AP356A

AP356A - Containerisation systems for agrochemicals and the like.

Info

Publication number: AP356A
Application number: APAP/P/1991/000302A
Authority: AP
Inventors: Leonard E Hodakowski; Samuel Terry Gouge; Chi-Yu Chen; Paul J Weber
Original assignee: Rhone Poulenc Agrochimie
Priority date: 1990-07-18
Filing date: 1991-07-18
Publication date: 1994-09-03
Also published as: MA22216A1; RO110895B1; CA2066424C; EP0493553A1; MY106818A; WO1992001374A1; BR9105833A; DE69125261D1; PL294073A1; AU8039691A; FI921139A; HU9200880D0; ZA915645B; ZA915641B; JP2518759B2; GR3023459T3; EP0493553B1; ATE150253T1; HUT63301A; KR920702194A

Abstract

This invention relates to a containerization system and to

Description

CONTAINERIZATION SYSTEM FOR AGROCHEMICALS AND THE LIKE

This invention relates to a containerization system and to 5 containers which are particularly suitable for storing, packaging and transporting toxic or hazardous products, e.g., agricultural chemical compounds, such as pesticides.

At present, most hazardous and toxic liquids are stored in metal drums or, where smaller quantities are involved, in plastic containers. Hazardous or toxic compounds, such as agrochemical compounds, are formulated in various compositions.

The expression toxic or hazardous compounds as used herein means an industrial chemical or agrochemical compound, which, if released in the quantity or concentration normally present in

5 storage and shipping containers, may cause damage to the environment or be injurious to a person contacted by it.

With respect to agricultural chemicals, liquid compositions, particularly in the form of concentrates, are most convenient for farmers because of the relative ease with which they can be handled, formulated and used. However, there are significant difficulties in handling such liquid compositions.

There is a danger of spillage or leakage if holes develop in the containers or if containers are accidentally dropped and thereby crack or fail. Containers have been developed which possess great resistance to impact and shock.

While such containers are secure under normal storage and handling conditions, in the event of an accident, for example during transporting, there remains an appreciable risk of spillage or leakage with rapid loss of liquid. Leakage of toxic and hazardous chemicals can create damage to the environment.

The chemical and packaging industries have long sought a secure container which provides sufficient safeguards for those handling it, such as farmers and transporters, as well as adequate protection for the environment.

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It is known, for example, to package agrochemicals in soluble bags or sachets made from films. However, such films may crack and break and thus cause leakage of the agrochemical contents. There are a variety of defects which can occur in films, which may lead to weaknesses of the film and become a potential source of leakage. For example, the presence of air bubbles, dust particles or foreign bodies in gel particles or the existence of thin points on or in the film are all potential weak points. If a film with such a weak point is subjected to a lot of handling or physical shock, the film may fail at a weak point.

This is especially a problem in the agrochemical industry where containers may be subjected to repeated and uncontrolled handling by distributors, transporters or farmers.

Another possibility is to provide agrochemicals in the form

5 of wettable powders which can be contained within a bag which may be water soluble or water dispersible. However, wettable powders are less and less used in agricultural farming.

Also suggested have been containing systems for pesticides in which the liquid-containing active ingredient is enclosed within soluble bags or sachets. However, the bags tend to develop pinholes and the contained liquid leaks under such conditions causing potential injury to the environment.

It has also been proposed for pesticides to be packaged in soluble bags or sachets which contain an air space to absorb

5 shocks and to avoid leakage. This feature does tend to reduce bag failure. However, this does not avoid the problems of pinholes.

In other industries such as pharmaceuticals and cosmetics, gel formulations have been used as a means for packaging pharmaceutical or cosmetic products. However, such gel

0 formulations are often utilized for aesthetic and other reasons and not as part of a containerization system for holding and securing toxic or hazardous chemicals. Furthermore, the gels used for pharmaceutical or cosmetic purposes are generally water- based.

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The present invention seeks to provide a new method and system for storing, containing and packaging toxic and hazardous compositions such as agrochemicals which is safe for handling.

The present invention further seeks to provide a new 5 system to contain agrochemicals which is easy to manipulate for the farmer.

The present invention further seeks to provide a new system for containing chemicals such as agrochemicals which enables such chemicals to be readily, rapidly and easily solubilized .10 and/or dispersed in water, preferably in less than five minutes under normal agitation.

The present invention further seeks to provide a new system for storing, containing and packaging chemicals such as agrochemicals, said system utilizing a minimum amount of

5 volumetric space.

