WO2002058468A1 - Pesticidal formulation - Google Patents

Pesticidal formulation Download PDF

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Publication number
WO2002058468A1
WO2002058468A1 PCT/EP2002/000716 EP0200716W WO02058468A1 WO 2002058468 A1 WO2002058468 A1 WO 2002058468A1 EP 0200716 W EP0200716 W EP 0200716W WO 02058468 A1 WO02058468 A1 WO 02058468A1
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WIPO (PCT)
Prior art keywords
liquid
formulation according
formulation
kagalite
balloon
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PCT/EP2002/000716
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French (fr)
Inventor
Hiroshi Hasegawa
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Syngenta Participations Ag
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Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to JP2002558811A priority Critical patent/JP4410993B2/en
Publication of WO2002058468A1 publication Critical patent/WO2002058468A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/34Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/26Biocides, 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 in coated particulate form

Definitions

  • the instant invention relates to a new pesticidal formulation with high active ingredient content which spreads rapidly over the surface of water, efficientcly releasing pesticidal active ingredients throughout the water surface, thereby saving labor load of farmers, storage volume during distribution as well as production costs thereof to a large extent.
  • Jumbo formulations Due to the water filling of paddy fields, it is not easy to apply pesticides in such a manner that they are scattered uniformly over the surface of water. As a result, if a farmer desires to uniformly apply pesticides, it is in principle necessary for him to enter the paddy field and scatter pesticides changing the position from which the farmer applies pesticides, demanding lots of works. Driven by the motivation to reduce labor load of farmers, the so-called Jumbo formulations have drawn attention among pesticide manufacturers. The Jumbo formulations have three aspects in common: (1) they float, (2) spread and (3) release pesticidal active ingredients on the surface of water. So far various types of Jumbo formulations have been proposed. However, there has been proposed no Jumbo formulation comprising a liquid active ingredient retained, adsorbed or fixed on a carrier allowing reduction in the amount of application, in the production costs while being environmentally friendly.
  • Jumbo formulations are generally finished in such a manner that they are packed in water-soluble bags made of water-soluble polymers e.g. polyvinylalcohol, which are directly applied to the surface of water. After the bags have dissolved in the water, particles of the Jumbo formulation spread on the surface of water releasing active ingredients.
  • water-soluble polymers e.g. polyvinylalcohol
  • the Jumbo formulations with liquid active ingredients so far developed contain active ingredients usually in amounts of 2-10% by weight (see for example JP Kokai Nos. 6-336403 and 8-99804), not achieving the reduction in amount of application thereof.
  • the low liquid active ingredient content presumably reflects the fact that there has so far been not available such a core material that floats on the surface of water and capable of absorbing liquid active ingredients in amounts higher than 10% by weight.
  • JP Kokai No. 11-310503 describes a Jumbo formulation in which Pretilachlor, which is a liquid active ingredient, is contained in an amount as high as 25% by weight.
  • a formulation comprising a liquid pesticidal active ingredient, Kagalite Balloon, at least one surfactant mainly providing spreadability and at least one anionic surfactant mainly enhancing emulsifying effect, which is very environmentally friendly, unexpectedly allows active ingredient contents as high as 25% by weight quite easily, whilst the process for the production thereof is extraordinarily simple and the spreadibility of the same is very high. Said formulation is therefore an object of the instant invention.
  • Kagalite balloon is an artificially modified natural pumice produced by KAGALITE KOGYO Co., LTD., Japan.
  • the "Kaga” of Kagalite balloon is an ancient name of the district around Kanazawa where said natural pumice is obtained, now called “Ishikawa Prefecture” facing the Japan Sea. It is still not known why Kagalite Balloon allows the achievement of the instant invention.
  • natural pumice can have different elements, different components, different crystal structure, different pore ratios etc. depending upon when and where it has been created. It is reasonably assumed that the combination of all of these factors embodying in Kagalite Balloon effects the achievement of the instant invention.
  • Kagalite Balloon particles of the above natural pumice having particle diameters of 300-2500 ⁇ m are used.
  • Kagalite Balloon is produced by instantaneous heat treatment of said particles at a temperature of 900-1000°C, preferably 930-980°C, in a fluidized bed type infurnace to thereby foam them.
  • silica sand is placed inside the furnace in order to achieve uniform temperature distribution.
  • the time during which the above natural pumice is heat treated is not longer than 10 seconds, usually 3-5 seconds.
  • the foamed particles thus prepared are subject to sieving and, thereby obtaining Kagalite Balloon.
  • Kagalite Balloon as actually supplied by KAGALITE KOGYO Co., LTD., Japan and the term Kagalite Ballon as used herein is not so limited.
  • the expression Kagalite Balloon as used herein includes any natural pumice, preferably natural pumice derived from the district around Kanazawa in Japan, treated according to a process as described above.
  • Kagalite Balloon has a bulk density of less than 1, preferably 0.1-0.8, more preferably 0.1-0.5. Its floatability, i.e. the ratio of particles floating on the surface or in the water, is not less than 50%, preferably not less than 70%, more preferably not less than 85%. It absorbs oily substances in amounts of not less than 20%. Particle size distribution of Kagalite Balloon is such that 80% by weight of the particles lie within the range of 300-3000 ⁇ m, preferably 500-2800 /m, most preferred 600-2800 m.
