CA1037427A - Packaged pesticide - Google Patents
Packaged pesticideInfo
- Publication number
- CA1037427A CA1037427A CA200,667A CA200667A CA1037427A CA 1037427 A CA1037427 A CA 1037427A CA 200667 A CA200667 A CA 200667A CA 1037427 A CA1037427 A CA 1037427A
- Authority
- CA
- Canada
- Prior art keywords
- water
- container
- pesticide according
- closure
- bag
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/18—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient
- B65D81/22—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient in moist conditions or immersed in liquids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/26—Phosphorus; Compounds thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
PACKAGED PESTICIDE
Abstract of the Disclosure A packaged pesticide comprises a phosphine-releasing metal phosphide and a solid oxidant in a gas permeable package.
The package comprises a container having a closure which opens quickly upon contact with water.
Abstract of the Disclosure A packaged pesticide comprises a phosphine-releasing metal phosphide and a solid oxidant in a gas permeable package.
The package comprises a container having a closure which opens quickly upon contact with water.
Description
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1~3~PZ7 This invention relates to the combination of a pesti-cide and a solid oxidant in a package. The pesticide comprises a compound having a toxic, active ingredient which releases phosphine upon contact with moisture. Typical o~ such active compounds are aluminum phosphide and magnesium phosphide.
; The solid oxidant comprises a substance or mixture o~ sub-stances which decompose with water the metal phosphide or residue remaining after the development of phosphine during processing. m e oxidant oxidizes into harmless compounds the phosphine (hydrogen phosphide) which may ~orm. The pack-age is permeable by gases such as air, water vapor or phosphine.
A ~orm o~ a combined administration o~ pesticides and oxidants is described ln German patent 2 206 487 and 2 206 494.
These references disclose a sheathing or envelope consisting o~ a durable film~which is wholly or partially permeable by gas, resistant to mechanical stress and provided with recesses.
Some~of the recesses house the oxidant, while the other recesses house the;pesticide. The recesses are covered by a substance, such as Japan~Paper, which is permeable by atmos-pheric moisture. I* use, these packages are placed in a ~horizontal position in an area to be ~umigated. The side permeable by a gas ~aces upward.
German patent 698 721 discloses a process for exterminating grain pests.~ According to this patent, paper bags containing phosphides are deposited ~or several days in the ~rain storage ~; space. After the grain has been treated, the bags containing the remainder o~ the pesticide are removed from the storage space. No special instructions are given ~or destruction o~
the residue w~ich accumulates during treatment; in particular, no provision has been made in this case ~or the inclusion in the paper bag of substances, such as solid oxidants~ ot~er than the phosphide.
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~037~7 Ge~man patent 709 748 describes another process for - fumigation with p~osphine. In this case, a phosphide and a water-releasing salt containing water of crystallization are enclosed by a gas-permeable envelope of, for example, unsized paper The resulting package is introduced into the space to be fumigated or deposited in the stored grain. The pro-portion of the water-releasing salt relative t0 the phosphide must be regulated in such a way that complete decomposition of the phosphide is assured within the required time.
A phosphide packed in paper bags does indeed represent a well acting pesticide ror the treatment of grain and simi-lar bulk goods, since the bags can be deposited deeply into the material to be treated where the desired development o~
phosphine is a~sured. After the treatment of the goods, the bags containing residues can be removed easily without contamination of the treated goods. Neverthelèss, there are ~ ~ diffLculties ln the safe destruction of the fumigant resi-,~; dues, particularly~in view of the increased emphasis on ~prese~rvation~of the environment. Where there ls only a gradual ~;20 ~ admission of moisture to the phosphide during the fumigation ~operation, a~complete decomposition of the phosphide is not guaranteed. ~Hi~therto, it was customary to bury or burn the bags containing the fumigant residues. These methods for thè
disposal of toxic resid~es are not entirely satisfactory.
,,., For example~ burying of fumigant resldues ha~ been prohibited in some countries because of the dangers involved. On the other hand, if the bags containing the fumigant residue are placed ln running water, then an aqueous solution containing l phosphine can res~lt. Disposal of such an aqu~ous solution ; ~ 30 raises new problems. ~
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It is the task of the present invention to provide a package for the administration of a phosphide-containing `
pesticide, which upon contact with water results in the quick, safe and substantially complete conversion of the fumigant residue so that the phosphine concentration in the resulting aqueous solution does not exceed about 0.01 ppm.
Accordingly, this invention provides a packaged pesti-;;; cide comprising a phosphine-releasing metal phosphide and a solid oxidant in a gas permeable package. The package 10 comprises a container having a closure, which opens quickly `! ' upon contact with running water. The closure comprises a minor proportion of the area of the surface of the package.
According to this invention, such natural or synthetic polymers are employed as the material for the closure, which i" 15 are durable and stable in the absencQ of running water, but . ., ::
which decompose quickly andtor dissolve ~uickly upon contact ~ , with water. Well sulted for use in this invention are ~
closing materials which decompose and/or dissolve within ~`
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thirty minutes of being contacted with water. Particularly preferred are sealing materials which dissolve and/or decompose within about twelve minutes after contact with water.
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Typical of the synthetic polymers which can be employed as closing or sealing materials are polyacrylamides having 25 recurring units of the following formula: j, ¦ R3 f ~;
~ Rl ... _ _ ~.`.,.:"','.'.'`"', ., ~ ....
, ,, " . - . . .
,.,:; ~,,; .
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i ' ,`' ,' '"' ` ' :,'.`: ,.. ' 10:~74Z7 ; Wherein Rl signifies a methyl radical and R2 and R3'signify "' hydrogen; o~ in which Rl is hydrogen~ ~ is hydrogen and R3 ,, is hydrogen or a methyl radical. Other materials include , polyethyleneoxides having ~olecular weights above about lOO,OOO;
, 5 polyvinyl alcohol; atactic polyvinylmethylether; polyrJinyl pyrrolidone; copolymers o~ ~inyl acetate and vinyl pyrrolidone , (about 60 p~rts vinyl py,rrolidone ~or each 40 parts of vinyl ,, acetate-); copolymers of poly~Jinyl alcohol, polyvinyl acetate ",, and polyethylene oxide (in a weight ratio of 50: about 20:
,~; lO about 20). Typical of the natural polymers are alginates, " cellulose ethers, dextrine, and gelatin. Particularly pre~erred ,,;, sealing materiflls are polyvinyl alcohol and polyethylene oxide.
,, In a preferred embodiment of this invention. the con-~ tainer is ~illed with the pesticide and oxidant~ and i8 closed ',, 15 by sewing it with a thread ~hich is decomposable or soluble in water and comprlsed of a natural or synthetic polymer of the type enumerated above. Particularly well suited for this ~purpose is a thread comprised of polyvinyl alcohol and having ,r~ a diameter of~ about 0.2 to about 1.8 mm. It ~rill be under-20~ stood that threads~having larger diameters can also be employed in other 6ituations.
