WO1998021961A1 - Novel solid compositions based on an insoluble cellulose derivative and a 1-arylpyrazole derivative - Google Patents

Novel solid compositions based on an insoluble cellulose derivative and a 1-arylpyrazole derivative

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Publication number
WO1998021961A1
WO1998021961A1 PCT/IB1997/001638 IB9701638W WO9821961A1 WO 1998021961 A1 WO1998021961 A1 WO 1998021961A1 IB 9701638 W IB9701638 W IB 9701638W WO 9821961 A1 WO9821961 A1 WO 9821961A1
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WO
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Patent type
Prior art keywords
according
invention
composition
preferably
cellulose
Prior art date
Application number
PCT/IB1997/001638
Other languages
French (fr)
Inventor
Marc Grenet
Masato Kobayakawa
Gunther Maurer
Norihiko Nakakura
Takashi Nakatsui
Eberhard Teufel
Original Assignee
Rhone-Poulenc Agrochimie
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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01MCATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M1/00Stationary means for catching or killing insects
    • A01M1/24Arrangements connected with buildings, doors, windows, or the like
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01MCATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M17/00Apparatus for the destruction of vermin in soil or in foodstuffs
    • 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, 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
    • 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, 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, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom

Abstract

The present invention relates to a solid composition of a water-insoluble cellulose derivative, comprising an effective quantity of at least one 1-arylpyrazole derivative, more particularly a composition in which the 1-arylpyrazole derivative is distributed homogeneously within the insoluble cellulose derivative, in the form of a solid solution. The invention likewise relates to a process for preparing the above compositions, and to their use in combating harmful insects, especially termites.

Description

Novei solid compositions based on an insoluble cellulose derivative and a I - arylpyrazole denvative

The present invention relates to a novei insecticidal composition based on a 1 - arylpyrazole derivative, to a process for its preparation and to its use for combating harmful insects.

The usefulness of 1 -aryipyrazoles for combating insects, especially termite.., is known in particular from the applications for patents WO 87/3781 , WO 9.V0089. WO 94/21606 or EP 295 117. Various formulations of 1 -aryipyrazoles have been descπbed in the prior art, especially in the form of powders, gels, concentrated aqueous suspensions or else emulsifiable compositions based on a weakly polar solvent and an emulsifier (WO 96/16544).

One of the major problems in the formulation of an insecticidal compound is to avoid the insecticidal compound coming into contact with the user of the formulation. The subject of the present invention consists of a novel formulation of 1- arylpyrazolc derivatives which is concentrated, homogeneous and stable over time and is effective against harmful insects, especially termites, while permitting ease of handling and improved safety.

The present invention therefore relates to a novei solid composition of a water- insoluble cellulose derivative, comprising an effective quantity of at least one 1 - arylpyrazole derivative.

Advantageously, 1 -arylpyrazole according to the invention refers to a compound of general formula (1)

in which

Rι is a halogen atom or a CN or methyl group; R2 is S(0)nR3;

R3 is an alkyl or haloalkyl radical;

R represents a hydrogen or halogen atom; an alkyl or haloalkyl radical; NRjR*, -S(0)mR7. C(0)R7, -C(0)0-R7, -N=C(R9)(R|0) or -OR8, R5 and e represent, independently of one another, a hydrogen atom, an alkyl or haloalkyl radical, -C(0)alkyl, -S(0)rCF ; or R5 and RA may together form a divalent alkylene radical which can be inteπupted by one or two divalent heteroato s such as oxygen or sulphur; R7 represents an alkyl or haloalkyl radical; R& represents an alkyl or haloalkyl radical or a hydrogen atom;

Rι> represents an alkyl radical or a hydrogen atom;

Rio represents a phenyl or heteroaryl group which is optionally substituted by one or more halogen atoms or groups such as OH, -O-alkyl, -S-alkyl, cyano or alkyl,

X represents a trivalent nitrogen atom or a radical C-Rn, the three other valencies of the carbon atom forming part of the aromatic ring; Rii and R12 represent, independently of one another, a hydrogen or halogen atom; R13 represents a halogen atom or a haloalkyl or haloalkoxy group. -S(0)qCF3 or -SF5; m, n. q and r represent, independently of one another, an integer equal to 0, 1 or 2; with the proviso that, when Rι is methyl, R3 is a haloalkyl group, R4 is NH2, Rn is Cl, Ru is CF3. and X is N.

According to the present invention the term alkyl radicals refers to straight-chain or branched alkyl radicals comprising in general from 1 to 6 carbon atoms. This definition also applies to the alkyl parts of radicals comprising an alkyl moiety, such as alkoxy, alkylthio, alkylcarbonyl, haloalkyl or haloalkoxy radicals.

Advantageously, the ring formed by the divalent alkylene radical represented by R5 and R$, and by the nitrogen atom to which R5 and t, are attached, is a 5-, 6- or 7- membered ring.

According to the present invention, the term halogen atom refers to atoms of fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine. This definition also applies tu the halogen atoms of haloalkyl or haloalkoxy radicals

One preferred class of compounds of formula (1) consists of compound!, for which R| is CN and/or R3 is haloalkyl and or R is NHi and/or Rn and Rn independently of one βnother are a halogen atom and/or Rι3 is haloalkyl. A particularly preferred compound of formula (I) in the invention is l-f2,6-Cl2-

4-CF3-phenyl]-3-CN-4-[SO-CF3]-5-NH2-pyrazole, referred to below as fipronii.

Compounds of formula (1) can be prepared according to one or other of the processes described in the applications for patents WO 87/3781, 93/6089. 94/21606 or European Patent 295 1 17, or any other process falling within the competence of the skilled worker who is a specialist in chemical synthesis.

The insoluble cellulose derivative can be in the form of powders, solid particles, granules, fibres, woven or nonwoven webs obtained with the said fibres, or else.

The insoluble cellulose derivative is advantageously an aliphatic ester of cellulose, preferably a cellulose acetate, more preferably a cellulose acetate whose degree of polymerization is between 150 and 250 units, preferably between 150 and

220, and/or with a degree of acetylation of between 1.2 and 2.8, preferably between 1.9 and 2.5.

The effective quantity of 1 -arylpyrazole derivative in the composition according to the invention will depend on the final form of the insecticidal composition, on its use and on the target insects of the said composition.

Advantageously, the effective quantity of 1 -arylpyrazole derivative in the composition according to the invention is between 0.0001 and 50% by weight relative to the total weight of the composition, preferably between 0.05 and 25% by weight.

The composition according to the invention can be in various solid forms;, in the form of fibres, woven or nonwoven webs obtained with the said fibres, in the form of solid particles, or else of granules.

For a composition in fibre form, the effective quantity of l-arylpyπuυle derivative is advantageously between 0.1 and 15% by weight.

For a composition in woven or nonwoven web form, the effective quantity of [- arylpyrazole derivative is between 0.01 and 25 g/m2, advantageously between 0.1 and 10 g/m2, and for certain utilities even between 1 and 5 g/m2.

For a composition in particle form, the effective quantity of 1 -arylpyrazole derivative is advantageously between 0.05 and 10% by weight.