  • a metallic net each aperture of which is 3350 ⁇ m in diameter, is placed exactly 20 cm above the top edge of a metal-made circular receiving container whose diameter is 50mm and volume is 100ml.
  • the sample whose bulk density is to be determinmed is gradually sieved into the receiving container till the sample forms a cone-like shape over the top edge of the receiving container. Then, the cone-like part is precisely removed and the weight W (g) of the sample remaining in the receiving container is measured.
  • the floatability is determined as follows:
  • the oil absorption is measured as follows:
  • Particle size distribution is determined as follows:
  • Kagalite Balloon is available at KAGALITE KOGYO Co., Ltd., Japan.
  • liquid pesticidal active ingredients to be used in the instant invention can be insecticides, fungicides, herbicides and/or plant growth regulators.
  • the "liquid pesticidal active ingredients" used in the instant invention are those which are liquids at 20°C under standard atmospheric conditions.
  • liquid insecticides include cyanophos, fenthion, fenitrothion, dichlofenthion, pirimiphos-methyl, diazinon, isoxathion, oxydeprofos, malathion, phenthoate, formothion, thiometon, disulfoton, prothiofos, sulprofos, profenofos, pyraclofos, dichlorvos, naled, chlorfenvinphos, propafos, isophenphos, ethion, carbosulfan, benfuracarb, allethrin, permethrin, cyhalothrin, cyfluthrin, fenvalerate, flucythrinate, fluvalinate, cycloprothrin, silafluofen, potassium oleate, propargite, halfenprox, ethoprophos, fosthiazate, chlorpicrin
  • liquid fungicides include calcium polysulf ide, edifenphos, propiconazole, pefurazoate, pyrifenox, tetraconazole, echlomezol, dinocap, metalaxyl-M and thiabendazole.
  • liquid herbicides examples include triclopyr, fluazifop, orbencarb, esprocarb, molinate, pretilachlor, metolachlor, dimethenamid, pelargonic acid, dalapon, piperophos, butamifos, glyphosate-trimesium, sethoxydim, clethodim, S-metolachlor and cinmethylin.
  • Liquid plant regulators examples include mepiquat chloride, decyl alcohol and piperonyl butoxide.
  • liquid active ingredients can be used alone or in combination.
  • solid pesticides can also be used if they can be dissolved in the liquid pesticides or liquid surfactants used in the formulation according to the instant invention.
  • Dimethametryne a herbicide of Syngenta AG
  • Pretilachlor a herbicide of Syngenta AG
  • the solid pesticides are regarded as liquid pesticidal active ingredients.
  • the ratio at which they are mixed is empirically determined in accordance with the desired pesticidal activities.
  • the surfactants mainly providing spreadability are those mainly providing spreadability to the Kagalite Balloon impregnated with liquid pesticidal active ingredients. Usually, they also have a function to some extent to emulsify the pesticidal active ingredients.
  • Such surfactants to be used in the instant invention are in general anionic and must be either liquids at 20°C or soluble in the liquid pesticidal active ingredients or other liquid surfactants used in the formulation according to the instant invention.
  • liquid surfactants providing spreadability include salts of dialkylsulfosuccinic acids, in particular the alkali metal, alkaline earth metal and ammonium salts. Particularly preferred is sodium dialkylsulfosuccinate.
  • the surfactants providing spreadability can be used alone or in combination. The ratio at which they are mixed is empirically determined in accordance with the desired performance.
  • Anionic surfactants mainly enhancing emulsifying effect are those mainly emulsifying the pesticidal active ingredients absorbed in Kagalite Balloon. Usually, they also have a function to some extent to provide spreadability to the Kagalite Balloon impregnated with liquid pesticidal active ingredients.
  • Such anionic surfactants to be used in the instant invention must be either liquids at 20°C or soluble in the liquid pesticidal active ingredients or other surfactants used in the formulation according to the instant invention.
  • Preferred liquid anionic surfactants enhancing emulsifying effect are for example polyoxyalkylenealkylarylethersulfates, polyoxyalkylenealkylethersulfa.es, polyoxyethylene/polyoxypropyleneaikylarylether sulfates, polyoxyethylene/polyoxypropylenearylethersulfates, sodium oleylmethyltaurid, polyoxyalkylenealkylarysulfonates, sodium polyoxyalkylenearylphenylethersulfates and calcium dodecylbenzenesulfonate. Particularly preferred are sodium polyoxyalkylenearylphenylethersulfate and calcium dodecylbenzenesulfonate.
  • the anionic surfactants enhancing emulsifying effect can be used alone or in combination. The ratio at which they are mixed is empirically determined in accordance with the desired performance.
  • nonionic surfactants may also be added. They not only contribute to reinforce the spreadability but also strengthen the emulsifying effect. Such nonionic surfactants must be either liquids at 20°C or soluble in the liquid pesticidal active ingredients or other surfactants used in the formulation according to the instant invention.
  • Preferred examples of nonionic surfactants are polyoxyethylenealkylethers, polyoxyethylene/polyoxypropylenealkylarylethers, polyoxyethylene/polyoxypropylenealkylethers, polyoxyethylene/polyoxypropylenearylether, polyoxyethylenesiloxane, castor oil polyglycolether and polyoxyethylenealkylethers. Particularly preferred are castor oil polyglycolether and polyoxyethylenealkylethers.
  • the nonionic surfactants can be used alone or in combination. The ratio at which they are mixed is empirically determined in accordance with the desired performance.