The present invention further seeks to provide a new container and a new system for containing hazardous compounds which diminishes the risks of leakage and pollution.

The present invention further seeks to avoid leakage 20 through pinholes of a bag containing hazardous compositions. Only one pinhole among thousands of bags is enough to cause a lot of trouble, because the liquid going through the pinhole contaminates all of its environment.

The present invention further seeks to avoid breakage of

5 the container with its contents. When the container is rigid, there is substantial possibility of simple breakage.

With a liquid in a bag this possibility is somewhat reduced, but the liquid still transmits the shocks and there is the problem of hydraulic hammer effect. The present invention seeks to avoid this hydraulic hammer effect, or at least to reduce it.

The present invention further seeks to dissipate, as much as possible, the force of a shock to a container.

The present invention further seeks to provide a shock absorbing system for containing agrochemicals, e.g., pesticides.

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- 4 The present invention further seeks to provide a containing system wherein less solvent is needed in the formulation of the chemical, which is a cost saving advantage both in shipping and manufacturing.

An additional advantage of the present invention is that higher concentrations of active ingredient can be obtained when using gels rather than liquids.

The present invention seeks to provide a new container system for agrochemicals which quickly dissolves when put into water. The invention further seeks to provide a new container system for agrochemicals which reduces the risk of clogging the spray nozzles or the filters of spray tanks.

Other objects and advantages of the invention will be apparent from the description which follows. Other objections of the invention will better appear from the following description.

The objects of the invention can be achieved in full or in part by means of the invention.

The present invention accordingly provides a containerisation system for holding and securing agricultural chemical compounds which comprises a water soluble or water dispersible bag which completely encloses a water dispersible gel, said gel comprising an agricultural chemical compound and being such as to avoid leakage of the gel through pinholes which may develop in the bag.

The present invention provides a containerization system comprising a water soluble or water dispersible bag which contains, i.e. encloses, holds and secures an agricultural chemical compound which can be a toxic or hazardous chemical;

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AP 3 5 β ίΐ the chemical compound is present in a gel which is of essentially organic material. The present invention is also directed to a containerization system that can self-dispense the active ingredient contained therein when placed in an aqueous medium. The present invention also concerns a method for containing, i.e. holding and securing, chemicals in a manner which reduces the chances of the chemical spilling, leaking or contacting with the environment during shipping and storage.

The containerization system of the present invention comprises a bag comprising a water soluble or water-dispersible film which envelops and encloses agricultural chemical present in a gel. The gel provides its own discrete advantages and applications as a concentrate for the chemical compound. When the gel of the present invention is used in conjunction with the enveloping bag, a containerization system is provided which is unique in its ability to maintain integrity and prevent leakage of the subject chemical into the environment.

The ultimate purpose of the containerization system is to preserve an agricultural chemical in a form which can be safely handled and which is secured in a manner preventing its rapid leakage into the environment. The invention achieves these objectives not merely by creating an enveloping barrier of protection but by employing a system integrally related to the subject chemical.

The present invention also includes a method for holding and securing agricultural chemical compounds, such as toxic and hazardous compounds, in a manner to prevent their contact with the environment during shipment and storage, said method

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- 5a comprising:

(i) mixing at an elevated temperature a chemical compound 5 with other gel ingredients until the chemical compound and ingredients are sufficiently dissolved or dispersed to appear visually as a substantially single phase, (ii) allowing the mixture to cool and to form a gel, and (iii) enclosing and sealing a predetermined amount of said gel within a bag of a water-soluble or water dispersible film. In a preferred embodiment the agricultural chemical compound is toxic or hazardous to the environment or to persons contacted by it.

Preferably the gel is composed substantially of organic 15 materials.

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In a further preferred embodiment the gel comprises the chemical compound and one or more ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelled or gelling agents.

In a further preferred embodiment gel comprises the chemical compound and nonionic surfactant. The surfactant is preferably a nonionic emulsifier.

Preferably the nonionic emulsifier is a sulfonate.

In a further preferred embodiment the organic solvent is a petroleum hydrocarbon selected from the group consisting of aromatic and aliphatic solvents.

In a further preferred embodiment the gel comprises the chemical compound and an organic solvent.

In a further preferred embodiment the gel comprises the • 5 compound, a gelling agent, a solvent and a surfactant.

Preferably the gel has a water content which is less than 5% by weight.

Preferably the gel has a viscosity of between 1000 and 30,000 centipoise.

In a further preferred embodiment the gel and the gel within the bag have a density greater than 1.