For a composition in granule form, the effective quantity of I -arylpyrazol derivative is advantageously less than about 10% by weight, preferably less than 7% by weight and more preferably between 0.05 and 5% by weight. Fibje

When the composition according to the invention is in fibre form, the fibres are cut into pieces with a size which is generally between about 2 and about 30 mm, preferably between about 6 and about 18 mm. Moreover, the fibres of the composition according to the invention may be of various forms in section, such as circular or Y-, X- or I-shaped. Their weight per unit length varies from about 1 to about 25 decite.x, a range from 1 to 5 decitex being more particularly preferred for more effective release of the I -arylpyrazole over time. One decitex is the weight, expressed in grams, per 10,000 m of fibre. The corresponding mean diameter is generally between about 10 and about 100 mm, preferably from 15 to 50 mm. Webs

When the composition according to the invention is in the form of a woven or nonwoven web obtained with the above fibres, it preferably has a thickness of between about 0.05 mm and about 2 cm, preferably between 0.1 and 1 cm and, depending on use, more preferably between 1 and 5 mm. The weight per m2 of the web according to the invention is advantageously between about 1 and about 2500 g/m2. It will depend in particular on the subsequent use of the web according to the invention. In the case of a web which is to be placed under the foundations of a house to combat termites, the weight per m2 of the web according to the invention is preferably between 100 and 1000 g/m2. In the case of a web used as a support for the germination and growth of seeds, in particular of rice, to protect them against insects, the weight per m2 of the web according to the invention is advantageously between 5 and 100 g/m2, preferably between 10 and 70 g/m2.

According to a preferred embodiment of the invention, the web has an air permeability of between about 50 and about 10,000 l.s"'.m"2, preferably between 70 and 5000 l.s*'.m"2. The air permeability is measured by the quantity of air which crosses two opposing surfaces of a standard surface area of the web (about 20 to 50 cm") in accordance with one of the following equivalent standard methods: ISO 9237, AFNOR G07-1 1 1. ASTM D737 or DIN 53887.

The dimensions of the woven or nonwoven webs according to the invention will vary depending on their method of manufacture and their use. A large-sized web may be used, for example, to be laid under the foundations of a house to combat termites. In this case, the width of the web according to the invention is between about 20 cm and about

4 m, advantageously between 30 cm and 3 m. —

When the web according to the invention is employed as a support for seeds and cultures, it can advantageously be employed in a seeding box. Seeding boxes, also referred to as nursery boxes, are currently used by rice-growers to obtain, after sowing, rice plantlets which are then easily planted out (or transplanted) into submerged rice fields, generally by mechanical means. The web according to the invention is very readily placed by the rice-grower into a seeding box. To do this it is sufficient to place it on a first layer of earth, with a height which is generally between 1 and 5 cm. The rice seeds are sown onto the web, and the whole is covered with a second layer of earth, with a height which is generally between 0.5 and 2 cm. The height of the first layer of soil is generally between 1 and 5 cm. The height of the second layer of soil, also called the surface layer, is advantageously between 0.5 and 2 cm, preferably between 1 and 2 cm. The bottom of the box may be covered, beneath the first layer of soil, with a paper, commonly referred to as a liner, of suitable basis weight. This variant is particularly advantageous when the seeding boxes are stored on the soil for the period of time between sowing and planting out. In fact, in the absence of such a layer of paper, the roots of the rice plantlets would be able to pass through the bottom of the box (which is pierced with a multitude of holes to allow the flow of the irrigation water) and to take root in the soil; this might damage the rice plantlets and would interfere considerably with the removal of the boxes for the purpose of planting out. The basis weight of the liner is generally between 20 and 80 g m2, preferably between 30 and 50 g/m2. The size of the seeding box and of the web is commonly chosen to correspond to from 100 to 300 boxes per hectare of crop, preferably 200 boxes. These boxes are generally rectangles with a length which is commonly between 50 and 65 cm and a width which is between 20 and 35 cm. A rectangle of 58 by 28 cm is customarily employed. The quantity of rice seeds contained in the boxes corresponds to a sowing of from 10 to 300 kg/ha, preferably from 20 to 200 kg/ha. Particles

When the solid composition according to the invention is in particle form, the particles are advantageously microparticles which are substantially spherical in shape and have a size of between about 0.3 and about 200 mm, preferably between 1 and 30 mm and, still more preferably, between 5 and 20 mm. The term substantially spherical refers, according to the invention, to a shape which can be approached geometrically by a sphere or an ellipsoid and which can be described by a single size parameter. The propensity of these microparticles to remain in suspension in water is advantageous. According to a preferred embodiment of the invention, the microparticles are hollow and are in the form of an envelope or shell with a thickness of between 0.1 and 3 mm, preferably between 0,5 and 1.5 mm. Such a thickness is particularly appropriate for termites, which arc able to consume the microparticles with great ease, thus enhancing the efficacy of the I -arylpyrazole derivatives against these insects. An advantageous measurement technique for measuring the thickness of the shell is to envelope 0.1 g of microparticles in a 5% agarose gel, to bring the said gel to a temperature of -40°C and to carry out cutting at this temperature using a steel blade The cut surface is then observed by low-revolution scanning microscopy, the sample being placed in an observation chamber in the presence of water vapour at a pressure of between 5 and 12 mmHg. A magnification of approximately 1000 is employed. Granules

The granules according to the invention preferably have a length of between about 0.5 and 2 mm, preferably about 1 mm, and a mean diameter of between about 0.5 and 2 mm, preferably about 1 mm. A granule size of this kind is particularly suitable for combating termites.

The composition according to the invention may additionally comprise customary additives which enter into the preparation of the various forms above. Among these additives mention may be made of binders, dyes, surfactants, diluents or plasticizers. The binders are particularly suitable for the preparation of woven or nonwoven fibrous webs according to the invention. Among the binders which are used, preference is given to a binder which is soluble or dtspersible in water, generally in the form of cut fibres. S ch binders are well known in the art. They arc water-.soluble or water- dispersible polymers: natural polymers, such as polysa harides, semi-synthetic polymers, such as carboxymcthylccUulose and its salts, or synthetic polymers, such as polyvinyl alcohol or polyvinylpyrrolidonc. Polyvinyl alcohol is particularly preferred. In the webs according to the invention the weight ratio of binder to fibres comprising the agrochemical product is generally between 1 and 20%. preferably between 5 and 15%.

The surfactants and diluents are particularly appropriate for compositions according to the invention in the form of particles, which may advantageously be employed in pesticidal compositions comprising at least 50%, preferably at least 95%, of particles as described above in combination with at least one surfactant and optionally a diluent.

The surfactant can be a dispersant or wetting agent of ionic or nonionic type, or a mixture of such surfactants. Mention may be made, for example, of the salts of polyacrylic acids, the salts of lignosulphonic acids, the salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (especially alkylphenols or arylphenols), salts of esters of sulphosuccinic acids, taurine derivatives (especially alkyl taαrates), phosphoric esters of alcohols or of polyethoxylated phenols, esters of fatty acids and polyols, and sulphate-, sulphonatc- and phosphate-functional derivatives of the above compounds.

