AP445A

AP445A - New packaging/containerization system for liquids.

Info

Publication number: AP445A
Application number: APAP/P/1992/000400A
Authority: AP
Inventors: Samuel Terry Gouge; Alan James Aldred; Ricahrd John Dudley Rose; Raymond Marion Chauncey; Evoy Stephen Foster Mc
Original assignee: Rhone Poulenc Agrochimie
Priority date: 1991-06-11
Filing date: 1992-06-09
Publication date: 1996-01-12
Also published as: CA2071077A1; NZ243095A; JPH05155704A; MX9202762A; IL102128A0; FI922682A7; IE921880A1; IL102128A; BR9202308A; AU664998B2; CS175992A3; HU9201934D0; FI922682L; AP9200400A0; KR930000346A; FI922682A0; AU1809292A; HUT70279A; CN1067859A; EP0522713A1

Abstract

A containerisation system which comprises a concentrated hazardous and liquid composition in a cold water soluble or water dispersible bag wherein the bag has a residual inflatability. The hazardous composition comprises especially an agrochemical.

Description

NEW PACKAGING/CONTAINERISATION SYSTEM FOR LIQUIDS c'

The invention relates to new containerisation systems containing hazardous products in a liquid composition which are safe for handling and for the environment. The invention relates also to methods of manufacturing the containerisation systems and to their use in protecting the agricultural environment and in increasing the safety of people working with agrochemicals.

At present, most hazardous liquids are stored in metal drums or, where smaller quantities are required, plastic containers.

Hazardous compounds, especially agrochemical compounds, are formulated in various compositions, solid or liquid. Liquid compositions are most convenient for farmers because of the relative ease with which they can be handled. There are, nevertheless, difficulties in handling such liquid compositions. There is a danger of spillage or leakage if there are holes in the containers previously used or if they are dropped. Although secure containers resistant to shock can be used, in the event of an accident, for example during transportation, the risk remains of spillage or leakage with rapid loss of liquid, for example leaking onto the ground.

It is also known to use water soluble bags in order to reduce the contact between people and hazardous products, but the bags may break so that some risk still exists.

It has been difficult to provide a formulation and a containing system which safeguards those handling it, including farmers and transporters, and the environment.

This difficulty is particularly increased because the farmers are generally not very careful when handling materials .

The present invention seeks to provide a new

BAD ORIGINAL ft containerisation system to contain hazardous products, especially agrochemicals, which is safe for handling, and for the environment.

The invention further seeks to provide a new containerisation system for agrochemicals which is as condensed as possible and uses the least amount of space possible.

The invention further seeks to provide a new containerisation system to contain hazardous compounds e.g. agrochemicals, which diminishes the risks of pollution.

As already said, it is known that agrochemicals may be contained in soluble bags or sachets made from films. Many kinds of active ingredients or pesticides may be used with water soluble bags. Due to the need of dispersibility in the tank of the farmer, the active ingredient should remain in a finely divided state. Powders may thus be used in water soluble bags, as well as liquid or gels or granules. However, water soluble bags may break when dropped, e.g. during transportation, handling, storage or the like. In particular, therefore, the invention seeks to provide containerisation systems comprising a cold water soluble bag and a hazardous compound such an agrochemical, which have good resistance to failure when dropped.

It has been proposed (WO 89/12590) to have water soluble bags containing a liquid with an air-space therein or contained in a container having a shock absorbing base. This is a good improvement, but it is still desirable to further improve the resistance of bags to shock or dropping. Furthermore, the bags described in this known patent application, may be loosely filled so that they can flex, but it is still desirable to obtain strong shock resistance ability. An incomplete filling of some bags with liquid before final heat sealing was also known therefrom but this was connection with practical conditions for filling and sealing.

The invention further seeks to provide an effective

BAD ORIGINAL $ packaging containing, as active ingredient, a hazardous compound, in the form of a liquid.

The invention further seeks to provide a shock absorbing containerisation system for containing agrochemicals, e.g. pesticides (such as insecticides, acaricides, fungicides, herbicides, nematicides) or plant protection agents or plant growth regulators.

The invention yet further seeks to provide a containerisation system for containing agrochemicals which has very efficient shock absorbing properties, especially when dropped.

‘The present invention seeks to provide a new formulation system for agrochemicals which quickly dissolves or disperses when put into water, especially cold water in tanks of farmers, such as those commonly used for preparing spray mixtures.

