CA2118311A1

CA2118311A1 - Packaging for hazardous compositions

Info

Publication number: CA2118311A1
Application number: CA002118311A
Authority: CA
Inventors: Leonard Hodakowski; Samuel Gouge; Glenn Knudsen; Steven Mcevoy
Original assignee: Individual
Current assignee: Bayer CropScience SA
Priority date: 1992-04-27
Filing date: 1993-04-26
Publication date: 1993-11-11
Also published as: EP0639145B1; US5330047A; GR3024696T3; JPH07506073A; WO1993022215A1; EP0639145A1; MX9302421A; ATE157944T1; US5279421A; DE69313844D1; ES2106345T3; DE69313844T2; DK0639145T3

Abstract

The present invention relates to a containerization system comprising at least one inner water soluble bag located within an outer water insoluble bag. The inner water soluble bag contains an agrichemical that does not sustantially dissolve the bag. The outer water insoluble bag is flexible and collapsible and has a low stretchability; it is made of laminated polypropylene (outer layer) polethylene (inner layer).

Description

2118~

~~ ~WO 93/22215 PCI~EP93/01007 PA~KAGING FOR HA~ARDO~S COMPOSITIONS

This application is a continuation-in-pa~ of U.S Serial n 08/02û.506 filed on Febru~r 22~ 1993, which is continuation-in-par~ of U.S. Serial n ~7i~74 608 filed on ApriI 27, 1992.
BACKGROUND OF THE INVENTION -I. Field of the invention The invention relates to a containerization system and ~o containers which are particularly suitable for storing, packaging and transporting fluid agricultural chen~ical compounds, such as pesticides and concentrates thereof.
:: II. Discussion of the Prior Art A~ present, most hazardous and toxic liquids are stored in metal drums 15 :~ or? :where smaller quantities are involved, in plastic containers. Hazardous composihons~ especially ag~icultural chemicals (agricherr~ical), are formulated n varlous compositions.
Agrichemicals in liquid form, parhcularly in the fonn of concentrates, are most convenie~lt for fanners because of the ~lative ease with which they can2 0 be handled. l~ere are, nevertheless, difficulties in handling such liquid compositions. There is a danger of splllage or leakage if holes develop in con~iners that are acciden~lly dropped and thereby crack or fail. Containers have been developed which possess: great resistance to impact and shock. W~ile such containers ar seeure under nonnal stora~e and handling condihons, in the 2 5 ~ event of ~ an accident, for ex~mple duIin~ ~ansporting, there remains an appreciable risk of spillage or leaka~e with rapid loss of liquid. Lealcage of toxic ,and hazardous chemicals can create dama~e to the envi~nment.
The chen~ical and pa~kaging indus~ies have long sou~ht a secure j -cont~incr which provides ~ suff1cient safegu~rd for those handling it, such as 3 0 farmers~and ~ansporters, as well as adequate protec~on ~r the environment.

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WC~ 93/22215 PC~/~:P93/010~7 ~ -It is known, for example, to package agrochemicals in soluble bags or sachets made frorn water soluble films. While considerable e~fort has been made and tremendous success in improving the strength of such bags, there s~ill remains problems with the fragility of such bags resulting from sudden impact, for example from dropping.
One solution for this problem is exempli~led in patent applica~ion WO
89/12590 where a water soluble bag containing a liquid ag~ichemical composition is encased in an outer container made of ngid or semi-ngid polymer such as polypropylene. Currently, ~here is a product available commercially in France called Geludose (Clba-Geigy) which is also a water soluble bag which is stored in a rigid polymeric container. U.S. patent 3,892,905 describes water soluble packages. In that patent, overwraps are described such as single layer polyole~lns cellophane glassine, foils, PVC, waxed paper and thelike or combinaisons of those as laminates. However the intented use of these ~ ~and the selechon criteria for these were base ~on the ability of these composi~ons to protect the inner bag from water or humidity contact. The only exasnples actually offered by~ the p~tent is a cellophane overwrap. Such external container may also break under violent shock and the broken con~ner may have edge which may cut ~he water soluble bag which is in~side of it.
2 0 In its working example. the pnor art describes a container wherein ~r.e outer container comprises a rigid body-part (which contains the inner bag, i.e.
the area within which Ihe bag c~ move and a shock absorbing rigid part separated from the body part by mean of shoulder. or shock absorbing s~ipes wherein the inner bag cannot move and/or deform completely. In other words, a body part which ls actually the outer container and another added shock absorbing ~art which is not p~ of the outside container.
' 1 ' When designin~ con~ainers for protec~ing objects having a de~ee of fragility, ngid m~terials a~ the firs~ choice despite ~hç high cost compared with many flexible polymers.

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:i WO 93/22~1~ YCIJEP93/01007 An object of the instant invention is to provide a new containerization system to contain hazardous chemicals which is safe for everybody because of its increased resistance ~o leakage.
Another object of the instant invention is to provide a new 5 containenzation systent ~o contain agrichemicals which is easy for the farmer to m~nipula~e.
Another object of the instant inven~ion is to provide a new cvntaineriz~tion system to contain agrichemicals which is as much condensed as possible, using the least amount of space.
Another object of the instant~invention is to provide a new con~ainerization~ system to contain agrichernicals which is easy to open, easy to manufacture (and thus cheap)j and which has a good shock absorption, that is to say, which has a good resistance tO shock as impact and blows.
Another object of the~ instant invention is to provide a new 15 ~ ~ containeriz~tion system to contain agrichemic~ls which is stable both at high and low temperatures.
Another object of the ins~ant invention is to provide a new containerization system andior a new method to contain agrichemicals which diminishes the risks of pollution. ~a 2 0 ~ A further oyect of the present invention is to provide a containerization system which has no lids, and is easier and cheaper to manu~ac~ure and has no problem of lids coming of~
A further objec~ of the present inven~on is to provide a new containerization for~grichemicals which reduces the waste disposal of contaminated con~ners and overpacks.
A further object of the present invention is to provide a new containenz~ion system for agrichemicals which allows very efficient packin~
and s~oring due to flexible, opnon~lly flat bags.
Other objects of the invention will ~eteer appear from the ~ollowing 3 0 descripion.