In a further preferred embodiment of this invention, the container~is filled with the pesticide and o~idant,, and an insert of~natural or synthetic polymers decomposaible and/
or soluble in water is placed between each open section o~
~ the Pilled container in order to close it. l'he insert is then sealed to the contalner by the application of heat and/or pressure.
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:~ ~ 79~27 In another preferred embodiment, the closure comprises a cap which is adhesively secured or sealed tightly to the material of the container~ and the c~osure in this case com-prises one of the a~orementioned natural or synthetic polymers.
: 5 In a particularly preferred embodiment, the cap conslsts essentially of a polyvinyl alcohol ~ilm. With such a cap the bag, after being charged with pesticide and oxidant, can be ; closed. A strip of the film can be applied along the longi-tudinal edge o~ the narrow side of the empty container in the area of the opening. The movable portion of the film can be folded back over the opening o~ the bag and sealed along the second longitldinal edge to the other wall o~ the container by the application o~ heat and pressure.
According to the present invention, the package for ~ 15 the pesiticides and solid oxidants comprises a container .. , having a closure which opens quickly upon contact with water.
s~ ~ Quick opening of~ the~container and the quick admission o~
~rater~into the container~can~be accelerated by holding the bag materlal unde~r a latent~tension in the area o~ the j ~`20~ opening~by means~of some pretreatment or by m~ans of a s~ ~permanently~elastLc material connected thereto. When the tenslon i9 released by the dissolution and/or decompositlon of the closing materlal~ at least a partial spreading o~
the opening o~ the co~tainer occursJ and results in an scceler-ated admission of water into the container. To accomplish t~hls result~ the bag material can be provided with permanent corrugations ln the area o~ the opening~ perhaps b~ the appli-cation o~ heat or steam in a press, and optionally wlth the use o~ chemical additives to aid in the ~ormation o~ suc~
3 corrugations. Upon closing o~ the container, ~or example by '' : . ,:
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sewin~ it together with a thread which dissolves or decom~
poses uoon contact with water, the edges of the bag are fitted smoothly against one another, but remain under latent tension, which leads to at least a partial spreading of the opening of the bag after elimination of the closing material. ~-In another alternative, one or more thin wires comprised of `
a permanently elastic material can be threaded into the con- ;
tainer material in the area of the opening. The elastic material is in tension which causes the opening of the con-tainer to spread after dissolution and/or decomposition of the closing material. In a further embodiment, one or more !.`"' permanently elastic threads comprised of natural rubber, -~
synthetic rubber or polyurethane elastomers are provided for ~`
this purpose in the area of the opening of the filled con~
tainer. Such threads are attached merely in the area of i the two longitudinal edges of the material of the container, ` and are under such tension that they will effect an at least :,; , ...
~; partial spreading open of the bag after dissolution and/or ; decomposition of the closing material.
It is essential in this invention that the closure, which dissolves and/or decomposes upon contact with water, .
comprise only a minor portion of the circumference of the container or a minor area of the total surface of the con~
tainer. In the case of alI the examples, the phosphine con- `
centration in the water used for~elimination of the residues did not exceed 0.01 ppm; such water can be safely added to ; ; i i~ customary sewa~e.
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Within the scope of the present invention, the pesticide and solid oxidant are placed together in a container. Sur-prisingly, it was observed that in bags which consist of a material that is normally readily permeable by water, `~
. 5 water will infiltrate only very slowly after fumigation.
Without being bound by the following explanation, it is assumed that in the case of gradual hydrolysis of metal phosphides, the residue accumulates and obstructs the pores `
of the bag material and/or reacts with the water first entering the bag in such a way that further admission of water is greatly delayed or completely prevented. As demon- `
strated in the;following examples, the closure of this in~
vention made of natural or synthetic polymers which decompose ;;
. ;, ,~,. : ,, and/or dissolve upon contact with running water, provides for the improved elimination of pesticide residue according to the task of the invention, even i~ such materials are ; ~i employed for bags which per se are readily permeable by ; running water.
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~; The container employed in this invention preferably comprises a gas-permeable, flame retardant, tear-proof fabric, such as for example, flber fleece or textile fabrics. The container material can be easily permeable by running water;
by~this~ lt is~meant~that l -cm of such a fabrlc is~penetrated by~at least one~m~l oP~water within 100 seconds under a pressure ;;~
~of 10 cm water column.; Preferably, the fabrics are com-prised of polyvlnyl chloride having a weight per unit area of 240 to about 400 g/m2.
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, :,; :, 1037,9Lzr7 By a PVC ~abric we understand a ~abric which consists predominantly of polyvinyl chloride, PVC-mixed fabrics comprising at least about 70 weight percent polyvinyl chloride - can also be employed.
- 5 Wlthin the scope of the present invention, tear-proof fabrics are used as t~e mAterial for the bag. Suitable fabrics , have a tear strength at least about 4 kg/cm both in their ;.~ dry and in their w~ a~ state.
Although the shape of the container is without any ;~-, 10 essential importance in view o~ the setting o~ the problem according to the invention, preferably the container is a ,~ bag. Preferred are bags which are obtained ~rom two slmilar rectangular pieces of material having a width o~ about 4 to about 12 cm and a length of about 6 to about 20 cm. Hose-15 shaped material having a diameter of about 3 to about 10 cm is particularly preferred. The hose-shaped material can be cut to the deeired length and closed at the open ends.
The pesticide employed in this invention contains as its active7~toxic ingredLent a compound which releases phos-`~; 20 ~ `phine~(PH3)~upon~c~ontact with~moisture. Typical of such ~phosphides are inorganic metal phosphides~ such as calcium ; - phosphide, magnesium ph~osphide and aluminum phosphide. The individual phosphide particles can be provided with a pro-tective coating to control the admission Q:~ moisture. Typical coating materials are para~in~ metal stearate, polyethylene oxide or wax like polyethylene glycols. In addition to the metal phosphides, one can also employ inert diluents (silicon dioxide, aluminum oxlde and clays), substance~ which release a gas at moderately increased temperature (ammonium carbamate, .`',` :
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ammonium ~arbo~ate a~d sodium blcarbo~ate~ ~trong~ solld bases (sodium oxide~ ~odium'hydrox~de and po~asslum hydroxlde~
,",,~ detergent~ (~lkyl sul~n~te~. ~lkyl~ryl ~ul~on~tes)p :, compressing aides (ta'lcum~ and other additives~ The~e, ~ddl- ~
, 5 tives can be within the protective coating ~or the metal "
," phosphide~ Well suited, for example, i8 a composition sold ,~ ;
,~ by the firm DEGESCH, Frankfurt, (West Germany) under the '';''"
,,~ I trademark "Phostoxin". The ingredient releasing the r. ''.
