been found suitable for the purposes of this invention are (a) 1,1,1-trichloroethane and (b) narrow boiling range petroleum hydrocarbon fractions having boiling ranges between the temperatures of about centigrade and about 400 centigrade. The petroleum hydrocarbons, commonly known as solvent naphtha, are available from many sources of supply. Typical examples of suitable petroleum hydrocarbons have the following properties: Shell Solvasol 01 36 No. 2 314 322 154 327 a 338 172 End Point 360 191 Mixtures of the two suspending media may be used if desired. Since it is preferable that the aerosol composition have a low flame projection when tested in accordance with the Interstate Commerce Commissions Regulations of Tariff No. 10, it is preferred to use only minor proportions of the petroleum hydrocarbons, on the order of 50% by weight or less of the total suspension medium in the aerosol concentrate. A particularly preferred suspension medium is one in which the weight ratio of 1,1,1-trichloroethane to solvent naphtha is in the range of from about 3 to 1 to about 10 to 1. However, it is to be stressed that although low flame projection is a desideratum it is not an absolute requirement, and therefore use of petroleum hydrocarbons as the sole suspending agent is not beyond the scope of this invention. The suspension stabilizer used in this invention is a low molecular weight organic alcohol or ketone. The alcohol or ketone should have no more than about carbon atoms and preferably has from 2 to 6 carbon atoms. Specific suspension stabilizers which can be used include methnol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanols, hexanols, 2-ethyl hexanol, 2-octanol, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, ethyl isopropyl ketone and the like. Mixtures of two or more stabilizing agents may be used if desired. As with the petroleum hyrdocarbon suspension medium, certain of the stabilizing agents will cause larger flame projections than others. However, as stated above, a low flame projection is not absolutely required and thus any of the stabilizing agents in the class defined above is to be deemed Within the scope of this invention. The preferred stabilizing agent, from the standpoint of economy, efliciency, low toxicity, low odor and low flame propagation is isopropanol. The amounts of suspension stabilizer used in the in vention are within the range of from about .25 part to about 1.5 parts by weight of agent per part by weight of finely divided silica. The minimum amount of stabilizing agent that can be used is that amount which gives a useful effect, while the maximum amount is that which causes the finey divided silica to settle into a hard diflicultly redispersible mass. From the data presented in the examples below, the optimum amount of any particular stabilizer will be obvious to one skilled in the art. The amount of preferred stabilizing agent, isopropanol, has been found to be between about 0.4 and about 1.2 parts per part by weight of silica. The method of preparing the aerosol concentrate of this invention is fully explained in the examples given hereinafter. Preparation of an aerosol composition therefrom by adding a propellant to the concentrate is also shown in the examples. Any suitable propellant may be used, although it is preferred to use the relatively non-toxic halofluorohydrocarbons commonly known as Freons. The most particularly preferred propellants in this invention are dichlorodifluoromethane and trichloromonofluoromethane. The amount of propellant used is between about 0.5 and about 1.5 parts by weight per part of aerosol concentrate. This is suflicient to provide an initial spraying pressure of from about to pounds per square inch gauge at 70 Fahrenheit and to substantially empty the aerosol container when the period of ordinary use is completed. In preparing the aerosol compositions, it is preferred to use a so-called knockdown agent in conjunction with the insecticidal finely-divided silica. A knockdown agent found to be most effective in the compositions of this invention was a synergistic mixture of piperonyl butoxide and a pyrethrum extract known to the art as pyrethrins (see Metcalf et al., Destructive and Useful Insects, third edition (1951), pp. 277-281). The pyrethrum extract used was obtained from a commercial source of supply as a 20% by weight concentrate of pyrethrins in petroleum hydrocarbons. As is shown in the examples below, use of a knockdown agent greatly enhances the effectiveness of the aerosol compositions of this invention. The knockdown agent is incorporated in the