CA1174967A - Aerosol formulations based on water - Google Patents
Aerosol formulations based on waterInfo
- Publication number
- CA1174967A CA1174967A CA000406784A CA406784A CA1174967A CA 1174967 A CA1174967 A CA 1174967A CA 000406784 A CA000406784 A CA 000406784A CA 406784 A CA406784 A CA 406784A CA 1174967 A CA1174967 A CA 1174967A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- aerosol formulation
- aerosol
- acid ester
- water
- 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
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
Abstract
Abstract Insecticidal or acaricidal aerosol formulations based on water consist of 0.01 to 6% by weight of, as active compound(s), at least one insecticidal and/or acaricidal substance selected from carbamates, pyrethroids and acetic acid ester derivatives, 0.1 to 2% by weight of at least one emulsifier, to 40% by weight of at least one organic solvent, to 70% by weight of water, to 50% by weight of propellant and if appropriate, 0.1 to 6% by weight of additives, the sum of the components being 100% by weight in each case. The formulations can be prepared by mixing the active compound(s), emulsifier, organic solvents and, if appropriate, additives, adding water to the mixture, and adding the propellant in a spray can.
The aerosol formulations find use as insecticides or acaricides in the domestic field and hygiene field or in agriculture and horticulture.
The aerosol formulations find use as insecticides or acaricides in the domestic field and hygiene field or in agriculture and horticulture.
Description
~;e~
The present invention relates to certain new aerosol formulations based on water, to a procPss for their preparation and to their use in the domestic field and hygiene field and in plant protection.
The application of active compounds in the domestic field and hygiene field and in plant protection with the aid of spray cans in which the active compounds in the aerosol formulations are contained in solution in organic solvents has already been disclosed. In this type of application relatively large amounts of organic solvents are sprayed; this is expensive, on the one hand, and is also undesirable for reasons of environmental protection, on the other hand. To eliminate this negative factor as far as possible, aerosol formulations were therefore developed in which a part of the organic solvents is replaced by water. A decisive disadvantage of the previously dis-closed aerosol formulations of this type however is that they exhibit a significantly lower action than the corres-ponding water-free aerosol formulations (see Bundesgesundheitsblatt tFederal Health Sheet) 24, No. 10.
pages 163-165 (1981)).
According to the present invention we provide, as new formulations, aerosol formulations based on water, characterised in that they consist of 0.01 to 6~o by weight of at least one insecticidal and/
or acaricidal substance selected from carbamates, pyrethroids, acetic acid ester derivatives and phosphoric acid ester derivatives, 0.1 to 2~o by weight of at least one emulsifier, to 40O by weight of at least one organic solvent, to 70O by weight of water, _ 10 to 50O by weight of propellant and if appropriate, 0.1 to 6~ by weight of additives, the sum of the components being 100,~ by weight in each case.
Le A 21 105 1 17496~
According to the present invention we further provide a process for the production of an aerosol formulation of the present invention, characterised in that a solution consisting of û.01 to 62~ by weight of at least one insecticidal and/or acaricidal substance selected from carbamates, pyrethroids, acetic acid ester derivatives and phosphoric acid ester derivatives, 0.1 to 2Co by weiyht of at least one emulsifier, 0 5 to 40~ by weight of at least one organic solvent and if appropriate, 0.1 to 6o by weight of additives, is mixed with 20 to 7030 by weight of water, and lO to 50O
by weight of propellant is added to the resulting mixture in a spray can, the sum of the components in the formul-ation being lOO~o by weight in each case, and the percentages by weight being relative to the resulting formulation.
Finally, it has been found that the aerosol formul-ations, according to the invention, based on water, can beused in the domestic field and hygiene field or in agri-culture and in horticulture.
It i9 to be regarded as extremely surprising that the aerosol formulations, according to the invention, which are based on water and contain insecticidal and/or acaricidal substances selected from carbamates, pyrethroids, acetic acid ester derivatives and phosphoric acid ester derivatives, possess a better action than the corresponding, previously known water-free aerosol formulations. A superior action of this type could not be expected on the basis of the known state of the art, since, according to previous experience, the water-free aerojol formulations exhibited in each instance a better activity than the analogous water-containing aerosol formulations.
However, the aerosol formulations, according to the invention, based on water, are distinguished in comparison Le A 21 105 117496~
to the corresponding, previously known water-Free aerosol formulations not only by an unexpectedly higher action, but also by the fact that a smaller amount of organic solvent is required. The aerosol formulations, according to the invention, based on water, can therefore be prepared more cheaply than the corresponding water-free aerosol formul-ations. In addition, the pollution of the environment by organic solvents is reduced in the case of the aerosol formulations according to the invention.
The aerosol formulations, according to the present invention, based on water, contain at least one insecti-cidal and/or acaricidal substance selected from carbamates, pyrethroids, acetic acid ester derivatives and/or phosphoric acid ester derivatives. The following may be mentioned as individual examples of active compounds of this type:
The present invention relates to certain new aerosol formulations based on water, to a procPss for their preparation and to their use in the domestic field and hygiene field and in plant protection.
The application of active compounds in the domestic field and hygiene field and in plant protection with the aid of spray cans in which the active compounds in the aerosol formulations are contained in solution in organic solvents has already been disclosed. In this type of application relatively large amounts of organic solvents are sprayed; this is expensive, on the one hand, and is also undesirable for reasons of environmental protection, on the other hand. To eliminate this negative factor as far as possible, aerosol formulations were therefore developed in which a part of the organic solvents is replaced by water. A decisive disadvantage of the previously dis-closed aerosol formulations of this type however is that they exhibit a significantly lower action than the corres-ponding water-free aerosol formulations (see Bundesgesundheitsblatt tFederal Health Sheet) 24, No. 10.
pages 163-165 (1981)).
According to the present invention we provide, as new formulations, aerosol formulations based on water, characterised in that they consist of 0.01 to 6~o by weight of at least one insecticidal and/
or acaricidal substance selected from carbamates, pyrethroids, acetic acid ester derivatives and phosphoric acid ester derivatives, 0.1 to 2~o by weight of at least one emulsifier, to 40O by weight of at least one organic solvent, to 70O by weight of water, _ 10 to 50O by weight of propellant and if appropriate, 0.1 to 6~ by weight of additives, the sum of the components being 100,~ by weight in each case.
Le A 21 105 1 17496~
According to the present invention we further provide a process for the production of an aerosol formulation of the present invention, characterised in that a solution consisting of û.01 to 62~ by weight of at least one insecticidal and/or acaricidal substance selected from carbamates, pyrethroids, acetic acid ester derivatives and phosphoric acid ester derivatives, 0.1 to 2Co by weiyht of at least one emulsifier, 0 5 to 40~ by weight of at least one organic solvent and if appropriate, 0.1 to 6o by weight of additives, is mixed with 20 to 7030 by weight of water, and lO to 50O
by weight of propellant is added to the resulting mixture in a spray can, the sum of the components in the formul-ation being lOO~o by weight in each case, and the percentages by weight being relative to the resulting formulation.
Finally, it has been found that the aerosol formul-ations, according to the invention, based on water, can beused in the domestic field and hygiene field or in agri-culture and in horticulture.
It i9 to be regarded as extremely surprising that the aerosol formulations, according to the invention, which are based on water and contain insecticidal and/or acaricidal substances selected from carbamates, pyrethroids, acetic acid ester derivatives and phosphoric acid ester derivatives, possess a better action than the corresponding, previously known water-free aerosol formulations. A superior action of this type could not be expected on the basis of the known state of the art, since, according to previous experience, the water-free aerojol formulations exhibited in each instance a better activity than the analogous water-containing aerosol formulations.