  • the surfactant mainly providing spreadability and the anionic surfactant mainly enhancing emulsifying effect are used at a ratio of from 5:1 to 1 :5 by weight, preferably from 3:1 to 1:3 by weight, more preferably from 2:1 to 1:2 by weight.
  • the surfactant mainly providing spreadability is composed of two or more surfactants, the term "weight” herein means the total weight of such surfactants. The same applies to the surfactant mainly enhancing emulsifying effect.
  • the weight ratio between these two types of surfactants is empirically determined in accordance with the desired performance. If nonionic surfactants are also used, their amount is preferably determined such that the ratio between the total weight of the surfactant providing spreadability with the anionic surfactant enhancing emulsifying effect and the weight of nonionic surfactant enhancing emulsifying effect is within the range of from 10:1 to 1 :10. This ratio is determined empirically.
  • the pesticidal active ingredient is used in an amount of 10-30% by weight, the surfactants in an amount of 1-15% by weight and Kagalite Balloon in an amount which makes the total amount from the pesticidal active ingredient, the surfactants and Kagalite Balloon 100%, based on the total weight of these components.
  • the process for the production of the Jumbo formulation according to the instant invention is extraordinarily simple. Firstly, a mixture comprising a liquid pesticidal active ingredient, a surfactant providing spreadability and an anionic surfactant enhancing emulsifying effect optionally with a nonionic surfactant enhancing emulsifying effect is prepared. Then, this mixture is subject to absorption by Kagalite Balloon, thereby yielding a formulation according to the instant invention.
  • the amounts of the above components are preferably selected such that the pesticidal active ingredient content is 10-30% by weight, the content of surfactants is 1-15% by weight and the content of Kagalite Balloon is the amount which makes the the total amount from the pesticidal active ingredient, the surfactants and Kagalite Balloon 100%, based on the total weight of these components.
  • the formulation according to the instant invention is preferably wrapped in a bag made of a water-soluble polymer such as polyvinylalcohol, polyvinylacetate, polyvinylpyrrolidone, carboxymethylcellulose or the like.
  • a water-soluble polymer such as polyvinylalcohol, polyvinylacetate, polyvinylpyrrolidone, carboxymethylcellulose or the like.
  • the amount of formulation to be contained in the water-soluble bag is 5-200g, preferably 10-150g, most preferred 15-1 OOg.
  • Another possible way of application of the formulation according to the instant invention is to pack it in bottles or bags having a hole through which the formulation can be scattered.
  • the formulation of the instant invention can, due to its excellent spreadability, be applied in the same manner as the flowable formulations which are scattered from the sides of the rice fields. Examples
  • Pretilachlor a herbicide, Novartis AG, purity 97%)
  • 50 g of NK EP-70G sodium dialkylsulfosuccinate, Takemoto Co.
  • 10 g of Emulsogen EL caster oil polyglycolether, Clariant Co.
  • 10 g of Phenysulfonate CA calcium dodecylbenzenesulfonate, Clariant Co.
  • TK homo mixer an automatic homo-mixer manufactured by Tokushu Kika Kohgyo Co.
  • Kagalite Balloon (Pumice balloon, a product of KAGALITE KOGYO Co.) contained in a coating pan HU (a coating pan manufactured by Hata Iron Works Co.), followed by mixing at a rotating speed of 25 rpm for 10 min, thereby obtaining a granular herbicidal formulation as indicated in Tablel .
  • Granular formulations are prepared in the same manner as in Example 1 except that the contents are varied as shown in Table 1.
  • NK FS-7S is a sodium polyoxyalkylenearylphenylethersulfate, a product of Takemoto Co.
  • Emulgen 109P is a polyoxyethylenealkylether, a product of Kao Co.
  • a granular formulation is prepared in the same manner as in Example 1 except that Perlite balloon or Shirasu balloon, which is another floatable material having a bulk density of less than 1 , is used instead of Kagalite Balloon as indicated by "C" inTable 1.
  • Perlite balloon or Shirasu balloon which is another floatable material having a bulk density of less than 1
  • Kagalite Balloon as indicated by "C” inTable 1.
  • the surface of the particles becomes wet, with the result that the particles adhere with one another, losing flowability.
  • This formulation cannot be used as a pesticidal formulation.
  • a container shaped as a right parallelepiped (cuboid shape) having a length of 4m and a width of 10cm is filled with 20I of water such that the water depth becomes about 5cm.
  • the water temperature is adjusted to 20°C.
  • 120mg of one of the granular formulations from Examples 1-9 are dropped onto the surface of water at a position 50cm distant from one of the edges of the container.
  • the time required for the formulation to reach the position 1 m, 2m or 3 m distant from the position at which the formulation has been dropped is measured.
  • the time required for the formulation to uniformly spread is measured and its diffusion behaviour is observed.
  • Table 2 Table 2
  • Test Example 2 Determination of active ingredient concentration
  • a container shaped as a right parallelepiped (cuboid shape) having a length of 4m and a width of 10cm is filled with 20I of water such that the water depth becomes about 5cm.
  • the water temperature is adjusted to 20°C.
  • 120mg of the granular formulation of Example 1 or 2, or 90mg of the granular formulation of Example 4 or 5 are wrapped with a water-soluble film (VF-HP#4000, a product of Kuraray, Kinuemboss) and dropped onto the surface of water at a position 50cm distant from one of the edges of the container.
