CA1163192A - Aqueous suspensions of insecticide - Google Patents
Aqueous suspensions of insecticideInfo
- Publication number
- CA1163192A CA1163192A CA000369438A CA369438A CA1163192A CA 1163192 A CA1163192 A CA 1163192A CA 000369438 A CA000369438 A CA 000369438A CA 369438 A CA369438 A CA 369438A CA 1163192 A CA1163192 A CA 1163192A
- Authority
- CA
- Canada
- Prior art keywords
- phosalone
- suspension according
- suspension
- thickener
- active
- 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
- 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
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
ABSTRACT
"AQUEOUS SUSPENSIONS OF INSECTICIDE"
The invention provides aqueous suspensions of phosalone comprising a thickener and a surface-active adjuvant which possess emulsifying properties at high temperatures (50°C) and dispersing properties at ambient temperatures (20°C).
"AQUEOUS SUSPENSIONS OF INSECTICIDE"
The invention provides aqueous suspensions of phosalone comprising a thickener and a surface-active adjuvant which possess emulsifying properties at high temperatures (50°C) and dispersing properties at ambient temperatures (20°C).
Description
i ~3.~
DESCRIPTION
"AQUEOUS SUSPENSIONS OF INSECTICIDE"
The present invention relates to insecticidal compositions, their preparation and their,use. More particularly, it relates to a new phosalone formulation.
Phosalone is an insecticide which has been known for a long timé and has the chemical formula:
~ ~ C~I2 ~ S - P ~ 5 Cl __ _ In the past, phosalone has been presented (and it is still currently presented) in various forms, especially in the form of emulsifiable concentrates or wettable powders or in the form of solutions in a water-immiscible oil.
The various known formulations exhibit disadvantages, namely that the emulsifiable concentrates and the solutions contain one or more organic solvents and/or oils. As a result, the emulsifiable concentrates and the solutions of phosalone constitute a fire hazard both during storage and during transportation. Furthermore, the frequent and substantial increases in the cost of petroleum and of the products derived therefrom tend to '~
~ ~63~
~f have parallel repercussions on phosalone formulations, which contain solvents and/or oils derived from petroleum.
The wettable powders also have various disadvantages, the main disadvantage being the dispersion of dusts into the atmosphere during the handling of these wettable powders, either during bagging or during their dilution with water shortly before application to the plants (in other words during the preparation of the slurry). As a consequence of the presence of these dusts in the atmosphere, the handling of the wettable powders is considered to be an unpleasant or even dangerous operation.
~ here is therefore a need for a phosalone formulation which does not exhibit the disadvantages of the known formulations. Although phosalone may be used as an insecticide in the form of aqueous compositions phosalone is sensitive to water and such compositions are therefore prepared shortly before application to e~g.
plants from for example non-aqueous solutions or wettable powders. The prior art has virtually argued against using or even testing an aqueous formulation for phosalone, because of its sensitivity to water and consequent instability: more than 90% disappears in less than 10 days according to Mekh. Deistviya Gerbits. Sint. Regul. Rosta Rast. Ikh Sud'ba ~iosfere, Mater. Mezhdunar SimpO Stran-Chlenov SEV, 10th, 1975, 2, pages 96-98, clted by Chemical Abstracts, 88, 165462.
j 1~3~9~
As a result of research and experimentation an aqueous formulation of p~osalone has no~r been found which avoids the use of solvents derived from petroleum or the risk of dust formation during preparation of compositions for use. Furthermore, chemically stable aqueous suspensions may be prepared, for example as hereinafter described in Example 1. The suspension according to the invention prepared in that Example was kept for three months at 35C and no substantial chemical degradation was observed at the end of that period. The stability of the c~mposition of the invention is unexpected in view of the known sensitivity of phosalone to water and, in particular, the prior art referred to above which ~_~eports the disappearance of 90/O of the phosalone in an aqueous formulation.
The present invention accordingly provides an aqueous suspen~ion of phosalone, comprising a thickener and a surface-active adjuvant possessing emulsifying properties at high temperature (50C), preferably as hereinafter defined,and dispersing properties at ambient temperature (20C), preferably as hereinafter defined.
The phosalone is generally present in the compositions according to the invention in an amount of 50 to 550 g/litre and preferably in an amount of 200 to 500 g/litre, the latter values relate particularly to the compositions intended for storage and for marketing.
.
~1~3i~
In the compositions according to the invention, the phosalone is present in the form of solid particles of which preferably 95% (percentage by number) have a diameter of less than 20 ~ and preferably of from 0.05 .~
to 10 ~. It is to be understood that the diameters referred to in this specification and the accompanying claims are apparent diameters, such as can be measured, for example, by microscopic observation of the largest dimension of the particle~
In the aqueous suspensions of the invention, the phosalone can be associated with other active ingredients which are known to be suitable for association with phosalone, in particular lindane and DDT (i.e.
dichlorodiphenyltr~chloroethane), The thickeners used in the invention are products which are such that, whén added to water or to aqueous solutions or suspensions of pesticides, they impart pseudo-plastic properties to the latterO r~he thickeners which can be used in the invention can be mineral or organic in naturen Preferred thickeners are the mineral-type thickeners, attapulgites, bentonites, laponites and colloidal silicas and the organic type thickeners, alginates.