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WO 93/22215 PCr/EP93/01ûû7 ~; ¦

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An object of the invenoon is to avoid this nsk of spill or po]luuon and . I
to increase the safety of water soluble packaging of agrichemicals. ~ -~; SUMMARY OF THE INVENTION
S The present invention relates to a containerization system comprising a cold water soluble inner bag cont~ining an agrochemical composition, the said inner bag being contained in an outer bag made of a material which is in the forrn of a flexible and sealed (preferably heat sealed) polymeric film and is insoluble bo~ in the cornposition (if liquid or gel) contained in the inner bag and in the solvent which may be comprised in the agrochemical composition contairled in the inner bag. the polymeriG film having a low stre~chability.
Fur~hennore, in a preferred embsdiment the surface of the area delimita~ed by the extemal largest outline of the inner bag when inside the outer bag should be at least 5% less than~the sur~ace area delimita~ed by the external :, ~.
largest outline of the e~fectively containing part of the outer bag when containing ehe inne~ bag. ~ ~ j The agrichen~ical composition which is contained in dle irmer bag of the invention may be solid, or preferably fluid. A solid composi~on may be in ; the~form of powder, dust, ~ules. By fluid co~position, it is meant a 2 0 ~ c~mposihon which may be in fonn of a liquid or a gel, or also of a solid such as powders or~dusts~ or~ granules, provided that this solid can deform or even floweasily. However, the gels are prefe~Ted in this inven~on.
Another~advant~ge of the ~flexible bags o~ the invention is that they have no p~s able~ ~o damage other nei~hbo:ring bags.
2 5 ~ ~ ~ Another ~dv~nta~e of the flexible b~gs of the invention is that they have no lids which may come o ff due to possibly we~k seals. ~
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By polymeric ~llm havin~ a low ssretchability. it is means a ~llm whose elonga~ion at bre~; i5 less than 100 %, preferably less than 30 % .
Due to their complete flexibili~y, the waser insoluble bags in this 3 0 ~ inven~ion~y coll~pse whén void.;This is espeeially advantageous by crea~ng ' less garbage ~or l~d filling than known sigid or semi-rigid outer containers.
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W;D 93/22215 PCr/EP93/01007 The objects of the invention can be achieved in full or in part by means of the inven~on.

DETAILED DESCRIPTION OF THE IN~E~TION
I~ has been discovered that when soluble bags are contained in a laminated outer bag that the objects of the invention can be met, especially theresis~nce to brealcage.
The containerization system of the present invention comprises one inner water soluble bag containing a hazardous composition wherein the inner bag is contained in a sealed outer bag and the walls of the outer bag comprisinga laminate of an outer layer of polypropylene and an inner layer of polyethylene.
The expression toxic or hazardous compositions, as used herein means an industrial chemical, for example an agrichemical composi~ion, which, if released in the quan~ity or concen~a~on normally in storage and shipping corltainers, may cause damage to the environment or be injunous to a person contacted by it and may either be in solid or liquid fonn, although liquid is preferred.
By outer bag, as used herein, is meant an overwrap designed for containing the inner water soluble bag and prot~cting it ~rom humidity and 2 0 water as well as provide an increased degree of protection rom breakage when compared with known over vraps in the art. Par~icularly, the overwrap compriscs a laminate OI an outer layer o~ polypropylene fillm and an inner layer- of polyethylene film. Each polymer may contain other ingredients, i.e. additive to a~ect sdffness, e.g. pl~s~icizers or for affecting other properlies as desired, ~; ~ 2 5 especially stretch~bility. The ~otal thickness of the film overwrap outer bag is from about 2~ to 500 microns, prefçrably 30 to l00 microns. llle thickness of each individual l~yer being ~pproximately half the total ~hickness although other thicknesses as desired can be chosen. The ~wo polymeric layers can ~ made into a laminate by ~ny means known in ~he art, for example by co-extrusion or 3 0 he~t lamina~ng a;fter individu~l extrusion. The outer ba~ is formed by sealing, preferably heat se~ling the three sides of a s~ck leavin~ an opening which tO
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2ll831~ i WO93/22215 PCI/EP93/01007 ~:

