Process for controlling pests with phosphine gas released from an applicator

Abstract: The present invention relates to a process for controlling pests with phosphine gas which is released from an applicator having gas and humidity pervious walls, containing a hydrolysable metal phosphide by the admission of humidity through such walls. The rate of hydrolysis of the metal phosphide and release of the phosphine is limited by restricting the combination of surface area and moisture premeability of the walls of the applicator thereby retarding the admission of humidity to the metal phosphide.

Description: The present invention is a divisional application of EP 92111619.0 which in turn is a divisional application of EP 88108349.7 and relates to a process for controlling pests with phosphine gas which is released from an applicator having gas and humidity pervious walls, containing a hydrolysable metal phosphide by the admission of humidity through such walls. The phosphine gas thus released is employed in a manner known per se for the fumigation of closed spaces and of commodities, in particular agricultural commodities contained in such closed spaces. Such processes had in the past been carried out with applicators in the form of sachets made of specially prepared paper. More recently the applicants developed (see US-PS 4,597,218; Eu-PS 0131 759) what is now being considered a new generation of applicator means for holding a gas evolving pest control agent, more particularly comprising a hydrolysable metal phosphide, from which, when exposed to environmental humidity, phosphine gas is released to the environment due to the hydrolysis of the metal phosphide. Such applicator means take the form of sachets, i.e. relatively small bags or envelope-like pockets made of non-woven thermoplastic sheet materials (by some authors nowadays referred to as "fleece") comprising more or less randomly orientated fibres of thermoplastics bonded together, usually with heat and pressure to form a felt-like or matted texture. These are usable as individual sachets or in the form of a plurality of these joined together in a flat composite structure, e.g. flexibly, such as an elongate belt adapted to be rolled up or folded up concertina-like for storage and transport, packed in airtight and moisture-proof containers such as sealed tins. These applicators are removed from the airtight container immediately prior to use and are then unrolled or unfolded (in the case of such belts) and exposed to the environment where fumigation is to take place (PCT Application WO-A-80/00119). The residue of the hydrolysed metal phosphide is retained in dust form by the applicator. These applicators are manufacture by thermal welding, the resulting welding seams serving to close the sides of the sachets or the like and to form flexible hinge lines between individual sachets. The flexibility of the seams and their physical strength is of obvious importance in the case of the aforesaid belt-like composite applicators, and is even important in the event that individual sachets are to be manufactured, because the manufacture thereof takes place in substantially the same manner as that of the composite belts (known in the art as "bag blankets") until the final manufacturing stage, when the continuous belts delivered by the machine, filled with pest control agent, are cut up along the seam lines into individual sachets. According to US-A-4 653 644 an applicator is made from a sheet of spinbonded synthetic filament material of high permeability which accelerates the decomposition of metal phosphide pellets or tablets by allowing the moisture to have free and substantially unrestricted access to the pellets or tablets. The purpose of US-A-4 653 644 is to prevent direct contact of the tablets with the environment and with the body of the fumigation operator. And further, the humid air must have unimpeded access to the tablets or pellets so that the designated rate of hydrolysis pattern is not interfered with by the applicator and that the tablet or pellet performs exactly in accordance with its pre-designed decomposition characteristics. Apart from some shortcomings discussed in the parent applications and in spite of the many desirable properties of the aforesaid "new generation" applicators, these still suffered from the defect that the applicator material itself exercised little or no control over the rate of access of water vapour to the pest control agent and over the rate at which the vaporous or gaseous contents of the applicators were released to the environment. One result has been an accumulation of sometimes extremely high concentrations, e.g. of phosphine gas in the immediate vicinity of the outer surfaces of the applicators, whereas it would have been desirable for these gases to be released more gradually and at a rate closer to that at which the gas is distributed in the environment to be fumigated by diffusion, circulation, convection or other mechanisms. Excessive local accumulations of phosphine occur particularly during the first few hours of exposure to the environment and particularly at high ambient temperatures. These local accumulations are not only undesirable for well known safety reasons, but also for pest control purposes. Excessive sudden phosphine concentrations can put insects into a comatose state in which they cease to inhale the gas and from which some insects may subsequently