; phosphine can be in the form of a powder~ a fairly coarse ~, !~'",~ 10 granulate or a pre~orm, pressed obJect. Depending upon size~ "each contal~er will generally contain about 10 to about 100 ,,, g phosphine as~active ingredient. ~ ;~
,' An important aspect o~ the present invention,involves `,, the Joint packing of the solid oxidant in the container ,~, 15 with the phosphlne-releasing actlve, toxic ingredient. The solid oxidant consists of a!substance o~ ixture of substanees .l , which in~ures the quick and co~.plete conversion oP the pesti-cide~ residues~lnto harmless products when the residues are contacted ~Jith water. 'l~en a mixture o~ substances is employed~ ' ,~
the mixture i8 C omprlsed mainly of the actual oxidant, andcan " include a material which will adapt ~he pH o~ ~he water to , the oxidant. In order to assure a quick reaction in water, ~,, .~ water soluble substances and mixtures oP substances can be ` ;~
"~,l employed, Mixtures oP calcium hypochlorite and citric acid ~
in a weight ratio of about 1:1 have proven succe~sful. ~ ' ,,, Potassium permanganate and sodium oxide in a weight ratio of ~ about 40:1 can also be employed. Other suitable oxidants "~"I include mixtures of sodium perborate or potasslum permanganate ,~ ~lith citric acid or sodium percarbonate with manganese salts.
~,l 30 Chromium (VI) oxide iL particularly prePerred. The mixture ~
of substances can also contain'a redox indlcator. The quan- ~ , ~,i tity o~ mixture oP subst~nce~ having an oxidizing e~fect ` ,'~
.
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; depends essentially on the quantity of phosphine-releasing, "4,' active ingredient; a ratio of about 0.2 to about 0.5 parts by weight by oxidizing substance to one par~ by weight .; phosphine-releaqing active ingredient has proven success~ul.
In order to prevent any reaction between the toxic, active ingredient and the solid oxidant before or during the actual use of the~pesticide for ~umigation, the oxidant can be encased ln a separate envelope made of an inert material, soluble and/or decomposable in water. For this purpose, a . 10 sheathing o~ polyvinyl alcohol or waxl.tko polyethylene glycol i8 particularly sultable. At the same tlme, individual ~j particles, granulates or molded article~ o~ the oxidant can be coated, ~or example, with polyethylene glycol. In the : alternative~ the entire quantity o~ oxidant can be within the ~;l 15 inert, water soluble envelope, ~or example inside a c~osed small bag of~ polyvinyl alcohol or polyethylene~glycol ~ilm.
~ ~ ~Chromium~VI)~ oxide iD~a small bag of 0.1 mm thick polyvinyl s~ ~alcohol film~has proven to be a particularly quick and safe : ; : ~ .
~ acting oxidant;~e~en in the case of a storage time o~ more . . 1 . ~, ~ ~
~ ~ than twelve months, there occurred neither a destruction o~
~the small bag, nor~any reaction of the Chromium (VI) oxide with the phosphine-releasing actlve ingredlent. The e~ective-ness o~ the Chromium (VI) oxide also remained unchanged.
Based~on present experience~ the best ~orm ~or admini-~l 25 stering the phosphide-containing pesticide and solid oxidant ~ 1 .
in a ~oint packing according to this invention consists o~
.l about 10 to about 100 g "Phostoxin" with about 3 to about 30 g Chromium (VI) oxide in a separate~ tight shaathing o~ 0.1 mm thick polyvinyl alcohol ~ilm. Both components are in a bag :
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'';'~, '' 37 gL~:7 - made of a flame retardan~, tear-resistant PVC fabric readily ~
permeable by steam or running water (weight per unit area ~ ~-about 320 g/m2) having measurements of 8.8 x 14 cm. Pro-vided in the area of the opening between the two lateral ;- 5 parts of the bag are two threads of urethane elastomer under - tension. The bag is closed with a seam formed by a 0.8 mm thick thread of polyvinyl alcohol. ~
; This invention will be more fully understood by refer- ^
. ,. ,. ~,, , , -ence to the following examples. `~
Example 1 Rectangular pieces of 31 x 10.5 cm are cut from a PVC
fabric having a weight per unit area of 322 g/m2, which is pen- ;
~ etrated within about 4 to 6 seconds by l ml running water per ;;, l cm of fabric under a pressure of a 10 cm water column. The ;~
; 15 pieces are placed on top of one another each ;time in double `
~ layers, and are sewn together with a PVC thread along the two .. . .
longitudinal sides. The little bag obtained is turned and ~, filled with 40 g phostoxin powder ("Phostoxin" is a trade mark for a powder containing aluminum phospide as a phosphine-releasing `~
~0 metal ~hosphide,and aluminum oxide and ammonium carbamate and ;~;
a coating of paraffin). 16 g Chromium (VI) oxide are added in a small, closed bag of 0.1 mm thick polyvinyl alcohol film.
'~ Subsequently, the~bag is closed on the still open narrow side by means of a seam formed by an 0.8 mm thick thread. ~;
Example 2 In the manner described in Example l, a bag is made of the 'l PVC fabric easily permeable by running water, and is filled with the components listed there. For closing of the bag, a ` strip (8.8 x 0.5 cm) made of 0.6 mm thick polyethylene oxide film is placed along the narrow side between the walls of said ,;
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bag, and for the purpose of closing is guided through a film ~
sealing device. ` ;
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Example 3 ~37~27 :: . .. ..
~; A bag is made in the manner described in Example 1 using the PVC fabric permeable by running water. Prior to ;
;` filling the bag, a strip ( 9 X 1 cm) made of 0.1 mm thick polyvinyl alcohol film is sealed along the open narrow side ., :,, .
to the outside of one wall of the bag. After filling with the components listed in Example 1, the sealed strip is folded back over the opening of the bag, and is then also sealed to the other wall of the bag.
Example 4 :: .
~i As skated in Example 1, a bag is made of PVC fabric easily permeable by running water, with weight per unit area of 322 g/m . The two pieces are sewed together so that the . .
seam will end along the two longitudinal sides in the area of the opening of said bag just 1 cm before the actual edge.
;; After filling of the bag with 40 g "Phostoxin" powder and 16 g separately enclosed Chromium (VI) oxide, the opening of the bag, with sllghtly folded up lateral parts, is moved over two urethane-elastomer threads, kept under tension,~and these threads, while maintaining their tension are sealed with;two~pieces of PVC fabric in the area of ~;
their two longitudinal~edges, and these two pieces of PVC ~
.. . ~ : . .
fabric are sealed together, too. Subsequently the still ~ open bag is closed by a seam of an 0.8 mm thick polyvinyl ; ~ 25 alcohol thread without interferring with the elastic threads.