Particularly preferred organic-type thickeners are hydrophilic biopolymers of the heteropolysaccharide type, these biopolymers being the most preferred 3 1 ~ ~
thickeners aceording to the invention.
The amount of thickener in the compositions according to the invention is generally O.Ol to 15%
by weight and is advantageously 0.05 to l~/o by weight, ~, when the thic~ener is a heteropolysaccharide hydro-philic biopolymer, the amount of thickener is generally 0.01 to 2% by weight and preferably 0.05 to 0~5% ~y weight~
The hydrophilic biopolymers of the hetero-polysaceharide type which can be used in the invention are known products. They have a molecular weight of more than 200,000 and preferably of moré than 1,000,000; they have pseudo-plastic properties and are generally obtained by the action of bacteria~ the xanthomonas species on carbohydrates (i.e. by fermentation).
These biopolymers are sometimes also designated by other, rather diverse expressions such as: hydrophilic colloids of xanthomonas, heteropolysaccharide gums, xanthan gums, or extracellular heteropolysaccharides originating from xanthomonas or from bacteria of the family of the Pseudomonadaceae. The word biopolymer is used in the sense of polymers produced by a biological process (in this case bacterial fermentation).
The bacteria used for the preparation of these ; 25 biopolymers are most frequently Xanthomonas campestris, but it is also possible to use other xanthomonas, such as Xanthomonas carotae, Xanthomonas incanae, Xanthomonas begoniae, Xanthomonas malvacearum, Xanthomonas vesicatoria, Xanthomonas translucens or Xanthomonas vasculorum. Suitable carbohydrates for fermentation by xanthomonas bacteria include glucose, sucrose, fructose, maltose, lactose, galactose and starch, e.g.
potato starch.
I The insecticidal compositions according to the invention comprise a surface-active adjuvant possessing emulsifying properties at high temperature (50C) and dispersing properties at ambient temperature (20C)O
Preferred surface active adjuvants for use in the compositions of the invention possess suitable emulsifying properties according to the stability test method MT 36.1.1. (subject to modifications expressly indicated below), the said method being described in CIPAC Handbook, Volume 1, published by Raw, 1970, pages 910-913.
According to this test, molten phosalone (50 g) and the surface-active adjuvant (5 g) are added to an amount of water, at 50C, sufficient to bring the volume of the mixture to 100 cc; the mixture is agitated to give a homogeneous emulsion and the emulsion is left to stand for 30 minutes at 50C in a graduated cylinder;
the amount of oily layer which may have separated out (and thus formed a distinct liquid phase) must then be .
less than 20 cc.
Preferred surface active adjuvants for use in the compositions of the invention also possess suitable dispersing properties according to the following test: an aqueous suspension ~100 cc~
containing phosalone (50 g), in the form of solid particleq having a diameter of between 1 and 10 ~, and the surface-active adjuvant (5 g)'is left to stand at 20C for 30 minutes in a graduated cylinder;
after standing, the upper nine-tenths of the volume of the suspension, is removed, without agitation~ and the solids content (residue after evaporation of the water) of the remaining tenth is measured: this solids content must not exceed 12% by weight of the solids content of 100 cc of the suspension on which the test is carried out.
The properties which have now been defined above are the preferred properties assessed overall for the surface-active constituents of the compositions ~0 according to the invention. It is to be understood that the surface-active adjuvant contained in these compositions can be a single product or a mixture of :products; consequently, the properties defined above for the surface-active adjuvant are either those of a single surface-active product or those of a mixture of surface-active productsO
6 - 8 ~ 3 ~
...
The surface-active adjuvants which are suitable for use in the compositions of the invention are generally solu~le in water and in an organic phase, such as molten phosalone.
The phosphates of polyoxyethyleneated tristyrylphenol optionally in the salified form, preferably in the form salified by an amine, may be mentioned as surface-active adjuvants which fulfil the requirements of the definitions given abo~e and which can consequently be used in the invention.
The compositions according to the invention generally contain from 20 to 120 g/l, preferably from 40 to 80 g/1, of surface-active agent.
The preparation of the composition according to the invention can be carried out by any known method for mixing the various constituents. (By the expression "known method'l as used in the specification ; is meant a method heretofore used or described in the literatureO) However, a preferred process is described below and constitutes a feature of the invention.
According to this process, the phosalone, the ~: .
water and the surface-active adjuvant or adjuvants are mixed, with agitation, at a temperature which is greater than or equal to the melting point of the phosalone ~this first step is carried out in the liquid phase), then simultaneously grinding and cooling the hot emulsion obtained during the first step to form a suspension (the phosalone crystallises or at least ~ 1~31~2 g ~olidifies during this cooling), and then adding the thickener to the aqueous suspension obtained.
During ~he first step of the process of the invention, the phosalone~ the water and the surface-active adjuvant are mi~xed, with agitation; preferably, the molten phosalone i8 poured into an agitated hot solution of the surface-active adjuvant in water~
The temperature at which this first step is carried out is preferably above the melting point of the phosalone and below 100C. A temperature which is 1C or more above the melting point of the phosalone and below 60C is preferred. The melting point of the phosalone is 48C in the case of pure phosalone, it can be lower and can even reach 42C in the case of technical-grade or impure phosa~eO
; After the first step of mixing at high temperature, with agitation and in the liquid phase, the mixture -thus obtained is cooled and ground at the same time. This grinding makes it possible to obtain a very homogeneous suspension of finely di~ided particles, the cooling is carried out to a temperature below the m.p.
of the p~osalone and preferably to a temperature below 35C (but above the freez-ing point of the mixture).