recover. A gradual, even release and distribution of the gas is therefore to be aimed for. But in previous uses and tests the plastics fleeces did not achieve or contribute to this desired effect. It has now, most surprisingly, been found that this most desirable effect can indeed be attained in a process as set out in the opening paragraph in that the rate of hydrolysis of the metal phosphide contained in the applicator and the release rate of the phosphine is limited by selecting, for a given available amount of phosphine gas releasable by the metal phosphide in powder or granular form, a combination of surface area and moisture permeability of the flexible walls of the applicator within such limits that the admission of humidity to the metal phosphide is thereby retarded in relation to the maximum rate at which the metal phosphide can react with such humidity. More particularly for restricting the moisture permeability a non-woven fleece of plastic fibres is used which has been calendered to give it a paper-like texture. Although the invention is not limited to specific plastics fibres, the objects of the invention can be attained particularly advantageously with certain suitably calendered polyolefin fibre fleeces in particular polyethylene fibre fleeces. Particularly good results were obtained where the moisture permeability of the walls is from 50 to 1000 g/m 2 /24h, more particularly 300 to 1000 g/m 2 /24h or more preferably from 500 to 750 e.g. 600 to 630 g/m 2 /24h as exemplified by the commercial product marketed under the registered trade mark Tyvek of du Pont de Nemours. A preferred type is that having a mass of about 75 g/m 2 , a thickness of about 200 microns, a tear resistance according to Elmendorf of 545/500 (ASTM D 689-62) gMD/XD. Its tensile strength (ASTM D 828-60) is 7,5/8,8 kg/cm MD/XD. Its elongation to break (DIN 53857 is 26/32 % MD/XD and it has an air permeability of 23 sec (Gurley Hill). Unpressurised liquid water will not penetrate through the sheet material. It has a smooth surface finish. The melting point of the fibres, which have an individual thickness of 0,005 mm, is about 135°C. Advantageously the ratio the surface area of the humidity pervios walls to the availableamount of phosphine gas releasable by the metal phosphide is from 0,8 to 25 cm 2 /g, preferably 1,6 to 16 cm 2 /g. With these applicators it is possible to attain the novel object of being adaptable to regulating in a predeterminable manner the rate at which phosphine gas is released to an environment. Perhaps most important of all, it was found surprisingly that the local concentrations of phosphine gas at or near the surface of the applicator means were very much lower under practical conditions of use, than in the case of the best prior art devices previously available. In this respect the new applicators proved superior by a whole order of magnitude. This improvement was neither expected nor predictable. It was found that the rate of the phosphine generation can be controlled to a substantial degree regardless of the ambient relative humidity in the fumigation environment. The choice of porosity thus becomes a more dominantly controlling factor even than temperature, because the permeability which controls the rate at which humidity can enter the applicator from the environment is not as highly temperature dependent as it is dependent on the porosity. It is thus possible to produce applicators designed to release phosphine gas at different predetermined rates, depending on requirements, because in some cases it is desired for phosphine gas to be available relatively quickly, whilst in other cases it is desirable for the release to be relatively slow. As will be shown further below in the examples, it is not the moisture permeability alone that counts but also the available surface area of the moisture permeable wall material. One way of restricting the rate of gas release in a controlled manner, will be by restricting the available gas pervious surface area of the sheet material per unit of composition enclosed in the applicator means. This may be achieved e.g. by a) making the applicator means partly (e.g. on one side) of sheet material having the aforesaid moisture permeability and for the remainder of a different but compatible sheet material having little or no gas and vapour permeability, e.g. a dense thermoplastic foil; b) coating a predetermined proportion of the gas pervious surface area with a coating of little or no permeability. The rate of gas release will be inversely proportional to the surface area which is pervious to gas and moisture. In the case of a), if the impervious foil has a melting point or region sufficiently lower than that of the fibres e.g. of the spunbonded polyolefin, it will even be possible to heat-weld the two materials together without the need for a special bonding layer. The impervious foil will then itself act as the bonding layer. Such applicator means may then be defined as comprising at least two layers of sheet material bonded together by heat-welded welding seams to form a pocket or pockets for containing a substance from which vapours or gases are to be released, one layer being composed of the fibre and another layer being composed of a suitable thermo-plastic foil or film weldable to the former and having a melting point or region sufficiently lower than that of the spun-bonded polyolefin sheet to permit heat