~ The effectiveness of the form of administration accor-;~ ding to the invention was examined with a view toward the safe and complete elimination of pesticide residue.
Specifically, the time required for complete conversion of ;~
`~ 30 residue in water, and the quantity of phosphine occurring ~;
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. `;thereby in the water were determined. For purposes of com- ~ `
- parison, other packings for phosphide-containing pesticides ;;
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were also tested~
. ;:: . , A. Bag of a PVC fabric, described in Example 1, ~
. 5 with contents as stated there; however, the ;
~. ~'.i.,.
bag was closed with conventional thread not dis~
solving or decomposing quickly in running water. '~
B. A joint form o administration for a phosphine- ;;
releasing, toxic, active ingredient and solid oxidant as in the German patent application : i.. -:
22 06 494.
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C. A paper bag as used in case of~a commercial ;`
; phosphine-releasing preparation (DETIA Ga~ B
- Trade Mark). The known bag was ~illed with 40 g "Phostoxin" powder and was closed again. C
, .
` D. The known paper bag, as stated in case of sample C ~DETIA Gas Ex-B - Trade Mark)~ was filled ;~, with 40 g "Phostoxin" powder and 16 g Chromium ....
` (VI) oxide in a separate envelope made o poly- `
.~ . :,:
', 20 vinyl alcohol film, and was closed again.
s~ As a starting materlal for the examinations, residues in the~above listed;samples were used which resulted after 120 ~;
hours~of fumigation o~f grain (the samples in each case were inserted 35 cm deep~into loosely heaped up and subsequently `=~
covered up grain) under the same conditions. For the elimi-` nation of the fumigation residues, the samples were added to ~ `~
.,., , ~ .
`~ 300 ml of water. ~They~were stirred in occasionally and sub-.l merged, and the time up to the complete conversion of all t¦~ phosphide residues~was determlned. After expiration o this time period, the concentration of phosphine occurring inS the water was also determined. The determination o the phosphine content was accomplished essentially according to .:, :, :, ~ ., , - 13 - ; ~
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~37~27 .. ~ the instructions by White and Bushey in J. Am. Chem. Soc. 66, pp. 1666-72 (1944). The complete elimination of the .. fumigation residues is accomplished when all phosphine developing components h~ve been converted.
. ~ 5 The results of the experiments are presented in tl;e . following table.
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;~ TABLE
Elimination of the residues ~rom the forms o~ administration .~ o~ phosphide containing pesticides~ according to the inven-~ 10 tion (1 to 4) and partly ~nown (A to D)~ accumulated a~ter i.~ their appllcation . . . _ .
,i, Samples Time to complete Phosphine content eliminatlon in the water used 1 70 to 180 min's below 0.01 ppm ; 15 2 ; ~80 to 220 min's below 0.01 ppm 3 ~ ~ 60 to 150 min's below 0.01 ppm ,........ .
4 ~ :50 to 140 min's below 0.01 ppm .' ~ ~ A~ ~ 500 ~o 800 min's~ below 0.01 ppm B ~: 3 to 450 min's below 0.01 ppm :
~1, :20 C after l?o hrs no above 50 ppm . complete conver-',,',;',,1~: slon .
D a~ter 120 hrs no above 50 ppm ;.. , complete conver-'~.'k~ 25 sion ..., ,~
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16~79~Z7 From the results of the experiments it is apparent that under the stated conditions, the same for all samples, the elimination of the resldue with the form of administration of this invention requires conslderably less time than the eli-mination of residue using kno~m forms. This is particularly remarkable in view of the fact that the materials used ~or the bags are really easily permeable by running water. It is completely surprising that there is no analytically determinable phosphine content in the water when packages of thls invention are employed ~or the el~mination o~ pestlclde residues. Since the complete elimination And/or complete convers~on o~ the phosphide-containing pesticides into harmless products repre-sents an essential aspect in case o~ use of such agents, the l present invention does lead to a superior type o~ pesticide.
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1~3~PZ7 This invention relates to the combination of a pesti-cide and a solid oxidant in a package. The pesticide comprises a compound having a toxic, active ingredient which releases phosphine upon contact with moisture. Typical o~ such active compounds are aluminum phosphide and magnesium phosphide.
; The solid oxidant comprises a substance or mixture o~ sub-stances which decompose with water the metal phosphide or residue remaining after the development of phosphine during processing. m e oxidant oxidizes into harmless compounds the phosphine (hydrogen phosphide) which may ~orm. The pack-age is permeable by gases such as air, water vapor or phosphine.
A ~orm o~ a combined administration o~ pesticides and oxidants is described ln German patent 2 206 487 and 2 206 494.
These references disclose a sheathing or envelope consisting o~ a durable film~which is wholly or partially permeable by gas, resistant to mechanical stress and provided with recesses.
Some~of the recesses house the oxidant, while the other recesses house the;pesticide. The recesses are covered by a substance, such as Japan~Paper, which is permeable by atmos-pheric moisture. I* use, these packages are placed in a ~horizontal position in an area to be ~umigated. The side permeable by a gas ~aces upward.
German patent 698 721 discloses a process for exterminating grain pests.~ According to this patent, paper bags containing phosphides are deposited ~or several days in the ~rain storage ~; space. After the grain has been treated, the bags containing the remainder o~ the pesticide are removed from the storage space. No special instructions are given ~or destruction o~
the residue w~ich accumulates during treatment; in particular, no provision has been made in this case ~or the inclusion in the paper bag of substances, such as solid oxidants~ ot~er than the phosphide.
~ , ~.
~037~7 Ge~man patent 709 748 describes another process for - fumigation with p~osphine. In this case, a phosphide and a water-releasing salt containing water of crystallization are enclosed by a gas-permeable envelope of, for example, unsized paper The resulting package is introduced into the space to be fumigated or deposited in the stored grain. The pro-portion of the water-releasing salt relative t0 the phosphide must be regulated in such a way that complete decomposition of the phosphide is assured within the required time.
A phosphide packed in paper bags does indeed represent a well acting pesticide ror the treatment of grain and simi-lar bulk goods, since the bags can be deposited deeply into the material to be treated where the desired development o~
phosphine is a~sured. After the treatment of the goods, the bags containing residues can be removed easily without contamination of the treated goods. Neverthelèss, there are ~ ~ diffLculties ln the safe destruction of the fumigant resi-,~; dues, particularly~in view of the increased emphasis on ~prese~rvation~of the environment. Where there ls only a gradual ~;20 ~ admission of moisture to the phosphide during the fumigation ~operation, a~complete decomposition of the phosphide is not guaranteed. ~Hi~therto, it was customary to bury or burn the bags containing the fumigant residues. These methods for thè
disposal of toxic resid~es are not entirely satisfactory.