Durin~ this cooling, the f1ne liquid droplets of ; ~ 25 phosalone solidify and generally crystallise. The grinding can be carried out using any known method, in ; particular using ball mills.
.
~3 .~
In order to cool at the same time as grinding it is advantageous to use mills fitted with a cooling system, e.g. of the type with a liquid circulating in a jacket.
The compositions of the invention may also comprise other compatible adjuvants suitable for use in liquid compositions for pesticidal use, for example anti-freeze agents such as ethylene glycol.
The compositions according to the invention may be applied to plants in order to carry out the pesticidal, and especially insecticidal, treatments in which phosalone is known to be effective. Most frequently, concentrated compositions according to the inven-tion may be used for storage and transport~ion, and these compositions may be diluted at the time of use~
The diluted compositions, such as those applied to plants, are-called slurrles and are generally obtained ~y dilution of the compositions according to the invention at a rate o~ 1 litre o~ composition to 50 to 300 litres o~
waterO
~ he handling of the compositions according to the invention does not give rise to any dust; the compositions do not constitute any fire hazard and avoid the use of solvents derived from petroleum. ~he phosalone applied by means of the compositions according to the invention is very resistant to washing off by rain.
3~
~he following F~ample~ illustrate the invention.
Example 1 Hot water (575 cc~ ethylene glycol (~nti-freeze agent; 50 g~ and an anionic surface-actiYe agent (a mixture ~f the monophosphate and the diphosphate of tristyrylphenol caxrying a polyoxyethylene chain containing about 18 oxyet~ylene repeat units 9 neutralised with triethanolamine, thi~ being a product marketed under the name Soprophor FL, 50 g) are introduced into a vat kept at 52C. ~Soprophor" is a trade mark. This surface-active adjuvant corresponds to the physical-charac-teristics defined above in a general manner for the invention.
In t~e test, hereinbefore described for assessing the emulsifying properties, the volume of the oil layer which separated-~ut was 9 cc.
In the test hereinbefore described for assessing the dispersing properti~s, the solids conterlt of the lower ~olume (one-tenth of the total~ was 10.~/o ~y weight of the solids content of the total volume.
The mixture obtained as described above is agitated vi~orously and molten phosalone (500 g) is addedO
This yields a hot a~ueous emulsion of molten p~osalone.
This emulsion is then ground in a ball mill with a jacket which permits rapid cooling. On leaving the mill, the mixture at 25C contains phosalone particles having a diameter of between 0.5 and 10 ~ (90/~ of the particles have a diameter of between 2 and 5 ~ )~
~ .
1 ~,319~
~ 12 -A biopolymer of the heteropofysaccharide type (1.5 g), produced by the fermentation of Xanthomonas campe-stris on carbohydrates (a product marketed under the name Rhodopol XB 23), is then added. "Rhodopol" is a trade mark.
This yields a stable a~ueous suspension during a period cff 3 months at 20~C, no settlin~ and no change in the physical appearance of the a~ueous suspension was observed, the suspension was kept for 3 months at 3',~C, no substantial chemical degradation was observed at the end of this period.
Examples 2 to 4 ~ rhese Exam~,les illustrate the results obtained b,y treating pla~ts with slurrie,~ a slurry being an a~ueous susp~nsion as used during its application to the plants) obtained by diluting the suspension described in Example 1 with a suf~icient amount of water to o,tain the phosalone concentration indicated below.
Comparisons were also made with treatments which were similar but were carried out with slurries obtained by diluting, with water, an emulsifiable concentrate of phosalone (i.e. a solution of phosalone and emulsifier (a mixture of polyoxyethyleneated alkylphenol and calcium alXylarylsulphonate) in an organic solvent essentially consisting of xylene).
Example 2 Rose bushes were treated in order tc, assess the , . . ~ f i ) 631~,?
selectivity of the compositions according to the invention towards these plants. The rose 'bushes were of the "Madame Meillant" variety and were 6 years old. They were treated by spraying with slurries co~taining 60 or 120 g of phosalone per ~ectolitre.
The effect on the rose bushes was noted by the percentage yellowing of the lea~es (in termsof the leaf surface area).
For a s~urry containing 60 g/hl of phosalone, the following results were obtained,T being the treatment date.
Percentage yeilowing of _ he leaves ,~
T + T ~ T ~
DESCRIPTION
"AQUEOUS SUSPENSIONS OF INSECTICIDE"
The present invention relates to insecticidal compositions, their preparation and their,use. More particularly, it relates to a new phosalone formulation.
Phosalone is an insecticide which has been known for a long timé and has the chemical formula:
~ ~ C~I2 ~ S - P ~ 5 Cl __ _ In the past, phosalone has been presented (and it is still currently presented) in various forms, especially in the form of emulsifiable concentrates or wettable powders or in the form of solutions in a water-immiscible oil.