place the inner saclc followed by a ~lnal sealing of the fourth edge. It will benoted that when forming a seal, the inner polyethylene layers are sealed together.
The heat seals are made at an external temperature and humidiy and 5 sueh that maximum handling strength is achieved. This is simply done by one skilled in the art and re~uires a minimum of experimentation. Since temperature an~ humidity will of course vary with the thickness of the laminate, as will theheat temperature and cont~ct time, this too is well within the skill of the art.After sealing, the resulting package resists d~mage due to impact better than 10 other known outer wrap materials. The size is pic~ed based on packaging consideration, bu~ it is preferred that the inner dimensions of the overwrap areno mare than lS % ~reater of the outer dimensions of the inner bag preferably ;; 10 %, most preferably less than S %.~
The~ overwrap is preferably not filled to complete capacity because the 15 unused capacity ~ves additional shock resistance, i.e., resistance to breakage when dropped, ~ansported or stored. This unused capacity may or may not eontain air or inert gas. An absence of air or inert gas in the unused capacity further improves shock resist~nce. However in deciding how mueh unused capacity, or absence of ~ir or iner~ gas, to provid~ the advan~ages of shock 2 0 resistanee must be b~laneed ag~inst the need, if any, for shock resistance and the cost of providing shock resist~nce. For example~ if the outer bag is stored and/or transpor~ed in a ri~id shock absorbing container, ~hen it may not be as helpful to provid~ this unused~ capaci~. ~
Also the capacity to which the ou~er bag is filled, and whether the 2 S~ unused capaci~r does or does not ~ont~in air is affected by whe~her it is desi3 ed to have~the bag sink or float.
The haz~rdous composition of the invention and the wall of the inner bag it con~ins are chosen so that the composi~ion does not substan~a}ly dissolve the w~ll of the b~g and does not substantially perrnea~e through i~ By 3 0 this, it is meant tha~ the dissolu~on and permeation are each independently less , ~
SUBS~tTlJTE SHEET

~ ~ W O 93/22215 2 ~1~ 3 11 pc~r/E ~ 3/01007 than 5 % more preferably less ~han 1 %, and most preferably less than 0,5 ~o of the total weight of the bag.
The preferred agrichemical compositions used in this invention are concentrated compositions which are supposed ~o be diluted with water in a 5 spray tank before use and spraying by the farmer.
The agrichemical compositions which may be used in this inven~on and which may be contained in the outer or the inner container may be in dif~erent physieal forms.
They may be in the form of a solid sueh as powders7 preferably water 10 wettable powders, or ~ranules, preferably watçr dispersible granules.
The agnchemical compositions of this invention may be also in the forrn of a (pre~erably non-aqueous) liquid, such as a solution or a dispersion or an emulsion in an organic solvent; this liquid may be more or less viscous; it may be a very fluid liquid such as a liquid having a Brookfield viseosi,y beh~een 100 and 1,000 centipoise, or it may be a viscous liquid, such as a liquid having a Broold~leld viseosity *om 1,000 up to 30,000 centipoise (Measurements of viscosities in this specif~cation are made with a Brookfield viscome~er at 30 C with a flat plate rotating at 20 revolutions per minute).
A ~urther advantageous physical form elf the agnchemical compositions 2. 0 of this inven~ion is the form of an organic gel.
Gels which are of p~icular interest in this invention are organic gels whieh have~ viscosities of 600 to 30,000 centipuise, prefera~ly 1,000 to 12,000 Cenhpoise~and sdll more prefer~bly 1,000 to S,000 centipoise.
Anolher feature of ~he ins~nt inveration is an insecticidal composi~on and S insecticidal unit wherein the storage modulus (G' measured as hereafter defined, under speed of oscillations of 1 rdls = radian per seconde~ is in the range of 1 to 10,000 Pascal, preferably 10 to 5,000 P~sc~
The gel m~terial which is used in this invention is essentially a material which has a phase di~ference phi between the controlled shear s~ess and the 3 0 resuldng shear str~in such that tg(phi) is less than or equal to 1.5, pre~erably less than or equ~l to 1~2. Tg(phi) is the tan~en~ of the phi an~le (or phase difference).