,,., For example~ burying of fumigant resldues ha~ been prohibited in some countries because of the dangers involved. On the other hand, if the bags containing the fumigant residue are placed ln running water, then an aqueous solution containing l phosphine can res~lt. Disposal of such an aqu~ous solution ; ~ 30 raises new problems. ~
` `-- -2-., ''l.
3~
It is the task of the present invention to provide a package for the administration of a phosphide-containing `
pesticide, which upon contact with water results in the quick, safe and substantially complete conversion of the fumigant residue so that the phosphine concentration in the resulting aqueous solution does not exceed about 0.01 ppm.
Accordingly, this invention provides a packaged pesti-;;; cide comprising a phosphine-releasing metal phosphide and a solid oxidant in a gas permeable package. The package 10 comprises a container having a closure, which opens quickly `! ' upon contact with running water. The closure comprises a minor proportion of the area of the surface of the package.
According to this invention, such natural or synthetic polymers are employed as the material for the closure, which i" 15 are durable and stable in the absencQ of running water, but . ., ::
which decompose quickly andtor dissolve ~uickly upon contact ~ , with water. Well sulted for use in this invention are ~
closing materials which decompose and/or dissolve within ~`
..... .....
thirty minutes of being contacted with water. Particularly preferred are sealing materials which dissolve and/or decompose within about twelve minutes after contact with water.
.,, ~ ~ ..... .
Typical of the synthetic polymers which can be employed as closing or sealing materials are polyacrylamides having 25 recurring units of the following formula: j, ¦ R3 f ~;
~ Rl ... _ _ ~.`.,.:"','.'.'`"', ., ~ ....
, ,, " . - . . .
,.,:; ~,,; .
- 3 - `` ~`
i ' ,`' ,' '"' ` ' :,'.`: ,.. ' 10:~74Z7 ; Wherein Rl signifies a methyl radical and R2 and R3'signify "' hydrogen; o~ in which Rl is hydrogen~ ~ is hydrogen and R3 ,, is hydrogen or a methyl radical. Other materials include , polyethyleneoxides having ~olecular weights above about lOO,OOO;
, 5 polyvinyl alcohol; atactic polyvinylmethylether; polyrJinyl pyrrolidone; copolymers o~ ~inyl acetate and vinyl pyrrolidone , (about 60 p~rts vinyl py,rrolidone ~or each 40 parts of vinyl ,, acetate-); copolymers of poly~Jinyl alcohol, polyvinyl acetate ",, and polyethylene oxide (in a weight ratio of 50: about 20:
,~; lO about 20). Typical of the natural polymers are alginates, " cellulose ethers, dextrine, and gelatin. Particularly pre~erred ,,;, sealing materiflls are polyvinyl alcohol and polyethylene oxide.
,, In a preferred embodiment of this invention. the con-~ tainer is ~illed with the pesticide and oxidant~ and i8 closed ',, 15 by sewing it with a thread ~hich is decomposable or soluble in water and comprlsed of a natural or synthetic polymer of the type enumerated above. Particularly well suited for this ~purpose is a thread comprised of polyvinyl alcohol and having ,r~ a diameter of~ about 0.2 to about 1.8 mm. It ~rill be under-20~ stood that threads~having larger diameters can also be employed in other 6ituations.
In a further preferred embodiment of this invention, the container~is filled with the pesticide and o~idant,, and an insert of~natural or synthetic polymers decomposaible and/
or soluble in water is placed between each open section o~
~ the Pilled container in order to close it. l'he insert is then sealed to the contalner by the application of heat and/or pressure.
~ .
.'''' ,"
''.`' ::~
::~
:~ ~ 79~27 In another preferred embodiment, the closure comprises a cap which is adhesively secured or sealed tightly to the material of the container~ and the c~osure in this case com-prises one of the a~orementioned natural or synthetic polymers.
: 5 In a particularly preferred embodiment, the cap conslsts essentially of a polyvinyl alcohol ~ilm. With such a cap the bag, after being charged with pesticide and oxidant, can be ; closed. A strip of the film can be applied along the longi-tudinal edge o~ the narrow side of the empty container in the area of the opening. The movable portion of the film can be folded back over the opening o~ the bag and sealed along the second longitldinal edge to the other wall o~ the container by the application o~ heat and pressure.
According to the present invention, the package for ~ 15 the pesiticides and solid oxidants comprises a container .. , having a closure which opens quickly upon contact with water.
s~ ~ Quick opening of~ the~container and the quick admission o~
~rater~into the container~can~be accelerated by holding the bag materlal unde~r a latent~tension in the area o~ the j ~`20~ opening~by means~of some pretreatment or by m~ans of a s~ ~permanently~elastLc material connected thereto. When the tenslon i9 released by the dissolution and/or decompositlon of the closing materlal~ at least a partial spreading o~
the opening o~ the co~tainer occursJ and results in an scceler-ated admission of water into the container. To accomplish t~hls result~ the bag material can be provided with permanent corrugations ln the area o~ the opening~ perhaps b~ the appli-cation o~ heat or steam in a press, and optionally wlth the use o~ chemical additives to aid in the ~ormation o~ suc~
3 corrugations. Upon closing o~ the container, ~or example by '' : . ,:
~ .
` ~37~;~7 ~:
sewin~ it together with a thread which dissolves or decom~
poses uoon contact with water, the edges of the bag are fitted smoothly against one another, but remain under latent tension, which leads to at least a partial spreading of the opening of the bag after elimination of the closing material. ~-In another alternative, one or more thin wires comprised of `
a permanently elastic material can be threaded into the con- ;
tainer material in the area of the opening. The elastic material is in tension which causes the opening of the con-tainer to spread after dissolution and/or decomposition of the closing material. In a further embodiment, one or more !.`"' permanently elastic threads comprised of natural rubber, -~
synthetic rubber or polyurethane elastomers are provided for ~`
this purpose in the area of the opening of the filled con~
tainer. Such threads are attached merely in the area of i the two longitudinal edges of the material of the container, ` and are under such tension that they will effect an at least :,; , ...
~; partial spreading open of the bag after dissolution and/or ; decomposition of the closing material.
It is essential in this invention that the closure, which dissolves and/or decomposes upon contact with water, .
comprise only a minor portion of the circumference of the container or a minor area of the total surface of the con~
tainer. In the case of alI the examples, the phosphine con- `
centration in the water used for~elimination of the residues did not exceed 0.01 ppm; such water can be safely added to ; ; i i~ customary sewa~e.
~, :
~ ~ ,, . ', - 6 - -~
', '~ ' `'`'.'.' '~:;;: ' .. ,; , ~.;i .
7~LZ7 ~
Within the scope of the present invention, the pesticide and solid oxidant are placed together in a container. Sur-prisingly, it was observed that in bags which consist of a material that is normally readily permeable by water, `~
. 5 water will infiltrate only very slowly after fumigation.