The various known formulations exhibit disadvantages, namely that the emulsifiable concentrates and the solutions contain one or more organic solvents and/or oils. As a result, the emulsifiable concentrates and the solutions of phosalone constitute a fire hazard both during storage and during transportation. Furthermore, the frequent and substantial increases in the cost of petroleum and of the products derived therefrom tend to '~
~ ~63~
~f have parallel repercussions on phosalone formulations, which contain solvents and/or oils derived from petroleum.
The wettable powders also have various disadvantages, the main disadvantage being the dispersion of dusts into the atmosphere during the handling of these wettable powders, either during bagging or during their dilution with water shortly before application to the plants (in other words during the preparation of the slurry). As a consequence of the presence of these dusts in the atmosphere, the handling of the wettable powders is considered to be an unpleasant or even dangerous operation.
~ here is therefore a need for a phosalone formulation which does not exhibit the disadvantages of the known formulations. Although phosalone may be used as an insecticide in the form of aqueous compositions phosalone is sensitive to water and such compositions are therefore prepared shortly before application to e~g.
plants from for example non-aqueous solutions or wettable powders. The prior art has virtually argued against using or even testing an aqueous formulation for phosalone, because of its sensitivity to water and consequent instability: more than 90% disappears in less than 10 days according to Mekh. Deistviya Gerbits. Sint. Regul. Rosta Rast. Ikh Sud'ba ~iosfere, Mater. Mezhdunar SimpO Stran-Chlenov SEV, 10th, 1975, 2, pages 96-98, clted by Chemical Abstracts, 88, 165462.
j 1~3~9~
As a result of research and experimentation an aqueous formulation of p~osalone has no~r been found which avoids the use of solvents derived from petroleum or the risk of dust formation during preparation of compositions for use. Furthermore, chemically stable aqueous suspensions may be prepared, for example as hereinafter described in Example 1. The suspension according to the invention prepared in that Example was kept for three months at 35C and no substantial chemical degradation was observed at the end of that period. The stability of the c~mposition of the invention is unexpected in view of the known sensitivity of phosalone to water and, in particular, the prior art referred to above which ~_~eports the disappearance of 90/O of the phosalone in an aqueous formulation.
The present invention accordingly provides an aqueous suspen~ion of phosalone, comprising a thickener and a surface-active adjuvant possessing emulsifying properties at high temperature (50C), preferably as hereinafter defined,and dispersing properties at ambient temperature (20C), preferably as hereinafter defined.
The phosalone is generally present in the compositions according to the invention in an amount of 50 to 550 g/litre and preferably in an amount of 200 to 500 g/litre, the latter values relate particularly to the compositions intended for storage and for marketing.
.
~1~3i~
In the compositions according to the invention, the phosalone is present in the form of solid particles of which preferably 95% (percentage by number) have a diameter of less than 20 ~ and preferably of from 0.05 .~
to 10 ~. It is to be understood that the diameters referred to in this specification and the accompanying claims are apparent diameters, such as can be measured, for example, by microscopic observation of the largest dimension of the particle~
In the aqueous suspensions of the invention, the phosalone can be associated with other active ingredients which are known to be suitable for association with phosalone, in particular lindane and DDT (i.e.
dichlorodiphenyltr~chloroethane), The thickeners used in the invention are products which are such that, whén added to water or to aqueous solutions or suspensions of pesticides, they impart pseudo-plastic properties to the latterO r~he thickeners which can be used in the invention can be mineral or organic in naturen Preferred thickeners are the mineral-type thickeners, attapulgites, bentonites, laponites and colloidal silicas and the organic type thickeners, alginates.
Particularly preferred organic-type thickeners are hydrophilic biopolymers of the heteropolysaccharide type, these biopolymers being the most preferred 3 1 ~ ~
thickeners aceording to the invention.
The amount of thickener in the compositions according to the invention is generally O.Ol to 15%
by weight and is advantageously 0.05 to l~/o by weight, ~, when the thic~ener is a heteropolysaccharide hydro-philic biopolymer, the amount of thickener is generally 0.01 to 2% by weight and preferably 0.05 to 0~5% ~y weight~
The hydrophilic biopolymers of the hetero-polysaceharide type which can be used in the invention are known products. They have a molecular weight of more than 200,000 and preferably of moré than 1,000,000; they have pseudo-plastic properties and are generally obtained by the action of bacteria~ the xanthomonas species on carbohydrates (i.e. by fermentation).
These biopolymers are sometimes also designated by other, rather diverse expressions such as: hydrophilic colloids of xanthomonas, heteropolysaccharide gums, xanthan gums, or extracellular heteropolysaccharides originating from xanthomonas or from bacteria of the family of the Pseudomonadaceae. The word biopolymer is used in the sense of polymers produced by a biological process (in this case bacterial fermentation).
The bacteria used for the preparation of these ; 25 biopolymers are most frequently Xanthomonas campestris, but it is also possible to use other xanthomonas, such as Xanthomonas carotae, Xanthomonas incanae, Xanthomonas begoniae, Xanthomonas malvacearum, Xanthomonas vesicatoria, Xanthomonas translucens or Xanthomonas vasculorum. Suitable carbohydrates for fermentation by xanthomonas bacteria include glucose, sucrose, fructose, maltose, lactose, galactose and starch, e.g.
potato starch.