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WO93J2~215 P~ P93/01~07 The measurement of phi is made by means o~ a dynamic rheometer. Dynamic rheome~ers which are appropriate to measure phi are known and available commercially. They usually have a flat fixed plate and a rotating eone or plate,~; or a so-called couette measuring system. Other mechanical systems are also 5 available. Generally the choice of one system or another is made according to the recornrnanda~ons of the seller of the rheometer, and is adapted to the kind of compound, gel or liquid, which is tested. The particular choice of a specific type of rheometer is something well known by one skilled in the art of rheology. A
ro~ating plate over another plate or a cone rotating over a plate are o~ten more10 appropnate when a ~el or a viscous liquid is tested. When two kinds of sys$emfor the rheometer are possible, similar values of phi are actually measured. Thecone (or the plate or the couette) is caused to rotate by means of a controlled speed motor, the rotation is a sinusoidal one, i.e., the strain and the angular displacement chan~e as a sine function with time. Tg(phi) is equal to the ratio 15 ~"/G', wherein G' is ehe storage modulus (represents the behavior of a perfect solid); G" is the loss modulus (represents the behavior of a pe~fect }iquid). G'and (:}" are expressed in Pascal for a given ro~ational speed (radian per second).
G' and G", and thus tg(phi), may depend on the amplitude of the osci]lations (percentage of str~in) of the rheom~ter; however, there is generally a 2 0 so-called Yiscoelastic plateau whereby the values G' and G" of a gel do not ~;~ depend substantially on the said a~T plitude. This means Ihat in ~he condiuons of ; ` the tost under ~he viscoelastic pl~teau, the structure of the gel is main~ed and n o des~uc~on ~o~ th~ gel into a liquid happens. Of course, the measurement of Ci' and G" of a gel~ is made under the conditions of this viscoelastic plateau, just2 5 because it corresponds to the nonnal ~el structure whlch is precisely what is tested.
G' and G", and thus tg(phi), m~y also depend on the speed of the oscillations (time to reach the chosen percent~ge of s~ain; expressed as .~dian :~ ; :
per secsnde) of the rheometer. However, when the ~el is well strucrured, there is 3 0 not so much YaI~at on from one speed to another. In order to have a reason;3ble measurement of the properties of a gel, it iS generally preferred to operate in SUBSnTUTE 5HEET
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211831~ ' -WO93/~2~1~ Pc~/~pg3/01~07 g conditions whereby the gel is not too much stressed, that is to say at speed such as 1 rd/s. Of course, measurements at higher speed may also be made.
It is known that a gel is generally a colloid in which the dispersed phase has combined wlth the continuous phnse to produce a viscous, jelly-like product; it is also a dispersed sys~em consisting typically of a high molecular weight compound or aggregate of small particles in very close association with a liquid. The gels used in this invention have basically an organic continuous phase. In contrast, most of the existing materials/gels are water-based and havean aqueous c~n~inuous phase. Furthermore, the gels used in this invention have essent;ally one physical phase, at least as can be seen when visually observed.
Preferred gels in this invention are also gels which can be divided by cutting and whose cut parts are able to merge together by simple juxtaposition.
When the fluid agrihemical composi~ions cont~uned in the inner bag of the invention is not a gel, it may be a material which has a phase difference phi besween the controlled shear stress and the resulting shear strain, such that tg(phi) is greater than or equal to l.S . More generally, it is ~hen a liquid which has a phase difference phi between the controlled shear stress and the resultingshear s~in, such ~hat tg(phi) is grater than or equal to 5. Such li~uid have generally a viscosity less than 12,000 cps 2 0 The non aqueous a~richemical compositions which are used in this in~ention are preferably less than 3 %7 more preferably less than 1 %.
The choice of the particula physical form of the agrichernicals used in this inven~on depends on the p~ticular agrichemicals which are imrolved.
The following features, alone or in combina~ion, constitute pre~erred 2 5 features of ~e invention: ~
Accordin~ to one feature, the hazarAous product is pre~erably an ; ! I a~richemical, or more precisely a plant protectian agent (including pesticides, such as insecticides, fungicides, hcrbieides, acaricides or nematocides) or plant growth re~ulators or plant nutnents, or an ~djuvant for the activity for plants as 3 0 activity promoters including penetratin~ agents, synergists, antidotes, sticking :

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WO 93/Z221~ PC~EP93/01007 _ agen~, spreaders, activators, compa~ibility agents; adjuvants for the water soluble b~gs as plasticizers.
The invention is not limited to some speci~lc agrichernicals; a list of many agrichem~cals which can be used in the poly-bag system of the invention 5 inc}udes:
fungicides such as triadimefon, tebuconazole, prochloraz, triforine, tridemorph, propiconazole, pirimicarb, iprodione, me~alaxyl, bitertanol, iprobenfos, flusilazol, fose~yl, propyzamide, chlorothalonil, dichlone, mancoæb, an~raquinone, maneb, vinclozolin, fenarimol, bendiocarb, eaptafol, benalaxyl, thirarn; : ~ -herbicides (or defoliants) such as quizalofop and its derivatives, acetochlor, metolachlor, imazapur and imazapyr, g}yphosate and gluphosinate, butachlor, acifluorfen, oxyfluorfen, bu~alin, fluazifop-butyl, bifenox, bromoxynil, ioxyni}, diflufenican, phenmedipham, desmedipham, oxadiazon, 15 mecoprop, MCPA, MCPB, linuron, isoproturon, flamprop and its derivatives, ethofumesate, diallate, carbetamide, alachlor, metsulfilron, chlorsulfuron, ~; ~ chloIpyralid, 2,4-D, tribufos, ~iclopyr, dielofop-methyl, sethoxydim, pendimethalin, trifluralin, ame~yn,: chloramben, amitrole, asulam, dicamba, bentazone, a~azine, cyanazine, ~iobenc~rb, pr8metryn, 2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin~3-one, fluome~uron, napropamide, paraquat, bentazole, molinate, propachlor, imazaquin, metlibuzin, tebuthiuron, oryzalin;
insecticides or nematicides such as ebufos, carbosulfan, amitraz, van~idothion, ethion,~tri~zophos, propoxur, phosalone, permethrin, cypermethrin, parathion, me~hylparathion, diazinon, methomyl~ malathi~n, 2 5 lindane, fenv~lerate, ethoprophos, endrin, endosulfan, dimethoate~ dieldrirl, dicrotophos, dichlolprop, dichlorvos, azinphos and i~. denvatives, aldrin, cyfluthrin, deltamethrin, disulfoton, chlordimefQml, chloIpyrifosi carbaryl, dicofol, thiodic~rb, prop~rgite, d~meton, phosalone; and plant ~rowth regulators such as gibberellic acid9 ethrel or 3 0 ethephon, cycocel, chlormequat, ethephon, mep;quat.