Without being bound by the following explanation, it is assumed that in the case of gradual hydrolysis of metal phosphides, the residue accumulates and obstructs the pores `
of the bag material and/or reacts with the water first entering the bag in such a way that further admission of water is greatly delayed or completely prevented. As demon- `
strated in the;following examples, the closure of this in~
vention made of natural or synthetic polymers which decompose ;;
. ;, ,~,. : ,, and/or dissolve upon contact with running water, provides for the improved elimination of pesticide residue according to the task of the invention, even i~ such materials are ; ~i employed for bags which per se are readily permeable by ; running water.
, .;.. , ..::
~; The container employed in this invention preferably comprises a gas-permeable, flame retardant, tear-proof fabric, such as for example, flber fleece or textile fabrics. The container material can be easily permeable by running water;
by~this~ lt is~meant~that l -cm of such a fabrlc is~penetrated by~at least one~m~l oP~water within 100 seconds under a pressure ;;~
~of 10 cm water column.; Preferably, the fabrics are com-prised of polyvlnyl chloride having a weight per unit area of 240 to about 400 g/m2.
'^ ~ '"~. '' `
: ~ ' ': ' .; . i ;, - 7 - ~;;
",',.'',;
, :,; :, 1037,9Lzr7 By a PVC ~abric we understand a ~abric which consists predominantly of polyvinyl chloride, PVC-mixed fabrics comprising at least about 70 weight percent polyvinyl chloride - can also be employed.
- 5 Wlthin the scope of the present invention, tear-proof fabrics are used as t~e mAterial for the bag. Suitable fabrics , have a tear strength at least about 4 kg/cm both in their ;.~ dry and in their w~ a~ state.
Although the shape of the container is without any ;~-, 10 essential importance in view o~ the setting o~ the problem according to the invention, preferably the container is a ,~ bag. Preferred are bags which are obtained ~rom two slmilar rectangular pieces of material having a width o~ about 4 to about 12 cm and a length of about 6 to about 20 cm. Hose-15 shaped material having a diameter of about 3 to about 10 cm is particularly preferred. The hose-shaped material can be cut to the deeired length and closed at the open ends.
The pesticide employed in this invention contains as its active7~toxic ingredLent a compound which releases phos-`~; 20 ~ `phine~(PH3)~upon~c~ontact with~moisture. Typical of such ~phosphides are inorganic metal phosphides~ such as calcium ; - phosphide, magnesium ph~osphide and aluminum phosphide. The individual phosphide particles can be provided with a pro-tective coating to control the admission Q:~ moisture. Typical coating materials are para~in~ metal stearate, polyethylene oxide or wax like polyethylene glycols. In addition to the metal phosphides, one can also employ inert diluents (silicon dioxide, aluminum oxlde and clays), substance~ which release a gas at moderately increased temperature (ammonium carbamate, .`',` :
., i',',' .
. ~.. , .. . ., , - ~ J
_ ~ 1' . . .... ~ .
~ '. , : . ~ ! .. ~
0 r~ , 1 ... ,. . . :
37~2~7 `.:
ammonium ~arbo~ate a~d sodium blcarbo~ate~ ~trong~ solld bases (sodium oxide~ ~odium'hydrox~de and po~asslum hydroxlde~
,",,~ detergent~ (~lkyl sul~n~te~. ~lkyl~ryl ~ul~on~tes)p :, compressing aides (ta'lcum~ and other additives~ The~e, ~ddl- ~
, 5 tives can be within the protective coating ~or the metal "
," phosphide~ Well suited, for example, i8 a composition sold ,~ ;
,~ by the firm DEGESCH, Frankfurt, (West Germany) under the '';''"
,,~ I trademark "Phostoxin". The ingredient releasing the r. ''.
; phosphine can be in the form of a powder~ a fairly coarse ~, !~'",~ 10 granulate or a pre~orm, pressed obJect. Depending upon size~ "each contal~er will generally contain about 10 to about 100 ,,, g phosphine as~active ingredient. ~ ;~
,' An important aspect o~ the present invention,involves `,, the Joint packing of the solid oxidant in the container ,~, 15 with the phosphlne-releasing actlve, toxic ingredient. The solid oxidant consists of a!substance o~ ixture of substanees .l , which in~ures the quick and co~.plete conversion oP the pesti-cide~ residues~lnto harmless products when the residues are contacted ~Jith water. 'l~en a mixture o~ substances is employed~ ' ,~
the mixture i8 C omprlsed mainly of the actual oxidant, andcan " include a material which will adapt ~he pH o~ ~he water to , the oxidant. In order to assure a quick reaction in water, ~,, .~ water soluble substances and mixtures oP substances can be ` ;~
"~,l employed, Mixtures oP calcium hypochlorite and citric acid ~
in a weight ratio of about 1:1 have proven succe~sful. ~ ' ,,, Potassium permanganate and sodium oxide in a weight ratio of ~ about 40:1 can also be employed. Other suitable oxidants "~"I include mixtures of sodium perborate or potasslum permanganate ,~ ~lith citric acid or sodium percarbonate with manganese salts.
~,l 30 Chromium (VI) oxide iL particularly prePerred. The mixture ~
of substances can also contain'a redox indlcator. The quan- ~ , ~,i tity o~ mixture oP subst~nce~ having an oxidizing e~fect ` ,'~
.
::~
~37~7 ..
; depends essentially on the quantity of phosphine-releasing, "4,' active ingredient; a ratio of about 0.2 to about 0.5 parts by weight by oxidizing substance to one par~ by weight .; phosphine-releaqing active ingredient has proven success~ul.
In order to prevent any reaction between the toxic, active ingredient and the solid oxidant before or during the actual use of the~pesticide for ~umigation, the oxidant can be encased ln a separate envelope made of an inert material, soluble and/or decomposable in water. For this purpose, a . 10 sheathing o~ polyvinyl alcohol or waxl.tko polyethylene glycol i8 particularly sultable. At the same tlme, individual ~j particles, granulates or molded article~ o~ the oxidant can be coated, ~or example, with polyethylene glycol. In the : alternative~ the entire quantity o~ oxidant can be within the ~;l 15 inert, water soluble envelope, ~or example inside a c~osed small bag of~ polyvinyl alcohol or polyethylene~glycol ~ilm.
~ ~ ~Chromium~VI)~ oxide iD~a small bag of 0.1 mm thick polyvinyl s~ ~alcohol film~has proven to be a particularly quick and safe : ; : ~ .
~ acting oxidant;~e~en in the case of a storage time o~ more . . 1 . ~, ~ ~
~ ~ than twelve months, there occurred neither a destruction o~
~the small bag, nor~any reaction of the Chromium (VI) oxide with the phosphine-releasing actlve ingredlent. The e~ective-ness o~ the Chromium (VI) oxide also remained unchanged.