I The insecticidal compositions according to the invention comprise a surface-active adjuvant possessing emulsifying properties at high temperature (50C) and dispersing properties at ambient temperature (20C)O
Preferred surface active adjuvants for use in the compositions of the invention possess suitable emulsifying properties according to the stability test method MT 36.1.1. (subject to modifications expressly indicated below), the said method being described in CIPAC Handbook, Volume 1, published by Raw, 1970, pages 910-913.
According to this test, molten phosalone (50 g) and the surface-active adjuvant (5 g) are added to an amount of water, at 50C, sufficient to bring the volume of the mixture to 100 cc; the mixture is agitated to give a homogeneous emulsion and the emulsion is left to stand for 30 minutes at 50C in a graduated cylinder;
the amount of oily layer which may have separated out (and thus formed a distinct liquid phase) must then be .
less than 20 cc.
Preferred surface active adjuvants for use in the compositions of the invention also possess suitable dispersing properties according to the following test: an aqueous suspension ~100 cc~
containing phosalone (50 g), in the form of solid particleq having a diameter of between 1 and 10 ~, and the surface-active adjuvant (5 g)'is left to stand at 20C for 30 minutes in a graduated cylinder;
after standing, the upper nine-tenths of the volume of the suspension, is removed, without agitation~ and the solids content (residue after evaporation of the water) of the remaining tenth is measured: this solids content must not exceed 12% by weight of the solids content of 100 cc of the suspension on which the test is carried out.
The properties which have now been defined above are the preferred properties assessed overall for the surface-active constituents of the compositions ~0 according to the invention. It is to be understood that the surface-active adjuvant contained in these compositions can be a single product or a mixture of :products; consequently, the properties defined above for the surface-active adjuvant are either those of a single surface-active product or those of a mixture of surface-active productsO
6 - 8 ~ 3 ~
...
The surface-active adjuvants which are suitable for use in the compositions of the invention are generally solu~le in water and in an organic phase, such as molten phosalone.
The phosphates of polyoxyethyleneated tristyrylphenol optionally in the salified form, preferably in the form salified by an amine, may be mentioned as surface-active adjuvants which fulfil the requirements of the definitions given abo~e and which can consequently be used in the invention.
The compositions according to the invention generally contain from 20 to 120 g/l, preferably from 40 to 80 g/1, of surface-active agent.
The preparation of the composition according to the invention can be carried out by any known method for mixing the various constituents. (By the expression "known method'l as used in the specification ; is meant a method heretofore used or described in the literatureO) However, a preferred process is described below and constitutes a feature of the invention.
According to this process, the phosalone, the ~: .
water and the surface-active adjuvant or adjuvants are mixed, with agitation, at a temperature which is greater than or equal to the melting point of the phosalone ~this first step is carried out in the liquid phase), then simultaneously grinding and cooling the hot emulsion obtained during the first step to form a suspension (the phosalone crystallises or at least ~ 1~31~2 g ~olidifies during this cooling), and then adding the thickener to the aqueous suspension obtained.
During ~he first step of the process of the invention, the phosalone~ the water and the surface-active adjuvant are mi~xed, with agitation; preferably, the molten phosalone i8 poured into an agitated hot solution of the surface-active adjuvant in water~
The temperature at which this first step is carried out is preferably above the melting point of the phosalone and below 100C. A temperature which is 1C or more above the melting point of the phosalone and below 60C is preferred. The melting point of the phosalone is 48C in the case of pure phosalone, it can be lower and can even reach 42C in the case of technical-grade or impure phosa~eO
; After the first step of mixing at high temperature, with agitation and in the liquid phase, the mixture -thus obtained is cooled and ground at the same time. This grinding makes it possible to obtain a very homogeneous suspension of finely di~ided particles, the cooling is carried out to a temperature below the m.p.
of the p~osalone and preferably to a temperature below 35C (but above the freez-ing point of the mixture).
Durin~ this cooling, the f1ne liquid droplets of ; ~ 25 phosalone solidify and generally crystallise. The grinding can be carried out using any known method, in ; particular using ball mills.
.
~3 .~
In order to cool at the same time as grinding it is advantageous to use mills fitted with a cooling system, e.g. of the type with a liquid circulating in a jacket.
The compositions of the invention may also comprise other compatible adjuvants suitable for use in liquid compositions for pesticidal use, for example anti-freeze agents such as ethylene glycol.
The compositions according to the invention may be applied to plants in order to carry out the pesticidal, and especially insecticidal, treatments in which phosalone is known to be effective. Most frequently, concentrated compositions according to the inven-tion may be used for storage and transport~ion, and these compositions may be diluted at the time of use~
The diluted compositions, such as those applied to plants, are-called slurrles and are generally obtained ~y dilution of the compositions according to the invention at a rate o~ 1 litre o~ composition to 50 to 300 litres o~
waterO
~ he handling of the compositions according to the invention does not give rise to any dust; the compositions do not constitute any fire hazard and avoid the use of solvents derived from petroleum. ~he phosalone applied by means of the compositions according to the invention is very resistant to washing off by rain.
3~
~he following F~ample~ illustrate the invention.