welding of the former to the latter substantially without damage to the latter. As for the remainder the teachings herein relating to the applicator means may be applied in an analogous manner. The contents of the applicator means need not be in powder form. They can also take the form of granulates or pressed bodies, e.g. pellets or tablets. In the latter case the applicator means may be used as a superior modification of devices which have become known in the art as "Ropes", as described in US-PS 4653,644, where pellets of nearly spherical configuration are enclosed individually in small cup-like pockets of a non-woven fibre sheet (fleece). In practical tests these ropes suffered from the disadvantage that they released dust. If the heat weldable sheet material according to the invention is used a much superior product results. These applicators used in the process according to the invention can be used for disinfesting commodities, buildings, packaging means transport means, e.g. vehicles or shipholds or transport containers by releasing phosphine gas there into from applicator means as described above and maintaining a pesticidal concentration of phosphine gas for a period effective to achieve disinfestation. The contents of parent application 881083497, now patent number 0292948, by cross-reference, are to be considered part of the present disclosure. It will thus be apparent that particularly suitable for the purposes of the present invention are applicators, wherein the moisture pervious walls have an air permeability of about 23 sec (Gurley Hill). Also particularly preferred are applicators wherein the moisture pervious walls have a moisture permeability substantially equivalent to that of a commercial product known as Tyvek (trade mark of du Pont de Nemours), code numbered type 1073 D, ± 20 %. This arises from the fact that Tyvek has a moisture permeability of 600 to 630, on average 614 g/m 2 /24h and that the disclosed preferred range is from 500 to 750 g/m 2 /24h. In the following the invention will be further explained by way of specific examples, but it should be noted that the invention is not limited to the examples given and that the specific examples should be read together with the more general preceding disclosure which will enable the person skilled in the art to practice the invention within the full scope of the claims. As for the remainder the teachings of the parent application apply analogously. In the drawings: Fig. 1 represents a diagrammatic cross-sectional view of a portion of a weldable sheet material in accordance with the invention; Fig. 2 represents a sect ion through a fumigant applicator means according to the invention made from a sheet material as shown in Fig. 1; Fig. 3 represents a plan view on a smaller scale of the applicator means, part of which is shown in section along line II - II in Fig. 2; Fig. 4 represents a top view on a tin can (lid removed) containing an alternative embodiment of a multiple sachet device according to the present invention for use as a fumigant applicator; Fig. 5 represents on a smaller scale a diagrammatic side elevation of one embodiment of a multiple sachet belt according to the invention in the process of being withdrawn from its package; Fig. 6 represents gas release curves obtained with a conventional paper sachet and an applicator according to the invention, each containing technical aluminium phosphide with 11,32 g available PH 3 . Figs. 7 to 11 represent sections similar to Fig. 2 of various alternative embodiments of fumigant applicators according to the invention which in the case of Figs. 7, 8 and 10 are made partly of sheet material as shown in Fig. 1. All of these are illustrated as individual sachets but they could also be in the form of a plurality of sachets, i.e. a multiple sachet device as described more fully with reference to Figs. 2, 3, 4 and 5. Figs. 12 and 13 represent front and side elevations respectively of the bottom portion of a belt-like applicator device in accordance with the invention; Fig. 14 represents a diagrammatic section parallel to the plane of Fig. 12 of an intermediate portion of the belt-like applicator; Figs. 15 and 16 represent respectively front and side elevations similar to Figs. 12 and 13, but of the top portion of the belt-like applicator device. Although the invention should be readily understandable to those skilled in the art from the aforegoing detailed description, those features lending themselves to pictorial representation will be briefly described in the following with reference to the drawings which are not to scale. The description which now follows should be read in conjunction with the details of the aforegoing description. Referring now first to Fig. 1, there is shown in section a sheet 1 of vapour permeable, substantially anhydrous non-woven fabric, being a spun-bonded paper-like polyolefin sheet composed of heat- and pressure-bonded minute polyolefin fibres, which whilst being vapour- and gas-pervious, is impervious to liquid water and dust, is naturally water-resistant and of high tensile and tear strength. The sheet material 1 carries a porous coating 2 having a rough surface finish composed of EVA of melting point 75 to 80°C, applied at an average rate of about 30 g/m 2 by so-called reverse coating, i.e. a method in which EVA powder is first sprinkle-coated onto a temporary support onto which it is fused to form a porous fused