Based~on present experience~ the best ~orm ~or admini-~l 25 stering the phosphide-containing pesticide and solid oxidant ~ 1 .
in a ~oint packing according to this invention consists o~
.l about 10 to about 100 g "Phostoxin" with about 3 to about 30 g Chromium (VI) oxide in a separate~ tight shaathing o~ 0.1 mm thick polyvinyl alcohol ~ilm. Both components are in a bag :
~', . -10-:,'.
'';'~, '' 37 gL~:7 - made of a flame retardan~, tear-resistant PVC fabric readily ~
permeable by steam or running water (weight per unit area ~ ~-about 320 g/m2) having measurements of 8.8 x 14 cm. Pro-vided in the area of the opening between the two lateral ;- 5 parts of the bag are two threads of urethane elastomer under - tension. The bag is closed with a seam formed by a 0.8 mm thick thread of polyvinyl alcohol. ~
; This invention will be more fully understood by refer- ^
. ,. ,. ~,, , , -ence to the following examples. `~
Example 1 Rectangular pieces of 31 x 10.5 cm are cut from a PVC
fabric having a weight per unit area of 322 g/m2, which is pen- ;
~ etrated within about 4 to 6 seconds by l ml running water per ;;, l cm of fabric under a pressure of a 10 cm water column. The ;~
; 15 pieces are placed on top of one another each ;time in double `
~ layers, and are sewn together with a PVC thread along the two .. . .
longitudinal sides. The little bag obtained is turned and ~, filled with 40 g phostoxin powder ("Phostoxin" is a trade mark for a powder containing aluminum phospide as a phosphine-releasing `~
~0 metal ~hosphide,and aluminum oxide and ammonium carbamate and ;~;
a coating of paraffin). 16 g Chromium (VI) oxide are added in a small, closed bag of 0.1 mm thick polyvinyl alcohol film.
'~ Subsequently, the~bag is closed on the still open narrow side by means of a seam formed by an 0.8 mm thick thread. ~;
Example 2 In the manner described in Example l, a bag is made of the 'l PVC fabric easily permeable by running water, and is filled with the components listed there. For closing of the bag, a ` strip (8.8 x 0.5 cm) made of 0.6 mm thick polyethylene oxide film is placed along the narrow side between the walls of said ,;
; ,il ~ .. ;,:
bag, and for the purpose of closing is guided through a film ~
sealing device. ` ;
:~'. ;; :. . :
. '. . , ', ' ' . - 11- ' .,''~; ',.
;.. . .
Example 3 ~37~27 :: . .. ..
~; A bag is made in the manner described in Example 1 using the PVC fabric permeable by running water. Prior to ;
;` filling the bag, a strip ( 9 X 1 cm) made of 0.1 mm thick polyvinyl alcohol film is sealed along the open narrow side ., :,, .
to the outside of one wall of the bag. After filling with the components listed in Example 1, the sealed strip is folded back over the opening of the bag, and is then also sealed to the other wall of the bag.
Example 4 :: .
~i As skated in Example 1, a bag is made of PVC fabric easily permeable by running water, with weight per unit area of 322 g/m . The two pieces are sewed together so that the . .
seam will end along the two longitudinal sides in the area of the opening of said bag just 1 cm before the actual edge.
;; After filling of the bag with 40 g "Phostoxin" powder and 16 g separately enclosed Chromium (VI) oxide, the opening of the bag, with sllghtly folded up lateral parts, is moved over two urethane-elastomer threads, kept under tension,~and these threads, while maintaining their tension are sealed with;two~pieces of PVC fabric in the area of ~;
their two longitudinal~edges, and these two pieces of PVC ~
.. . ~ : . .
fabric are sealed together, too. Subsequently the still ~ open bag is closed by a seam of an 0.8 mm thick polyvinyl ; ~ 25 alcohol thread without interferring with the elastic threads.
~ The effectiveness of the form of administration accor-;~ ding to the invention was examined with a view toward the safe and complete elimination of pesticide residue.
Specifically, the time required for complete conversion of ;~
`~ 30 residue in water, and the quantity of phosphine occurring ~;
,.. .
.. ~:
j -12-. . ~ .
3~ Lf~~
. `;thereby in the water were determined. For purposes of com- ~ `
- parison, other packings for phosphide-containing pesticides ;;
.. ~ . ;.
were also tested~
. ;:: . , A. Bag of a PVC fabric, described in Example 1, ~
. 5 with contents as stated there; however, the ;
~. ~'.i.,.
bag was closed with conventional thread not dis~
solving or decomposing quickly in running water. '~
B. A joint form o administration for a phosphine- ;;
releasing, toxic, active ingredient and solid oxidant as in the German patent application : i.. -:
22 06 494.
. !`: '. . ~.
C. A paper bag as used in case of~a commercial ;`
; phosphine-releasing preparation (DETIA Ga~ B
- Trade Mark). The known bag was ~illed with 40 g "Phostoxin" powder and was closed again. C
, .
` D. The known paper bag, as stated in case of sample C ~DETIA Gas Ex-B - Trade Mark)~ was filled ;~, with 40 g "Phostoxin" powder and 16 g Chromium ....
` (VI) oxide in a separate envelope made o poly- `
.~ . :,:
', 20 vinyl alcohol film, and was closed again.
s~ As a starting materlal for the examinations, residues in the~above listed;samples were used which resulted after 120 ~;
hours~of fumigation o~f grain (the samples in each case were inserted 35 cm deep~into loosely heaped up and subsequently `=~
covered up grain) under the same conditions. For the elimi-` nation of the fumigation residues, the samples were added to ~ `~
.,., , ~ .
`~ 300 ml of water. ~They~were stirred in occasionally and sub-.l merged, and the time up to the complete conversion of all t¦~ phosphide residues~was determlned. After expiration o this time period, the concentration of phosphine occurring inS the water was also determined. The determination o the phosphine content was accomplished essentially according to .:, :, :, ~ ., , - 13 - ; ~
~ 3~;
::
~37~27 .. ~ the instructions by White and Bushey in J. Am. Chem. Soc. 66, pp. 1666-72 (1944). The complete elimination of the .. fumigation residues is accomplished when all phosphine developing components h~ve been converted.
. ~ 5 The results of the experiments are presented in tl;e . following table.
''`'':' . .
;~ TABLE
Elimination of the residues ~rom the forms o~ administration .~ o~ phosphide containing pesticides~ according to the inven-~ 10 tion (1 to 4) and partly ~nown (A to D)~ accumulated a~ter i.~ their appllcation . . . _ .
,i, Samples Time to complete Phosphine content eliminatlon in the water used 1 70 to 180 min's below 0.01 ppm ; 15 2 ; ~80 to 220 min's below 0.01 ppm 3 ~ ~ 60 to 150 min's below 0.01 ppm ,........ .