However, the aerosol formulations, according to the invention, based on water, are distinguished in comparison Le A 21 105 117496~
to the corresponding, previously known water-Free aerosol formulations not only by an unexpectedly higher action, but also by the fact that a smaller amount of organic solvent is required. The aerosol formulations, according to the invention, based on water, can therefore be prepared more cheaply than the corresponding water-free aerosol formul-ations. In addition, the pollution of the environment by organic solvents is reduced in the case of the aerosol formulations according to the invention.
The aerosol formulations, according to the present invention, based on water, contain at least one insecti-cidal and/or acaricidal substance selected from carbamates, pyrethroids, acetic acid ester derivatives and/or phosphoric acid ester derivatives. The following may be mentioned as individual examples of active compounds of this type:
2-isopropoxy-phenyl N-methylcarbamate, 2,2,2-trichloro-1-(3,4-dichlorophenyl)-ethyl acetate, ~-cyano-m-phenoxybenzyl (1R, 3R)-3-(2,2-dibromovinyl)-2,2-dimethyl-cyclopropane-1-carboxylate, 2,3,4,5-tetrahydrophthalimido-methyl chrysanthemumate, ~-cyano-3-phenoxy-4-fluorobenzyl
3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-carboxylate, (pentafluorophenyl)-methyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-carboxylate, natural pyrethrum, 0,0-diethyl thionophosphoryl-a-oxlmino-phenyl acetic acid nltrile and 0,0-diethyl thionophosphoryl-X-oximino-(2-chlorophenyl)-acetic acid nitrile. 2-isopropoxy-phenyl N-methylcarbamate is particularly preferred.
Polyoxyethylenesorbitane fatty acid ester and sorbitane fatty acid ester are preferred as emulsifiers which are contained in the aerosol formulations according to the invention. The following may be mentioned as examples: polyoxyethylene-sorbitane monolaurate, monopalmitate, monostearate and monooleate, having in each case an average of 20 -~H2-CH2-0 groups per molecule, and also sorbitane monolaurate, monopalmitate, monostearate, tristearate, monooleate and trioleate.
The emulsifiers can be contained individually or in the form of mixtures in the aerosol formulations Le A 21 105 1 17496~
according to the invention.
The following are preferred as organic solvents which are contained in the aerosol formulations according to the invention: saturated aliphatic hydrocarbons of boiling point between 150C and 250C (such as dodecane and deodorised kerosenes), ~d ~so low-boiling chlorinated aliphatic hydrocarbons (such as methylene chloride~ and furthermore alcohols having up to 3 carbon atoms (such as ethanol, n-propanol and iso-propanol) and in addition, low-boiling ketones (such as acetone and methyl ethyl ketone).
The organic solvents can be contained individually or in the form of mixtures.
Distilled w~t-r is preferred as the water in the case of aerosol formulations according to the invention.
Mixtures of propane and butane are preferred as propellants which are contained in the aerosol formuiations according to the invention.
Synergists, aroma substances and stabilisers are suitable as additives which can be contained in the 2û aerosol formulations, according to the invention, based on water.
Piperonyl butoxide may be mentioned as an example of a synergist.
Perfume oils are suitable as aroma substances.
The aroma gubstance obtainable under the designation "FrischduFt 760 712 H + R!' from Haarmann & Reimer GmbH, Holzminden, may be mentioned in particular.
Sodium benzoate and amphoteric tensides may be mentioned as examples of stabilisers.
The percentage proportions of the components contained in the aerosol formulations, according to the invention, based on water, can be varied within the specified ranges. The proportion of active compound or active compounds is preferably between 0.04 and 3O by weight. The proportion of emulsifier is preferably 0.2 to Le A 21 1û5 .
1 17496~
1.5~o by weight. Organic solvents are present preferably in proportions between 6 and 35O by weight. The pro-portion of propellant is preferably between 20 and 40O by weight. Additives can be contained in proportions of preferably 0.5 to 5O by weight.
The percentage proportion of water in the aerosol formulations according to the invention is calculated in each cass as the difference between 100~o by weight and the sum of the percentage portions of the remaining components.
Preferably between 30 and 65~ by weight, of water are contained in the formulations.
In the preparation of the aerosol formulations, according to the invention, based on water, by the process according to the invention, all those components can be used which have already been mentioned in connection with the description of the aerosol formulations themselves.
Those substances which have been mentioned individually above as preFerred or as examples are preferred.
In carrying out the process according to the 2û invention, the process temperatures can be varied within a certain range. The process is carried out in general at a teMperature between 0C and 50C, preferably between 10C and 30C.
In carrying out the process according to the invention, in general the following procedure is followed:
a solution of the active compound or active compounds, emulsifier and organic solvent and, if appropriate, additives, is introduced into a spray can which already contains the desired amount of water, the spray can is then closed with a valve, and the propellant is introduced by customary methods. The sequence in which the components are combined in the preparation of the organic phase is variable. Like-wise, the mixing of the organic phase with water and the addition of a propellant in a customary manner can also be varied.
_e A 21 105 1174~6~
The aerosol formulations, according to the invention, based on water, can be applied in the prepared form. The amount used depends on the con-centration in which the active compound is present, and on the particular indication.
The present invention also provides a method of combating insects or acarids which comprises applying to the insects or acarids, or to a habitat thereof, an aerosol formulation of the present invention.
The present invention also provides a method of freeing or protecting domesticated animals from insects or acarids which comprises applying to said animals an aerosol formulation according to the present invention.
The present invention further provides crops protectsd from damage by insects or acarids by being grown in areas in which immediately prior to and/or during the time of the growing an aerosol formulation of the present invention.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The present invention further provides domesticated animals whenever freed or protected from insects or acarids by the application to said animals of an aerosol formulation according to the presnt invention.
Furthermore, it is possible to spray other areas or objects on which the active components are to develop their action with the formulations. If the active components are intended to act in rooms, the formulations are sprayed in these rooms.
The following Examples illustrate the preparation and the use of the aerosol formulations according to the present invention.
Le A 21 105 117496~
Preparative Exampl~s Example l To prepare an aerosol formulation based on water, 40 9 of distille~ water were initially introduced into a spray can having a gross volume of 120 ml, and a solution which contained 2 9 of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2 g of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, l g of piperonyl bùtoxide, 1 9 of sorbitane monooleate, 0.2 9 of the aroma substance obtainable under the name "Frischduft 760 712 H * R" from Haarmann ~ Reimer GmbH, Holzminden, 10 9 of methylene chloride and 15.6 9 of isopropanol was added. Thereafter, the spray can was provided with a valve and filled with 30 9 of a propel-lant gas mixture which consisted of 15o by weight of propane and 85o by weight of butane.
The aerosol formulations listed in the examples below were also prepared according to the method given in Example 1.
Example 2 Aerosol formulation of the following composition:
2 96 by weight of 2-isopropoxy-phenyl N-methyl-carbamate 0.2 ~ by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 96 by weight of piperonyl butoxide, 96 by weight of sorbitane monooleate, 0,2 ~ by weight of "Frischduft 760 712 H + R" (see Example 1), Le A 21 105 1 17496~
10 ~0 by weight of methylene chloride, 20 O by weight of isopropanol, 5 O by weight of dodecane, 30.6 O by weight of distilled water and 30 O by weight of propane/butane = 15 : 85.