layer which is then transferred and bonded whilst still in a fused state onto the polyolefin sheet, whilst substantially retaining its porosity. The drawing shows diagrammatically the rough finish of this coating and that the powder particles have been fused only to the extent that they have not been fused together completely, forming individual gooseflesh-like humps with substantially open pore areas 3 therebetween. For example the cross-sectional diameter of the pores of the layer can suitably be between about 1 to 10 µm. The EVA coating is present on one side of the sheet only and its porosity is so high that it virtually does not interefere with the gas and vapour permeability of the sheet. Referring now to Fig. 2, a multiple sachet is shown in section composed of two sheets 1' and 1'' corresponding to sheet 1 in Fig. 1, each coated on one side with EVA 2, the coated side of the two sheets facing each other. As shown more specifically also in Fig. 3 in plan view, the two layers of sheet material 1,2 have been heat-welded along longitudinal welding seam lines 3, 4 and 5 and along transverse heat-welded seam lines 6 to form two parallel longitudinal rows of sachet-like pockets 7, each pocket containing a measured a mount of aluminium phosphide or magnesium phosphide powder with or without additives. The welding seam lines 3 and 5 form the two sides of the belt-like device, whilst the longitudinal seam 4 is centrally longitudinally disposed. The welding seams 3, 4, 5 and 6 can have a width of at least 0.5 cm, preferably 0.5 to 3 cm, in particular 0.5 to 2 cm. The welding seam lines are produced by heat-welding means as employed in machines for the continuous packaging of commodities in thermoplastic films. Such heat welding with pressure at a temperature sufficiently high to cause fusion of the EVA, but not high enough to cause any fusion of the fibres of the sheets 1 (1', 1'') causes complete bonding together of the two sheets along the welding seam lines as shown in Fig. 2. As regards the contents 8 of pest control agent inside each cavity 7, reference is made to the teachings of US Patent 4,597,218 and 4,215,508 and PCT Application WO-A-80/00119 (corresponding to ZA-PS 79/2263) and corresponding patents in many other countries. However, it should be noted that for the reasons stated above, it is now possible to omit the additives of the metal phosphide compositions entirely and to use instead an additive-free or substantially additive-free metal phosphide powder or granulate, more particularly technical magnesium phosphide or aluminium phosphide (the meaning of which terms is wellknown in the pest control art). Nevertheless, it is preferred to impregnate the metal phosphide with a minimum amount of hydrophobising agent in a manner known per se, e.g. 1 to 5, say 3% solid paraffin, or an organo silicon compound, more particularly as disclosed in US-PS 4,421,742 and 4,600,589, particularly because this also affords protection during manufacturing stages preceding the sealing of the products into the applicator. The amount of metal phosphide is so chosen that for each pocket or sachet between 5 and 15 g available (i.e. releasable) phosphine are provided, 11,32 g available phosphine being the standard for aluminium phosphide compositions in sachets. Optionally, the individual sachets may be cut apart along cutting lines 9 which pass through the centre of each welding seam separating the individual cavities 7 from one another. In this form individual sachets are formed which may be packed individually or in predetermined numbers in air-tight containers for storage and transport. In this manner access of moisture to the metal phoshide is prevented until the package is opened and the sachets are removed for use as fumigation applicators. However, as shown in Figs. 3, 4 and 5, the applicator means according to the invention may also be present in the form of belts of predetermined length comprising in the shown example two parallel rows of interconnected sachets, e.g. altogether 100 sachets which in a rolled-up or folded condition are stored in air-tight containers until used. Referring to Fig. 5, a multiple sachet as described with reference to Figs. 2 and 3 is shown in side elevation. The areas 10 represent the transverse welding seams 6 which separate the individual sachet pockets filled with pest control agent. The last such welding seam, being a strong and relatively tear-resistant region, has been provided with an aperture 15 for the attachment of the applicator means, e.g. by means of a string passed through the hole 15. Optionally the hole 15 may be reinforced with a metal or plastics eyelet. The multiple sachet belt device is packed folded in concertina fashion in a gas-tight container 16. The concertina folds coincide with the transverse welding seams 10 between the individual sachet pockets. In Fig. 5 the container 16 has been opened on one side 18, through which the device is shown being withdrawn in the direction of the arrow. Referring now to Fig. 4, an alternative embodiment of a multiple sachet belt device 19 is shown composed of a large number, e.g. 100 individual sachets 20, interconnected via welding seams 10 (corresponding to welding seams 6 in Figs. 2 and 3) to form a continuous belt-like device rolled up and accommodated inside the gas-tight tin can 21. Again one end of the device is fitted with a fastening string as in Fig. 5. In tests the