4 ~ :50 to 140 min's below 0.01 ppm .' ~ ~ A~ ~ 500 ~o 800 min's~ below 0.01 ppm B ~: 3 to 450 min's below 0.01 ppm :
~1, :20 C after l?o hrs no above 50 ppm . complete conver-',,',;',,1~: slon .
D a~ter 120 hrs no above 50 ppm ;.. , complete conver-'~.'k~ 25 sion ..., ,~
. ..
' . -14-;~''',''`
,;,, I .
,::, ~
~:
16~79~Z7 From the results of the experiments it is apparent that under the stated conditions, the same for all samples, the elimination of the resldue with the form of administration of this invention requires conslderably less time than the eli-mination of residue using kno~m forms. This is particularly remarkable in view of the fact that the materials used ~or the bags are really easily permeable by running water. It is completely surprising that there is no analytically determinable phosphine content in the water when packages of thls invention are employed ~or the el~mination o~ pestlclde residues. Since the complete elimination And/or complete convers~on o~ the phosphide-containing pesticides into harmless products repre-sents an essential aspect in case o~ use of such agents, the l present invention does lead to a superior type o~ pesticide.
'""'"''1; ~ .
, I : : ' : ;
:~ ; 1 ; ~ ~
:
`'~
'"''.: ' . .
'1 ~ .
,~, ,'''.1 ' .` , .
Claims (13)
1. A packaged pesticide comprising:
a container having walls of a gas permeable material and an opening;
a closure for the opening of a material that decomposes quickly or dissolves quickly upon contact with water, said closure comprising a minor proportion of the area of the surface of the closed package;
a metal phosphide within the container able to release phosphine upon contact with moisture; and a solid oxidant within the container able to oxidize the metal phosphide residue to non-toxic products when the oxidant and residue are contacted with water.
a container having walls of a gas permeable material and an opening;
a closure for the opening of a material that decomposes quickly or dissolves quickly upon contact with water, said closure comprising a minor proportion of the area of the surface of the closed package;
a metal phosphide within the container able to release phosphine upon contact with moisture; and a solid oxidant within the container able to oxidize the metal phosphide residue to non-toxic products when the oxidant and residue are contacted with water.
2. Packaged pesticide according to claim 1 in which the container is a bag.
3. Packaged pesticide according to claim 1 in which said container is closed with a natural or synthetic polymer, which decomposes quickly upon contact with running water or dissolves quickly in water.
4. Packaged pesticide according to claim 3 in which said polymers decompose or dissolve within about 30 minutes of contacting water.
5. Package d pesticide according to claim 4 in which said polymers decompose or dissolve within about 12 minutes.
6. Packaged pesticide according to claim 1 in which said closure comprises a seam made by a thread, said thread comprising a natural or synthetic polymer which decomposes quickly upon contact with running water or dis-solves quickly in water.
7. Packaged pesticide according to claim 1 in which the closure comprises an insert of natural or synthetic polymers deposited inside an opening between the walls of the package and soluble or decomposable in water.
8. Packaged pesticide according to claim 1 in which said container has an opening and the closure comprises a cap encompassing the bag opening, said cap comprising a natural or synthetic polymer soluble or decomposable in water.
9. Packaged pesticide according to claim 1 in which the closure is comprised of polyvinyl alcohol.
10. Packaged pesticide according to claim 2 in which the closure comprises a material which is soluble or decomposable in water, said closure material engaging sub-stantially permanently elastic material, said elastic material being under tension, and further wherein said elastic material facilitates the at least partial opening of the bag after the closure material dissolves or decomposes in the water.
11. Packaged pesticide according to claim 1 in which the container comprises a flame resistant, tear-proof fabric, secured along free edges to define the container.
12. Packaged pesticide according to claim 11 in which the fabric is permeable to the extent of permitting the passage of at least 1 ml of water through 1 cm2 of fabric within 100 seconds under a pressure of 10 cm water column.
13. Packaged pesticide according to claim 12 in which the fabric consists essentially of polyvinyl chloride, said fabric having a weight per unit area of about 240 to about 400 g/m2.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2414548A DE2414548C3 (en) | 1974-03-26 | 1974-03-26 | Pesticide and solid oxidizer in one package |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1037427A true CA1037427A (en) | 1978-08-29 |
Family
ID=5911213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA200,667A Expired CA1037427A (en) | 1974-03-26 | 1974-05-23 | Packaged pesticide |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5024435A (en) |
| AT (1) | AT333544B (en) |
| CA (1) | CA1037427A (en) |
| DE (1) | DE2414548C3 (en) |
| ZA (1) | ZA743259B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287171A (en) * | 1978-06-10 | 1981-09-01 | Degesch Gmbh | Storage stable quickly acting tablets for combatting vertebrates preponderantly in underground structures |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2607638C2 (en) * | 1976-02-25 | 1984-08-16 | Degesch Gmbh, 6000 Frankfurt | Device for pesticides containing earth metal phosphide and / or alkaline earth metal phosphide |
| JPS54155179U (en) * | 1978-04-20 | 1979-10-29 | ||
| DE7906765U1 (en) * | 1979-03-10 | 1979-07-05 | Haufe Ludwig | Pesticide Pouch |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2206487B1 (en) * | 1972-02-11 | 1973-08-02 | Deutsche Gesellschaft fur Schad hngsbekampfung mbH, 6000 Frankfurt | DEVICE FOR EARTH METAL PHOSPHIDE AND / OR EARTH CALIMUM METAL PHOSPHIDE CONTAINING ANIMALS |
| DE2206494C2 (en) * | 1972-02-11 | 1973-12-13 | Deutsche Gesellschaft Fuer Schaedlingsbekaempfung Mbh, 6000 Frankfurt | Process for treating the residues of pesticides containing earth metal phosphides and / or alkaline earth metal phosphides that remain after the outgassing |
-
1974
- 1974-03-26 DE DE2414548A patent/DE2414548C3/en not_active Expired
- 1974-04-17 AT AT318974A patent/AT333544B/en not_active IP Right Cessation
- 1974-05-21 ZA ZA00743259A patent/ZA743259B/en unknown
- 1974-05-23 CA CA200,667A patent/CA1037427A/en not_active Expired
- 1974-06-11 JP JP49066444A patent/JPS5024435A/ja active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287171A (en) * | 1978-06-10 | 1981-09-01 | Degesch Gmbh | Storage stable quickly acting tablets for combatting vertebrates preponderantly in underground structures |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2414548B2 (en) | 1978-09-21 |
| DE2414548C3 (en) | 1979-05-17 |
| JPS5024435A (en) | 1975-03-15 |
| ATA318974A (en) | 1976-03-15 |
| AU6979074A (en) | 1975-12-11 |
| DE2414548A1 (en) | 1975-10-02 |
| ZA743259B (en) | 1975-08-27 |
| AT333544B (en) | 1976-11-25 |
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