  • Active ingredient concentration at positions 0m, 1 m and 3m distant from the position at which the formulation has been dropped is measured.
  • This measurement is carried out by sampling and analyzing 100ml of the water from each of the above positions 3 hours and 24 hours after the formulation has been dropped, with the proviso that the measurement after 3 hours is not performed for the position 0m distant from the position at which the formulation has been dropped. 50ml of hexane are added to the water sampled, which then is thoroughly shaked to thereby extract the active ingredient. Thereafter, the hexane phase is separated, condensed and dried, followed by dilution by adding 4ml of acetone to obtain a specimen for analysis. The specimen thus obtained is subject to capillary gas chromatography under the following conditions to thereby determine the concentration of the active ingredient.
  • Carrier gas He, 10ml/min.,
  • the formulation according to the instant invention has the following advantages: 1.
  • the process for the production is extraordinarily simple, requiring only mixing a liquid mixture comprising a liquid pesticidal active ingredient and surfactants with floatable granular particles, which has not been achieved by the prior art.
  • the formulation can quite easily contain a pesticidal active ingredient in such a high amount as 25% by weight.
  • the difference of the formulation according to the instant invention from those of the prior art is obvious from the result of Comparative Example which is a representative example of the prior art. It cannot contain even 15% by weight of a pesticidal active ingredient.
  • the spreadability of the formulation is sufficiently large. It spreads within about 1 minute by 3m and completes uniform distribution over an area 4m long and 10cm wide within about 3 minutes even in the case where the pesticidal active ingredient content is as high as 25% by weight.
  • the formulation also exhibits very preferable diffusion behaviour. It takes only 24 hours till the active ingredient concentration becomes homogeneous. No prior art gives to those skilled in the art any suggestion or motivation to develop such Jumbo formulations as those of the instant invention.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A formulation comprising a liquid pesticidal active ingredient, Kagalite Balloon, at least one surfactant providing spreadability and at least one anionic surfactant enhancing emulsifying effect. Said formulation enable the reduction of amounts of formulations to be applied, the storage volume during distribution as well as the production costs thereof in an environmentally friendly manner.

Description

Pesticidal formulation
The instant invention relates to a new pesticidal formulation with high active ingredient content which spreads rapidly over the surface of water, efficientcly releasing pesticidal active ingredients throughout the water surface, thereby saving labor load of farmers, storage volume during distribution as well as production costs thereof to a large extent.
Due to the water filling of paddy fields, it is not easy to apply pesticides in such a manner that they are scattered uniformly over the surface of water. As a result, if a farmer desires to uniformly apply pesticides, it is in principle necessary for him to enter the paddy field and scatter pesticides changing the position from which the farmer applies pesticides, demanding lots of works. Driven by the motivation to reduce labor load of farmers, the so-called Jumbo formulations have drawn attention among pesticide manufacturers. The Jumbo formulations have three aspects in common: (1) they float, (2) spread and (3) release pesticidal active ingredients on the surface of water. So far various types of Jumbo formulations have been proposed. However, there has been proposed no Jumbo formulation comprising a liquid active ingredient retained, adsorbed or fixed on a carrier allowing reduction in the amount of application, in the production costs while being environmentally friendly.
It is of substantial importance to increase the amounts of active ingredients in Jumbo formulations since it enables the reduction in amounts of formulation to be applied, the storage volume during distribution as well as the production costs thereof. Another prerequisite for a successful Jumbo formulation is a satisfactorily large spreadability, which together with the sufficient active ingredient content contributes to the above effects. Without sufficient spreadability, the amount of application cannot be reduced, eventually leading to the necessity in large storage amounts and high production costs. Therefore, a sufficiently high active ingredient content and a satisfactorily large spreadability are the most important factors for the production of advantageous Jumbo formulation. In addition to these factors, it is also important to consider environmental aspects. If an environmentally not preferable ingredient is contained in a Jumbo formulation, it cannot be regarded as being advantageous. Jumbo formulations are generally finished in such a manner that they are packed in water-soluble bags made of water-soluble polymers e.g. polyvinylalcohol, which are directly applied to the surface of water. After the bags have dissolved in the water, particles of the Jumbo formulation spread on the surface of water releasing active ingredients.
The Jumbo formulations with liquid active ingredients so far developed contain active ingredients usually in amounts of 2-10% by weight (see for example JP Kokai Nos. 6-336403 and 8-99804), not achieving the reduction in amount of application thereof. The low liquid active ingredient content presumably reflects the fact that there has so far been not available such a core material that floats on the surface of water and capable of absorbing liquid active ingredients in amounts higher than 10% by weight. JP Kokai No. 11-310503 describes a Jumbo formulation in which Pretilachlor, which is a liquid active ingredient, is contained in an amount as high as 25% by weight. However, there is no description about the spreadability thereof, giving no motivation to those skilled in the art to develop a Jumbo formulation containing liquid active ingredients in amounts higher than 10% by weight, spreading rapidly over the surface of water and capable of being produced in a simple process. Moreover, this formulation contains about 25% by weight of powderd polyvinylchloride, which is not preferred from the environmental point of view.