In a further preferred embodiment the bag is made of a polymeric water soluble film having a thickness between about 10 and 500 microns, and is not permeable to and not substantially

5 soluble or dispersible in the organic components of the gel.

As already explained, a toxic or hazardous chemical can be any compound which can cause injury to persons exposed to the chemical or which can damage the environment. One class of such

0 compounds is agricultural chemicals or agrochemicals such as pesticides (e.g., herbicides, fungicides, nematocides, insecticides, etc.) and plant protection agents (e.g., plant growth regulators, nutrients, etc.).

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In practice, the gel material used in the invention comprises the active ingredient, which is the hazardous or toxic chemical in association with ingredients that participate in or assist in the formation of the gel, for example, surfactants, dispersants, thickeners, solvents and gelled or gelling agents.

A gel is generally a colloid in which the dispersed phase has combined with the continuous phase to produce a viscous, jelly-like product. A gel can be a dispersed system consisting typically of a high molecular weight compound or aggregate of

0 small particles in very close association with a liquid. The gels used in the invention usually have an organic continuous phase, in contrast to most existing gel materials which are water-based and have an aqueous continuous phase.

Furthermore, the gels used in the invention have essentially :Ί one physical phase, at least as can be seen when visually observed. Gels that are preferred for the invention are those which can be divided by cutting and whose cut parts are able to merge together by simple juxtaposition.

Solvents useful in the gel of the present invention are organic solvents such as petroleum hydrocarbons which include aliphatic and aromatic solvents. Surfactants that can be used in the invention are nonionic and anionic surfactants and combinations thereof. Illustrative gelling agents that can be used include mixtures of dioctyl sulfosuccinate salt and sodium benzoate, tetramethyl decynediol ethoxylated dialkylphenol, combinations of modified clay and propylene carbonate, hydrogenated castor oil, ethoxylated vegetable oil, dioctyl ester of ίΤ'-Σ V sodium cuooinio aeid- and sodium benzoate, diatomaceous earth, and * i mixtures of dimethyl hexane and hexyne diol.

(30 The gel 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 less than or equal to 1.5, preferably less than or equal to 1.2. Tg(phi) is the tangent of the phi angle (or phase difference).

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The measurement of phi is made by means of a rheometer having a flat fixed plate and a rotating cone above this plate such as the .angle between them is less than 10°, preferably 4°. The cone is caused to rotate by means of a controlled speed motor; the rotation is a sinusoidal one, i.e,, the torque and the angular displacement change as a sine function with time. This angular displacement corresponds to the hereabove mentioned shear strain; the torque of the controlled speed motor (which causes the angular displacement) corresponds to the hereabove mentioned

0 controlled shear stress.

The gel which may be used in the invention is primarily organic, which means that it has a low water content, generally less than 5% (by weight), preferably less than 3%, more preferably less than 1%.

“> Generally, the gel which may be used in the invention is a material having a viscosity from 500 centipoise (measurement made with a Brookfield viscometer at 23° C with a flat plate rotating at 20 round per minute) to 50000 centipoise, preferably from 1000 to 30000 centipoise, and still more preferably from 1 000 to 5 000 centipoise.

It is to be understood that all measurements and test procedures in this specification, unless otherwise stated, are taken at 23°C (room temperature).

According to one embodiment of the invention, the gels

5 which are used in the invention are successful when submitted to the following puncture test: 500 g of a material/gel are placed in a polyvinyl alcohol water soluble bag (having a 50 micron thick wall) and heat sealed. The bag is suspended using a binder clip at which time a dissecting needle (the diameter of which is 0.1 mm) is inserted into the lower third of the bag and withdrawn.

The material/gel is observed for 30 minutes to determine leakage.

A gel which is successful in the present test shows no leakage and preferably may be used in the invention. A droplet of material

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AP 3 5 6 may appear on the hole, but no persistent flowing or leakage occurs.

Preferred characteristics of a gel which is appropriate for the invention are (alone or in combination):

* The viscosity should be generally from 500 to 50000 centipoise, preferably from 1000 to 30000 centipoise, and still more preferably from 1 000 to 5 000 centipoise (measurement made with a Brookfield machine).

♦ The dispersibility in water should be substantially complete when the gel is subjected to normal agitation in water after a 15 minutes interval, preferably after a 10 minutes interval.

* The gel preferably contains an essentially non-aqueous solvent.