The present invention provides a containerisation system which comprises a concentrated hazardous and liquid composition in a water soluble or water dispersible bag wherein the bag has a residual inflatability greater than 15% of the volume of the inflated bag.

The bag used is a cold water soluble or water dispersible bag, which is soluble or dispersible, preferably soluble, in water at a temperature less than 35°C.

The present invention further provides a method of manufacturing such containerisation systems and their use in the storage or transport of agrochemicals.

The bag used in the invention is inflatable to a volume greater than the initial volume of the contents (hazardous composition and air or gas space) of the bag, to provide the residual inflatability. Thus, the bag of the invention is filled to less than complete capacity, with the hazardous composition, and the unused capacity may partially, but not totally, be filled with air or any other gas preferably an inert gas. The unused capacity which

BAD ORIGINAL does not contain gas provides the residual inflatability,

More precisely, the residual inflatability has the following meaning : assuming that the inside volume of a bag completely filled or completely inflated is 100 volume units, and that it contains y volume unit of hazardous composition and x volume units of air space (air or any other inert gas) when closed, the residual inflatability (expressed in the form of a percentage) is 100 - x -y.

This.is the definition and wording which is constantly used hereafter. Thus the actual volume of the closed bag is x + y volume units, but could be 100 if completely inflated or filled.

According to the invention, the bag of the containerisation system has a residual inflatability of more than 15% (as previously defined, it is a percentage of the volume of the inflated bag) and generally less than

70%. Preferably the residual inflatability is less than 40%, more preferably less than 30% and most preferably less than 20% of the volume of the inflated bag.

In the containerisation system of the invention, an air or gas space may fill a part of the volume of the bag. However it is considered that the residual inflatability is most efficient in imparting resistance to shock and dropping of water soluble bags containing agrochemicals, if the volume of air or gas space is partially or totally reduced. Thus, air or gas space may be generally less than 20%, preferably less than 10%, of the volume of the bag in its uninflated state. In one specific embodiment it is advantageous, to have no air or gas space in the bag (or an air or gas space less than 1%).

With or without an air or gas space within the bag, the bag may be inflated to a volume greater than the content of the bag (that is to say the actual volume of the composition contained in the closed bag plus the volume of the optional air space).

BAD ORIGINAL ft

The advantageous effect cf the invention upon liquid compositions is substantial, due to the fact such compositions transmit shock well so that bags containing them are more easily broken and/or more easily leak than those containing other kinds of compositions. Furthermore, the consequences of such a breakage or leakage are more damaging when there is spilling.

The compositions used in the invention are not diluted compositions for direct application on the soil or on the plant or on the area to be treated (whether it is a crop area or a non crop area), but they are in a concentrated form, that is to say in the form which is common for commercialization and they need to be diluted before use, especially before spraying. Thus the compositions used in the invention comprise generally more than 1 % and up to 95 % of hazardous product, preferably more than 20 % and up to 60 % (percentage arc w/w unless contrary indicated) of hazardous product

Of course, the compositions used in the invention may contain all the known ingredients such as solvent(s), surfactant(s), dispersant(s), emulsifier(s), thickener(s) or

Γ thickening agent(s), or other additives, such as stabilizer(s), antifoaming agent(s), buffers), antifreezing agent(s).

Among the compositions of the invention as hereabove defined, some are preferred, especially those comprising one or more of the following constituents, (and/or having one or more of tire following characteristics):

the size of the suspended particles, if any, is less than 50 microns, preferably less than 20 microns, they comprise 1 to 95 %, more preferably 15 to 80 %, of the active ingredient or hazardous product they comprise 0.1 to 50 %, more preferably 2 to 15 %, of the surfactant they comprise 0 to 50 %, more preferably 1 to 10 %, of the thickeners), they comprise 0 to 94 % of the solvent more preferably 3 to 75 %, they comprise 0 to 20 % of other additives (as herein before defined), preferably,

0.1 to 10%, they comprise less than 3 % by weight of water, preferably less than 1 %.

According to a particular feature of the invention, the components of the r compositions are chosen in such a way that the liquid compositions of the invention . have a loss modulus (G measured as hereafter defined, under speed of oscillations of 1 ( radian per seconde = rd/s) less than 1 Pascal, preferably less than 0.5 .