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21183~ ~ ' i . .,~ ! .
WO 93/~2~15 P~r/EP93/01~07 According to another feature, the inner bags of the inven~on are filled to at leas~ 60 % of capacity with the agrichemical composition, more preferably to at least 70 % of capac;ty, s~ill more preferably 80 to 99 % of capacity and most pre~erably 85 to 95 % of capacity.
When the bag is filled with solids, the capacity is rela~ive to buLk volume of the solids, not the actual particle volume of the solids.
In practice the agrichemical compositions used in the instant invention generally comprises the active ingredient(s) in association with other ingredients, for example surf~ctants, dispersants, thiclceners, antifoaming, -10 antifreezing, gelled~ agents or ~elling agents.
According to another feature the inner bags used in this invention are made of a polymenc water soluble film, more precisely a cold water soluble film. Cold water soluble means soluble in water at temperature less than 35DC, general!y be~ween 5C ar d 35C. The thickness of this film is generally between10 and 500 microns, preferably between 20 and 100 microns.
; The chernical nature of the enveloping fillrn constituting the inner bag can vary quite widely. Suitable materials are water soluble (or possibly wa~er dispersible) maten~ls which ~e~insoluble In the organic solvents used to dissolve or disperse the a~richemical ac~ive ingredient. Specific suitable 2 0 materials include polye~hylene oxide, such as polyethylene glycol; s~arch and modified starch; a~kyl and hydroxyalkylcellulose, such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropyl cellulose;
carboxymethylcelluloso; polyvinylethers sush as poly methyl vinylether or poly(2 methoxyethoxyethylene); poly(2,4-dime~hyl-6-~iazinyle~hylene;poly~3-2 5 morpholinyl ethylone~; poly(n-1 ,2,4-~iazolylethylene); poly(vinylsulfonic acid) ; polyanhydrides; low molecular wei~ht melan~ine-~ormaldehyde resins; low molecular weight urea formaldehyde resins; poly~2-hydroxyethyl methacr~late) ; polyacrylic acid and its homolo~s. Prefer~bly the enveloping fillm comprises or is made from poiy~inyl alcohol (PVA). PVA is generally par~ially or fully 5~-3 0 alcoholysed or hydrolysed e.g. 40-100 %, preferably ~0-99 % alcoholysed or 5lJ8STITUTE SHEET
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hydrolysed, polyvinyl acetate (or other ester) ~llm; copolymers or other derivatives of such polymers can also be used.
Preferred materials for constituting the bags in this invention are polyethylene oxide or rnethylcellulose, or polyvinyl alcohol. When poly~inyl S alcohol is used, it is advan~ageously a 40-100 % alcoholysed or hydrolysed, ` preferably 80-99 % alcoholysed or hydrolysed, polyvinyl acetate film.
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The polymeric material constituting the wall of the inner bag may be dissolved in similar conditions in co]d water (cold means less than 35~C).
The inner bag of the containerization system of the invention may be 10 opened preferably through an easy ~earing tab. Optionally, the bag may have anoteh permitung to easier tear off the tab, An advantage of polyester water ~;
insoluble bag is to permit to ~tear off the tab more easily than polyole~1ns water insoluble bags. Thus there is less risk to damage the inner bag when it has to be opened;~ less nsk to damage includes less risk of break and leakage. This is 15~ ; especially impor~nt;for fD~ners who, rather often, have wet hands or are ;wearing g~oves and may have unsuitable moves causing damage to the bag.
For the~same reasons, the water insoluble~bags are preferably biags which can be easily~ resealed. Thi~s is easier to make with polyesters films. The resealable part of ~the bag may have a pressur~seal, such as a pressure resealable 2 0 ~ ~ top, or a so-called zip-lock bag ~eal; it may be too a zippored top; this resealable top may ~be unzipped (opened) and rezipped (reelos,.,d). l'hese resoluble bags are mor~ envLronment friendly embodiment of the invention because any spill of ; agrichemicals in~the~outer~bsg at the time~the inner bag is o~ened may be c on~lned inside thé outer~ water insoluble bag. ~ - -2 5~ The~ preparanon ~or m~nufacturing of the containenzation system of the invension can be done according the~l~nown process o~prepara~on or mjanufacturing of iwater soluble bags. As a prac~ical manner, the f~st bagi(that isl, -: to say the inner bag, or inner bags if ~more than one) is~ prepared ~rom a water soluble,~film, oF~tionally by p~lni sealin~ or he~t sealing Then i~ is filled with 3 0 ~ agriche~T~ical comp,3sition and~the bag is finally closed.

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Another particular embodiment of the invention is a containenzation system which comprises at le~st one inner cold water soluble bag containing an ~, agnchemical compositionS the containerization system further comprising an outer water insoluble bag made of a flexible and sealed (opeionally heat sealed)polymeric ~llm, which is insoluble both in the composition (if liquid or gel) contained in the inner bag and in the solven~ which may be comprised in the agrichemical composition eontained in the inner bag, the polymeric film having a low s~etchability.
Another particular embodiment of the invention is a containenzation - 10 system which comprises at least one inner cold water soluble bag con~ining an a~richemical composi~ion, the containerization system further comprising an outer wa~r insoluble bag made of a flexible and sealed (optionally heat seaied) polymeric filrn, and wherein, the surface of the area delimitated by the external largest outline of the inner bag when inside the outer bag is at least 5 % less than : ~ ~ 15 the surface area delimitated by the exterTIal largest outline of the effec~ively containing p~ of the outer bag when containing the inner bag. That is to say theinner bag is able to moYe freely in the outer bag in such a way ~hat if any side of the inner bag comes into close contact with the outer bag~ the opposite side of : the said inner b~g is at a dist~ce from the closest side of the wall of the outer `;2 0 bag which is at leas~ 5% of the distance between ~he contac$ing side and the ~;: opposite noncontacting side. This allows room ~ the inner bag to recoil when :: con~ct is made ~rom an abrupt impact.
Another particular embodiment of the inven~ion is a containerization system which comprises at le~st one inner cold water soluble bag containing an 2 5 : a:grichemic~l co~nposi~ion, the containenzation system further comprising an outer water insoluble bag m~de of a flexible and sealed ~optionally heat sealed) .
polymeric film, which is insoluble both in the cumposition (if liquid N gel) con~ned in the inner b g and in the solvent which may be comprised in the agrichemical composi~ion contained in the inner bag, I:lhe polymeric fiIm having3 0 a low stretchability. and wherein, the surf~ce of the area delimitated by the :` extern~l lar~est outline of the inner ba~ when inside ~he outer ba~ is at least 5%