Example 3 ~
Aerosol formulation of the following composition:
2 ~O by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2 gO by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, O by weight of piperonyl butoxide, 90 by weight of sorbitane monooleate, 0.2 ~O by weight of "Frischduft 760 712 H + R" (see Example 1), 5 Zo by weight of methylene chloride, 20 O by weight of isopropanol, 35.6 O by weight of distilled water and 20 30 ~0 by weight of propane/butane = 15 : 85.
Example 4 Aerosol formulation of t.hefollowing composition:
2 O by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2 ~O~ by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 5~ by weight of piperonyl butoxide, ~O by weight of a mixture of 9 parts by weight of sorbitane monooleate and l part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2_o groups per molecule, Le A 21 105 1 174~6~
g 0.2% by weight o~ "Frischduft 760 712 H + R" (see Example 1), 10.6% by weight of methylene chloride, 10 % by weight o~ isopropanol, 5 5 % by weight of dodecane, 40 % by weight of distilled water and 30 % by weight of propane/butane = 15: 85 ExamPle 5 Aerosol formulation of the following composition:
10 2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate~
1 % by weight of piperonyl butoxide, 15 1 % by weight of sorbitane monooleate, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 15.6% by weight of isopropanol, 10 % by weight of dodecane, 20 40 % by weight of distilled water and 30 % by weight of propane/butane = 15: 85.
Exam~le 6 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidanethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, % by weight of piperonyl butoxide, % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight o~ polyoxyethylene-sorbitane monooleate having an average OI 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 10 % by weight of methylene chloride, 15.6% by weight o~ isopropanol, 40 % by weight of distilled l~ater and Le A 21 105 1 17496~
30 % by weight of propane/butane = 25 : 75.
Example 7 Aerosol formulation o~ the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of a mixture of 9 pàrts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 15.6% by weight of isopropanol, 10 % by weight of dodecane, 40 % by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
ExamPle 8 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 5 % by weight of methylene chloride, y by weight of isopropanol, % by weight of dodecane, 35.6% by weight of distilled water and Le A 21 105 1 17496~
30 % by weight of propane/butane = 25: 75.
Example 9 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 12 % by weight of methylene chloride, 5 % by weight of dodecane, 48.6% by weight of distilled water and 30 % by weight o~ propane/butane = 25: 75.
Exam~le 10 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidcmethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide 1 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 5 % by weight of methylene chloride, 35 15 % by weight of isopropanol, 5 % by weight of dodecane, 40.6% by weight of distilled water and Le A 21 105 ~174967.
30 /0 by weight of propane/butane = 25: 75 Example 11 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 ~0 by weight of sorbitane monooleate, 0.2% by weight of "Frischduft 760 712 H ~ ~" (see Example 1), 15.6% by weight of methylene chloride, 10 % by weight of dodecane, 40 /0 by weight of distilled water and 30 % by weight of propane/butane = 15 : 85.
Example 12 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyI 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of sorbitane monooleate, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 12 % by weight of methylene chloride, 5 /0 by weight of dodecane, 48.6% by weight of distilled water and 30 % by weight of propane/butane = 15: 85.
30 Example 13 Aerosol formulation of the following composition:
2 /0 by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of sorbitane monooleate, Le A 21 10~
3L17496~
0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 5 % by weight of ~odecane, 16.5% by weight of isopropanol, 5 44.1% by weight of distilled water, 30 % by weight of propane/butane = 15: 85.
Example 14 Aerosol formulation of the following composition:
0.04% by weight of c~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.3% by weight of a mixture OI 9 parts by weight of sorbitane monooleate and l part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3 % by weight of dodecane, 3.5% by weight of acetone, 63.16% by weight of distilled water and 20 30 % by weight of propane/butane = 15: 85.
Example 1~
Aerosol formulation of the following composition:
0.04% by weight of ~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.2 % by weight of piperonyl butoxide, - 0.3 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and l part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3 % by weight of dodecane, 3.5 % by weight of acetone, 62.96% by weight of distilled water and 35 30 % by weight of propane/butane = 25: 75.
Example 16 Aerosol formulation of the following composition:
0.04% by weight of (pentafluorophenyl)-methyl 3-(2,2-Le A 21 105 ~ 174967 _ 14 --dichlorovinyl)-2,2-dimethylcyclo-propanecarboxylate, 0.025%byweight of ~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.2 % by weight of piperonyl butoxide, 0.3 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3 % by weight of dodecane, 3.5 % by weight of acetone, 62.935%by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
Example 17 Aerosol formulation of the following composition:
0.04% by weight of (pentafluorophenyl)-methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclo-propanecarboxylate, 0.3 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 CH2-CH2-0 groups per molecule, 3 % by weight of dodecane, 3.5 % by weight of acetone, 63.16% by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
Example 18 Aerosol formulation of the following composition:
2 % by weight of 2,2,2-trichloro-1-(3,4-dichloro-phenyl)-ethyl acetate, 0.2 % by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 % by weight of piperonyl butoxide, 0.75% by weight of sorbitane monooleate, Le A 21 105 l 174967 % by weight of dodecane, % by weight of isopropanol, 46.05% by weight of distilled water and % by weight of propane/butane = 25 : 75.
Example 19 Aerosol formulation of the following composition:
2 % by weight of 2,~,2-trichloro-1-(3,4-dichloro-phenyl)-ethyl acetate, 0.2 % by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 % by weight of piperonyl butoxide, 0.75% by weight of sorbitane monooleate, % by weight of dodecane, 46.05% by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
ExamPle 20 Aerosol formulation of the following composition:
2 % by weight of 2,2,2-trichloro-1-(3,4-dichlorophe-nyl)-ethyl acetate, 0,2 % by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 % by weight of piperonyl butoxide, 0.75% by weight of sorbitane monooleate, % by weight of dodecane, % by weight of isopropanol, 46.05% by weight of distilled water and ~o by weight of propane/butane = 25 : 75.
Example 21 Aerosol formulation of the following composition:
1 ~ by weight of 0,0-diethyl-thionophosphoryl-~-oximino-phenyl acetic acid nitrile, 0.2 % by weight of natural pyrethrum, 1 ~ by weight of piperonyl butoxide, 0.4 ~ by weight of a mixture of Le A 21 10_ 1 17~96~
9 parts by weight of sorbitane mono-oleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3.6 ~ by weight of dodecane, 3.5 % by weight of acetone, 60.3 % by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
Example 22 Aerosol formulation of the following composition:
1 % by weight of 0,0-diethyl-thionophosphoryl-~-oximino-(2-chlorophenyl~ acetic acid nitrile, 0.2 % by weight of natural pyrethrum, 1 ~ by weight of piperonyl butoxide, 0.4 % by weight of a mixture of 9 parts by weight of sorbitane mono-oleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3.6 % by weight of dodecane, 3.5 % by weight of acetone, 60.3 % by weight of distilled water and % by weight of propane/butane = 25 : 75.
ExamPle 23 Aerosol formulation of the following composition:
2 ~ by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.04% by weight of ~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.2 % by weight of piperonyl butoxide, 1 % by weight of sorbitane monooleate, 0.2 % by weight of "Frischduft 760 712 H + R"
(see Example 1), Le A 21 105 ~ by weight of methylene chloride, % by weight of isopropanol, % by welght of dodecane, 30.6 % by weight of distilled water, % by weight of propane/butane = 15 : 85.