Example 1 Hot water (575 cc~ ethylene glycol (~nti-freeze agent; 50 g~ and an anionic surface-actiYe agent (a mixture ~f the monophosphate and the diphosphate of tristyrylphenol caxrying a polyoxyethylene chain containing about 18 oxyet~ylene repeat units 9 neutralised with triethanolamine, thi~ being a product marketed under the name Soprophor FL, 50 g) are introduced into a vat kept at 52C. ~Soprophor" is a trade mark. This surface-active adjuvant corresponds to the physical-charac-teristics defined above in a general manner for the invention.
In t~e test, hereinbefore described for assessing the emulsifying properties, the volume of the oil layer which separated-~ut was 9 cc.
In the test hereinbefore described for assessing the dispersing properti~s, the solids conterlt of the lower ~olume (one-tenth of the total~ was 10.~/o ~y weight of the solids content of the total volume.
The mixture obtained as described above is agitated vi~orously and molten phosalone (500 g) is addedO
This yields a hot a~ueous emulsion of molten p~osalone.
This emulsion is then ground in a ball mill with a jacket which permits rapid cooling. On leaving the mill, the mixture at 25C contains phosalone particles having a diameter of between 0.5 and 10 ~ (90/~ of the particles have a diameter of between 2 and 5 ~ )~
~ .
1 ~,319~
~ 12 -A biopolymer of the heteropofysaccharide type (1.5 g), produced by the fermentation of Xanthomonas campe-stris on carbohydrates (a product marketed under the name Rhodopol XB 23), is then added. "Rhodopol" is a trade mark.
This yields a stable a~ueous suspension during a period cff 3 months at 20~C, no settlin~ and no change in the physical appearance of the a~ueous suspension was observed, the suspension was kept for 3 months at 3',~C, no substantial chemical degradation was observed at the end of this period.
Examples 2 to 4 ~ rhese Exam~,les illustrate the results obtained b,y treating pla~ts with slurrie,~ a slurry being an a~ueous susp~nsion as used during its application to the plants) obtained by diluting the suspension described in Example 1 with a suf~icient amount of water to o,tain the phosalone concentration indicated below.
Comparisons were also made with treatments which were similar but were carried out with slurries obtained by diluting, with water, an emulsifiable concentrate of phosalone (i.e. a solution of phosalone and emulsifier (a mixture of polyoxyethyleneated alkylphenol and calcium alXylarylsulphonate) in an organic solvent essentially consisting of xylene).
Example 2 Rose bushes were treated in order tc, assess the , . . ~ f i ) 631~,?
selectivity of the compositions according to the invention towards these plants. The rose 'bushes were of the "Madame Meillant" variety and were 6 years old. They were treated by spraying with slurries co~taining 60 or 120 g of phosalone per ~ectolitre.
The effect on the rose bushes was noted by the percentage yellowing of the lea~es (in termsof the leaf surface area).
For a s~urry containing 60 g/hl of phosalone, the following results were obtained,T being the treatment date.
Percentage yeilowing of _ he leaves ,~
T + T ~ T ~
2 days 7 days 1~ days ~ _ slurry composltion , obtained according 15 10 6 from to the invention _ emulsifiable concentrate 36 23 19 For a slurry containing 120 g/hl of phosalone the following results were obtained, T being the treatment date:
IL ~ 3 1 4 ~
Percentage yeIlowing of the leaves T ~ T + T t : 2 days 7 days 14 days slurry composition _ .
obtained according 29 21 19 from to the nvention _ ; . emulsifiable 51 44 ~0 concentrate_ The compositions according to the invention ; which were tested show improved selectivity~
Example 3 Potato plants ("Bintje" variety~ which were : 15 2 months old and infested with greenfly (Myzus persicae, Macrosiphum euphorbiae and Aphis nasturtii) were treated with slurries which contained 60 g/hl of phosalone and which were used at a rate of 1,500 l~hia.
- These slurries were obtained by diluting a flowable formulation containing phosalone according to the invention with water~
.
-~he effectivenes~ was measured by the percentage of greenfly destroyed, compared with untreated control plants, T being the treatment date.
. . .
.
~ ~ ~ 3 ~
~ffectiveness t%) , T + 2 days T ~ 7 days Slurry composition _ obtained according 85 87 from to the invention emulsifiable 92 65 concentrate _ l The compositions according to the invention which were tested show improved persistence.
Example 4 Example 3 is repeated, but plants infested with Doryphore (Leptinotarsa decemlineata) are used.
T is the treatment date. On the 13th day, the plants _ were artificially recontaminated with further doryphores.
Effectiveness (%) T + T ~ T +
_ 1 day 8 days 16 days Slurry composition obtained according 98 96 90 from to the invention ~ _ emulsifiable ; concentrate The compositions according to the invention which were tested show improved persistence~
~; - 16 ~ 3~
Similar results to those obtained in the foregoing Examples are obtained using compositions according to the invention containing either ~5 g of surface-a~tive agent (instead of 50 g) and 580 cc of wa~er ~nstead of 575 cc) or 70 g of surface~active agent (instead of 50 g) and 555 cc of water (instead of 575 cc).