It has now been surprisingly found that a formulation comprising a liquid pesticidal active ingredient, Kagalite Balloon, at least one surfactant mainly providing spreadability and at least one anionic surfactant mainly enhancing emulsifying effect, which is very environmentally friendly, unexpectedly allows active ingredient contents as high as 25% by weight quite easily, whilst the process for the production thereof is extraordinarily simple and the spreadibility of the same is very high. Said formulation is therefore an object of the instant invention.
Kagalite balloon is an artificially modified natural pumice produced by KAGALITE KOGYO Co., LTD., Japan. The "Kaga" of Kagalite balloon is an ancient name of the district around Kanazawa where said natural pumice is obtained, now called "Ishikawa Prefecture" facing the Japan Sea. It is still not known why Kagalite Balloon allows the achievement of the instant invention. However, natural pumice can have different elements, different components, different crystal structure, different pore ratios etc. depending upon when and where it has been created. It is reasonably assumed that the combination of all of these factors embodying in Kagalite Balloon effects the achievement of the instant invention. For the production of Kagalite Balloon, particles of the above natural pumice having particle diameters of 300-2500μm are used. Kagalite Balloon is produced by instantaneous heat treatment of said particles at a temperature of 900-1000°C, preferably 930-980°C, in a fluidized bed type infurnace to thereby foam them. Usually, silica sand is placed inside the furnace in order to achieve uniform temperature distribution. The time during which the above natural pumice is heat treated is not longer than 10 seconds, usually 3-5 seconds. The foamed particles thus prepared are subject to sieving and, thereby obtaining Kagalite Balloon. It is to be understood that the scope of the present invention is not restricted to Kagalite Balloon as actually supplied by KAGALITE KOGYO Co., LTD., Japan and the term Kagalite Ballon as used herein is not so limited. The expression Kagalite Balloon as used herein includes any natural pumice, preferably natural pumice derived from the district around Kanazawa in Japan, treated according to a process as described above.
Kagalite Balloon has a bulk density of less than 1, preferably 0.1-0.8, more preferably 0.1-0.5. Its floatability, i.e. the ratio of particles floating on the surface or in the water, is not less than 50%, preferably not less than 70%, more preferably not less than 85%. It absorbs oily substances in amounts of not less than 20%. Particle size distribution of Kagalite Balloon is such that 80% by weight of the particles lie within the range of 300-3000μm, preferably 500-2800 /m, most preferred 600-2800 m.
The above bulk density is determined as follows:
A metallic net, each aperture of which is 3350μm in diameter, is placed exactly 20 cm above the top edge of a metal-made circular receiving container whose diameter is 50mm and volume is 100ml. The sample whose bulk density is to be determinmed is gradually sieved into the receiving container till the sample forms a cone-like shape over the top edge of the receiving container. Then, the cone-like part is precisely removed and the weight W (g) of the sample remaining in the receiving container is measured. The bulk densities are determined according to the formula: Bulk density = W/100.
The floatability is determined as follows:
S (g), which is about 20.0g, of a sample which has precisely been weighed is charged into a cone-shaped flow meter having a shape like a separating funnel, which is then stirred while gradually adding water till the limit within which the water does not overflow. After 30 minutes, the particles floating are completely removed, and the dry weight C (g) of the precipitated particles is measured. The floatabilities are determined according to the formula: Floatibility (%) = (S-C)/Sx100.
The oil absorption is measured as follows:
S (g), which is about 10g, of a sample which has precisely been weighed is charged into a Meyer flask equipped with a stopper, to which linseed oil is gradually added so that the oil is focused to the central part of the sample. The flask is then thoroughly shaked. Defining the time at which no more linseed oil is able to be absorbed, namely the time at which the flowability of the sample decreases and the linseed oil starts to adhere to the surface of the sample, as the terminal point, the amount H (g) of the linseed oil used till the terminal point is measured. The oil absorption is determined according to the formula: Oil absorption (%) = H/SxlOO.
Particle size distribution is determined as follows:
S (g), which is about 60g, of a sample is placed in a Rotap sieve analyzer, followed by sieving the sample. The weight D (g) of the sample remaining on each net is measured. The particle size distribution is determined according to the formula: Particle size distribution (%) = D/SxlOO.
Kagalite Balloon is available at KAGALITE KOGYO Co., Ltd., Japan.
The liquid pesticidal active ingredients to be used in the instant invention can be insecticides, fungicides, herbicides and/or plant growth regulators. The "liquid pesticidal active ingredients" used in the instant invention are those which are liquids at 20°C under standard atmospheric conditions.
Examples of liquid insecticides include cyanophos, fenthion, fenitrothion, dichlofenthion, pirimiphos-methyl, diazinon, isoxathion, oxydeprofos, malathion, phenthoate, formothion, thiometon, disulfoton, prothiofos, sulprofos, profenofos, pyraclofos, dichlorvos, naled, chlorfenvinphos, propafos, isophenphos, ethion, carbosulfan, benfuracarb, allethrin, permethrin, cyhalothrin, cyfluthrin, fenvalerate, flucythrinate, fluvalinate, cycloprothrin, silafluofen, potassium oleate, propargite, halfenprox, ethoprophos, fosthiazate, chlorpicrin and metam-ammonium. Examples of liquid fungicides include calcium polysulf ide, edifenphos, propiconazole, pefurazoate, pyrifenox, tetraconazole, echlomezol, dinocap, metalaxyl-M and thiabendazole.