Example 24 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.04% by weight of (pentafluorophenyl)-methyl-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclo-propanecarboxylate, 0.2 % by weight of piperonyl butoxide, 1 % by weight of sorbitane monooleate, 0.2 % by weight of "Frischduft 760 212 H + R"
(see Example 1), 10 ~ by weight of methylene chloride, 20 % by weight of isopropanol, 5 ~ by weight of dodecane, 30.6 % by weight of distilled water, 20 30 % by weight of propane/butane = 15 : 85.
Example 25 Aerosol formulation of the following composition:
2 % by weight of 2,2,2-trichloro-1-(3,4-dichlorophenyl)-ethyl acetate, 0.04~ by weight of (pentafluorophenyl)-methyl-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclo-propanecarboxylate, 0.75% by weight of sorbitane monooleate, 15 % by weight of dodecane, 30. 5 % by weight of isopropanol, 47.21% by weight of distilled water, 30 % by weight of propane/butane = 2S : 75.
Comparative ExamPles Example I
Aerosol formulation of the following composition:
0.04% by weight of X-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 5 ~ by weight of methylene chloride, Le A 21 105 117496~
% by weight of dodecane and 0.01~ by weight of "Frischduft 760 712 H + R"
(see Example 1), 84.95% by weight of propane/butane = 15 : 85.
Example II
Aerosol formulation of the ollowing composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2 % by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 % by weight of piperonyl butoxide, 11.8 % by weight of dodecane, % by weight of methylene chloride and % by weight of propane/butane = 15 : 85.
Example III
Aerosol formulation of the following composition:
0.04% by weight of a-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.2 % by weight of piperonyl butoxide, 5 % by weight of methylene chloride, 9.76% by weight of dodecane and 85 % by weight of propane/butane 15 : 85.
Example IV
Aerosol formulation of the following composition:
0.04~o by weight of (pentafluoromethyl)-methyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclo-propanecarboxylate, 0.025%by weight of ~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cycloprop~necarboxylate, 0.2 % by weight of piperonyl butoxide, 9.735%by weight of dodecane and 85 % by weight of propane/butane = 15 : 85.
35 ExamPle V
Aerosol formulation of the following composition:
0.04% by weight of (pentafluorophenyl)-methyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclo-propanecarboxylate, Le A 21 105 1 17496~
O by weight of methylene chloride, 9.96 O by weight of dodecane and O by weight of propane/butane = 15 : 85.
Example VI
Aerosol formulation of the following composition:
2 O by weight of 2,2,2-trichloro-1-(3,4-dichlorophenyl)-ethyl acetate, 0.2 O by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 O by weight of piperonyl butoxide, 0.01 O by weight of "Frischduft 760 712 H + R'l (see Example 1), 10 O by weight of methylene chloride, oO by weight of dodecane and 71.79o by weight of propane/butane 15 : 85.
Example VII
Aerosol formulation of the following composition:
1 ~ by weight of O,O-diethyl-thionophosphoryl-~-oximino-phenyl acetic acid nitrile, 0.2 ~ by weiqht of natural pyrethrum, 1 % by weight of piperonyl butoxide, 18 ~ by weight of isopropanol, 12 ~ by weight of dodecane, 67.8 % by weight of propane/butane = 15 : 85.
The insecticidal activity of the compositions ac-cordlng to this invention is illustrated by the following biotest-Examples.
Example A
Aerosol test Test animals: Musca domestica 0~ (resistant) 3 wire cages were suspended from the ceiling in two identical rooms A and B of 30 m~ capacity each, and 20 3 to 4 day old flies of the species ~lusca domestica were introduced into each wire cage so that there were 60 flies in each room.
The room temperature is 22C in both rooms.
Through a flap in the doors to both rooms, 16.9 9 of the formulation of Example 14 were then sprayed into r~om A
and 16.9 9 of the formulation of Example 1 were sprayed Le A 21 105 1 17496~
into room B. Thereafter,the condition of the test animals was constantly checked from outside, through a glass window, and the times (minutes) required for a 50O
(k.d. 50) or 100o (k.d. lO0) knock-down effect on the flies were determined.
The values determined can be seen in Table A
below.
Table A
Aerosol test Musca domestica ~ (resistant) Formulation K.d. 50 K.d. lO0 according (minutes) (minutes) to ExampIe .. ..
(known) -(according to the invention) . . . _ . . . _ . _ Example B
Aerosol te~t Test animals; l~usca domestica ~ (resistant) 3 wire cages were suspended from the ceiling in each of three identical rooms A, B and C of 30 m3 capacity, before each sxperiment. Each wire cage contained 20 3 to
Polyoxyethylenesorbitane fatty acid ester and sorbitane fatty acid ester are preferred as emulsifiers which are contained in the aerosol formulations according to the invention. The following may be mentioned as examples: polyoxyethylene-sorbitane monolaurate, monopalmitate, monostearate and monooleate, having in each case an average of 20 -~H2-CH2-0 groups per molecule, and also sorbitane monolaurate, monopalmitate, monostearate, tristearate, monooleate and trioleate.
The emulsifiers can be contained individually or in the form of mixtures in the aerosol formulations Le A 21 105 1 17496~
according to the invention.
The following are preferred as organic solvents which are contained in the aerosol formulations according to the invention: saturated aliphatic hydrocarbons of boiling point between 150C and 250C (such as dodecane and deodorised kerosenes), ~d ~so low-boiling chlorinated aliphatic hydrocarbons (such as methylene chloride~ and furthermore alcohols having up to 3 carbon atoms (such as ethanol, n-propanol and iso-propanol) and in addition, low-boiling ketones (such as acetone and methyl ethyl ketone).
The organic solvents can be contained individually or in the form of mixtures.
Distilled w~t-r is preferred as the water in the case of aerosol formulations according to the invention.
Mixtures of propane and butane are preferred as propellants which are contained in the aerosol formuiations according to the invention.
Synergists, aroma substances and stabilisers are suitable as additives which can be contained in the 2û aerosol formulations, according to the invention, based on water.
Piperonyl butoxide may be mentioned as an example of a synergist.
Perfume oils are suitable as aroma substances.
The aroma gubstance obtainable under the designation "FrischduFt 760 712 H + R!' from Haarmann & Reimer GmbH, Holzminden, may be mentioned in particular.
Sodium benzoate and amphoteric tensides may be mentioned as examples of stabilisers.
The percentage proportions of the components contained in the aerosol formulations, according to the invention, based on water, can be varied within the specified ranges. The proportion of active compound or active compounds is preferably between 0.04 and 3O by weight. The proportion of emulsifier is preferably 0.2 to Le A 21 1û5 .
1 17496~
1.5~o by weight. Organic solvents are present preferably in proportions between 6 and 35O by weight. The pro-portion of propellant is preferably between 20 and 40O by weight. Additives can be contained in proportions of preferably 0.5 to 5O by weight.
The percentage proportion of water in the aerosol formulations according to the invention is calculated in each cass as the difference between 100~o by weight and the sum of the percentage portions of the remaining components.
Preferably between 30 and 65~ by weight, of water are contained in the formulations.
In the preparation of the aerosol formulations, according to the invention, based on water, by the process according to the invention, all those components can be used which have already been mentioned in connection with the description of the aerosol formulations themselves.
Those substances which have been mentioned individually above as preFerred or as examples are preferred.
In carrying out the process according to the 2û invention, the process temperatures can be varied within a certain range. The process is carried out in general at a teMperature between 0C and 50C, preferably between 10C and 30C.