According to a particular feature of the invention, the components of the compositions are chosen in such a way that the liquid compositions of the invention have a viscosity of 50 to 10000 centipoises, more preferably of 100 to 6000 centipoises (these viscosities are Brookfield viscosities measured with a viscosimeter in form of a flat plate rotating at 20 revolutions per minute at 20‘C). Low viscosities are generally helpful to get easy dispersibility of the formulation in water by the user (such as the farmer). However, in order to reduce possible leakages when punctures happen, higher viscosities are more favorable.

According to One feature, the Compositions used in the invention preferably have a specific gravity greater than 0.8, preferably greater than 0.90

According to a particular feature of the invention, the components of the compositions arc chosen in such a way that the compositions of the invention have a spontaneity (as hereafter defined) less than 75, preferably less than 25.

The spontaneity is assessed according to the following method: A mixture of 1 ml formulation with 99 ml water arc put into a 150 ml glass tube which is stoppered and inverted through 180' (upside down). The number of times (that is to say of inversions) required to disperse 99 % of the formulation is called the spontaneity.

BAD ORIGINAL ft

The liquid material which is used in the invention is essentially a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi) is greater than 1.5, preferably greater than or equal to 5. Tg(phi) is the tangent of the phi angle (or phase difference). The measurement of phi is made by means of a dynamic rheometer. Dynamic rheometers which are appropriate to measure phi are known and available commercially. They usually have a flat fixed plate and a rotating cone or plate, or a so-called couette system. Other mechanical systems are also available. Generally the choice of one system or another is made according to the recommandations of the seller of the rheometer, and is adapted to the kind of compound which is tested. The particular choice of a specific type of rheometer is something well known of the man stalled in the art of rheology. When two kinds of system for the rheometer arc possible, similar values of phi are actually measured. The cone (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 change as a sine function with time. Tg(phi) is equal to the ratio G/G, wherein: G' is the storage modulus (represents die behaviour of a perfect solid); G is the loss modulus (represents the behaviour of a perfect liquid). G' and G are expressed in Pascal for a given rotational speed (radian per second).

G’ and G, and thus tg(phi), may depend on the amplitude of the oscillations (percentage of strain) of the rheometer; however, there is generally a socalled viscoelastic plateau whereby the values G' and G of a liquid do not depend substantially on the said amplitude or percentage of strain. Of course, the measurement of G' and G” of a liquid is made under the conditions of this viscoelastic plateau, just because it corresponds to the normal liquid state which is precisely what is tested.

G' and G, and thus tg(phi), may also depend on the speed of the oscillations (time to reach the chosen percentage of strain; expressed as radian per seconde) of the rheometer. In order to have reasonable measurement of properties, it is generally preferred to operate at 1 rd/s, and optionally at other speed too.

By die words thickeners or thickening agents, it is meant a material corresponding to the active ingredient in such a way that, when mixed, at 50/50 w/w and 25‘C, with (and optionally ground with) an organic solvent, a thickened suspension can be obtained. The thickeners in the invention can be either liquid or solid at 23‘C and have, when they are solid, a particle size lower than 100 microns, preferably less than 20 microns.

Thickeners which may be used in the invention include tetramethyl decyne diol, ethoxylated dialkylphenol, methylated clay, propylene carbonate, hydrogenated castor oil, ethoxylated vegetable oil, dioctyl sodium sulfosuccinate, hexynediol, sodium lauryl sulfate, sodium acetate or benzoate or sulfate, calcium sulfate, polyacrylic acid or its salts; silica or alumina; and mixtures thereof. Low molecular weight polymers can also be used as thickeners. These thickeners are generally used in an amount enough to thicken, but preferably unsufficient to create a gel.