The term diluent refers according to the invention to a natural or synthetic, organic or inorganic substance with which the particles according to the invention are combined in order to facilitate their application to the sites that are to be treated. This vehicle can be solid (clays, natural or synthetic silicates, silica, resins, waxes, etc ) or liquid (generally water).

According to a preferred variant the nature and the amount of the surfactant(s) are chosen such that the wettability time of the solid composition is between 10 seconds and 3 minutes, preferably between 10 and 50 seconds, and the degree of suspensibility is greater than 50%, preferably than 70%. The following definitions arc used for the expressions "wettability time" and "degree of suspensibility".

The wettability time is measured in accordance with technique MT 53.3.1 described in the CIPAC HANDBOOK, volume 1, pages 966-967. edited by G.R. Raw. 1970. It essentially consists in measuring the wetting time of 5 g of solid composition with 100 ml of water.

The degree of suspensibility is measured according to technique MT 15 I note 4 described in the CIPAC HANDBOOK, volume 1, pages 861-865. It consists essentially in pouring 2.5 g of solid composition into a 250 ml test-tube containing 250 ml of hard water, in inverting the test-tube and its contents 30 times, in allowing them to rest for 30 minutes and in measuring the mass of material present in the bottom 25 ml 10% of the volume of the test-tube) of the test-tube; the degree of suspensibility is then expressed by the percentage of material remaining in suspension in the upper 90% of the test-tube.

To obtain the solid composition according to the invention, the particles arc mixed intimately in appropriate mixers with the additional substances. This gives. wertable powders whose wettability and suspension behaviour are advantageous and which can be suspended with water to any desired concentration in order to prepare the liquid that is to be sprayed.

The plasticizers are preferably employed for the preparation of compositions according to the invention in the form of granules. In this case, the quantity of plasticizer is advantageously greater than or equal to 10% by weight relative to the total weight of the composition, preferably greater than about 20% by weight and more preferably between 20 and 50% by weight,

Among the customary plasticizers mention may be made of ail plasticizers known as plasticizers for cellulose acetate, especially those described in [reference to be inserted], and more particularly the esters of polyols, such as glycerol triacetate

(triacetin) or triethylene glycol diacetate, or the esters of hydroxy carboxylic acids, such as the esters of citric acid or of phtnalic acid.

According to a preferred embodiment of the invention, the 1 -arylpyrazole derivative is distributed homogeneously in the insoluble cellulose derivative, more preferably in the form of a solid solution.

According to the present invention, the term solid solution refers to homogeneous molecular distribution of the 1 -arylpyrazole derivative in the cellulose derivative.

More preferably, the solid solution according to the invention comprises substantially no crystals of the 1 -arylpyrazole derivative under observation of said solid composition or a fraction thereof or a cut thereof with the scanning electron microscope at a magnification of 30,000.

Advantageously, the solid composition according to the invention docs not substantially comprise pores. The phrase "does not substantially comprise pores" is taken to mean, in accordance with the invention, that the pores present ir. the solid composition according to the invention have a diameter of less than about 10 nanometres, preferably less than 2 nanometres. Such a feature can also be observed by means of a scanning electron microscope. Owing to the absence of pores, the 1 - arylpyrazole derivative is not present in the pores but is mixed uniformly with the insoluble cellulose derivative. This particularly advantageous property makes it possible to avoid the risks connected with the direct contact of the skin of the user with the insecticidal compound.

The present invention also relates to a process for preparing compositions according to the invention, the said process consisting in mixing the insoluble cellulose derivative and the I -arylpyrazole derivatives, alone or optionally in the presence of a solvent or of an appropriate additive, and then in giving them the final form appropriate to the use to which they will be put.

According to a preferred embodiment of the invention, the insoluble cellulose derivative and the 1 -arylpyrazole derivatives, alone or optionally in the presence cf a solvent or of an appropriate additive, are melted, particularely for the preparation of compositions according to the invention where the I -arylpjτazole derivative is distributed homogeneously in the insoluble cellulose derivative.

For the preparation of fibres, the 1 -arylpyrazole is incorporated into the fibres by mixing the product, in solution in a first organic solvent which is suitable for solubilizing the 1 -arylpyrazole derivatives, with a solution of the cellulose derivative in a second organic solvent which is suitable for solubilizing the cellulose derivative, the first and second organic solvents being compatible and preferably identical. The mixture is then extruded through an appropriate die, which is generally made of metal, and is solidified by evaporation of the solvent(s). The fibre thus prepared is then cut into fragments of the desired size. Advantageously, the suitable solvent is acetone.

The particles according to the invention can be prepared according to a similar process by dissolving the 1 -arylpyrazole derivative and the cellulose derivative in an appropriate solvent, advantageously acetone, then by spraying the said solution and drying it. A device suitable for this purpose is, in particular, a sprayer equipped with a multi-fluid nozzle, in which the organic solution is sprayed by air at a pressure of between 2 and 8 bar, preferably between 4 and 6 bar, spraying taking place in the presence of a stream of drying air which has been brought to a temperature of between 80 and 160°C, preferably between 90 and 1 1 °C. at a flow rate of between 30 and 150 m3 (s t.p.) per hour.

The granules according to the invention are advantageously prepared by coextrusion: the cellulose derivative, the 1 -arylpyrazole derivative and, if used, the p isticizer are introduced together, or mixed beforehand and then introduced, into the feed hopper of an extruder, the melt then being extruded through an appropriate die in order to give strands of the diameter required which are subsequently cut to the desired length. The present invention relates, finally, to a method of combating insects, preferably termites, characterized in that an effective dose of at least one 1 -arylpyrazole derivative in the form of a solid composition as defined above is applied to a site which is frequented, or likely to be frequented, by the said insects.

The composition according to the invention is particularly suitable for combating termites. The effective amount applied depends on the nature of the soil and of the construction material, and on the required persistence of action. This amount is generally between 0.05 mg/m2 and 5 g/m2, preferably between 0.1 mg m2 and 0.5 g/m".

The composition in particle form can be applied by spraying or by injection onto or into the site that is to be treated. The volume of liquid for spraying or injecting is generally between 1 and 5 l/m2.

The composition in web form is advantageously employed for protecting the foundations of buildings against termites, the web being placed on the soil before constructing the foundations. When the web is used to line the excavations of building foundations, the strips are advantageously arranged parallel to each other and overlapping with each other, over the required length. An important advantage of the web according to the invention is that its efficacy is maintained even if the: strips do not quite overlap, and even if they show a substantial number of punches or holes or cracks. Despite the possible presence of cracks in the strips, owing to possible manufacturing defects, the risk of these cracks leading to tearing of the strips when they are laid in the excavations of building foundations is advantageously reduced.

The following examples are given purely by way of illustration of the present invention and should not in any case be interpreted as limiting its scope. In these examples, the compound of formula (I) used is: l-[2,6-Cl2-4-CF3-phenyl]-3-CN-4-[SO-CF3]-5-NH2-pyrazole, also called fipronil. It is understood that the same examples can be carried out with other 1 -arylpyrazole derivatives. The percentages arc by weight.