In carrying out the process according to the invention, in general the following procedure is followed:
a solution of the active compound or active compounds, emulsifier and organic solvent and, if appropriate, additives, is introduced into a spray can which already contains the desired amount of water, the spray can is then closed with a valve, and the propellant is introduced by customary methods. The sequence in which the components are combined in the preparation of the organic phase is variable. Like-wise, the mixing of the organic phase with water and the addition of a propellant in a customary manner can also be varied.
_e A 21 105 1174~6~
The aerosol formulations, according to the invention, based on water, can be applied in the prepared form. The amount used depends on the con-centration in which the active compound is present, and on the particular indication.
The present invention also provides a method of combating insects or acarids which comprises applying to the insects or acarids, or to a habitat thereof, an aerosol formulation of the present invention.
The present invention also provides a method of freeing or protecting domesticated animals from insects or acarids which comprises applying to said animals an aerosol formulation according to the present invention.
The present invention further provides crops protectsd from damage by insects or acarids by being grown in areas in which immediately prior to and/or during the time of the growing an aerosol formulation of the present invention.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The present invention further provides domesticated animals whenever freed or protected from insects or acarids by the application to said animals of an aerosol formulation according to the presnt invention.
Furthermore, it is possible to spray other areas or objects on which the active components are to develop their action with the formulations. If the active components are intended to act in rooms, the formulations are sprayed in these rooms.
The following Examples illustrate the preparation and the use of the aerosol formulations according to the present invention.
Le A 21 105 117496~
Preparative Exampl~s Example l To prepare an aerosol formulation based on water, 40 9 of distille~ water were initially introduced into a spray can having a gross volume of 120 ml, and a solution which contained 2 9 of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2 g of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, l g of piperonyl bùtoxide, 1 9 of sorbitane monooleate, 0.2 9 of the aroma substance obtainable under the name "Frischduft 760 712 H * R" from Haarmann ~ Reimer GmbH, Holzminden, 10 9 of methylene chloride and 15.6 9 of isopropanol was added. Thereafter, the spray can was provided with a valve and filled with 30 9 of a propel-lant gas mixture which consisted of 15o by weight of propane and 85o by weight of butane.
The aerosol formulations listed in the examples below were also prepared according to the method given in Example 1.
Example 2 Aerosol formulation of the following composition:
2 96 by weight of 2-isopropoxy-phenyl N-methyl-carbamate 0.2 ~ by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 96 by weight of piperonyl butoxide, 96 by weight of sorbitane monooleate, 0,2 ~ by weight of "Frischduft 760 712 H + R" (see Example 1), Le A 21 105 1 17496~
10 ~0 by weight of methylene chloride, 20 O by weight of isopropanol, 5 O by weight of dodecane, 30.6 O by weight of distilled water and 30 O by weight of propane/butane = 15 : 85.
Example 3 ~
Aerosol formulation of the following composition:
2 ~O by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2 gO by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, O by weight of piperonyl butoxide, 90 by weight of sorbitane monooleate, 0.2 ~O by weight of "Frischduft 760 712 H + R" (see Example 1), 5 Zo by weight of methylene chloride, 20 O by weight of isopropanol, 35.6 O by weight of distilled water and 20 30 ~0 by weight of propane/butane = 15 : 85.
Example 4 Aerosol formulation of t.hefollowing composition:
2 O by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2 ~O~ by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 5~ by weight of piperonyl butoxide, ~O by weight of a mixture of 9 parts by weight of sorbitane monooleate and l part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2_o groups per molecule, Le A 21 105 1 174~6~
g 0.2% by weight o~ "Frischduft 760 712 H + R" (see Example 1), 10.6% by weight of methylene chloride, 10 % by weight o~ isopropanol, 5 5 % by weight of dodecane, 40 % by weight of distilled water and 30 % by weight of propane/butane = 15: 85 ExamPle 5 Aerosol formulation of the following composition:
10 2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate~
1 % by weight of piperonyl butoxide, 15 1 % by weight of sorbitane monooleate, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 15.6% by weight of isopropanol, 10 % by weight of dodecane, 20 40 % by weight of distilled water and 30 % by weight of propane/butane = 15: 85.
Exam~le 6 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidanethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, % by weight of piperonyl butoxide, % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight o~ polyoxyethylene-sorbitane monooleate having an average OI 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 10 % by weight of methylene chloride, 15.6% by weight o~ isopropanol, 40 % by weight of distilled l~ater and Le A 21 105 1 17496~
30 % by weight of propane/butane = 25 : 75.
Example 7 Aerosol formulation o~ the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of a mixture of 9 pàrts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 15.6% by weight of isopropanol, 10 % by weight of dodecane, 40 % by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
ExamPle 8 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 5 % by weight of methylene chloride, y by weight of isopropanol, % by weight of dodecane, 35.6% by weight of distilled water and Le A 21 105 1 17496~
30 % by weight of propane/butane = 25: 75.
Example 9 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 12 % by weight of methylene chloride, 5 % by weight of dodecane, 48.6% by weight of distilled water and 30 % by weight o~ propane/butane = 25: 75.
Exam~le 10 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidcmethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide 1 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 5 % by weight of methylene chloride, 35 15 % by weight of isopropanol, 5 % by weight of dodecane, 40.6% by weight of distilled water and Le A 21 105 ~174967.
30 /0 by weight of propane/butane = 25: 75 Example 11 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 ~0 by weight of sorbitane monooleate, 0.2% by weight of "Frischduft 760 712 H ~ ~" (see Example 1), 15.6% by weight of methylene chloride, 10 % by weight of dodecane, 40 /0 by weight of distilled water and 30 % by weight of propane/butane = 15 : 85.
Example 12 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyI 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of sorbitane monooleate, 0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 12 % by weight of methylene chloride, 5 /0 by weight of dodecane, 48.6% by weight of distilled water and 30 % by weight of propane/butane = 15: 85.
30 Example 13 Aerosol formulation of the following composition:
2 /0 by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2% by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-di-methyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate, 1 % by weight of piperonyl butoxide, 1 % by weight of sorbitane monooleate, Le A 21 10~
3L17496~
0.2% by weight of "Frischduft 760 712 H + R" (see Example 1), 5 % by weight of ~odecane, 16.5% by weight of isopropanol, 5 44.1% by weight of distilled water, 30 % by weight of propane/butane = 15: 85.
Example 14 Aerosol formulation of the following composition:
0.04% by weight of c~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.3% by weight of a mixture OI 9 parts by weight of sorbitane monooleate and l part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3 % by weight of dodecane, 3.5% by weight of acetone, 63.16% by weight of distilled water and 20 30 % by weight of propane/butane = 15: 85.
Example 1~
Aerosol formulation of the following composition:
0.04% by weight of ~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.2 % by weight of piperonyl butoxide, - 0.3 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and l part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3 % by weight of dodecane, 3.5 % by weight of acetone, 62.96% by weight of distilled water and 35 30 % by weight of propane/butane = 25: 75.
Example 16 Aerosol formulation of the following composition:
0.04% by weight of (pentafluorophenyl)-methyl 3-(2,2-Le A 21 105 ~ 174967 _ 14 --dichlorovinyl)-2,2-dimethylcyclo-propanecarboxylate, 0.025%byweight of ~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.2 % by weight of piperonyl butoxide, 0.3 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3 % by weight of dodecane, 3.5 % by weight of acetone, 62.935%by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
Example 17 Aerosol formulation of the following composition:
0.04% by weight of (pentafluorophenyl)-methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclo-propanecarboxylate, 0.3 % by weight of a mixture of 9 parts by weight of sorbitane monooleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 CH2-CH2-0 groups per molecule, 3 % by weight of dodecane, 3.5 % by weight of acetone, 63.16% by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
Example 18 Aerosol formulation of the following composition:
2 % by weight of 2,2,2-trichloro-1-(3,4-dichloro-phenyl)-ethyl acetate, 0.2 % by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 % by weight of piperonyl butoxide, 0.75% by weight of sorbitane monooleate, Le A 21 105 l 174967 % by weight of dodecane, % by weight of isopropanol, 46.05% by weight of distilled water and % by weight of propane/butane = 25 : 75.