IL ~ 3 1 4 ~
Percentage yeIlowing of the leaves T ~ T + T t : 2 days 7 days 14 days slurry composition _ .
obtained according 29 21 19 from to the nvention _ ; . emulsifiable 51 44 ~0 concentrate_ The compositions according to the invention ; which were tested show improved selectivity~
Example 3 Potato plants ("Bintje" variety~ which were : 15 2 months old and infested with greenfly (Myzus persicae, Macrosiphum euphorbiae and Aphis nasturtii) were treated with slurries which contained 60 g/hl of phosalone and which were used at a rate of 1,500 l~hia.
- These slurries were obtained by diluting a flowable formulation containing phosalone according to the invention with water~
.
-~he effectivenes~ was measured by the percentage of greenfly destroyed, compared with untreated control plants, T being the treatment date.
. . .
.
~ ~ ~ 3 ~
~ffectiveness t%) , T + 2 days T ~ 7 days Slurry composition _ obtained according 85 87 from to the invention emulsifiable 92 65 concentrate _ l The compositions according to the invention which were tested show improved persistence.
Example 4 Example 3 is repeated, but plants infested with Doryphore (Leptinotarsa decemlineata) are used.
T is the treatment date. On the 13th day, the plants _ were artificially recontaminated with further doryphores.
Effectiveness (%) T + T ~ T +
_ 1 day 8 days 16 days Slurry composition obtained according 98 96 90 from to the invention ~ _ emulsifiable ; concentrate The compositions according to the invention which were tested show improved persistence~
~; - 16 ~ 3~
Similar results to those obtained in the foregoing Examples are obtained using compositions according to the invention containing either ~5 g of surface-a~tive agent (instead of 50 g) and 580 cc of wa~er ~nstead of 575 cc) or 70 g of surface~active agent (instead of 50 g) and 555 cc of water (instead of 575 cc).
Claims (19)
1. An aqueous suspension of phosalone, comprising in addition to phosalone,a thickener and a surface-active adjuvant possessing emulsifying properties at high temperature (50°C) and dispersing properties at ambient temperature (20°C).
2. A suspension according to claim 1 wherein the thickener is an attapulgite, a bentonite, a laponite, a colloidal silica or an alginate.
3. A suspension according to claim 1 wherein the thickener is a heteropolysaccharide hydrophilic biopolymer.
4. A suspension according to claim 3 wherein the biopolymer is produced by bacterial fermentation of carbohydrates using bacteria of the xanthomonas species.
5. A suspension according to claim 1 wherein the surface-active adjuvant is a phosphate ofpolyxyethyl-eneated tristyrylphenol optionally in the salified form.
6. A suspension according to claim 5 in which the phosphate is salified by an amine.
7. A suspension according to claim 1 which comprises from 20 to 120 g/l of surface-active agent.
8. A suspension according to claim 1 which comprises from 40 to 80 g/l of surface-active agent.
9. A suspension according to claim 1 which contains from 50 to 550 g/litre of phosalone.
10. A suspension according to claim 1 which contains from 200 to 500 g/litre of phosalone.
11. A suspension according to claim 1 which contains 0.01 to 15% by weight of thickener.
12. A suspension according to claim 1 which contains 0.05 to 10% by weight of thickener.
13. A suspension according to claim 3 which contains 0.01 to 2% by weight of biopolymer.
14. A suspension according to claim 3 which contains 0.05 to 0.5% by weight of biopolymer.
15. A suspension according to claim 1 wherein the phosalone-is in the form of solid particles of which 95% by number have a diameter of less than 20 µ.
16. A suspension according to claim 15 wherein 95% of the solid phosalone particles have a diameter of from 0.05 to 10 µ.
17. A suspension according to claim 1 wherein the surface-active adjuvant is such that:
(a) when molten phosalone (50 g) and the surface-active adjuvant (5 g) are added to an amount of water, at 50°C, sufficient to bring the volume of the mixture to 100 cc, the mixture is agitated to give a homogeneous emulsion and then left to stand for 30 minutes at 50°C in a graduated cylinder, the emulsion does not give rise to the separation of an oily phase having a volume of more than 20 cc; and (b) when an aqueous suspension (100 cc) containing phosalone (50 g),in the form of solid particles having a diameter of between 1 and 10 µ, and the surface-active adjuvant (5 g) is left to stand at 20°C for 30 minutes in a graduated cylinder, the upper nine-tenths of the volume of the suspension is removed, without agitation, and the solids content (residue after evaporation of the water) of the remaining tenth is measured, the solids content does not exceed 12% by weight of the solids content of the total suspension.
(a) when molten phosalone (50 g) and the surface-active adjuvant (5 g) are added to an amount of water, at 50°C, sufficient to bring the volume of the mixture to 100 cc, the mixture is agitated to give a homogeneous emulsion and then left to stand for 30 minutes at 50°C in a graduated cylinder, the emulsion does not give rise to the separation of an oily phase having a volume of more than 20 cc; and (b) when an aqueous suspension (100 cc) containing phosalone (50 g),in the form of solid particles having a diameter of between 1 and 10 µ, and the surface-active adjuvant (5 g) is left to stand at 20°C for 30 minutes in a graduated cylinder, the upper nine-tenths of the volume of the suspension is removed, without agitation, and the solids content (residue after evaporation of the water) of the remaining tenth is measured, the solids content does not exceed 12% by weight of the solids content of the total suspension.