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2118~
WO 93/22215 PCr1EP93/01007 less than the surface area delirnitated by the external largest outline of the effectively con~a~ning part of the outer bag when containing the inner bag.
Another particular embodiment of the invention is a containerization system which comprises at least one inner cold water soluble bag containing an S agrichemical composition, the containerization system further comprising an outer water insoluble bag made of a flexible and sealed (optionally heat sealed)polymeric ~11m, and wherein the inner bag of the containerization system of the invention may be opened through a te~ring tab.
Another particular embodiment of the invention is a containerization 10 ~ ~system which comprises at least one inner cold water soluble ~ag containing an agricherr~ical composition, the containerization system further comprising an outer water insoluble bag made of a flexlble and sealed (optionally heat sealed)polymenc film, which is insoluble both in the composi~on (if liquid or gel) contained in the inner bag and in the solYent which may be compnsed in the 15 ~ agrichemical eomposition contained in the inner bag, the polymeric film having a low~stletchability, and wherein the inner bag of the con~nerization system of the invèntion may be;opened through~a tearing tab.
Another particular embodiment of the invention is a containeriza~ion system which cQmprises at least one inner cold ~sater soluble bag containing an 2 0 ~ ~ agn~hemical composition, thecontainerizaton sys~emf~ercomprisingan outer water insoluble bag made of a flexible and sealed (ophonally heat sealed) polymeric;f~lm,~and wherein, the surface of the area delimitated by the externallargest outllne of the~inner bag when inside the outer bag is at least 5% less than the su~ace area delimitated by the extern~ rgest outline of the ef~ectively 2 5 ; ~ containing~p~ of the outer bag when containing the inner bag, and wherein the inner b~g of the conta:inerization system of ~e imention may be opened through , ~ , a tea~ing tab.
Another p~icular embodiment of the invention is a containeriza~on system which compnses ~t le~st` one inner cold water soluble bag containing an 3~0 agrichemic~l composition, the containenzation system further comprising an outer w~er insoluble b~g m~de o~ a flexible and sçaled (optional}y he~t sealed) .. : ~ :

~ ~:: :::

3~ I i WO 93/22215 PCr/EP93~01007 ` 15 ' ~.

polymenc film, which is insoluble both in ~he composiuon (if liquid or gel) contained in the inner bag and in the solYent which may be comprised in the agrichemieal composition contained in the inner bag, the polymeric film having a low stretchability, and wherein, the surface of the area delimita~ed by the S external largest outline of the inner bag when inside ~he outer bag is at least 5%
less than ~he su~face area delimitated by the external largest outline of the effectively con~aining part of the outer bag when containing the inner bag, and wherein the inner bag of the containerization system of the invention may be : opened through a tearing tab.
- 10 Another particular embodiment of the invention is a con~ainenza~ion system which comprises at least one inner cold water soluble bag containing an agrochen~ical composition, the containerization system further comprising an : ~ outer water insoluble bag made of a flexible and sealed (op~onally heat sealed) polymeric fîlm, a~d wherein the polymeric film is collapsible and has an 15 elongation at rupture less than 100%.
Another partieular embodimene of the invention is a containerization system which comprises at least one inner cold water soluble bag Gontaining an agrichemical composition, the containe~zation s,~stem fu~er comprising an outer water insoluble bag made of a flexible and sealed (op~onally heat sealed) 2 0 : ~ polyme:dc fîlm, which is msoluble both in the composi~on in the a~ichen~ical somposi~on con~ained in the inner bag, the polymeric film h~ing a low stretchability, and wherein the polymeric film is collapsible and has an elong~tion at rupture less th~n 10û%.
Another particular embodiment of the inYen~on is a conta~nerization 2 5 ~ ~ sysLem which comprises at le~st one inl}er cold water soluble bag con~ining an agrichemical composilîon, ~he containerization system further comprising an outer wate~ insoluble b~g m~de o~ a flexible and se~lçd (optionally heat sealed)polymeric film, and wherein, the surface of the area delimitated by the externallargest outline of the inner ~g when inside the outer b~g is ~t least 5% less than 3 0 the su~face ~rea delimitated by the externnl l~gest outline of the effecti~ely .
~:~
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~ Sl)E~STI~lJTF SHEET