aerosol by mixing it into the aerosol concentrate prior to combining the concentrate with the propellent. The knockdown agent is added in amounts to provide from about 0.05 to about 0.25 percent by weight of pyrethrins and from about 0.1 to about 1.0 percent by weight of piperonyl butoxide in the final aerosol composition. The invention is further illustrated by the non-limiting specific examples which follow. In each of the examples the finely divided silica used was the Dri-Die 67 described in the Tarshis article cited previously herein. This silica has an average particle size of about 3 microns, with a particle size ran e of from about 2 to 6 microns, and contains about 1 to about 4 percent by weight of fluorine. Finely divided silicas of the size previously stated with or without any fluorine additive can be effectively in- 4. corporated into aerosol concentrates and aerosol compositions in the same manner as specific silica used 111 the examples. EXAMPLE I 30 grams of isopropyl alcohol was thoroughly mixed with 370 grams of l,l,l-trichloroethane and 387 grams of this mixture added to 63 grams of fine particle size silica. The mixture was hand-stirred until all of the silica was thoroughly wetted by the solvent and then was thoroughly blended by rapid agitation for five minutes. The freshly prepared suspension was sufliciently fluid to permit easy spraying. It was aged one month. At the end of this period the suspension was found to be thixotropic but became fluid when mildly shaken and was satisfactory for use in preparing an aerosol composition. The characteristics of the aerosol concentrate pro duced by Example I should be contrasted with those of the following formulation in which no alcohol was used. EXAMPLE LA 7 grams of fine particle size silica was added to 93 grams of 1,1,1-trichloroethane. The mixture was hand-stirred until all of the silica was thoroughly wetted by the trichloroethane and then was thoroughly blended by rapidly agitating the mixture for five minutes. Immediately after agitation, the viscosity of the suspension was low enough to permit spraying. Shortly thereafter, a thixotropic change occurred. After standing 24 hours, the suspension was very thick. The dispersion could be thinned by shaking but thickened rapidly on standing. After storage for six months, it was found to have the same thixotropic properties as had been observed after the 24 hour aging period. It was not a satisfactory aerosol concentrate. EXAMPLE II 58.1 grams of isopropyl alcohol was mixed with 441.9 grams of solvent naphtha. 430 grams of this mixture was added to grams of fine particle size silica and thoroughly blended by five minutes of violent agitation. The suspension was aged for six months. The suspension was stable, somewhat thixotropic, but returned to a fluid state with mild agitation. It thickened very slowly after shaking, and was quite suitable as an aerosol concentrate. The effectiveness of the concentrate of Example II should be contrasted with the characteristics of the following solvent naphtha suspension. EXAMPLE II-A 90 grams of solvent naphtha was added to 10 grams of fine particle size silica. The mixture was hand-stirred until all of the silica Was wetted by the naphtha and then blended thoroughly by violent agitation for five minutes. The suspension was aged for six months. At the end of this period it was found to be a thixotropic gel which thinned when shaken but thickened almost instantly upon standing. It was not suitable for use in preparing an aerosol composition. EXAMPLE III 57 grams of isopropyl alcohol, 171.5 grams of 1,l,1-tri chloroethane and 171.5 grams of solvent naphtha were mixed together. The mixed solvents were added to grams of fine particle size silica, hand-stirred until the silica was completely wetted and then violently agitated for five minutes. The suspension was thixotropic but stable. At the end of four months this condition remained. The thixotropic suspension thinned easily When disturbed and thickened slowly when allowed to stand. It was a good aerosol concentrate. Without alcohol, the silica in a naphtha-chlorinated hydrocarbon mixture behaved as follows: EXAMPLE III-A A naphtha-chlorinated hydrocarbon mixture was prepared by adding 184 grams of solvent naphtha to 184 grams of 1,l,1-trichloroethane. This mixed solvent was added to 32 grams of fine particle size silica and stirred by hand until the silica was thoroughly wetted. It then was violently agitated for five minutes. The suspension was very thick and thixotropic before and after aging. Agitation caused the suspension to