new applicator means proved to be so strong and completely dustproof as to eliminate for practical purposes any risk of even minor amounts of poisonous dust entering the environment e.g. foodstuffs or feeds treated with the fumigant. For that reason the applicator means according to the invention (sachets or belts) can now be contacted directly with sensitive food products, e.g. flour, rolled oats, infant food, dried fruit, nuts and tobacco, without the prior art need to interpose paper bags, cartons or similar partitioning means. Sachets left in the commodities by accident are quite unlikely to be ripped open when the commodities are moved, e.g. for re-storage or transport, as happened occasionally with prior art paper sachets. The gas generation characteristics of a sachet according to the invention (Fig. 3) are compared with those of a conventional paper sachet in Fig. 6. The conventional technical aluminium phosphide used was not treated in any way which might have affected the gas generation characteristics. It was employed as a conventional mixture of 70% w/w of technical aluminium phosphide powder and 30% inert ingredients. The sachets were tested in a gas-tight test chamber (0,5 m 3 ) at 70% relative humidity and 20°C. It will be seen that the gas generation from the sachet according to the invent ion was very even, following an almost rectilinear pattern up to day 7, when the contents of available PH 3 had been exhausted. Referring now to rigs. 7 and 8 of the drawings, one side of each of these sachets is again in each case formed by a sheet as described with reference to Fig. 1, the reference numbers having the same meanings as there described, whereas the opposite side of the sachet is formed of a different sheet material, the two sheets being heat-welded together at 6 along the edges of the sachet. In the case of Fig. 7 this different sheet material 31 is a substantially gas-impervious material and could for example be either a poplyolefin-aluminium foil laminate or a substantially gas-tight multiple laminate of polyethylene and a substantially more gas-tight synthetic resin, for example polyvinilidine chloride (PVDC). Accordingly, the sachet in accordance with Fig. 7 will admit humidity to the interior 7 containing the metal phosphide composition in powder or granulate form (indicated diagrammatically by a multitude of dots 8) at approximately half the rate at which such humidity would be admitted if both sides were composed of the same sheet 1, 2, 3. Accordingly, in this case the phosphine gas is generated and released similarly at half the rate at which this occurs in the case of sachets as illustrated in Fig. 2. Referring more specifically to Fig. 8, the second sheet 1''' is again composed of the same spun-bonded paper-like polyolefin sheet as in the case of the first layer 1, but without the sprinkle-coated porous layer 3. Instead thereof portions 32 of the sheet 1''' are coated with a dense coating of fused EVA powder which for practical purposes prevents access of humidity to those portions. This means that the access of humidity is restricted to the surface area of the sheet 1 on one side and to the uncoated portion 33 of the second sheet 1''' resulting in a phosphine gas generation rate proportional to the rate of humidity admission. Referring now to Fig. 9; one side of the sachet there shown is composed of a sheet 1''' as in Fig. 8, devoid of a sprinkle-coated porous layer 2, 3, whereas the other side is formed of a dense substantially gas and moisture-impervious sheet material 31 which is heat-welded along seams 6 as in Figs. 7 and 8 to the sheet 1''' to form the sachet cavity 7 filled with pest control agent 8. At least that side of sheet material 31 which faces the sheet 1''' has a melting region lower than that of the fibres of sheet material 1''', sufficiently so to permit heat welding without fusing the polyolefin fibres of sheet 1'''. Alternatively, a suitable melting adhesive layer may be applied in the position of the welding seams 6 prior to heat welding, for example in the manner shown in Fig. 11 to be described further below. The rate at which humidity will be admitted to the pest control agent 8 and phosphine gas will be generated, will be substantially similar to that of a sachet as described with reference to Fig. 7. Referring now to Fig. 10, yet a further modification is shown of the embodiment of a sachet described with reference to Figs. 7, 8 and 9. in this case one side 31 of the sachet is again composed of substantially gas and humidity impervious sheet material 31. The second side is composed in part of strips 31' of the same gas and humidity impervious sheet material, leaving therebetween a gap 34 which is covered by a gas and humidity pervious strip 35, of the sheet material 1, 2, 3 described with reference to Fig. 1. This strip 35 is heat-welded onto the edges of strips 31' in the regions of overlap. The edges of the sachet are heat welded at 6 as in all previous embodiments. If the strips 31' are by themselves heat-weldable to strip 35, without the need of the bonding material 2, the bonding layer 2, 3 may be omitted. Alternatively, the bonding material may be confined to the regions of overlap. In this embodiment the admission of humidity is substantially confined to the region 34 and controlled by the permeability of the material 1, 2, 3 in that region. The size of region 34 therefore controls the rate at which