Example 19 Aerosol formulation of the following composition:
2 % by weight of 2,~,2-trichloro-1-(3,4-dichloro-phenyl)-ethyl acetate, 0.2 % by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 % by weight of piperonyl butoxide, 0.75% by weight of sorbitane monooleate, % by weight of dodecane, 46.05% by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
ExamPle 20 Aerosol formulation of the following composition:
2 % by weight of 2,2,2-trichloro-1-(3,4-dichlorophe-nyl)-ethyl acetate, 0,2 % by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 % by weight of piperonyl butoxide, 0.75% by weight of sorbitane monooleate, % by weight of dodecane, % by weight of isopropanol, 46.05% by weight of distilled water and ~o by weight of propane/butane = 25 : 75.
Example 21 Aerosol formulation of the following composition:
1 ~ by weight of 0,0-diethyl-thionophosphoryl-~-oximino-phenyl acetic acid nitrile, 0.2 % by weight of natural pyrethrum, 1 ~ by weight of piperonyl butoxide, 0.4 ~ by weight of a mixture of Le A 21 10_ 1 17~96~
9 parts by weight of sorbitane mono-oleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3.6 ~ by weight of dodecane, 3.5 % by weight of acetone, 60.3 % by weight of distilled water and 30 % by weight of propane/butane = 25 : 75.
Example 22 Aerosol formulation of the following composition:
1 % by weight of 0,0-diethyl-thionophosphoryl-~-oximino-(2-chlorophenyl~ acetic acid nitrile, 0.2 % by weight of natural pyrethrum, 1 ~ by weight of piperonyl butoxide, 0.4 % by weight of a mixture of 9 parts by weight of sorbitane mono-oleate and 1 part by weight of polyoxyethylene-sorbitane monooleate having an average of 20 -CH2-CH2-0 groups per molecule, 3.6 % by weight of dodecane, 3.5 % by weight of acetone, 60.3 % by weight of distilled water and % by weight of propane/butane = 25 : 75.
ExamPle 23 Aerosol formulation of the following composition:
2 ~ by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.04% by weight of ~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.2 % by weight of piperonyl butoxide, 1 % by weight of sorbitane monooleate, 0.2 % by weight of "Frischduft 760 712 H + R"
(see Example 1), Le A 21 105 ~ by weight of methylene chloride, % by weight of isopropanol, % by welght of dodecane, 30.6 % by weight of distilled water, % by weight of propane/butane = 15 : 85.
Example 24 Aerosol formulation of the following composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.04% by weight of (pentafluorophenyl)-methyl-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclo-propanecarboxylate, 0.2 % by weight of piperonyl butoxide, 1 % by weight of sorbitane monooleate, 0.2 % by weight of "Frischduft 760 212 H + R"
(see Example 1), 10 ~ by weight of methylene chloride, 20 % by weight of isopropanol, 5 ~ by weight of dodecane, 30.6 % by weight of distilled water, 20 30 % by weight of propane/butane = 15 : 85.
Example 25 Aerosol formulation of the following composition:
2 % by weight of 2,2,2-trichloro-1-(3,4-dichlorophenyl)-ethyl acetate, 0.04~ by weight of (pentafluorophenyl)-methyl-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclo-propanecarboxylate, 0.75% by weight of sorbitane monooleate, 15 % by weight of dodecane, 30. 5 % by weight of isopropanol, 47.21% by weight of distilled water, 30 % by weight of propane/butane = 2S : 75.
Comparative ExamPles Example I
Aerosol formulation of the following composition:
0.04% by weight of X-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 5 ~ by weight of methylene chloride, Le A 21 105 117496~
% by weight of dodecane and 0.01~ by weight of "Frischduft 760 712 H + R"
(see Example 1), 84.95% by weight of propane/butane = 15 : 85.
Example II
Aerosol formulation of the ollowing composition:
2 % by weight of 2-isopropoxy-phenyl N-methyl-carbamate, 0.2 % by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 % by weight of piperonyl butoxide, 11.8 % by weight of dodecane, % by weight of methylene chloride and % by weight of propane/butane = 15 : 85.
Example III
Aerosol formulation of the following composition:
0.04% by weight of a-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, 0.2 % by weight of piperonyl butoxide, 5 % by weight of methylene chloride, 9.76% by weight of dodecane and 85 % by weight of propane/butane 15 : 85.
Example IV
Aerosol formulation of the following composition:
0.04~o by weight of (pentafluoromethyl)-methyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclo-propanecarboxylate, 0.025%by weight of ~-cyano-3-phenoxy-4-fluorobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cycloprop~necarboxylate, 0.2 % by weight of piperonyl butoxide, 9.735%by weight of dodecane and 85 % by weight of propane/butane = 15 : 85.
35 ExamPle V
Aerosol formulation of the following composition:
0.04% by weight of (pentafluorophenyl)-methyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclo-propanecarboxylate, Le A 21 105 1 17496~
O by weight of methylene chloride, 9.96 O by weight of dodecane and O by weight of propane/butane = 15 : 85.
Example VI
Aerosol formulation of the following composition:
2 O by weight of 2,2,2-trichloro-1-(3,4-dichlorophenyl)-ethyl acetate, 0.2 O by weight of 3,4,5,6-tetrahydrophthalimidomethyl 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylate, 1 O by weight of piperonyl butoxide, 0.01 O by weight of "Frischduft 760 712 H + R'l (see Example 1), 10 O by weight of methylene chloride, oO by weight of dodecane and 71.79o by weight of propane/butane 15 : 85.
Example VII
Aerosol formulation of the following composition:
1 ~ by weight of O,O-diethyl-thionophosphoryl-~-oximino-phenyl acetic acid nitrile, 0.2 ~ by weiqht of natural pyrethrum, 1 % by weight of piperonyl butoxide, 18 ~ by weight of isopropanol, 12 ~ by weight of dodecane, 67.8 % by weight of propane/butane = 15 : 85.
The insecticidal activity of the compositions ac-cordlng to this invention is illustrated by the following biotest-Examples.
Example A
Aerosol test Test animals: Musca domestica 0~ (resistant) 3 wire cages were suspended from the ceiling in two identical rooms A and B of 30 m~ capacity each, and 20 3 to 4 day old flies of the species ~lusca domestica were introduced into each wire cage so that there were 60 flies in each room.
The room temperature is 22C in both rooms.
Through a flap in the doors to both rooms, 16.9 9 of the formulation of Example 14 were then sprayed into r~om A
and 16.9 9 of the formulation of Example 1 were sprayed Le A 21 105 1 17496~
into room B. Thereafter,the condition of the test animals was constantly checked from outside, through a glass window, and the times (minutes) required for a 50O
(k.d. 50) or 100o (k.d. lO0) knock-down effect on the flies were determined.
The values determined can be seen in Table A
below.
Table A
Aerosol test Musca domestica ~ (resistant) Formulation K.d. 50 K.d. lO0 according (minutes) (minutes) to ExampIe .. ..