become fluid but it thickened with great rapidity. It was not an acceptable aerosol concentrate. EXAMPLE IV A solvent composed of 75 grams of isopropyl alcohol, 150 grams of 1,1,1-trichloroethane and 150 grams of solvent naphtha was added to 75 grams of fine particle size silica. The mixture was stirred and blended as is described above and 90 grams of the resultant suspension was placed in an aerosol container and to this was added 30 grams of dichlorodifluoromethane. The container was capped, fitted with an aerosol valve and an activator button and then was stored for four months during which time it was examined at intervals. The aerosol sprayed regularly without shaking. Examination showed that the material was somewhat thixotropic but became highly fluid with the slightest agitation and thickened quite slowly when allowed to stand undisturbed. The aerosol valve and button did not clog even when operated intermittently. When alcohol was not present in aerosol formulations, only very low concentrations of silica produced operable bombs as shown in the following test formulations in Examples IV-A to IV-C: EXAMPLE IV-A 184 grams of solvent naphtha and 184 grams of 1,1,1- trichloroethane were added to 32 grams of fine particle size silica. The slurry was stirred by hand until the silica was completely wetted and then blended by being shaken violently for 5 minutes. 104 grams of the above suspension was placed in an aerosol container and to this was added 56 grams of dichlorodifiuoromethane. The aerosol container was capped, and was fitted with an aerosol valve and an activator button. The aerosol was stored for a period of four months and examined at intervals. The aerosol sprayed satisfactorily and no clogging of the aerosol valve or the activator button occurred. EXAMPLE IV-B The proportion of fine particle size silica was raised from 5.2 percent to 7.8 percent by Weight as follows: 176 grams of 1,1,1,-trichloroethane was blended with 176 grams of solvent naphtha. This mixture of solvents was added to 48 grams of fine particle size silica. The mixture was stirred until the silica was wetted and then blended by agitation for five minutes. 78 grams of the above suspension was placed in an aerosol container and to this, 42 grams of dichlorodifluoromethane was added. The container was capped and fitted with an aerosol valve and activator button as before. At all times the silica suspension in the container was stable, thixotropic, and had high viscosity. The suspension thinned when it was shaken but thickened almost instantly to a non-fiowable state if allowed to stand undisturbed. The aerosol sprayed satisfactory as long as the inlet of the dip tube remained flooded, but this condition could only be brought about by the constant shaking of the container. This formulation does not function as a satisfactory aerosol, EXAMPLE IV-C The silica content of this type of aerosol was increased still further to 9.0 percent of fine particle size silica by placing grams of the silica-chloroethane-naphtha suspension of Example IV-B in an aerosol container and then adding 30 grams of dichlorodifluoromethane. The container was capped, fitted with an aerosol valve and activator button as before and stored for four months, during which period it was examined periodically. The silica suspension in the aerosol bomb was stable, thixotropic and very thick. The suspension thinned when shaken and thickened to an essentially non-flow state almost instantly when allowed to stand undisturbed. The aerosol sprayed satisfactorily as long as the inlet of the dip tube remained flooded, but this condition could not be maintained unless the bomb was constantly shaken. This formulation cannot be considered a satisfactory aerosol spray. EXAMPLE V A suspension medium consisting of 35.6 grams of isopropyl alcohol, 107 .2 grams of 1,1,1-trichloroethane and 107.2 grams of solvent naphtha was added to 50 grams of fine particle size silica. This mixture was stirred and blended as before and 75.6 grams of the suspension was placed in an aerosol container, to which was added 59.4 grams of trichlorornonofluoromethane and 45 grams of dichlorodifiuoromethane. The container was sealed with an aerosol valve and fitted with a valve actuator. The insecticidal properties of the material were determined as follows: Weighed pieces of paper measuring 4 x 5 inches were sprayed with aerosol to give a uniform residual deposit. After spraying, the papers were dried for five minutes under an infrared lamp and then weighed. The weight of the deposit was maintained at 100110 milligrams. The