2~ 31 ~ ~' WO 93/2221~ pcr~Ep93/oloo7 --~

containing par~ of the ou~er ba,g when containing the inner bag, and wherein thepslymeric film is collapsible and has an elongation at rupture less than 100%.
Another particular embodiment of the invention is a containerization system which comprises at least one inner cold water soluble bag containing an 5 agrichemical composihon, the containerization system further comprising an outer water insoluble bag made of a flexible and sealed (optionally heat sealed)polymeric ~llm, which is insoluble both in the composition (if liquid or gel) contained in the inner bag and in the solvent which may be comp~ised in the agrichemical composition contained in the inner ba~ the polymeric ~llm having 10 a low stretch~bility, and wherein, the surface of the area delimitated by theextemal largest outline of the inner bag when inside the outer bag is at leas~ 5%
less than the surface area delim~tated by the external largest outline of the .
e~fecovely containing part of the outer bag when containing the inner bag~ and wherein the polymeric ~llm is collapsible and has ~n elongation at rupn~e less than 100%.
Another particul~r embodiment of the invention is a containerization system which comprises ~t least one inner cold water soluble bag containing an agrichernical composition7 the containerization system further comprising an outer water insoluble bag made of a flexible an~sealed (optionally heat sealed) , 2 0 polymer,ic film, and wherein the inner bag of the containeri~ation system of the :, ~ inYentîon may be opened through a tea~ing t~b, and wherein the polymenc film is collapsible and has an elongation; a~ rupture less than 10~%.
: ~ ~ Another p~icular embodiment ~f the inven~ion is a con~neriza~on system which comprises at le~st one inner cold wa~er soluble bag eontaining an :25 agr~hemical composi~ion, the con~inenzation system further comprising an ou~er wa~er insoluble b~g made of ~ flexible and sealed (optionally heat sealed), j polymeric film, which is insolu~le both in the composi~ion (if liquid or gel~
contained in the inner bag and in the solvent which m~y be compnsed in the agrichemical composition contained in the inner bag, the polymenc film having 3 0 a low stretchability, ~nd wherein the inner b~g of the containerization system of ::
: ~ .
~ ~ S~.IBS~ITUTE SHE~T

~`
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` ~ WO 93/2221!; 2~1~3 11 pcr/Ep93/oloo7 .

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the invention may be opened throu~h a tearing tab, and wherein the polymeric lm is collapsible and has an elongation ~t rupture less th~n 100%.
Another par~icular embodiment of the invention is a containerization system which comprises at least one inner cold water soluble bag containing an 5: agrochemical composition, the: containerization system further comprising an outer water insoluble bag made of a flexibie and sealed (optionally heat sealed)pQlymeric ~llm, and~ wherein, the surface of :the area delimitated by the external largest:outline of the Inner bag when inside the outer bag is at least 5% less than the surface are delimi~ated by the ex~ernal largest outline of the effectively 10 containing part of the outer bag when containing the inner bag, and wherein the ~: . inner bag of the containerization system of the invention may be ~pened through a tearing tab, and wherein the polymeric film is collapsible and has an elongation at rupnlre less than 100%.
Another particular embodiment of the invention is a containenzation 15 system which comprises at least one inner cold water soluble bag containing an agriehemic~l compositioh, and containerization system further comprising an outer water:ins~luble bag made of a flexible and senled (optionally heat sealed) polymeric filsn, which is msoluble both ln:the c~mposition (if liquid or gel) contained in the inner bag and in the solYent which may be comprised in the :0 ~ : agrichernical comp~sition con~ined in the inner bag, the polymeric film having a low stretchability,~ ~d wherein, the surface of the area delirni~ated by the externaI largest outline of :the inner ba~ when inside the outer bag is at least 5%
less;than the surface area delimitated by~he external largest outline of the e:ffectively containing part of the outer bag when con~ining the inner bag, and :2 5 wherein the inner b~g o~ the con~ineriza~ion system of the invention may beopened through a te~ing tab, ~nd wherein the polymenc; ~ilm is collapsible and has an elon~ahon at rupture less than 100%.
Another p~icular embodiment of the inven~ion is a containeriza~on systerrl according to anyone of the previous embodimen~s wherein the 3 0 ag~iehemical:composi~ion;is solid ~ .

, .

SUB~TlTlJTE SHEET

~J Ll~3 WC) 93/22~15 P~r/EP93/01007 Ano~her particular embodiment of the invention is a cotttainerization system according to anyone of the previous embodiments wherein the agrichemical composition is fluid.
Another par~icular embodiment of the invention is a containerization 5 system according to anyone of the previous embodiments wherein the agrichemioal composition is a liqu;d or a gel.
Another partlcular embodiment of the invention is a containeri~a~ion system according to anyone of the previous embodiments wherein the agrichemical composition is a powder or a dust or graslules.
Ano~her particular emboditnent of the invention is a containerization system according to ~nynne of the previous embodiments wherein the polyrneric film has an elongation at rupture less than 30 %.
~; Ano~her particular embodiment of the invention is a containerization : ~ system according to ~nyone of the previous embodiments wherein the agrichemica~ i5 selected in the group comprising plant protection agents, pesucides, insecticides, fungicides; herbicides, acancides, nematocides, plant growth regulators, plaDt nutrients, or an adjuvant for the activity for plants as activity promoters including penetr~ting agents"~ynergis~s, an~idotes, sticking agents, spreaders~ activa~ors, eompatibility a~ents; adjuvants for the water 2 0 soluble bags as plas~icizers.
An~ther particular embodiment of the invention is a containeriza~on system according to anyone of the previous embodiments wherein the water soluble polymeric film consdtu~ing 6he inner bag comprises polyethylene oxide or methylcellulose, or polyvinyl alcohol.
2 5 ~ The following examples are given for illustra~ive purposes and should not be understood ~s res~ricting the invenhon.
In these ex~mples~ the Brookfield viscosity w~s measured, as previously indicated~ with a Brookfield viscome~er which had a flat plate .}
rotating ~t 2~ ~evolu~ons per minute.
3 0 In all the following ex~mples, the prepared ~els had a tg(phi) of between 0.75 and 1.5. .