the pest control agent 8 generates phosphine gas and releases it to an environment to be fumigated. The embodiment according to Fig. 10 can be modified in a variety of manners. The strip 35 need not be symmetrically disposed as shown, but instead there may be a single strip 31', and a single strip 35 which at the same time replaces the second strip 31' . Also, instead of strips 31' being heat welded to sheet 31 along the seams 6, the strips 31' may be formed by folding over the edges of strip 31. Referring now to Fig. 11, an alternative embodiment of an applicator device according to the invention is shown in which both sides of the sachet are composed of uncoated spun-bonded polyolefin sheet 1''' as used for example in Fig. 9. However, in this case the welding regions, where the edge seams 6 are to be formed have been coated with bonding layers 36 of e.g. EVA having a melting point substantially lower than that of the fibres of layer 1'''. On the right hand side of Fig. 11 the bonding layers 36 have already been fused together at 6, whereas on the left hand side the two bonding layers are about to be pressed and heat welded together as indicated by arrows 37. In this embodiment as in all previous embodiments , the cavity 7 may again be filled with a metal phosphide composition, e.g. in powder or granulate form. Referring now specifically to Figs. 12 to 16 of the drawings, there is shown a specific embodiment of a belt-like applicator device in accordance with the invention wherein the high tensile strength of the sheet material is utilised in a particularly effective manner. This is a modification of the embodiment described with reference to Figs. 2 to 5, but which could also be modified in the various manners described with reference to Figs. 7 to 11, although this is not preferred. One of the main differences as compared with Figs. 2 and 3, resides in the fact that this belt-like device, composed of a multitude of sachets interconnected by flexible hinge regions is of comparatively narrow configuration, there being provided but a single row of the sachets connected end to end, the individual sachet formations being comparatively narrow with two comparatively short sides adjoining the hinge regions and two by comparison much longer sides coinciding with the side edges 39 of the applicator. The reason is that this belt-like device generally indicated as 40 is not intended to be laid out flat on a supporting surface or on or near the top of heaped commodities. The embodiment of Figs. 12 to 16 is instead intended to be pushed by means of a rod-shaped long insertion probe down from the top as deeply as possible into heaped commodities such as grain. Past attempts to make such an applicator, using the fleece materials proposed in the prior art described above were not quite successful, because the fleece materials had insufficient tearing strength, and sometimes the sachets burst open even whilst still in the packaging container. Moreover, the comparative roughness of the prior art materials increased the frictional resistance when attempts to push the devices far down into grain and similar heaped commodities. These problems have been overcome in accordance with the present invention. In a typical example the total length of the belt 40 is 3080 mm. The belt 40 is basically composed of two layers 40' and 40'' of the material described with reference to Fig. 1, welded lengthwise along the edges 39 by longitudinal welding seams 46 and subdivided into altogether 22 sachets 47 (in a typical example) by transverse pairs of welding seams 44 and 44' separated by a narrow gap 45, e.g. of about 5 mm. In a typical embodiment the seams are 8 mm wide, the overall width of the belt is. 70 mm and the length of each sachet, including seams of 140 mm. The two end sachets are kept empty, whilst the remainder are filled with pest control agent, in a typical example 25 grammes each of the composition described in Example 1 further below. At the bottom end (Figs. 12 and 13) the empty end sachet of the belt is folded over at 41 to form a loop accommodating a strong stirrup device 42 made of steel. The loop 41 is closed by a strong eyelet device 43. Alternatively, but less preferably this may be done by welding, if desired using a welding bonding layer as taught by the present invention. At the top end of the device (Figs. 15 and 16) in the region 48 a loop 49 of a strong plastics fabric is inserted between the layers 40' and 40'' of the open-ended empty end sachet and is fixed in place, strongly held between the two layers by a further eyelet 50. Once again (less preferably), welding may be resorted to. The complete device is rolled up in the same manner as illustrated in Fig. 4 and sealed into a tin like tin 21 in Fig. 4. In practice there may be several, e.g. four belt devices accommodated in one such tin which is sealed gas- and moisture-tight for storage and shipping. Alternatively, the belt device may be folded concertina-like and packaged in the manner described with reference to Fig. 5. Practical tests have shown that as a result of the smooth surface of the sheet material 40', 40'' and the great stength of the device, it is possible to push down the belt by means of a rod-shaped probe, the end of which is hooked into the stirrup device 42, vertically down into the grain for the full length of the belt, and this ensures improved vertical gas distribution throughout the grain