weighed papers were then placed in aluminum fiat bottom, 4 x 5 inch pans. The top edges of the pans were greased with a thin coat of petroleum jelly. Comparison samples were prepared by placing 4 x 5 inch papers in identical pans. These papers were dusted with 30 milligrams of fine particle size silica per pan. Six (6) adult male German roaches were placed in one of the aerosol sprayed pans and the same number and type of roaches were placed in one of the dusted pans. The test was repeated each day for 10 days using new paper inserts each day. The roaches were examined every EXAMPLE VIa TO VI-jj These examples illustrate the wide variety of alcohols and ketones that can be used as stabilizing agents in the aerosol concentrates and aerosol compositions of this invention. In each example an aerosol concentrate containing about 15 percent by weight of finely divided silica, 14 percent by weight of solvent naphtha, varying amounts of stabilizing agent as shown in the table which follows, and sufficient amounts of 1,1,1-trichloroethane to provide 71 percent by weight in the concentrate of the combined stabilizing agent and trichloroethane, was prepared as described in Examples I through V above, and its shelf stability for 30 days determined. Thereafter, there was added to each concentrate a mixture containing about 46.8 percent by weight of dichlorodifluoromethane and about 53.2 percent by weight of trichloromonofiuoromethane in an amount of about 1.15 parts of said mixture per each part of the respective concentrate. The aerosol compositions thus prepared were placed in an aerosol container and the flame projection and the shelf stability of each was determined. Results are summarized in the following Table I. Aerosol bombs containing the aerosol compositions described hereinabove have adequate, dependable commercial life. Despite the solid phase insecticidal, the bombs discharge dependably in household use and have the great advantage that they can be safely used in areas where soluble insecticidal materials toxic to humans would be intolerable. What is claimed is: 1. An arosol concentrate suitable for preparing aerosol compositions which comprises a suspension medium selected from the group consisting of 1,1,1-trichloroethane, solvent naphtha and mixtures thereof; an efiective amount of a low molecular weight suspension stabilization agent selected from the group consisting of alcohols and ketones, said alcohols and ketones containing no more than 10 carbon atoms and from about 10 to about 20 percent by weight, based on the weight of the total concentrate, of finely divided silica. 2. Concentrate as defined in claim 1 wherein the solvent is naphtha is a narrow boiling range petroleum hydrocarbon fraction having a boiling range between about 140 centigrade and about 400 centigrade. 3. Concentrate as defined in claim 1 wherein the amount of suspension stabilization agent is from about 0.25 to about 1.5 parts by weight per part by weight of said silica. 4. Concentrate as defined in claim 1 wherein said finely divided silica has an average particle size of less than about 5 microns. 5. An insecticidal aerosol composition comprising the aerosol concentrate of claim 1 and from about 0.5 to about 1.5 parts by weight of a propellant per part by weight of said concentrate. 6. An aerosol bomb containing the insecticidal composition of claim 5. 7. Aerosol concentrate suitable for use in preparing aerosol compositions which comprises from about to about 20 percent by weight, based on the total weight of said concentrate, of a finely divided silica having an average particle size of less than about 5 microns; a suspending medium for said silica containing a mixture of 1,1,1-trichloroethane and solvent naphtha in a weight ratio of from about 3 to 1 to about to 1 of the respective ingredients, and from about 0.25 to about 1.5 parts by weight per part by weight of said silica of a low molecular weight suspension stabilizing agent selected from the group consisting of alcohols and ketones, said alcohols and ketones containing no more than 10 carbon atoms. 8. An aerosol concentrate suitable for use in preparing aerosol compositions which comprises a suspension medium selected from the group consisting of 1,1,1-trichloroethane, solvent naphtha and mixtures thereof, an efiective amount of an alcohol suspension stabilization agent, said alcohol containing no more than 10 carbon atoms and from about 10 to about percent by weight, based on the weight of the total concentrate, of finely divided silica. 