Example I; Web for protecting building foundations against termites Example I

Cellulose acetate is dissolved with fipronil in acetone in order to obtain a spinning solution containing (weight %) cellulose acetate: 30% fipronil: 1% acetone: 69%

This solution is forced under pressure through a metal die containing many tiny holes into a heated zone where the continuous filaments solidify as the solvent evaporates. This continuous filament, with a circular section, is cut into pieces of 18 mm in length. These pieces have a diameter of around 80 mm and a linear weight of 15 decitex. Sections of these pieces are exar ined by means of scanning electron microscopy with a magnification of 30000: no pores are observed. The fipronil content of the fibre is around 3%. Polyvinyl alcohol fibres of 2 mm length are mixed, as a binder, with these pieces in a proportion of 10% by weight and the whole mixture is processed in conventional papermaking equipment. The nonwoven web of paperlike material obtained is 2 mm thick, has a weight per square meter equal to 150 g/m , and a fipronil content equal to 3 g m2. The air permeability of this nonwoven web is 2000 l.s 'm'2. A disc of 30 mm of this nonwoven web is laid on a horizontal wooden board and is used to close the open end of a vertical cylindrical chamber with a length of 110 mm and an internal diameter of 25 mm. This chamber is filled with ordinary sand to two thirds of its height, 50 termites of the species Reticulitar e.s suntonensts have been introduced in the upper third of the chamber. The sand is maintained at a constant moisture during the test, by introducing water every day ( 1 volume of water to 4 volumes of sand). The nonwoven disc is sealed to the vertical chamber by means o α suitable glue not toxic to the termites. After 4 days, a mortality rate of 100% is observed. The mortality rate observed in a control test using the same disc of nonwoven fabric but without incorporating fipronil is 0%. This test shows the excellent efficacy of the webs according to the invention against termites. Example 1.2

Example 1.1 is repeated but introducing termites of the species Heterotermes indicola instead of Reticulitermes santonensis. After 5 days, the same results as m Example 1 are obtained. Example 3

Example 1.1 is repeated using a 30 mm disc of nonwoven web, with a hole of 1 cm in its centre, in parallel with a 30 mm disc without a hole, for webs with a fipronil content of 0,5 g/m2, 3 g/m2 and 6 g/m2. The efficacy of such discs, measured the number of days necessary to observe a mortality rate of 100%, is shown in the following table:

This test shows that the efficacy of the web according to the invention is maintained, even when there happens to be holes in it.

Example 1.4

A 30 mm disc of nonwoven cellulose acetate fibres containing fipronil in an amount of 0; 0.5; 3; 6 g m2 is obtained as in Example 1.1. These 4 discs are used in test devices similar to the one described in Example 1 , Each disc is laid on a horizontal wooden board A; a second horizontal wooden board B, I cm thick, is laid on the disc and a vertical cylinder chamber as used in Example 1.1 is fixed on the wooden board B in such a way that the disc and the vertical chamber are co-axial.

The experiment of Example 1.1 is reproduced, after introducing 250 termites in each of the 4 test devices. The following results are observed after 3 weeks, For the disc without fipronil: the mortality rate was 0%. Furthermore, board B was pierced by termites, there was a hole of 1 cm diameter in the disc, and board A also showed signs of attack by termites. For the disc with a fipronil content of 0.5 g/m*: the mortality rate was 98%, Board B was pierced, there was a hole of 3 mm diameter in the disc, but board A showed no sign of attack by termites. For the disc with a fipronil content of 3 g/m2: the mortality rate was 100%. Board B was pierced, there was a hole of 1 mm diameter in the disc, and board A showed no sign of attack by termites, For the disc with a fipronil content of 6 g/m2: the mortality rate was 100%. Board B was not pierced by the termites, and neither the disc nor board A showed any sign of attack by termites, Example LS

Example 1.1 was repeated but using 3 discs of nonwoven web containing fipronil in an amount of 0.5; 3; and 6 g/m2. These discs had been previously allowed to stay during 3 weeks in a non-sterile soil, with an atmosphere at 80% relative humidity and at a temperature of 30αC, After 6 days a mortality rate of 100% was observed lor the 3 amounts.

This test shows that the web according to the invention retains its efficacy even after being buried in the soil for a period of time.

Example II: Seeding box web Example II.1

A cellulose acetate with a degree of acetylation of 2.5 is used and is solubilized with fipronil in acetone so as to give a spinning solution containing (percentage by weight): cellulose acetate: 33% fipronil: 2% acetone: 65% This viscous solution is extruded through an appropriate die into a zone with a circulating stream of hot air. where a filament is formed by evaporation of the solvent. This continuous filament, with a circular section, is cut into pieces of 12 mm. These pieces have a diameter of approximately 80 mm and a linear weight of 15 decitex. Sections of these pieces are examined by scanning electron microscopy at a magnification of 30,000: neither pores nor fipronil crystals are observed. The fipronil content of the fibre is 6%. The above pieces are mixed with pol vinvl alcohol in the form of fibres 2 mm in length, in a proportion of 10 g of polyvinyl alcohol per 100 g of cellulose acetate plus fipronil. This mixture is treated by agglomeration using a papcrmaking machine. The resulting nonwoven web looks like paper and has a thickness of 1 5 mm, a weight per unit area of 55 g/m2 and a fipronil content of about 3 g/m2. Its rate of biodegradability after 6 months is greater than 80%. Example II.2: Effect of the seeding box application of the nonwoven of Example 1 on the protection of rice in submerged rice fields against the planthopper (Nilaparvata lugens) and the leaf-folder (Cnaphalacrosis medicalis)

Rectangles of 28 by 58 cm are cut from the web prepared in Example II.1. The bottom of seeding boxes (with internal dimensions of 28 by 58 cm) with a height of 3 cm are lined with a paper of density 37 g/m2 over which a first layer of soil 2 cm in height is spread. The rectangular web according to the invention, cut out beforehand, is placed on this layer. 250 g of rice seed (variety Koshihikari) are then sown, after which a second layer of soil, 1 cm in height, is arranged to cover the seeds. Each seeding box prepared in this way contains 0.5 g of fipronil. The seeding boxes are then placed for 3 days in a chamber at a temperature of 30βC and a relative humidity of 100%. 3 days after sowing, a root-up rate of essentially 0% is observed. The seeding boxes are then placed under glass for 1 1 days at an average temperature of 20°C and at a relative humidity of 60%. Fourteen days after sowing, the rice plantlets are planted out into the submerged rice field. Thirty-nine days after planting out. 2 whole rice plants are takόn from the rice field, and introduced into a test tube at the bottom of which a piece of cotton wool soaked with water has been placed. The plants are then infested by introducing into the said test tube 10 ravaging insects known by the name brown planthopper and by the latin name Nilaparvata lugens. Three days after infestation, a count is made of the number of dead insects, which is divided by the number of insects introduced, to give a mortality rate of 74%. Likewise thirty-nine days after planting out, 2 rice-plant leaves are taken from the rice field and introduced into a Petri dish. Infestation then takes place by introducing into the said Petri dish 5 larvae of ravaging insects known by the name rice leaf-folder, in latin Cnaphaluur sis- medkalii. Five days after infestation, a count is made of the number of dead larvae, which is divided by the total number of larvae introduced to give a mortality rate of 62%. This examples shows that the web according to the invention, applied conveniently at the time of sowing, doe.. not impair the germination of the seeds and, moreover, provides the rice plants, more than one month after planting out into the submerged rice field, with good protection against harmful insects. Example 11,3