even in heaps of considerable heights, e.g. in shipholds. The loop 49 serves for the withdrawal of the applicator device after completion of the fumigation. Practical dosage rates for this device, range from 0,7 g to 28 g PH 3 /ton of grain (i.e. 1 belt per 6-238 tons), preferably 3-11 g/ton (i.e. 1 belt per 15 to 55 tons), more particularly about 4g PH 3 per ton (i.e. 1 belt per 42 tons), where 1 belt contains about 500 g of the preparation, containing about 167 g available PH 3 . Example 1 Sachets as described with reference to Fig. 2 are each filled with 34 grammes of a standard aluminium phosphide pest control powder mixture having the following composition : 70% technical AlP, 18,5% urea, 7.5% mixture of mono ammonium phosphate and sodium carbonate (1:1) and 4% aluminium stearate. The dimensions of each sachet were approximately 100 x 90 mm. For purposes of comparison prior art paper sachets of similar dimensions (100 x 80 mm) and containing the same amounts of the identical aluminium phosphide composition were prepared and also polyester fleece sachets, 100 x 90 mm (similarly according to the prior art), containing the same amount of powder having the identical composition. These sachets were tested in a laboratory gas chamber having a volume of 0,5 m 3 , containing a dish filled with water for the maintenance of humidity and kept at a constant temperature of 20°C. After various times the phosphine concentration in the gas chamber was measured. The results are apparent from the following table 1. The residual contents of aluminium phosphide after the end of the experiment were as follows: 3,4% AlP and 3,2% AlP in the case of paper sachets and prior art polyester fleece sachets respectively and 2,6% AlP in the case of sachets according to the invention. This superior, more complete decomposition of the contents of sachets in accordance with the invention has been observed persistently. The reason for this superior result is unknown and an unexpected advantage of the invention. It will also be seen that the rate of gas emission from the sachets according to the invention is more gradual, which is also a desirable effect for purposes of practical pest control. Example 2 Bag blankets made in accordance with Fig. 2 hereof and similar bag blankets made of the prior art polyester fleece were used side by side in the fumigation of a grain store containing 700 tons of wheat. The following table 2 represents typical phosphine concentration measurements at different fumigation exposure times, when concentration measurements are taken in direct contact with the blanket and at a level of 8 cm above the blanket in the grain, when applying the pest control agent at a rate of 27 grammes available phosphine per ton of grain. (2,5 pockets per ton, each containing 34 g AlP mixture as in Example 1, altogether 18 bag blankets). This is a conventional dosage rate in some countries. The bag blankets were covered by about 20 cm of grain. The entire grain heap Was covered with a gastight plastics foil. The following table reflects the much more gradual release of phosphine from applicators according to the invention, whereby excessive concentrations at or close to the surface of the bag blankets are avoided and the distribution of phosphine gas throughout the grain is much more uniform. PH 3 -Concentrations in ppm Time direct on blanket 8 cm above blanket in grain Tyvek prior art Tyvek prior art 5 h 17500 30000 800 11400 24 h 15000 33000 1200 3300 48 h 6000 13500 600 6000 72 h 3300 15000 500 7500 5 days 1200 2550 100 1350 6 days 550 1140 100 880 Example 3 Three types of sachets as described with reference to Fig. 10 of the drawings were prepared and tested. The sachets had the dimensions: 100 x 90 mm and the strips 35 of sheet material as described with reference to Fig. 1 had the following dimensions: a) 1 cm x 9 cm, b) 2 cm x 9 cm and c) 3 cm x 9 cm. Each sachet was filled with 24 g technical magnesium phosphide, impregnated with 3% solid paraffin. The sachets were exposed to moist air under the following conditions. The volume of the gas chamber was 0,5 m 3 . The chamber contained a dish of water to provide adequate humidity and the air was maintained at a constant temperature of 20°C. The magnesium phosphide was sufficient to produce a final gas concentration of 15 300 ppm after complete decomposition. However, the test was stopped after 144 hours. The rates of phosphine release to the gas chamber are apparent from table 3. Time (h) 1 cm strip (ppm) 2 cm strip (ppm) 3 cm strip (ppm) 1 5 7,5 8 10 2 9 18 20 25 4 15 30 30 50 6 25 50 60 100 24 150 400 500 800 48 450 600 800 1200 72 600 900 1200 1800 144 2000 3900 4200 6500 It will be seen that the gas release was approximately proportional to the surface area of the gas pervious strip. Example 4 Sachets according to the invention as described with reference to Fig. 2, prior art paper sachets (with machine-sewn seams ) and prior art polyester fleece sachets (all sachets being of the same dimensions) were each filled with 24 g technical magnesium phosphide impregnated with 3% solid paraffin as a hydrophobising agent. The sachets were subjected to the following tests to determine their safety performance in the event of malpractices: 1. Drip experiment Two sachets of each sample were so placed into a sheet metal trough (200 x 150 x 50 mm) but they overlapped halfway. Water at 70°C was dripped onto the sachets by means of a dropping funnel for 1 hour (1 drop per second). The experiment was conducted at an air temperature of 35°C. 2. Spray experiment A sheet metal trough containing sachets was used as in Experiment 1. 