(known) -(according to the invention) . . . _ . . . _ . _ Example B
Aerosol te~t Test animals; l~usca domestica ~ (resistant) 3 wire cages were suspended from the ceiling in each of three identical rooms A, B and C of 30 m3 capacity, before each sxperiment. Each wire cage contained 20 3 to
4 day old flies. The temperature in the rooms ~as 22C.
16.9 9 of can content per ro-om were sprayed successively into the rooms from spray cans, through a flap in the door.
The condition of the test animals was constantly checked through a window in the door, and the times (minutes) required for a 50O (K.d. 5û) and a 100~o (K.d. lO0) knock-down effect on the flies were determined. In this manner several spray can formulations were tested in succession. Between the individual tests, the rooms were thoroughly ventilated until they were again insecticide-free.
The formulations used and the values determined can be seen in Tables B-l to B-6 below.
Le A 21 105 1 17496~
Table B-l Aerosol test Musca domestica 0~ (resistant) Formulation K.d. 50 K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
Table B-2 Aerosol test Musca domestica od (resistant) Formulation K.d. 5û K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
Le A 21 105 ~ 17496~
Table B-3 .
Aerosol test Musca domestica ~ (resistant) Formulation K.d. 50 K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
Table B-4 Aerosol test Musca domestica ~0 (resistant) Formulation K.d. 50 K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
Table B-5 Aerosol test Musca domestica ~ (resistant) Formulation K.d. 50 K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
, _ Le A 21 105 1 1 7496~
Tablo B-6 Aerosol test Musca domestica ~ (resi3tant) Formulation K.d. 50 K.d. lO0 according to ~minute~) (minute~) Example _ known: ~
VII 26 ~ 60 according to the invention:
Le A 21 105
16.9 9 of can content per ro-om were sprayed successively into the rooms from spray cans, through a flap in the door.
The condition of the test animals was constantly checked through a window in the door, and the times (minutes) required for a 50O (K.d. 5û) and a 100~o (K.d. lO0) knock-down effect on the flies were determined. In this manner several spray can formulations were tested in succession. Between the individual tests, the rooms were thoroughly ventilated until they were again insecticide-free.
The formulations used and the values determined can be seen in Tables B-l to B-6 below.
Le A 21 105 1 17496~
Table B-l Aerosol test Musca domestica 0~ (resistant) Formulation K.d. 50 K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
Table B-2 Aerosol test Musca domestica od (resistant) Formulation K.d. 5û K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
Le A 21 105 ~ 17496~
Table B-3 .
Aerosol test Musca domestica ~ (resistant) Formulation K.d. 50 K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
Table B-4 Aerosol test Musca domestica ~0 (resistant) Formulation K.d. 50 K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
Table B-5 Aerosol test Musca domestica ~ (resistant) Formulation K.d. 50 K.d. lO0 according to (minutes) (minutes) Example known:
according to the invention:
, _ Le A 21 105 1 1 7496~
Tablo B-6 Aerosol test Musca domestica ~ (resi3tant) Formulation K.d. 50 K.d. lO0 according to ~minute~) (minute~) Example _ known: ~
VII 26 ~ 60 according to the invention:
Le A 21 105
Claims (20)
PROPERTY OF PRIVILEGE IS DEFINED ARE CLAIMED AS FOLLOWS:
1. Aerosol formulation based on water, comprising 0.01 to 6% by weight of at least one insecticidal and/or acaricidal substance selected from carbamates pyrethroids, acetic acid ester derivatives and/or phosphoric acid ester deri-vatives, 0.1 to 2% by weight of at least one emulsifier, 5 to 40% by weight of at least one organic solvent, 20 to 70% by weight of water, 10 to 50% by weight of propellant and, where required, 0.1 to 6% by weight of additives, the sum of the components being 100% by weight.
2. Aerosol formulation as claimed in claim 1, in which the insecticidal and/or acaricidal substance is a carbamate.
3. Aerosol formulation as claimed in claim 2, in which the carbamate is 2-isopropoxy-phenyl N-methylcarbamate.
4. Aerosol formulation as claimed in claim 1, in which the insecticidal and/or acaricidal substance is a pyrethroid.
5. Aerosol formulation as claimed in claim 4, in which the pyrethroid is .alpha.-cyano-m-phenoxybenzyl (1R, 3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopro-pane-1-carboxylate.
6. Aerosol formulation as claimed in claim 4, in which the pyrethroid is 3,4,5,6-tetrahydrophthalimidomethyl-2,2-dimethyl-3-(2-methylpropenyl)-cyclo-propanecarboxylate.
7. Aerosol formulation as claimed in claim 4, in which the pyrethroid is .alpha.-cyano-3-phenoxy-4-fluorobenzyl-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclo-propanecarboxylate.
8. Aerosol formulation as claimed in claim 4, in which the pyrethroid is (pentafluorophenyl)-methyl-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-carboxylate.
9. Aerosol formulation as claimed in claim 1, in which the insecticidal and/or acaricidal substance is an acetic acid ester derivative.
10. Aerosol formulation as claimed in claim 9, in which the acetic acid ester derivative is 2,2,2-trichloro-1-(3,4-dichlorophenyl)-ethyl acetate.
11. Aerosol formulation as claimed in claim 1, in which the insecticidal and/or acaricidal substance is a phosphoric acid ester derivative.
12. Aerosol formulation as claimed in claim 11, in which the phosphoric acid ester derivative is 0,0-diethyl-thionophosphoryl-.alpha.-oximino-phenyl acetic acid nitrile.
13. Aerosol formulation as claimed in claim 11, in which the phosphoric acid ester derivative is 0,0-diethyl-thionophosphoryl-.alpha.-oximino-(2-chlorophenyl) acetic acid nitrile.
14. Aerosol formulation as claimed in claim 1, in which the emulsifier is selected from polyoxyethylene-sorbitan monolaurate, monopalmitate, monostearate and monooleate, having in each case an average of 20 -CH2-CH2-O groups per molecule, and sorbitan monolaurate, monopalmitate, monostearate, tristearate, monooleate and trioleate.
15. Aerosol formulation as claimed in claim 1, in which the organic solvent is selected from saturated aliphatic hydrocarbons of a boiling point between 150°C and 250°C, low-boiling chlorinated aliphatic hydrocarbons, alcohols having up to 3 carbon atoms, and low-boiling ketones.
16. Aerosol formulation as claimed in claim 1, in which the propellant is a mixture of propane and butane.
17. Aerosol formulation as claimed in claim 1, in which the additives are selected from synergists, aroma substances and stabilisers.
18. Process for the production of aerosol formulations based on water, in which process a solution comprising 0.01 to 6% by weight of at least one insecticidal and/or acardicidal substance selected from carbamates, pyrethroids, acetic acid ester derivatives and phosphoric acid ester derivatives, 0.1 to 2%
by weight of at least one emulsifier, 5 to 40% by weight of at least one organic solvent and if appropriate, 0.1 to 6% by weight of additiues, is mixed with 20 to 70% by weight of water, and 10 to 50% by weight of propellant is added to the resulting mixture in a spray can, the sum of the components being 100% by weight in each case, and the percentages by weight being relative to the resulting formulation.
by weight of at least one emulsifier, 5 to 40% by weight of at least one organic solvent and if appropriate, 0.1 to 6% by weight of additiues, is mixed with 20 to 70% by weight of water, and 10 to 50% by weight of propellant is added to the resulting mixture in a spray can, the sum of the components being 100% by weight in each case, and the percentages by weight being relative to the resulting formulation.
19. Method of combating insects and acarids in the domestic field, the hygiene field, in agriculture or in horticulture, said method comprising applying to the insects and acarids, or to a habitat thereof, an aerosol formulation according to claim 1.