The procedure of Example 11,1 is repeated, preparing a fibre containing 1 % by weight of fipronil, cutting fibre pieces of a length of 6 mm, and preparing a nonwoven web with a weight per unit area of 25 g/m2. This web has a thickness of 1 mm and contains about 3 g/m2 of fipronil. Its rate of biodegradability after 6 months is again greater than 80%. Example H.4: Laboratory study of the root-up of rice seeds sown on the webs prepared according to Example II.1 and II.3

For the purpose of this laboratory study, special seeding micro-boxes are used measuring 1 1 by 16 cm and with a height of 3 cm. Seeding boxes of this kind are not normally used under actual conditions by rice-growers. In a manner similar to that described in Example II.2, a nonwoven web prepared in accordance with Example II.1 and a nonwoven web prepared in accordance with Example II.3, respectively, are applied to each of the two micro-boxes. 400 seeds (or 13.3 g of seed) of rice (variety Koshihikari) are sown in each case. Such a seed density is less by approximately half than that commonly practised by the agriculturalists, and generally produces a greater root-up phenomenon. In both cases, the height of the lower layer of soil, situated below the nonwoven web, is 2 cm, and the height of the upper layer of soil, covering the seeds, is 0.8 cm. This height of the surface layer, less than the minimum height of 1 cm which is generally recommended, is commonly a factor which aggravates the phenomenon of root-up.

The 2 seeding boxes are placed for 3 days in a chamber at a temperature of 28βC and with a relative humidity of 100%. 3 days after sowing, an estimate is made of the number of rice seeds which have given rise to the phenomenon of root-up - that is. the number of seeds which, because of the growth of their root, have been lifted above the upper layer of soil, and this number is divided by the number of seeds sown in order to obtain a root-up rate.

This gives, for the web prepared: - in accordance with Example II.1 a root-up rate of 9%; and - in accordance with Example II.3 a root-up rate of 4%.

Example II.4 shows that, even under application conditions which are severe in the sense that they normally promote a high root-up rate, the webs according to the invention give rise to a root-up rate which is acceptable to the rice-grower

Example III: Microparticles

Exam le ffM

A cellulose acetate having a degree of polymerization of between 150 and 220 and a degree of acetylation of between 2.2 and 2.5 is used. The cellulose acetate is dissolved with the fipronil in acetone, with stirring, to give a solution containing: cellulose acetate: 10% fipronil: 1 % acetone: 89%

This solution is filtered through a nonwoven cloth with a mesh size greater than 5 mm. It is then directed towards an atomizer, at a flow rate of 1 1/h, in which it is sprayed at ambient temperature using a bi-fluid nozzle with a diameter of 2.4 mm, in the presence of air which has been brought to a flow rate of 100 m3 (s.t.p.) per hour and to a pressure of 5 bar. The product obtained is subsequently dried by air which has been brought to a temperature of 100°C. Microparticles of cellulose acetate containing 10% by weight of fipronil arc obtained which are substantially spherical in form with a size of between 1 mm and 50 mm, preferably between 5 and 20 mm.

On observation with the scanning electron microscope at a magnification of 30,000, not a single crystal is observed. From this it is inferred that the compound is in solid solution in the cellulose acetate. A sample of the microparticles obtained, the said sample being prepared by the procedure described in the description, is observed by low-resolution scanning electron microscopy at a magnification of 1000. It is observed that the microparticles are hollow and have the form of a shell with a thickness of between 0.5 and 1.5 mm. These microparticles are substantially spherical in shape, are more or less flattened, and have folds or furrows on their surface.

Observation of the microparticles with the scanning electron microscope does not reveal pores, or at any rate a pore size less than 2 nanometres, owing to the magnification employed. Example III.2

Example III.1 is repeated using an organic acetone solution containing cellulose acetate : 10% fipronil : 0.1% acetone : 89.9% Cellulose acetate microparticles are obtained which have 1% by weight of fipronil and the same characteristics of form and structure. Example HL3

Example III.1 is repeated using an organic acetone solution containing, cellulose acetate 10% fipronil 0.01% acetone 89,99%

Cellulose acetate microparticles are obtained which have 0.1% by weight of fipronil and the same characteristics of form and structure.

Example BIf4 The microparticles prepared in Example I are mixed with the following pulverulent ingredients, in the proportions indicated: sodium alkylnaphthalenesulphonate: 2% sodium polynaphthalenesulphonate: 10% microparticles prepared according to Example 1: 88%

A product with the appearance of a powder is obtained whose wettability is good and which has a degree of suspensibility greater than 50%, therefore being perfectly suited to mixing with water and to spraying. Example 1Ϊ1.S A glass tube is used which is arranged vertically and has a diameter of approximately 2 cm, a height of 15 cm and a thickness of 2 mm, and is sealed at both its ends by an aluminium foil. Into this tube there are placed, starting from the bottom- over a height of 5 cm, a mixture of fine twigs and bundles of paper housing 80 worker termites and 1 soldier termite of the species Reticulitermes santonensis, then a separating layer of agar, with a height of about 3 cm; and then a layer of sand which has a height of 5 cm and is treated (or untreated in the case of the control) with a certain quantity of one of the samples of microparticles prepared in accordance with one of Examples 1 to 3; followed by a separating layer of agar with a height of approximately 1 cm: and then a layer of fine bundles of paper, with a height of 1 cm, which forms a target feed source for the termites. The microparticle samples tested arc those with 10% and 0.1% of fipronil. described in Examples III.l and III.3 respectively. The entire contents of the tube are regularly re-humidified throughout the duration of the test. The layer of sand is treated by incorporation of a defined quantity of microparticles according to the invention, in a likewise defined volume of sand, and then the whole is homogenized before removal of the sample placed in the glass tube. This gives the quantity or dose of microparticles applied per volume of sand, expressed in weight of fipronil (in mg) per cm3 of soil. This volume dose, which takes account of the practical circumstances of application b> specialists, is likewise expressed by weight per unit area treated (or surface dose), assuming that the product penetrates under practical conditions through 5 cm of soil. The doses thus applied are indicated in the table below. Throughout the test, the entire apparatus is maintained in darkness, except at the time of observation, and at ambient temperature. Observation is carried out 1, 2, 3, 4 and 7 days after the beginning of the test, by counting the number of visible termites, the number of dead termites and the number of survivers. A calculation is made of the mortality rate, which is equal to the number of dead termites divided by the total number of termites visible. In the case of the control apparatus (with an untreated layer of sand) the termites explore the layer of sand over its entire height (penetration of 5 cm, galleries readily visible) up to the target feed layer. Up to 5 days after the beginning of the test, the observed mortality rate is 0%.