By the word surfactant, it is meant an organic material which is able to substantially reduce the surface tension of water which is 73 dynes/cm at 20’C

Surfactants which can be used include lignosulfonic acid salts, phenolsulfonic or naphtalene sulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines; substituted phenols such as alkyl- or aryl- phenols; salts of sulfosuccinic acid; taurine derivatives such as alkyl taurides; polycondensates of ethylene oxide with phosphoric acid esters of alcohols or phenols; alkyl aryl polyoxyethylene glycol phosphate esters; alkyl aryl polyoxyethylene ethanol phosphate esters; branched chain alcohol sulfates; alkylbenzene sulfonates salts, such as calcium dodecyl benzene sulfonate; ethoxylated tristyryl phenols, and sulfates and phosphates thereof; alkyl poylethoxyether phosphates esters, either in acid or in salt form; ethoxylated fatty acids or alcohols; ethoxylated alkyl phenols or dialkyl phenols; ethoxylated castor oil; ethoxylated propoxylated block copolymers; ethoxylated propoxylated alkylphenol block copolymers; ethoxylated propoxylated tristyrylphenols; glycerol esters, especially esters of fatty acids; glycol esters, especially esters of fatty acids; lccitliin and lecithin derivatives; sugar esters and other derivatives, as sorbitol, and sucrose or glucose esters or derivatives; sucroglycerides.

BAD ORIGINAL

By the expression hazardous product as used herein is meant a product which may cause damage to the environment or be injurious to a person handling it. Hazardous compounds which are used in agriculture are mainly contemplated in the invention to be contained in water soluble bags with residual inflatability. Such hazardous compounds are ingredients active in agriculture, such as agrochemicals, and more precisely pesticides (such as herbicides, fungicides, insecticides, acaricides, nematicides) or plant protection agents (including plant growth regulators or plant nutrient) or adjuvants for the activity for plants as activity promoters including penetrating agents, synergists, antidotes, sticking agents, spreaders, activators, and compatibility agents. Pesticides are however preferred.

The invention is not limited to some specific agrochemicals; a list of many agrochemicals which can be used in the invention includes :

Fungicides such as Triadimefon, Tebuconazole, Prochloraz, Triforine,

Tridemorph, Propiconazole, Pirimicaib, Iprodione, Metalaxyl, Bitertanol, Iprobenfos, Flusilazol, Fosetyl, Propyzamide, Chlorothalonil, Dichlone, Mancozeb, Anthraquinone, Maneb, Vinclozolin, Fenarimol, Bendiocarb, Captafol, Benalaxyl, Thiram,

Chlorothalonil, Captan, Zineb, Tridimefon, Metalaxyl, Iprodione, Fenarimol, Sulfur, Quintozene, copper salts, Vinclozolin, Thiophanate-methyl, Tricyclazole, Dicloran,

Benomyl,

Herbicides (or defoliants) such as quizalofop and its derivatives, Acetochlor, Metolachlor, Imazapur and Imazapyr, Glyphosate and Gluphosinate, Butachlor,

Acifluorfen, Oxyfluorfen, Butralin, Fluazifop-butyl, Bifenox, Bromoxynil, Ioxynil, Diflufenican, Phenmedipham, Desmedipham, Oxadiazon, Mecopropo, MCPA, MCPB, MCPP, Linuron, Isoproturon, Flamprop and its Derivatives, Ethofumesate, Diallate, Carbetamide, Alachlor, Metsulfuron, Chlorsulfuron, Chlorpyralid, 2,4-d, Tribufos,

Triclopyr, Diclofop-methyl, Sethoxydim, Pendimethalin, Trifluralin, Ametryn,

Chloramben, Amitrole, Asulam, Bentazone, Atrazine, Cyanazine, Thiobencarb,

Prometiyn, 2-(2-chlorobenzyl)-4,4-dimethyl-l,2-oxazolidin-3-one, Fluometuron, Napropamide, Paraquat, Bentazole, Molinatc, Propachlor, Imazaquin, Metribuzin, Tebuthiuron, Oryzahn, Dicamba, Bromoxynil ester, Pursuit, Norflurazon, Simazine, Acifluorfen sodium, Trichlopyr, sulfonyl ureas and Trialkoxydim,

Insecticides or nematicides such as Ebufos, Carbosulfan, Amitraz, Vamidothion,

Ethion, Triazophos, Propoxur, Permethrin, Cyperraethrin, Parathion, Methylparathion, Diazinon, Methomyl, Lindane, Fenvalerate, Elhoprophos, Endrin, Endosulfan,

Dimethoate, Dieldnn, Dicrotophos, Dichlorprop, Dichlorvos, Azinphos and its derivatives, Aldrin, Cyfluthrin, Deltamethrin, Disulfoton, Chlordimeform, Chlorpyrifos, Carbaryl, Dicofol, Thiodicarb, Propargite, Demeton, Phosalone, Acephate, Azinophosmethyl, Carbaryl, Carbofuran, Methamidofos, Fenbutalin oxide, Trichlorfon,

Abamectin, Aldicarb, Malathion, and pyrethroids, Bacillis Thuringensis,

Plant growth regulators such as gibberellic acid, Ethrel or Ethephon, Cycocel, Chlormequat, Ethephon, Dimethipin, Mepiquat, and other biological biocides and mixtures thereof.