18. A process for the preparation of a suspension according to claim 1 which comprises mixing the phosalone, the water and the surface-active adjuvant or adjuvants, with agitation, at a temperature which is greater than or equal to the melting point of the phosalone, then simultaneously grinding and cooling the hot emulsion obtained, and then adding the thickener to the aqueous suspension obtained.
19. A method for the pesticidal treatment of plants which comprises applying to the plants a suspension according to claim 1 or obtained from such a suspension.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8002309A FR2474278A1 (en) | 1980-01-29 | 1980-01-29 | AQUEOUS INSECTICIDE SUSPENSIONS, THEIR PREPARATION AND THEIR USE |
| FR80/02309 | 1980-01-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1163192A true CA1163192A (en) | 1984-03-06 |
Family
ID=9238142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000369438A Expired CA1163192A (en) | 1980-01-29 | 1981-01-27 | Aqueous suspensions of insecticide |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0033291B1 (en) |
| JP (1) | JPH0238561B2 (en) |
| AR (1) | AR227411A1 (en) |
| BG (1) | BG40311A3 (en) |
| BR (1) | BR8100480A (en) |
| CA (1) | CA1163192A (en) |
| CS (1) | CS257752B2 (en) |
| DD (1) | DD157441A5 (en) |
| DE (1) | DE3161606D1 (en) |
| DK (1) | DK37581A (en) |
| FR (1) | FR2474278A1 (en) |
| HU (1) | HU189970B (en) |
| PL (1) | PL129801B1 (en) |
| YU (1) | YU22881A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666940A (en) * | 1984-08-20 | 1987-05-19 | Werner & Mertz Gmbh | Acaricidal cleaning composition for controlling house dust mites and process of using |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5953402A (en) * | 1982-09-21 | 1984-03-28 | Sumitomo Chem Co Ltd | Wettable powder of fenitrothion |
| DE3302648A1 (en) * | 1983-01-27 | 1984-08-02 | Hoechst Ag, 6230 Frankfurt | PLANT PROTECTION AGENT IN THE FORM OF MIXED DISPERSIONS |
| CA1289065C (en) * | 1986-05-23 | 1991-09-17 | Leonard John Morgan | Aqueous suspension concentrate compositions |
| JP2926495B2 (en) * | 1988-04-06 | 1999-07-28 | クミアイ化学工業株式会社 | Suspended pesticide composition |
| JP2764270B2 (en) * | 1988-05-10 | 1998-06-11 | 日本農薬株式会社 | Stable aqueous suspension pesticide composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL59151C (en) * | 1945-08-22 | |||
| NL269411A (en) * | 1960-10-20 | |||
| US3948636A (en) * | 1972-11-09 | 1976-04-06 | Diamond Shamrock Corporation | Flowable aqueous composition of water-insoluble pesticide |
-
1980
- 1980-01-29 FR FR8002309A patent/FR2474278A1/en active Granted
-
1981
- 1981-01-26 BG BG050533A patent/BG40311A3/en unknown
- 1981-01-27 DE DE8181420008T patent/DE3161606D1/en not_active Expired
- 1981-01-27 EP EP19810420008 patent/EP0033291B1/en not_active Expired
- 1981-01-27 CA CA000369438A patent/CA1163192A/en not_active Expired
- 1981-01-27 AR AR28408081A patent/AR227411A1/en active
- 1981-01-28 HU HU18781A patent/HU189970B/en unknown
- 1981-01-28 PL PL22941881A patent/PL129801B1/en unknown
- 1981-01-28 BR BR8100480A patent/BR8100480A/en unknown
- 1981-01-28 JP JP1146181A patent/JPH0238561B2/en not_active Expired - Lifetime
- 1981-01-28 DK DK37581A patent/DK37581A/en not_active Application Discontinuation
- 1981-01-29 DD DD22728281A patent/DD157441A5/en unknown
- 1981-01-29 CS CS81655A patent/CS257752B2/en unknown
- 1981-01-29 YU YU22881A patent/YU22881A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666940A (en) * | 1984-08-20 | 1987-05-19 | Werner & Mertz Gmbh | Acaricidal cleaning composition for controlling house dust mites and process of using |
Also Published As
| Publication number | Publication date |
|---|---|
| CS65581A2 (en) | 1987-11-12 |
| FR2474278B1 (en) | 1983-10-07 |
| EP0033291B1 (en) | 1983-12-14 |
| JPS56120609A (en) | 1981-09-22 |
| FR2474278A1 (en) | 1981-07-31 |
| AR227411A1 (en) | 1982-10-29 |
| BG40311A3 (en) | 1986-11-14 |
| DD157441A5 (en) | 1982-11-10 |
| EP0033291A3 (en) | 1981-08-12 |
| DE3161606D1 (en) | 1984-01-19 |
| PL129801B1 (en) | 1984-06-30 |
| BR8100480A (en) | 1981-08-18 |
| YU22881A (en) | 1984-10-31 |
| DK37581A (en) | 1981-07-30 |
| PL229418A1 (en) | 1981-10-16 |
| HU189970B (en) | 1986-08-28 |
| CS257752B2 (en) | 1988-06-15 |
| EP0033291A2 (en) | 1981-08-05 |
| JPH0238561B2 (en) | 1990-08-31 |
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| MKEX | Expiry |