The results in the case of treatment are indicated below. In this table, the penetration corresponds to the height reached within the treated layer of sand, 7 days after the beginning of the test, by the termites (maximum length of the galleries observed).

The mortality results show an excellent efficacy of the compositions according to the invention. Moreover, the treated layer of sand is devoid of visible galleries throughout its height for all of the doses tested. In other words, the layer thus treated represents an unbreachable barrier.

Example IV: Granules

Example IV.lt Preparation of the granules

Granules according to the invention are prepared employing a twin-screw laboratory extruder separated into 15 individual zones. The screws have a diameter of 25 mm and a length of 48 cm. The temperature of the various zones is as follows:

- zone 1 : 30°C

- zones 2 and 3 : 110°C zone 4 l50βC zones 5 to 1 1 180°C zones 12 to 15 190°C.

The extruder rotates at a speed of 150 revolutions/minute to give a homogeneous melt, which is extruded through a circular die to form a strand which makes it possible, using a granulator, to form granules with a length of 1 mm and a diameter of I mm. The output of the extruder is 4 kg h of granules.

A cellulose acetate is employed which has a degree of polymerization of 220 and a degree of acetylation of 2.5. The piasticizer is triacetin,

Cellulose acetate is introduced into the first zone of the extruder, the piasticizer into the second zone of the extruder, in a proportion by weight of 1 relative to the weight of the cellulose acetate, and fipronil into the third zone of the extruder, in a proportion of 5% by weight. Granules are obtained which contain, by weight, 47.5% of cellulose acetate,

47.5% of piasticizer (triacetin) and 5% of fipronil. Example IV.2: Analysis of the granules

Four samples of granules, containing respectively 0%. 0.1%, 1 % and 5% by weight of fipronil, obtained by the process according to Example IV 1 , were examined by scanning electron microscopy under strictly comparative conditions. I Methods of observation Random sample selection. A continuous, uniform layer of the granules to be studied is first of all placed on a surface which is smooth and not hard (web of cardboard), allowing a slight pressure to be exerted on the granules without deforming them.

For observation in the native state, a standard scanning microscopy stage is covered with double-sided adhesive tape whose protection has been removed. The adhesive is brought into contact with the bed of granules, and 20 to 30 granules are retained on the adhesive surface. This sample is kept under dry conditions while awaiting the metallizing stage.

To observe the internal structure, the granules are collected on a support made from plastic, consisting of the levelled surface of an inclusion capsul lor ultramicrotomy, filled with polymerized cpoxy resin, by way of a drop of cyanυacrylic glue (which sets almost instantaneously) spread over the surface. Cutting technique The samples whose internal structure is to be examined are cut on an ultramicrotome equipped with a diamond cutter, and the smooth surfaces thus revealed immediately undergo metallization. Metallization The cut and uncut samples are transferred to a cathodic sputtering apparatus and receive a layer of gold with a thickness of approximately 10 nm, under a rarefied argon atmosphere. They are then stored in a desiccator until the time of observation. Observation The preparations are observed at an acceleration of 10 V with the aid of a Hitachi S800 electron microscope equipped with a field emission gun having a theoretical resolution of better than 2 nm. 3 Results

External surfaces and original cut faces (whole granules) The granules have the form of a short cylinder, whose diameter is approximately equal to the height. Owing to the random method of collection and the roughly isodimensional form of the granules, the latter can be found to be fixed either laterally or by their end, thus permitting observation of the lateral cylindrical surface as well as of the sections. The observations are made across a range of magnifications between 60 and 5000.

All the granules have the same general aspect, associated with the method of extrusion: the lateral faces are relatively smooth, with traces left by the die, while the ends are partly cut transversely and partly broken.

The control granules have the appearance of a solidified amorphous material, with more or less splinter-like fracture, which is fairly characteristic of hard plastics. No crystalline texture is visible on any of the observed faces, and no trace of heterogeneity can be seen even at the highest magnifications. The granules containing 0.1 , 1 and 5% of active substance are indistinguishable from the control granules containing 0%. No trace of texture nor of heterogeneity is evident, even magnified 5000 times. The addition of the active substance does not modify in any way the microscopic appearance of the granules. Granules cut with the microtome (fresh sections) The fresh sections carried out on the control granules and the granules with a concentration of less than or equal to 5% show no differences, A perfectly smooth surface is observed in all cases,

4 Comments and conclusion The observations made with various concentrations of fipronil in the cellulose acetate matrix show that the addition of the active substance does not in any way modify the texture of the granules and that no form of crystallization is visible up to a concentration of 5%.

The active substance can be considered as being in the dissolved state within the cellulose acetate matrix, which in turn is considered as a solvent of "infinite" \ iscosity Therefore, a true solid solution of fipronil in cellulose acetate is obtained.