9. Concentrate as defined in claim 8 wherein the said stabilizing agent is methanol in an amount of from about 0.5 to about 1.2 parts by weight per part by weight of silica. 10. Concentrate as defined in claim 8 wherein the said stabilizing agent is ethanol in an amount of from about 0.5 to about 1.0 part by weight per part by weight of silica. 11. Concentrate as defined in claim 8 wherein the said stabilizing agent is n-butanol in an amount of from about 0.25 to about 0.75 part by weight per part by weight of silica. l2. Concentrate as defined in claim 8 wherein the said stabilizing agent is sec-butanol in an amount of from 10 about 0.5 to about 1.0 part by weight per part by weight of silica. 13. Concentrate as defined in claim 8 wherein the said stabilizing agent is 2-octanol in an amount of from about .5 to about 1.0 part by weight per part by weight of silica. 14. Concentrate as defined in claim 8 wherein the said stabilizing agent is isopropanol in an amount of from about 0.4 to about 1.2 parts by weight per part by weight of silica. 15. An insecticidal aerosol composition comprising the aerosol concentrate of claim 14 and from about 0.5 to about 1.5 parts by weight of a propellant per part by weight of said concentrate. 16. An insecticidal aerosol as defined in claim 15 wherein the propellant is selected from the group consisting of trichloromonofiuoromethane, dichlorodifluoromethane and mixtures thereof. 17. An aerosol bomb containing the insecticidal composition of claim 16. 18. An insecticidal aerosol as defined in claim 16 wherein the said composition also contains from about 0.05 to about 0.25 percent by weight of pyrethrins and from about 0.1 to about 1.0 percent by weight of piperonyl butoxide based on the total weight of the composition. 19. An aerosol bomb containing the insecticidal composition of claim 18. 20. An insecticidal aerosol composition comprising the aerosol concentrate of claim 8 and from about 0.5 to about 1.5 parts by weight of a propellant per part by weight of said concentrate. 21. An aerosol bomb containing the insecticidal composition of claim 20. 22. An aerosol concentrate suitable for use in preparing aerosol compositions which comprises a suspension medium selected from the group consisting of 1,1,1-trichloroethane, solvent naphtha and mixtures thereof, an effective amount of a ketone suspension stabilization agent, said ketone containing no more than 10 carbon atoms and from about 10 to about 20 percent by weight, based on the weight of the total concentrate, of finely divided silica. 23. Concentrate as defined in claim 22 wherein the said stabilizing agent is acetone in an amount of from about 1.0 to about 1.5 parts by weight per part by weight of silica. 24. An insecticidal aerosol composition comprising the aerosol concentrate of claim 22 and from about 0.5 to about 1.5 parts by Weight of a propellant per part by weight of said concentrate. 25. An aerosol bomb containing the insecticidal composition of claim 24. 26. Aerosol concentrate suitable for use in preparing aerosol compositions which comprises from about 10 to about 20 percent by weight, based on the total weight of said concentrate, of a finely divided silica having an average particle size of less than about 5 microns, a suspended medium for said silica containing a mixture of 1,1,l-trichloroethane and solvent naphtha in a weight ratio of from about 3 to 1 to about 15 to 1 of the respective ingredients, and from about 0.25 to about 1.5 parts by Weight per part by weight of said silica of an alcohol suspension stabilizing agent, said alcohol containing no more than 10 carbon atoms. 27. Aerosol concentrate suitable for use in preparing aerosol compositions which comprises from about 10 to about 20 percent by weight, based on the total weight of said concentrate, of a finely divided silica having an average particle size of less than about 5 microns, a. suspended medium for said silica containing a mixture of 1,1,1-trichloroethane and solvent naphtha in a weight ratio of from about 3 to 1 to about 15 to 1 of the respective ingredients, and from about 0.25 to about 1.5 parts by weight per part by weight of said silica of a ketone suspension stabilizing agent, said ketone containing no more than 10 carbon atoms. References Cited in the file of this patent UNITED STATES PATENTS 12 FOREIGN PATENTS Great Britain June 15, 1960 OTHER REFERENCES 5 Powder Aerosols, Soap and Chem. Specialities, January 1955, pages 139, 141 and 169. DiGiacomo: Drughand Cosmetic Industry, September 1956, 79, 3 pages, 382329. Ebeling et al.: Journal of Economic Entomology, vol. 10 52, No. 2, pp. 190-207, April 1959.