20. Method of freeing or protecting domesticated animals from parasites,said method comprising applying to the animals an aerosol formulation according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3127061.1 | 1981-07-09 | ||
| DE19813127061 DE3127061A1 (en) | 1981-07-09 | 1981-07-09 | AEROSOL WATER-BASED FORMULATIONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1174967A true CA1174967A (en) | 1984-09-25 |
Family
ID=6136462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000406784A Expired CA1174967A (en) | 1981-07-09 | 1982-07-07 | Aerosol formulations based on water |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0069906A3 (en) |
| JP (1) | JPS5815901A (en) |
| KR (1) | KR840000173A (en) |
| AU (1) | AU8576582A (en) |
| BR (1) | BR8203973A (en) |
| CA (1) | CA1174967A (en) |
| DE (1) | DE3127061A1 (en) |
| DK (1) | DK306982A (en) |
| ES (1) | ES513822A1 (en) |
| FI (1) | FI822413L (en) |
| GR (1) | GR78219B (en) |
| IL (1) | IL66236A0 (en) |
| MA (1) | MA19528A1 (en) |
| NO (1) | NO822091L (en) |
| OA (1) | OA07147A (en) |
| PT (1) | PT75143B (en) |
| ZA (1) | ZA824863B (en) |
| ZW (1) | ZW11682A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107047549A (en) * | 2017-06-15 | 2017-08-18 | 浙江绿岛科技有限公司 | Environment-friendly type aerial fog pesticide and preparation method thereof |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60104004A (en) * | 1983-11-09 | 1985-06-08 | Fumakiraa Kk | Aerosol psticide composition having low toxicity |
| JPS60104003A (en) * | 1983-11-09 | 1985-06-08 | Fumakiraa Kk | Aerosol pesticide composition having low phytotoxicity |
| AU605652B2 (en) * | 1987-12-15 | 1991-01-17 | Sumitomo Chemical Company, Limited | Insecticidal aerosol |
| AU605939B2 (en) * | 1987-12-15 | 1991-01-24 | Sumitomo Chemical Company, Limited | Mono-layer water-based insecticidal aerosol |
| JP2598938B2 (en) * | 1988-01-25 | 1997-04-09 | 大日本除蟲菊株式会社 | Water-based insecticide propellant |
| EP0478578A4 (en) * | 1989-04-17 | 1992-10-07 | S.C. Johnson & Son, Inc. | Water-soluble stable arthropodicidally-active foam matrix and method of manufacture |
| FR2692904A1 (en) * | 1992-06-30 | 1993-12-31 | Nln Sa | Liquid compositions propelled into a pressurized container of compressed gas for non-flammable and low-impact spraying. |
| JP3272105B2 (en) * | 1993-05-25 | 2002-04-08 | アース製薬株式会社 | Aerosol insecticide and insecticide method |
| ZA96514B (en) * | 1995-01-27 | 1996-08-13 | Johnson & Son Inc S C | Insecticidally-active composition |
| DE19534906C2 (en) * | 1995-09-20 | 1998-03-19 | Deutsche Automobilgesellsch | Sensor arrangement for measuring the mass of a flowing medium according to the principle of the hot film anemometer |
| FR2793112B1 (en) * | 1999-05-07 | 2001-07-27 | Pharmygiene Scat Lab | INSECTICIDE PREPARATION FOR SPRAYING |
| JP5641868B2 (en) * | 2010-10-19 | 2014-12-17 | 大日本除蟲菊株式会社 | Aqueous insecticide |
| CN107136055A (en) * | 2017-07-04 | 2017-09-08 | 佛山市顺德区香江精细化工实业有限公司 | A kind of water-base pesticide agent and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2524590A (en) * | 1946-04-22 | 1950-10-03 | Carsten F Boe | Emulsion containing a liquefied propellant gas under pressure and method of spraying same |
| US2964165A (en) * | 1956-11-13 | 1960-12-13 | Chempel Inc | Corrosion resistant aerosol package containing hydrolyzable material |
| GB952004A (en) * | 1962-02-15 | 1964-03-11 | Cooper Mcdougall & Robertson | Pressure-packed self-propelling compositions, containers therefor and the manufacture thereof |
| US3694545A (en) * | 1963-09-20 | 1972-09-26 | Geigy Ag J R | Three-phase aerosol spraying system |
| US3303091A (en) * | 1964-09-10 | 1967-02-07 | Johnson & Son Inc S C | Pesticidal aerosol compositions |
| FR2322543A1 (en) * | 1973-01-08 | 1977-04-01 | Cpc International Inc | NEW AQUEOUS INSECTICIDE COMPOSITION APPLICABLE BY SPRAYING AND ITS APPLICATION TO THE CONTROL AGAINST INSECTS |
-
1981
- 1981-07-09 DE DE19813127061 patent/DE3127061A1/en not_active Withdrawn
-
1982
- 1982-02-22 GR GR68672A patent/GR78219B/el unknown
- 1982-06-10 ZW ZW116/82A patent/ZW11682A1/en unknown
- 1982-06-22 NO NO822091A patent/NO822091L/en unknown
- 1982-06-28 EP EP82105707A patent/EP0069906A3/en not_active Withdrawn
- 1982-06-29 PT PT75143A patent/PT75143B/en unknown
- 1982-07-06 JP JP57116341A patent/JPS5815901A/en active Pending
- 1982-07-06 IL IL66236A patent/IL66236A0/en unknown
- 1982-07-07 FI FI822413A patent/FI822413L/en not_active Application Discontinuation
- 1982-07-07 CA CA000406784A patent/CA1174967A/en not_active Expired
- 1982-07-08 OA OA57738A patent/OA07147A/en unknown
- 1982-07-08 DK DK306982A patent/DK306982A/en not_active Application Discontinuation
- 1982-07-08 ES ES513822A patent/ES513822A1/en not_active Expired
- 1982-07-08 KR KR1019820003049A patent/KR840000173A/en unknown
- 1982-07-08 BR BR8203973A patent/BR8203973A/en unknown
- 1982-07-08 ZA ZA824863A patent/ZA824863B/en unknown
- 1982-07-08 MA MA19736A patent/MA19528A1/en unknown
- 1982-07-09 AU AU85765/82A patent/AU8576582A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107047549A (en) * | 2017-06-15 | 2017-08-18 | 浙江绿岛科技有限公司 | Environment-friendly type aerial fog pesticide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GR78219B (en) | 1984-09-26 |
| DE3127061A1 (en) | 1983-01-27 |
| ZW11682A1 (en) | 1982-09-01 |
| PT75143A (en) | 1982-07-01 |
| FI822413A0 (en) | 1982-07-07 |
| EP0069906A3 (en) | 1984-06-13 |
| PT75143B (en) | 1984-07-02 |
| AU8576582A (en) | 1983-01-13 |
| DK306982A (en) | 1983-01-10 |
| KR840000173A (en) | 1984-02-18 |
| IL66236A0 (en) | 1982-11-30 |
| ES513822A1 (en) | 1984-11-01 |
| OA07147A (en) | 1984-03-31 |
| ZA824863B (en) | 1983-04-27 |
| NO822091L (en) | 1983-01-10 |
| FI822413L (en) | 1983-01-10 |
| BR8203973A (en) | 1983-07-05 |
| MA19528A1 (en) | 1983-04-01 |
| JPS5815901A (en) | 1983-01-29 |
| EP0069906A2 (en) | 1983-01-19 |
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