Claims

1. Solid composition of a water- insoluble cellulose derivative, characterized in that it comprises an effective quantity of at least one 1 -arylpyrazole derivative. 2. Composition according to claim 1, characterized in that the
1 -arylpyrazole derivative is a compound of general formula (I)
in which
Ri is a halogen atom or a CN or methyl group: R2 is S(0)„R ;
R3 is an alkyl or haloalkyl radical,
R4 represents a hydrogen or halogen atom; an alkyl or haloalkyl radical:
NRsRj, -S(0)mR7, C(0)R7, -C(0)O.R7, -N-C(R9)(Rl0) or -OR*, 5 and R* represent, independently of one another, a hydrogen atom, an alkyl or haloalkyl radical, -C(0)alkyl, -S(0)rCF3; or
Rs and R* may together form a divalent alkylene radical which can be inteπupted by one or two divalent heteroatoms such as oxygen or sulphur;
R7 represents an alkyl or haloalkyl radical;
Rg represents an alkyl or haloalkyl radical or a hydrogen atom; R9 represents n alkyl radical or a hydrogen atom;
Rio represents a phenvl or heteroaryl group which is optionally substituted by one or more halogen atoms or groups such as OH, -O-alkyl, -S-alkyl, cyano or alkyl;
X represents a trivalent nitrogen atom or a radical C-Rι_, the three other valencies of the carbon atom forming part of the aromatic ring; Rιι and R12 represent, independently of one another, a hydrogen or halogen atom; Rι j represents a halogen atom or a haloalkyl or haloalkoxy group. -S(0)(|CF3 or -SF«; m. n. q and r represent, independently of one another, an integer equal to 0, 1 or 2; with the proviso that, when Rι is methyl, R3 is a haloalkyl group, RΛ is H2. Rn is Cl, Rl3 is CF3, and X is N.
3. Composition according to claim 2, characterized in that Rι is CN and/or P.j is a haloalkyl radical and or R4 is NH2 and/or Rn and R,2 independently of one another are a halogen atom and/or R13 is a haloalkyl radical 4. Composition according to one of claims 1 to 3, characterized in that the
1 -arylpyrazole derivative is fipronil.
5. Composition according to one of claims 1 to 4, characterized in that the insoluble cellulose derivative is an aliphatic ester of cellulose, preferably a cellulose acetate, 6. Composition according to claim 5, characterized in that the insoluble cellulose derivative is a cellulose acetate whose degree of polymerization is between 150 and 250 units, preferably between 150 and 220.
7. Composition according to either of claims 5 and 6, characterized in that the cellulose acetate has a degree of acetylation of between 1.2 and 2.8, preferably between 1.9 and 2.5.
8. Composition according to one of claims I to 7, characterized in that the effective quantity of 1 -arylpyrazole derivative in the composition according to the invention is between 0.0001 and 50% by weight, preferably between 0.05 and 25% by weight. 9. Composition according to one of claims 1 to 8, characterized in that it is in the form of fibres.
10. Composition according to claim 9, characterized in that the effective quantity of 1 -arylpyrazole derivative is advantageously between 0, 1 and 15% by weight.
11. Composition according to one of claims 1 to 8, characterized in that it is in the form of a woven or nonwoven web obtained with the fibres according to claim 9 or 10.
12. Composition according to claim 11, characterized in that the effective quantity of 1 -arylpyrazole derivative is between 0.01 and 25 g/m\ advamageousl> between 0.1 and 10 g/m2, and for certain utilities even between 1 and 5 g/m2.
13. Composition according to either of claims 1 1 and 12. characterized in that it additionally comprises a binder, the ratio by weight of binder to fibres containing the 1 -arylpyrazole derivative being between 1 and 20%, preferably between 5 and 15%.
14. Composition according to one of claims 1 to 8, characterized in that it is in the form of particles.
15. Composition according to claim 14, characterized in that the effective quantity of 1 -arylpyrazole derivative is advantageously between 0 05 und 10% by weight,
16. Composition according to either of claims 14 and 15, characterized in that the particles are microparticles which are substantially spherical in shape and have a size of between about 0.3 and about 200 mm, preferably between 1 and SO mm, still more preferably between 5 and 20 mm. 17. Composition according to claim 16, characterized in that the microparticles are hollow and are in the form of an envelope or shell with a thickness of between 0.1 and 3 mm, preferably between 0.5 and 1.5 mm.
18. Composition according to one of claims 13 to 17, characterized in that it additionally comprises surfactants and/or diluents. 1 . Composition according to one of claims 1 to 8, characterized in that it is in the form of granules.
20. Composition according to claim 1 , characterized in that the effective quantity of 1 -arylpyrazole derivative is less than about 10% by weight, preferably less than 7% by weight, more preferably between 0.05 and 5% by weight. 21. Composition according to either of claims 21 and 22, characterized in that the granules have a length of between about 0.5 and 2 mm, preferably about 1 mm. and a mean diameter of between about 0.5 and 2 mm, preferably about 1 mm.
22. Composition according to one of claims 19 to 21, characterized in that it additionally comprises a piasticizer. 23. Composition according to claim 22, characterized in that the quantity of piasticizer is greater than or equal to 10% by weight relative to the total weight of the composition, preferably greater than about 20% by weight and more preferably between 20 and 50% by weight.
24. Composition according to one of claims 1 to 8, characterized in that it is in the form of powder.
25. Composition according to one of claims 1 to 24, characterized in that the 1 -arylpyrazole derivative is distributed homogeneously within the insoluble cellulose derivative.
26. Composition according to claim 25, characterized in that it is in the form of a solid solution.
27. Composition according to either of claims 25 and 26. characterized in that it comprises essentially no pores.
28. Process for preparing compositions according to one of claims 1 to 27, the said process consisting in mixing the insoluble cellulose derivative and the 1 -arylpyrazole derivatives, alone or optionally in the presence of a solvent or of an appropriate additive, and then in giving them the final form appropriate to the use to which they will be put,
29. Process according to claim 28, characterized in that the insoluble cellulose derivative and the 1 -arylpyrazole derivatives, alone or optionally in the presence of a solvent or of an appropriate additive, are melted.
30. Method of combating harmful insects, characterized in that an effective dose of at least one 1 -arylpyrazole derivative in the form of a solid composition according to one of claims 1 to 27 is applied to a site which is frequented, or likely to be frequented, by the said insects. 1. Method according to claim 30, characterized in that the harmful insects are termites.
PCT/IB1997/001638 1996-11-22 1997-11-20 Novel solid compositions based on an insoluble cellulose derivative and a 1-arylpyrazole derivative WO1998021961A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US3168496 true 1996-11-22 1996-11-22
EP19960118739 EP0843962A1 (en) 1996-11-22 1996-11-22 Flexible web containing 1-arylpyrazole pesticide
EP96118739.0 1996-11-22
FR9701828A FR2759249A1 (en) 1997-02-11 1997-02-11 Solid insecticidal composition effective against termites
FR97/01828 1997-02-11
FR97/08059 1997-06-20
FR9708059A FR2764775A1 (en) 1997-06-20 1997-06-20 Solid insecticidal composition effective against termites
US60/031,684 1997-11-22

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9101124B2 (en) 2006-12-21 2015-08-11 Dow Agrosciences Llc Composite material including a thermoplastic polymer, a pest food material and a pesticide
US9833001B2 (en) 2008-08-19 2017-12-05 Dow Argosciences Llc Bait materials, pest monitoring devices and other pest control devices that include polyurethane foam

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0142658A1 (en) * 1983-10-15 1985-05-29 Gesellschaft für Strahlen- und Umweltforschung mbH (GSF) Carrier of organic material with integrated active substances
DE3538429A1 (en) * 1984-10-30 1986-04-30 Elan Corp Plc Powders with controlled release, process for its preparation and pharmaceutical composition containing the
EP0295117A1 (en) * 1987-06-12 1988-12-14 Rhone-Poulenc Agriculture Limited Derivatives of N-phenylpyrazoles
JPS6419002A (en) * 1987-07-14 1989-01-23 Hokko Chem Ind Co Labor-saving control of blight and vermin and formed agricultural chemical having form of water-soluble paper
JPH01312933A (en) * 1988-06-10 1989-12-18 Asahi Chem Ind Co Ltd Culture soil for seedling raising of paddy rice plant
WO1990014004A1 (en) * 1989-05-16 1990-11-29 Chemical Enterprises (Aust) Pty. Limited Pesticidal blanket
JPH0331202A (en) * 1989-06-29 1991-02-12 Nippon Tokushu Noyaku Seizo Kk Control of plant blight
US5028471A (en) * 1988-12-23 1991-07-02 Monsanto Company Antiflea fibers
US5223251A (en) * 1989-05-30 1993-06-29 Purepac, Inc. Skin fragrance compositions
JPH05239263A (en) * 1992-02-26 1993-09-17 Asahi Chem Ind Co Ltd Water-containing gel composition
EP0565250A1 (en) * 1992-03-19 1993-10-13 Albany International Corp. Pesticidal blanket
EP0576270A1 (en) * 1992-06-26 1993-12-29 Sumitomo Chemical Company, Limited Fabric protectants
FR2696906A1 (en) * 1992-10-20 1994-04-22 Rhone Poulenc Agrochimie Insecticidal treatment of rice plants or esp. seeds - by applying systemic insecticide, pref. 1-phenyl-3-cyano:pyrazole deriv., giving lasting protection against leaf hopper and stem borers
JPH06212510A (en) * 1992-10-27 1994-08-02 Teijin Ltd Cellulosic acetate fiber having regulated biodegradability, its production and seedling cultivating container and greening sheet formed from the same fiber
WO1994023573A1 (en) * 1993-04-20 1994-10-27 E.I. Du Pont De Nemours And Company Water-soluble fibers and nets as agricultural formulations
WO1995018532A1 (en) * 1994-01-05 1995-07-13 Cecil S.A. Method and materials giving termite protection to buildings
JPH07242504A (en) * 1994-03-03 1995-09-19 Nippon Bayeragrochem Kk Method for controlling disease damage of paddy rice plant
JPH0889086A (en) * 1994-09-20 1996-04-09 Keibunshiya Seisakusho:Kk Underlay for nursery box
JPH08120524A (en) * 1994-10-20 1996-05-14 Nippon Ester Co Ltd Polyester fiber
JPH08134720A (en) * 1994-11-09 1996-05-28 Teijin Ltd Functional conjugate fiber and insectproof rug
WO1996016544A2 (en) * 1994-11-30 1996-06-06 Rhone-Poulenc Agrochimie Emulsifiable composition for the control of insects
JPH08182435A (en) * 1994-12-28 1996-07-16 Maruei Sangyo Kk Method for raising mat seedling for packing rice transplanter and embossed water resistant paper for mat seedling