The preparation or manufacturing of the compositions of the invention can be made by any known method. A convenient way is to mix together the different constituents of the mixture/composition and to stir them, optionally with grinding or milling and/or heating. Grinding and/or milling are generally necessary in order to obtain the active ingredient in the form of particles to be suspended having the size as hereinbefore defined. Sometimes it is easier to operate with a slow addition of the constituents of the composition and it might be also useful that the thickening agent is added last

BAD ORIGINAL ft

The chemical nature of the enveloping film constituting the bags which may contain the composition of the invention can vary quite widely. Suitable materials are water soluble or water dispersible, preferably water soluble, materials which are insoluble in the organic solvents used to dissolve or disperse the active ingredient. Specific suitable materials include polyethylene oxide, such as polyethylene glycol; starch and modified starch; alkyl and hydroxyalkylcellulose, such as hydroxymethyIcellulose, hydroxyethylcellulose, hydroxypropylcellulose; carboxymethylcellulose;

_z- polyvinylethers such as poly methyl vinylether; poly(2,4dimethyl-6-triazolylethylene); poly(vinylsulfonic acid); polyanhydrides; low molecular weight urea-formaldehyde resins; low molecular weight melamine-formaldehyde resins; poly(2-hydroxyethyl methacrylate); polyacrylic acid and its homologs; but preferably the enveloping film comprises or is made from polyvinylalcohol (PVA). It might be that some active ingredients, may react with some polymers constituting the wall of the bags; in such a situation, the material constituting the wall of the bag is changed into a material which is inert to the active ingredient.

Preferred material for constituting the bags used in the invention include polyethylene oxide or (' methylcellulose, or polyvinylalcohol. When polyvinylalcohol is used, it is advantageously a 40-100%, preferably 80-99% alcoholized or hydrolysed, polyvinyl acetate film.

The films which are used to make the bags may be any water soluble or water dispersible film known per se. In order to make a bag, the film needs to be shaped (possibly partially sealed) and then filled with the composition comprising the hazardous compound. When filled (as hereinbefore defined), the bag is closed generally by sealing, for example heat sealing.

According to the invention, the bags are not completely filled with the hazardous compositions. They are only partially filled and then sealed. When they are

BAD ORIGINAL sealed, they nay be sealed close to the hazardous composition so as to include either no air space or only very little air space. They may also be closed so as to maintain some air space between the composition and the wall of the bag. Nevertheless, in all cases the bag when filled, is not expanded so as to be completely inflated.

On the contrary, the walls of the bag are maintained in such a position that further substance could be put in the bag if this were desired, and the bag is closed (generally by sealing) before it is completely inflated.

The invention relates also to a method of manufacturing the containerisation systems of the present invention which method comprises manufacturing a water soluble or water dispersible bag by partially filling the bag with a concentrated hazardous composition, and closing the filled bag to provide residual inflatability therein.

The invention relates also to the use of the containerisation system of the present invention in the storage or transport of agrochemicals. Such use may provide effective protection of the agricultural environment.

The containerisation systems of the invention may be used to provide spray mixtures, suitable for use in agriculture, by dissolving or dispersing them in water, for example in a spray tank.

The following examples are given for illustrative purposes and should not be understood as restricting the invention .

EXAMPLES

The following general procedure was used.

The water soluble film which was used to make the water soluble bag is known. In order to make a bag, the film was shaped and partially sealed and then partially filled with a composition of the invention. This composition was able to flow, even if at a slow rate due to the high viscosity. When filled, the bag was heat sealed to close it.

BAD ORIGINAL ft

The concentrated composition was prepared by adding ingredients and additives while shearing and/or milling (attrition milling). The surfactants and active ingredient(s) were then added and mixed.

In this example, the Brookfield viscosity was measured, as previously indicated, with a Brookfield viscosimeter which had a flat plate rotating at 20 revolutions per minute at 20’C.