Examples of liquid herbicides include triclopyr, fluazifop, orbencarb, esprocarb, molinate, pretilachlor, metolachlor, dimethenamid, pelargonic acid, dalapon, piperophos, butamifos, glyphosate-trimesium, sethoxydim, clethodim, S-metolachlor and cinmethylin.
Examples of Liquid plant regulators include mepiquat chloride, decyl alcohol and piperonyl butoxide.
These liquid active ingredients can be used alone or in combination. Moreover, solid pesticides can also be used if they can be dissolved in the liquid pesticides or liquid surfactants used in the formulation according to the instant invention. For example, Dimethametryne, a herbicide of Syngenta AG, is soluble in Pretilachlor within the weight ratio of Pretilachlor : Dimethametryne = 10:1 - 5:1 yielding a liquid mixture. In such a case, the solid pesticides are regarded as liquid pesticidal active ingredients. When using two or more active ingredients in combination, the ratio at which they are mixed is empirically determined in accordance with the desired pesticidal activities.
The surfactants mainly providing spreadability are those mainly providing spreadability to the Kagalite Balloon impregnated with liquid pesticidal active ingredients. Usually, they also have a function to some extent to emulsify the pesticidal active ingredients. Such surfactants to be used in the instant invention are in general anionic and must be either liquids at 20°C or soluble in the liquid pesticidal active ingredients or other liquid surfactants used in the formulation according to the instant invention. Examples of liquid surfactants providing spreadability include salts of dialkylsulfosuccinic acids, in particular the alkali metal, alkaline earth metal and ammonium salts. Particularly preferred is sodium dialkylsulfosuccinate. The surfactants providing spreadability can be used alone or in combination. The ratio at which they are mixed is empirically determined in accordance with the desired performance.
Anionic surfactants mainly enhancing emulsifying effect are those mainly emulsifying the pesticidal active ingredients absorbed in Kagalite Balloon. Usually, they also have a function to some extent to provide spreadability to the Kagalite Balloon impregnated with liquid pesticidal active ingredients. Such anionic surfactants to be used in the instant invention must be either liquids at 20°C or soluble in the liquid pesticidal active ingredients or other surfactants used in the formulation according to the instant invention. Preferred liquid anionic surfactants enhancing emulsifying effect are for example polyoxyalkylenealkylarylethersulfates, polyoxyalkylenealkylethersulfa.es, polyoxyethylene/polyoxypropyleneaikylarylether sulfates, polyoxyethylene/polyoxypropylenearylethersulfates, sodium oleylmethyltaurid, polyoxyalkylenealkylarysulfonates, sodium polyoxyalkylenearylphenylethersulfates and calcium dodecylbenzenesulfonate. Particularly preferred are sodium polyoxyalkylenearylphenylethersulfate and calcium dodecylbenzenesulfonate. The anionic surfactants enhancing emulsifying effect can be used alone or in combination. The ratio at which they are mixed is empirically determined in accordance with the desired performance.
Optionally, nonionic surfactants may also be added. They not only contribute to reinforce the spreadability but also strengthen the emulsifying effect. Such nonionic surfactants must be either liquids at 20°C or soluble in the liquid pesticidal active ingredients or other surfactants used in the formulation according to the instant invention. Preferred examples of nonionic surfactants are polyoxyethylenealkylethers, polyoxyethylene/polyoxypropylenealkylarylethers, polyoxyethylene/polyoxypropylenealkylethers, polyoxyethylene/polyoxypropylenearylether, polyoxyethylenesiloxane, castor oil polyglycolether and polyoxyethylenealkylethers. Particularly preferred are castor oil polyglycolether and polyoxyethylenealkylethers. The nonionic surfactants can be used alone or in combination. The ratio at which they are mixed is empirically determined in accordance with the desired performance.
If no nonionic surfactant is used, the surfactant mainly providing spreadability and the anionic surfactant mainly enhancing emulsifying effect are used at a ratio of from 5:1 to 1 :5 by weight, preferably from 3:1 to 1:3 by weight, more preferably from 2:1 to 1:2 by weight. If the surfactant mainly providing spreadability is composed of two or more surfactants, the term "weight" herein means the total weight of such surfactants. The same applies to the surfactant mainly enhancing emulsifying effect. If the total amount of the surfactants is the same, the higher the content of the surfactant mainly providing spreadability, the higher the spreadability and the lower the emulsifying effect whilst the higher the content of the surfactant mainly enhancing emulsifying effect, the higher the emulsifying effect and the lower the spreadability. The weight ratio between these two types of surfactants is empirically determined in accordance with the desired performance. If nonionic surfactants are also used, their amount is preferably determined such that the ratio between the total weight of the surfactant providing spreadability with the anionic surfactant enhancing emulsifying effect and the weight of nonionic surfactant enhancing emulsifying effect is within the range of from 10:1 to 1 :10. This ratio is determined empirically.
In a preferred embodiment of the instant invention, the pesticidal active ingredient is used in an amount of 10-30% by weight, the surfactants in an amount of 1-15% by weight and Kagalite Balloon in an amount which makes the total amount from the pesticidal active ingredient, the surfactants and Kagalite Balloon 100%, based on the total weight of these components.