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0142658A1 (en) * 1983-10-15 1985-05-29 Gesellschaft für Strahlen- und Umweltforschung mbH (GSF) Carrier of organic material with integrated active substances
DE3538429A1 (en) * 1984-10-30 1986-04-30 Elan Corp Plc Powders with controlled release, process for its preparation and pharmaceutical composition containing the
EP0295117A1 (en) * 1987-06-12 1988-12-14 Rhone-Poulenc Agriculture Limited Derivatives of N-phenylpyrazoles
JPS6419002A (en) * 1987-07-14 1989-01-23 Hokko Chem Ind Co Labor-saving control of blight and vermin and formed agricultural chemical having form of water-soluble paper
JPH01312933A (en) * 1988-06-10 1989-12-18 Asahi Chem Ind Co Ltd Culture soil for seedling raising of paddy rice plant
US5028471A (en) * 1988-12-23 1991-07-02 Monsanto Company Antiflea fibers
WO1990014004A1 (en) * 1989-05-16 1990-11-29 Chemical Enterprises (Aust) Pty. Limited Pesticidal blanket
US5223251A (en) * 1989-05-30 1993-06-29 Purepac, Inc. Skin fragrance compositions
JPH0331202A (en) * 1989-06-29 1991-02-12 Nippon Tokushu Noyaku Seizo Kk Control of plant blight
JPH05239263A (en) * 1992-02-26 1993-09-17 Asahi Chem Ind Co Ltd Water-containing gel composition
EP0565250A1 (en) * 1992-03-19 1993-10-13 Albany International Corp. Pesticidal blanket
EP0576270A1 (en) * 1992-06-26 1993-12-29 Sumitomo Chemical Company, Limited Fabric protectants
FR2696906A1 (en) * 1992-10-20 1994-04-22 Rhone Poulenc Agrochimie Insecticidal treatment of rice plants or esp. seeds - by applying systemic insecticide, pref. 1-phenyl-3-cyano:pyrazole deriv., giving lasting protection against leaf hopper and stem borers
JPH06212510A (en) * 1992-10-27 1994-08-02 Teijin Ltd Cellulosic acetate fiber having regulated biodegradability, its production and seedling cultivating container and greening sheet formed from the same fiber
WO1994023573A1 (en) * 1993-04-20 1994-10-27 E.I. Du Pont De Nemours And Company Water-soluble fibers and nets as agricultural formulations
WO1995018532A1 (en) * 1994-01-05 1995-07-13 Cecil S.A. Method and materials giving termite protection to buildings
JPH07242504A (en) * 1994-03-03 1995-09-19 Nippon Bayeragrochem Kk Method for controlling disease damage of paddy rice plant
JPH0889086A (en) * 1994-09-20 1996-04-09 Keibunshiya Seisakusho:Kk Underlay for nursery box
JPH08120524A (en) * 1994-10-20 1996-05-14 Nippon Ester Co Ltd Polyester fiber
JPH08134720A (en) * 1994-11-09 1996-05-28 Teijin Ltd Functional conjugate fiber and insectproof rug
WO1996016544A2 (en) * 1994-11-30 1996-06-06 Rhone-Poulenc Agrochimie Emulsifiable composition for the control of insects
JPH08182435A (en) * 1994-12-28 1996-07-16 Maruei Sangyo Kk Method for raising mat seedling for packing rice transplanter and embossed water resistant paper for mat seedling

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 124, no. 1, 1 January 1996, Columbus, Ohio, US; abstract no. 3044, XP002044111 *
DATABASE WPI Section Ch Week 8909, Derwent World Patents Index; Class A97, AN 89-066014, XP002044112 *
DATABASE WPI Section Ch Week 9005, Derwent World Patents Index; Class A97, AN 90-034140, XP002044115 *
DATABASE WPI Section Ch Week 9342, Derwent World Patents Index; Class A11, AN 93-331523, XP002044117 *
DATABASE WPI Section Ch Week 9435, Derwent World Patents Index; Class A11, AN 94-283800, XP002044113 *
DATABASE WPI Section Ch Week 9629, Derwent World Patents Index; Class A23, AN 96-283981, XP002045589 *
DATABASE WPI Section Ch Week 9631, Derwent World Patents Index; Class A23, AN 96-307145, XP002045590 *
DATABASE WPI Section PQ Week 9624, Derwent World Patents Index; Class P13, AN 96-233191, XP002044114 *
DATABASE WPI Section PQ Week 9638, Derwent World Patents Index; Class P13, AN 96-378072, XP002044116 *
PATENT ABSTRACTS OF JAPAN vol. 15, no. 154 (C - 0825) 18 April 1991 (1991-04-18) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9101124B2 (en) 2006-12-21 2015-08-11 Dow Agrosciences Llc Composite material including a thermoplastic polymer, a pest food material and a pesticide
US9775341B2 (en) 2006-12-21 2017-10-03 Dow Agrosciences Llc Composite material including a thermoplastic polymer, a pest food material and a pesticide
US9861097B2 (en) 2006-12-21 2018-01-09 Dow Agrosciences Llc Method of making a composite material including a thermoplastic polymer, a pest food material and a pesticide
US9833001B2 (en) 2008-08-19 2017-12-05 Dow Argosciences Llc Bait materials, pest monitoring devices and other pest control devices that include polyurethane foam
US9848605B2 (en) 2008-08-19 2017-12-26 Dow Agrosciences Llc Bait materials, pest monitoring devices and other pest control devices that include polyurethane foam

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