Tg(phi) is measured as previously indicated with a dynamic rheometer (sold in USA under the name RFS) with a percentage of strain of 1 % and a speed of oscillations of 1 rd/s. Tg(phi) was more than 5 .

EXAMPLE 1

The components are listed below and the per cent given:

COMPONENT PERCENT

Bromoxynil octanoate (active ingredient) 28.7

Bromoxynil heptanoate (active ingredient) 27.6

Alkyl benzenes with 10 -12 carbon atoms (flash point 150 *C; solvent) 34.65 Polydimethylsiloxane (antifoaming agent) 0.05

Calcium dodecylbenzene sulfonate (emulsifier) 5.0

Polyalkylene glycol ether (emulsifier) 4.0

The components were mixed together. The viscosity of this mixture is approximately 45 centipoise. The spontaneity was 1.

This formulation was then packaged in water soluble polyvinyl alcohol bag. The bag was made from a folded polyvinyl alcohol film. The polyvinyl alcohol was cold water soluble and had a hydrolysis rate of acetate groups of 88 % . The film was folded so as to form a vertical tube and heat sealed according to an horizontal line at the bottom; a second seal was made according to a vertical line crossing the first seal at the lowest part of the seal; after filling, the closing of the bag was made through a third seal which was made according to a horizontal line crossing the vertical seal at its upper pan.

The bag could have been filled up to a volume of 1000 ml if completely filled. Only 700 ml of pesticidal composition were put into the bag, leaving very little air space (less than 1 %). Thus the residual inflatability was about 30 %

100 identical bags were dropped 2 times from 1.2 m upon the ground. No breaking or leakage is observed.

( EXAMPLES 2 to 5 _f Similar bags with similar residual inflatability are prepared with followng specificities :

Example 2

Bromoxynil Octanoate 35.4 %

Isooctyl ester of methylchloropropionic acid 35.0 %

Sulfonate Nonionic Blend Emulsifier 3.5 %

Calcium Alkylarylsulfonate 1.5%

Aromatic Naphthalenic Solvent 24.6 %

The ingredients are mixed until solution is achieved. 500 ml sample is poured into polyvinylalcohol bag.

500 ml of the liquid mixture were poured into a polyvinylalcohol cold water soluble bag and heat sealed. The residual inflatability of this bag was about 33 % and a very small air space (less than 1 %) was present. 100 filled bags were made in the same way and dropped from 88 cm. No bag broke

Example 3

Alachlor 64.6 %

Cyclohexanone 30.4 %

Block polymer of polyhydroxystcaric acid and polyethylene glycol 4.5 %

Mixture of calcium dodccylbcnzenc sulfonate with an aromatic solvent and with block copolymer of ethylene oxide and propylene oxide and cthoxylatcd nonyl phenol 0.5 %

BAD ORIGINAL ft

The ingredients arc mixed until solution is achieved. 700 ml sample is poured into polyvinylalcohol bag.

700 ml of the liquid mixture were poured into a polyvinylalcohol cold water soluble bag and heat sealed. The residual inflatability of this bag was about 30 % and no air space was present 10 filled bags were made in the same way and repeatedly dropped from 88 cm until each bags fails. The drop average required to reach failure was 14

Example 4

Bromoxynil Octanoate 36.0 %

Sulfonate Nonionic Blend Emulsifier 5.5 %

Calcium Alkylarylsulfonate 1.5%

Aromatic Solvent .. 57.0 %

The ingredients are mixed until solution is achieved. 700 ml sample is poured into polyvinylalcohol bag.

700 ml of the liquid mixture were poured into a polyvinylalcohol cold water soluble bag and heat sealed. The residual inflatability of this bag was about 30 % and a very small air spaceless than 1 %) was present 50 filled bags were made in the same way and dropped from 137 cm. 7 bags failed.

Example 5

Ethoprop 70.0 %

Phosphate Ester 5.0 %

Aromatic solvent 25.0 %

The ingredients are mixed until solution is achieved. 1 liter sample is poured into polyvinylalcohol bag.

1000 ml of the liquid mixture were poured into a polyvinylalcohol cold water soluble bag and heat sealed. The residual inflatability of this bag was about 25 % and a very small air space (less than 1 %) was present 25 filled bags were made in the same way and dropped from 137 cm. 6 bags failed.