tC
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5UBSTITUTE SH E~7 2118~11 , .. ..
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WO ~3/22215 PCr/EP93/0lO07 Further inform~tion regarding general aspects of water soluble packaging may be found in the following copending app}ications, ~e diselosures of Da~id B. Edwards, William J. Mc Carthy, Leonard E.
Hodakowski, Chi-Yu R. Chen, S~muel T. Ciouge and PauI J. Weber for 5 "Laminated Bags for con~ainerization of Toxic or Hazardous Materials" filed June 11, 1991; U.S. Serial N 07nl3,682, applica~ion of Samuel T. Gouge, Leonar~ E. Hodakowski, Paul J. Weber and Chi-Yu R. Chen for "Gel Fonnulauons for Hazardous Products" filed June 11, 1991; U.S. Serial ND
~7nl3,701, application of Leonard E. Hodakowski, Chi-Yu R. Chen, Samuel T.
10 ~ouge nd Paul J. Weber for "Water Dispersible Gel Folmula~ions" ~lled June 11, 1991; U.S. Serial N 07/713,685, application of Leonard E. Hodakowski, Ricky W. Couch, Samuel T. (:iouge and Rober~ C. Ligon for "Gel Fonnulations"
filed J~ne 11, 1991; and U.S. Se3ial N 07n13,683, application of I,eonald E.
Hodakowski, Chi-Yu R. Chen, Samuel T. Gou~e and Paul J. Weber for "Gel ~: 15Formulations for Use in Toxic or Hazardous Product (:~on~ainerization Systems"
eldJune ll, lg91.
:
: : EXAMPL~ 1 : A gel was made by s~rring and shaking at 50 C a mixture of the 2 O following in~dien~s until they were each dissolved or dispersed:
activeingredient: ~heherbicide2,4-D;
phenoxy benzoic acld (isooctyl es~er): 64.8%
solvent: aromatic solvent with flash point of 65 C: 24.2%
~ ~ .
2 5 adjuvants: : ~
: :~ nonionic/sulfonateblendedemulsifier: 4 %;
calci~m alkylbenzene sulfonate: 1 %;
mixture of dioctylsulfosuccin~te salt and sodium benzoate 6 %.
During s~ring, a dissolu~ion or dispersion appe~red, and thereafter 3 0 gelation. Gelation incre~sed as the mix~ure cooled to ~bout 20 C.
:` : The Brookfield viscosity of the gel was 3,000 centipoise.

SUB5TlTUTE SHEET

21~3 W~ 93/~2215 P~r/~P~3/01û07 ~ -I
~0 , 800 g of this gel were put in a one-liter bag made of a film of PYA (88%
hydrolyzed polyvinyl aceta~e; cold water soluble; thickness: 55 microns). The bag was p~i~lly full and had a residual inflatability of 20 % . The oudine of this bag was 25.4 cm long and 15 cm wide.
This bag was put in an outer bag, or overpack, whose outline was 28 cm long and 16 cm wide. The ou~er bag was made of a flexible laminated film made of one layer of polypropylene (outer layer) and one (inner) layer of polyethylene. Both bags were heat sealed.
The bag in the outer bag was dropped repeatedly from 0.79 m above the 10 ground. An average of 36 drops were necessary to ob~ain failure of the outer bag. Even in this case, the inner bag had no f~ilure.
The bag alone or ~he bag in a known rigid container had failure with a subs~antially less number of repeated drops, and ~he inner bag n-.ay be injured.When compared with o~her outer wraps, the invention overwrap is less lilcely to 1 5 rupnlre.
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SIJBSTI~TE SHT

Claims

21 What is claimed is:

1. A containerization system which comprises an inner water soluble bag containing a hazardous composition wherein the inner bag is contained in a sealed outer bag, the walls of the outer bag comprising a laminate of an outer layer of polypropylene and an inner layer of polyethylene.

2. A containerization system, according to claim 1, wherein the hazardous composition is an agricultural composition.

3. A containerization system, according to claim 1, wherein the overwrap has a low stretchability.

4. A containerization system, according to claim 1, wherein the inner dimension is no more than 15% greater than the outer dimension of the inner bag.

5. A containerization system, according to claim 4, wherein the inner dimension is no more than 10% greater than the outer dimension of the inner bag.

6. A containerization system, according to claim 5, wherein the inner dimension is no more than 5% greater than the outer dimension of the inner bag.

7. A containerization system, according to claim 1, which has a low stretchability and the inner dimension are no more than 15% of the outer dimension of the inner bag.

8. A containerization system, according to claim 1, which comprises tearing tab.

9. A containerization system, according to claim 1, which has an elongation at rupture of less than 100%.

10. A containerization system, according to claim 1, wherein the thickness is from 20 to 500 microns.

11. A containerization system, according to claim 1, wherein the thickness is 30 to 100 microns.

12. A containerization system, according to claim 1 or 2, wherein the composition is a solid.

13. A containerization system, according to claim 1 or 2, wherein the composition is a fluid.

14. A containerization system, according to claim 1, wherein the composition is a gel.

15. A containerization system according to anyone of claims 1 to 14 wherein the agrichemical is selected in the group comprising plant protection agents, pesticides, insecticides, fungicides, herbicides, acaricides, nematocides, plant growth regulators, plant nutrients, or an adjuvant for the activity for plants as activity promoters including penetrating agents, synergists, antidotes, sacking agents, spreaders, activators, compatibility agents; adjuvants for the water soluble bags as plasticizers.

16. A containerization system according to anyone of claims 1 to 14 wherein the water soluble polymeric film constituting the inner bag comprises polyethylene oxide or methylcellulose, or polyvinylalcohol.