The process for the production of the Jumbo formulation according to the instant invention is extraordinarily simple. Firstly, a mixture comprising a liquid pesticidal active ingredient, a surfactant providing spreadability and an anionic surfactant enhancing emulsifying effect optionally with a nonionic surfactant enhancing emulsifying effect is prepared. Then, this mixture is subject to absorption by Kagalite Balloon, thereby yielding a formulation according to the instant invention. The amounts of the above components are preferably selected such that the pesticidal active ingredient content is 10-30% by weight, the content of surfactants is 1-15% by weight and the content of Kagalite Balloon is the amount which makes the the total amount from the pesticidal active ingredient, the surfactants and Kagalite Balloon 100%, based on the total weight of these components.
The formulation according to the instant invention is preferably wrapped in a bag made of a water-soluble polymer such as polyvinylalcohol, polyvinylacetate, polyvinylpyrrolidone, carboxymethylcellulose or the like. By employing this technique, it is enabled to apply the formulation according to the instant invention without being exposed thereto. The amount of formulation to be contained in the water-soluble bag is 5-200g, preferably 10-150g, most preferred 15-1 OOg. Another possible way of application of the formulation according to the instant invention is to pack it in bottles or bags having a hole through which the formulation can be scattered. By employing this technique, the formulation of the instant invention can, due to its excellent spreadability, be applied in the same manner as the flowable formulations which are scattered from the sides of the rice fields. Examples
The instant invention will further be explained with reference to the following examples, which of course are meant to illustrate the invention .
Example 1
160 g of Pretilachlor (a herbicide, Novartis AG, purity 97%), 50 g of NK EP-70G (sodium dialkylsulfosuccinate, Takemoto Co.), 10 g of Emulsogen EL (caster oil polyglycolether, Clariant Co.), 10 g of Phenysulfonate CA (calcium dodecylbenzenesulfonate, Clariant Co.) are charged into a 500ml container, followed by agitation using a TK homo mixer (an automatic homo-mixer manufactured by Tokushu Kika Kohgyo Co.). Thereafter, this mixture is applied to 770 g of Kagalite Balloon (Pumice balloon, a product of KAGALITE KOGYO Co.) contained in a coating pan HU (a coating pan manufactured by Hata Iron Works Co.), followed by mixing at a rotating speed of 25 rpm for 10 min, thereby obtaining a granular herbicidal formulation as indicated in Tablel .
Examples 2-9
Granular formulations are prepared in the same manner as in Example 1 except that the contents are varied as shown in Table 1. In these examples, NK FS-7S is a sodium polyoxyalkylenearylphenylethersulfate, a product of Takemoto Co. and Emulgen 109P is a polyoxyethylenealkylether, a product of Kao Co.
Table 1
Figure imgf000010_0001
Units: % by weight
Comparative Example
A granular formulation is prepared in the same manner as in Example 1 except that Perlite balloon or Shirasu balloon, which is another floatable material having a bulk density of less than 1 , is used instead of Kagalite Balloon as indicated by "C" inTable 1. However, the surface of the particles becomes wet, with the result that the particles adhere with one another, losing flowability. This formulation cannot be used as a pesticidal formulation.
Test Example 1 (Spreadability Test)
A container shaped as a right parallelepiped (cuboid shape) having a length of 4m and a width of 10cm is filled with 20I of water such that the water depth becomes about 5cm. The water temperature is adjusted to 20°C. Thereafter, 120mg of one of the granular formulations from Examples 1-9 are dropped onto the surface of water at a position 50cm distant from one of the edges of the container. The time required for the formulation to reach the position 1 m, 2m or 3 m distant from the position at which the formulation has been dropped is measured. The time required for the formulation to uniformly spread is measured and its diffusion behaviour is observed. The results are shown in Table 2. Table 2
Figure imgf000011_0001
Test Example 2 (Determination of active ingredient concentration) A container shaped as a right parallelepiped (cuboid shape) having a length of 4m and a width of 10cm is filled with 20I of water such that the water depth becomes about 5cm. The water temperature is adjusted to 20°C. Thereafter, 120mg of the granular formulation of Example 1 or 2, or 90mg of the granular formulation of Example 4 or 5, are wrapped with a water-soluble film (VF-HP#4000, a product of Kuraray, Kinuemboss) and dropped onto the surface of water at a position 50cm distant from one of the edges of the container. Active ingredient concentration at positions 0m, 1 m and 3m distant from the position at which the formulation has been dropped is measured. This measurement is carried out by sampling and analyzing 100ml of the water from each of the above positions 3 hours and 24 hours after the formulation has been dropped, with the proviso that the measurement after 3 hours is not performed for the position 0m distant from the position at which the formulation has been dropped. 50ml of hexane are added to the water sampled, which then is thoroughly shaked to thereby extract the active ingredient. Thereafter, the hexane phase is separated, condensed and dried, followed by dilution by adding 4ml of acetone to obtain a specimen for analysis. The specimen thus obtained is subject to capillary gas chromatography under the following conditions to thereby determine the concentration of the active ingredient.
Cap-GLC: Hewlett Packard HP6890
Column: DB-1701 fused silica capillary column, 0.53mm id x 15m, film thickness 1.0μm, manufactured by J &W Co.
Column temperature: 170°C for 18min., elevated to 240°C at a rate of 4°C/min., kept for 5 min. at 240°C
Detector temperature: 300°C
Injector temperature : 250°C
Carrier gas: He, 10ml/min.,
Linear velocity: 93 cm/sec
Make up gas: Nitrogen, 25ml/min.
Injection volume: 2μ\
The results are shown in Table 3.