Claims

1. A containerisation system which comprises a concentrated hazardous and liquid composition in a cold water soluble or water dispersible bag wherein the bag has a residual inf latability greater than 15% of the volume of the inflated bag.

2 . A containerisation system according to claim 1 wheisein the hazardous composition comprises a compound active in agriculture.

3. A containerisation system according to claim 2 wherein the hazardous composition comprises an agrochemical.

4. A containerisation system according to claim 3 wherein the hazardous composition comprises a pesticide.

5. A containerisation system according to claim 3 or 4 wherein the hazardous composition comprises a compound which is a herbicide, a fungicide, an insecticide, an acaricide, a nematicide, a plant protection agent, a plant growth regulator, a plant nutrient, an adjuvant for the activity for plants, an activity promoter, a penetrating agent, a synergist, an antidote, a sticking agent, a spreader, an activator or a compatibility agent.

6. A containerisation system according to any one of the preceding claims wherein the bag has a residual inflatability less than 70% of the volume of the inflated bag.

7. A containerisation system according to

BAD ORIGINAL ft claim 6 wherein the bag has a residual inflatability less than 40% of the volume of the inflated bag.

8. A containerisation system according to any one of the preceding claims wherein the bag has an air or gas space of less than 20% of the volume of the bag.

9. A containerisation system according to claim 8 wherein the bag has an air or gas space of less^ than 10% of the volume of the bag.

10. A containerisation system according to claim 9 wherein the bag has no air or gas space or an air or gas space less than i% of the volume of the bag.

11. A containerisation system according to any one of the preceding claims wherein the composition comprises from 1% to 95% by weight of hazardous product.

12. a containerisation system according to claim ll wherein the composition comprises from 15% to 80% by weight of hazardous product.

13. a containerisation system according to claim 12 wherein the composition comprises from 20% to 60% by weight of hazardous product.

14. A containerisation system according to any one of the preceding claims wherein the composition comprises suspended particles, whose size is less than 50 microns.

15. A containerisation system according to claim 14 wherein the composition comprises suspended particles, whose size is less than 20 microns.

16. A containerisation system according to any one of the preceding claims wherein the composition comprises from 1% to 95% by weight of hazardous product, 0.1 to 50% by weight of surfactant, 0 to 50% by weight of thickener, 0 to 94% by weight of solvent, 0 to 20% by

BAD ORIGINAL £ weight of other additives, and less than 3% by weight of water.

17 . a containerisation system according to claim 16 wherein the composition comprises from 1% to 95% by weight of hazardous product, 2 to 15% by weight of surfactant, 1 to 10% by weight of thickener, 3 to 75% by weight of solvent, 0.1 to 10 % by weight of other additives, and less than 1% by weight of water.

_t

18. A containerisation system according to any one of the preceding claims wherein the composition has a visopsity from 50 to 10,000 centipoise.

19· A containerisation system according to claim 18 wherein the composition has a viscosity from 1,000 to 6,000 centipoise.

20. a containerisation system according to any one of the preceding claims wherein the composition has a specific gravity greater than 0.8.

21. A containerisation system according to any one of the preceding claims wherein the composition has a spontaneity less than 75.

22. A containerisation system according to any one of the preceding claims wherein the composition is a liquid having a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi) is greater than 1.5.

23. A containerisation system according to claim 22, wherein tg(phi) is greater than or equal to 5.

24. a containerisation system according to any one of the preceding claims wherein the water soluble or water dispersible bag comprises an enveloping film comprising polyethylene oxide, polyethylene glycol; starch or modified starch; alkyl or hydroxyalkylcellulose; carboxymethylcellulose; a polyvinylether; poly(2,4dimethyl-6-triazolylethylene); poly(vinylsulfonic acid); a polyanhydride; a low molecular weight urea-formaldehyde resin; a low molecular weight melamine-formaldehyde resin;

CAD ORIGINAL ft poly(2-hydroxyethyl methacrylate); polyacrylic acid or a homolog thereof; or polyvinylalcohol.

25. A method of manufacturing a containerisation system as claimed in any one of the preceding claims which method comprises manufacturing a water soluble or water dispersible bag by partially filling the bag witn a concentrated hazardous composition, and closing the filled bag to provide residual inflatability therein.

26. Use of a containerisation system as claimed in any one of claims 1 to 24 in the storage or transport of agrochemicals.