10 ml water was sprayed onto the sachets by means of a spraying flask. After 15 minutes a further 10 ml water was sprayed onto the sachets. This procedure was repeated for 1 hour. 3. Tin can experiment 3 sachets were placed into a 2 l tin can and 100 ml water at 70°C were poured over the sachets. The can was left standing for 4 hours. 4. Bath experiment The sachets were placed individually into a metal dish and so much water was poured thereover that the top of the sachet was at least 5 mm below the water surface. The dish was left standing for 4 hours. 5. Immersion test An 800 ml glass beaker was filled with water. The test sachet was dipped for 5 to 10 seconds into the water, then withdrawn and shaken in air to remove the water. Thereafter the sachet was left lying for 4 hours. 6. Powder experiment 15 g of the powder mixture were introduced into a 150 ml glass beaker of narrow configuration. The beaker was heated in an airbath to a temperature of 50°C. When a temperature of 35°C had been reached, 5 ml water were added through a pipette. The beaker was left standing for 1 hour. All sachets ignited, except the sachets in accordance with the invention in their undamaged condition. In the powder experiment ignition took place, as was to be expected. Example 5 Grain was fumigated as in Example 2 but at a temperature which on average was about 10°C higher and using a dosage rate of 68 g of the composition per ton of grains. In one experiment bag blankets according to the invention were used as in Example 2. In the comparative test conventional bag blankets were used wherein the composition was prepacked in paper sachets which were in turn enclosed in the conventional bag blankets. The concentrations of PH 3 (in ppm) measured in the grain at a distance of 15 cm from the bag blankets were as in Table 4. 5 h 24 h 48 h 77 h 92 h 168 h Tyvek blanket: 2 400 12 000 12 000 12 000 15 000 1 800 Paper sachets in convent. blanket 6 000 18 600 24 000 21 000 15 900 1 100 It will be seen again that the phosphine generation according to the invention was much more evenly regulated, an effect which manifests itself in a much more even distribution of the gas throughout the grain over a prolonged period. The claims filed herewith are to be considered a part of the present disclosure.

Claims: Process for controlling pests with phosphine gas which is released from an applicator in the form of single or multiple sachet-like pockets having flexible gas and humidity pervious walls, containing a hydrolysable metal phosphide in powder or granular form by the admission of humidity through such walls, characterised in that the rate of hydrolysis of the metal phosphide contained in the applicator and the release rate of the phosphine is limited by selecting, for a given available amount of phosphine gas releasable by the metal phosphide in powder or granular form, a combination of surface area and moisture permeability of the flexible walls of the applicator within such limits that the admission of humidity to the metal phosphide is thereby retarded in relation to the maximum rate at which the metal phosphide can react with such humidity. Process according to claim 1, characterized in that for a given available amount of phosphine gas releasable by the metal phosphide a surface area of the gas and humidity pervious flexible walls is selected which, having regard to the moisture permeability of the material of those walls, retards the admission of humidity to the metal phosphide.. Process according to claim 1 or 2, characterized in that for a given size of applicator and moisture permeability of the gas and humidity pervious flexible walls, the moisture permeable flexible wall surface area is restricted by a) making the applicator partly of moisture permeable flexible sheet material and for the remainder of a different but compatible flexible sheet material having little or no gas and vapour permeability and/or b) coating a predetermined proportion of the gas pervious surface area with a coating of little or no permeability. Process according to any one or more of the preceding claims, characterized in that the ratio of the surface area of the humidity pervious flexible walls to the available amount of phosphine gas releasable by the metal phosphide powder is from 0,8 to 25 cm 2 /g, preferably 1,6 to 16 cm 2 /g Process according to any one or more of the preceding claims, characterized in that the moisture pervious flexible walls have an air permeability of about 23 sec (Gurley Hill). Process according to any one or more of the preceding claims, characterized in that the moisture permeability of the walls has been restricted by calendering, preferably to achieve a moisture permeability of from 50 to 1000g/m 2 /24 h. Process according to any one or more of the preceding claims, characterized in that the moisture pervious walls have a moisture permeability substantially equivalent to that of a commercial product known as Tyvek (trade mark of du Pont de Nemours) code numbered type 1073D.

Inventors: BARTH VOLKER ERWIN DR, FRIEMEL WOLFGANG DR, BARTH, VOLKER ERWIN, DR., FRIEMEL, WOLFGANG, DR.
Applicants: DETIA FREYBERG GMBH
Application year: 1988
Main classification: B65D65
IPC codes: B65D65, A01N59, A01N25