Description

Topics

Download Full PDF Version (Non-Commercial Use)

Patent Citations (5)

    Publication numberPublication dateAssigneeTitle
    GB-837465-AJune 15, 1960Riker Laboratories IncSelf-propelling, powder-dispensing compositions
    US-2358986-ASeptember 26, 1944Claude R WickardCombined insecticide and germicide
    US-2959325-ANovember 08, 1960Risdon Mfg CoMethod and apparatus for dispensing dry powders
    US-2980582-AApril 18, 1961Du PontAerosols
    US-3014844-ADecember 26, 1961Riker Laboratories IncSelf-propelling powder dispensing compositions

NO-Patent Citations (0)

    Title

Cited By (21)

    Publication numberPublication dateAssigneeTitle
    FR-2381470-A1September 22, 1978Ciba Geigy AgInsecticide spray for porous surfaces - contg. insecticide, solvent, propellant and finely divided solid with high specific surface
    JP-S4885723-ANovember 13, 1973
    US-2003099680-A1May 29, 2003Gem Of The North Pty Ltd.Pesticide composition containing finely ground amorphous silica
    US-2004220056-A1November 04, 2004Glenn David Michael, John Mosko, Pluta Richard C., Puterka Gary J.Pest control compositions
    US-3219476-ANovember 23, 1965Stanford Research InstMethod of encapsulation of aerosols by in situ polymerization
    US-3468814-ASeptember 23, 1969Allied ChemSelf-propelled aerosol composition and method of using same to coat plates useful in thin-layer chromatography
    US-3547663-ADecember 15, 1970Nalco Chemical CoSilica organo sol friction treatment composition and method of application
    US-5122518-AJune 16, 1992Vrba Cenek HInsecticides
    US-5368842-ANovember 29, 1994The Gillette CompanyHigh efficacy aerosol antiperspirant composition
    US-5576007-ANovember 19, 1996Kabushiki Kaisha Shikoku Sogo KenkyushoZeolite insecticide for termites
    US-5908708-AJune 01, 1999Engelhard Corporation, The United States Of America As Represented By The Secretary Of AgricultureAqueous dispersion of a particulate solid having a hydrophobic outer surface and films produced thereby
    US-6027740-AFebruary 22, 2000Engelhard CorporationMethod for protecting surfaces from arthropod infestation
    US-6060521-AMay 09, 2000Engelhard Corporation United States Department Of AgricultureAqueous dispersion of a particulate solid having a hydrophobic surface and films produced thereby
    US-6069112-AMay 30, 2000Englehard CorporationMethod for preventing physiological disorders without diminishing photosynthesis
    US-6110867-AAugust 29, 2000Engelhard CorporationMethod for providing enhanced photosynthesis
    US-6156327-ADecember 05, 2000Engelhard Corporation, The United States Of America As Represented By The Secretary Of AgricultureTreated horticultural substrates
    US-6235683-B1May 22, 2001Engelhard Corporation, The United States Of America As Represented By The Secretary Of AgricultureMethod for enhanced supercooling of plants to provide frost protection
    US-6403058-B1June 11, 2002Sumitomo Chemical Company, LimitedPesticidal aerosol formulation
    US-6464995-B1October 15, 2002Engelhard Corporation, The United States Of America As Represented By The Secretary Of AgricultureTreated horticultural substrates
    US-6908629-B2June 21, 2005Gem Of The North Pty LtdPesticide composition containing finely ground amorphous silica