Table 3
Figure imgf000012_0001
Units: ppm
As obvious from the above examples, the formulation according to the instant invention has the following advantages: 1. The process for the production is extraordinarily simple, requiring only mixing a liquid mixture comprising a liquid pesticidal active ingredient and surfactants with floatable granular particles, which has not been achieved by the prior art.
2. The formulation can quite easily contain a pesticidal active ingredient in such a high amount as 25% by weight. The difference of the formulation according to the instant invention from those of the prior art is obvious from the result of Comparative Example which is a representative example of the prior art. It cannot contain even 15% by weight of a pesticidal active ingredient.
3. The spreadability of the formulation is sufficiently large. It spreads within about 1 minute by 3m and completes uniform distribution over an area 4m long and 10cm wide within about 3 minutes even in the case where the pesticidal active ingredient content is as high as 25% by weight. The formulation also exhibits very preferable diffusion behaviour. It takes only 24 hours till the active ingredient concentration becomes homogeneous. No prior art gives to those skilled in the art any suggestion or motivation to develop such Jumbo formulations as those of the instant invention.
The above advantages enable the reduction of amounts of formulations to be applied, the storage volume during distribution as well as the production costs thereof in an environmentally friendly manner. Therefore, the contribution of the instant invention to modern agriculture and pesticidal industry is of substantial value.

Claims

What is claimed is:
1. A formulation comprising a liquid pesticidal active ingredient, Kagalite Balloon, at least one surfactant mainly providing spreadability and at least one anionic surfactant mainly enhancing emulsifying effect.
2. A formulation according to claim 1 , wherein said liquid pesticidal active ingredient is a liquid fungicide, a liquid insecticide, a liquid herbicide or a liquid plant growth regulator.
3. A formulation according to claim 2, wherein said liquid fungicide is selected from the group consisting of calcium polysulfide, edifenphos, propiconazole, pefurazoate, pyrifenox, tetraconazole, echlomezol, dinocap, metalaxyl-M and thiabendazole.
4. A formulation according to claim 2, wherein said liquid insecticide is selected from the group consisting of cyanophos, fenthion, fenitrothion, dichlofenthion, pirimiphos-methyl, diazinon, isoxathion, oxydeprofos, malathion, phenthoate, formothion, thiometon, disulfoton, prothiofos, sulprofos, profenofos, pyraclofos, dichlorvos, naled, chlorfenvinphos, propafos, isophenphos, ethion, carbosulfan, benfuracarb, allethrin, permethrin, cyhalothrin, cyfluthrin, fenvalerate, flucythrinate, fluvalinate, cycloprothrin, silafluofen, potassium oleate, propargite, halfenprox, ethoprophos, fosthiazate, chlorpicrin and metam-ammonium.
5. A formulation according to claim 2, wherein said liquid herbicide is selected from the group consisting of are triclopyr, fluazifop, orbencarb, esprocarb, molinate, pretilachlor, metolachlor, dimethenamid, pelargonic acid, dalapon, piperophos, S-metolachlor, butamifos, glyphosate-trimesium, sethoxydim, clethodim and cynmethylin.
6. A formulation according to claim 2, wherein said liquid plant growth regulator is selected from the group consisting of mepiquat chloride, decyl alcohol and piperonyl butoxide.
7. A formulation according to claim 5, wherein said liquid pesticide is pretilachlor.
8. A composition according to claim 1 , wherein said surfactant mainly providing spreadability is selected from the group consisting of salts of dialkylsulfosuccinic acids.
9. A formulation according to claim 8, whberein said surfactant mainly providing spreadability is sodium dialkylsulfosuccinate.
10. A formulation according to claim 1 , wherein said anionic surfactant mainly enhancing emulsifying effect is selected from the group consisting of sodium polyoxyalkylenearylphenylethersulfate and calcium dodecylbenzenesulfonate.
11. A formulation according to claim 1 , further comprising a nonionic surfactant.
12. A formulation according to claim 11 , wherein said noinion surfactant is selected from the group consisting of castor oil polyglycolether and polyoxyethylenealkylether.
13. A formulation according to claim 1 , wherein said pesticidal active ingredient is contained in an amount of 10-30% by weight, the surfactants in an amount of 1-15% by weight and Kagalite Balloon in an amount which makes the total amount from the pesticidal active ingredient, the surfactants and Kagalite Balloon 100%, based on the total weight of these components.
14. An agrochemical product comprising a formulation according to claim 1, which is contained in a water-soluble bag made of a water-soluble polymer.
15. A product according to claim 14, wherein said water-soluble polymer is polyvinylalcohol.
16. An agrochemical product comprising a formulation according to claim 1 , which is contained in a bottle or a bag having an opening through which the formulation can be scattered.
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CN102726376A (en) * 2011-04-08 2012-10-17 中国中化股份有限公司 Clethodim emulsifiable pulvis
CN105475344A (en) * 2015-12-29 2016-04-13 南京华洲药业有限公司 Synergistic insecticidal composition containing propargite and silafluofen and application thereof
CN105475339A (en) * 2015-12-29 2016-04-13 南京华洲药业有限公司 Synergistic insecticidal composition containing propargite and cycloprothrin and application thereof
CN105475344B (en) * 2015-12-29 2018-04-20 南京华洲药业有限公司 A kind of Synergistic insecticidal compositions and its application containing propargite and silicon ethofenprox

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