The chemical nature of the enveloping film constituting the J 5 bag can vary quite widely. Suitable materials are water soluble (or possibly water dispersible) materials which are insoluble in the organic solvents used to dissolve or disperse the active ingredient (e.g., agrochemical). Specific suitable materials include polyethylene oxide, such as polyethylene glycol; starch and 20 modified starch; alkyl and hydroxyalkylcellulose, such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropyl cellulose; carboxymethylcellulose; polyvinylethers such as poly methyl vinylether or poly(2-methoxyethoxyethylene); poly(2,4dimethyl-6-triazinylethylene; poly(3-morpholinyl ethylene); poly(N2 5 1,2,4-triazolylethylene); poly(vinylsulfonic acid); polyanhydrides;

low molecular weight melamine-formaldehyde resins; low molecular weight urea formaldehyde resins; poly(2-hydroxyethyl methacrylate); polyacrylic acid and its homologs.

A preferred enveloping film comprises or is made from polyvinylalcohol (PVA). When PVA is used, it is preferably partially or fully alcoholyzed or hydrolyzed, e.g., 40—100%, preferably 8099% alcoholyzed or hydrolyzed, as a polyvinyl acetate (or other ester) film. Copolymers or other derivatives of such polymers can also be used.

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Additional preferred materials for constituting the bags in the invention are polyethylene oxide, methylcellulose, and polyvinylalcohol.

The following features, alone or in combination, constitute 5 additional preferred features of the invention:

According to another feature, the gels and the bag containing gel of the invention preferably have a specific gravity greater than 1, preferably greater than 1.1.

According to another feature the gels contained in the bags 10 of the invention preferably have spontaneity (as hereafter defined) less than 75, preferably less than 25.

According to another feature, the bags of the invention generally have a capacity of from 0.01 to 12 litres; preferably they have a capacity of from 0.2 to 12 litres, more preferably from

5 0.45 to 6 litres.

According to another feature the bag is preferably made of a polymeric water soluble film. The thickness of this film is generally from 10 to about 500 microns, preferably from 20 to about 100 microns.

According to another feature, the bag of the invention is not filled to capacity: the bag is then generally filled to at least 60% of capacity with the gel, which preferably comprises an agricultural chemical, more preferably to at least 70% of capacity, still more preferably 80% to 99% of capacity and most preferably

5 85% to 95% of capacity. The bag is preferably not filled to complete capacity because the unused capacity gives the bag resistance to breakage when dropped, transported or stored. This unused capacity may or may not contain air or an inert gas. The unused capacity, whether or not it contains air or gas improves shock resistance. However, in deciding how much unused capacity to provide, the advantages of shock resistance and the cost of providing unused capacity must be balanced against the need, if any, for shock resistance and the cost of unused capacity. Thus, if the bag is stored and/or transported in a shock absorbing

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1 container, then it may not be as helpful to provide this unused capacity.

Also, the capacity to which the bag is filled, and whether the unused capacity does or does not contain air or a gas is affected by whether it is desirable to have the bag sink or float.

Also, whether the bag sinks or floats will depend not only on the unused capacity, but also the density of the bag contents.

The water soluble films which are used to make the water soluble bags are known. In order to make a bag, the film needs to be shaped (possibly partially sealed) and then filled with the gel. Generally the gels are able to flow, even if it is a slow rate due to high viscosity. If necessary the gel is propelled in to the bag with pressure. A container, which is used to contain a gel, has not been used up to now in agriculture.

When filled with the gel compositin hereinbefore described, the bag has to be finally sealed, generally heat sealed, to be closed. The sealing may be made according to known manner.

EXAMPLES

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

5 In these examples, the Brookfield viscosity was measured, as previously indicated, with a Brookfield viscosimeter which had a flat plate rotating at 20 revolutions per minute. In all of the following examples, the prepared gels had a tg(phi) of between 0.75 and 1.5.

The emulsion stability of the prepared gels is evaluated according to the following method: 1 ml of the gel is mixed with 99 ml water in a 150 ml tube; the tube is inverted-10 times at the rate of 1 complete inversion per second. Rating of the emulsion stability is made by reading the relative amount of phases after

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AP3 5 6 hours. The emulsion stability is rated as follows: excellent if the amount of emulsion (phase looking like milk) represents 98 to 100% (y/ν) of the total, the balance being cream or thin; good if the amount of emulsion represents 90 to 98% (v/v) of the total, ·' the balance being mainly cream with no more than 5 ml being thin; fair if the amount of emulsion represents 70 to 90% (v/v) of the total, the balance being cream or thin; and poor if the total of emulsion represents 70 or less % (v/v) of the total.

The spontaneity is assessed according to the following 10 method: A mixture of 1 ml gel with 99 ml water are put into a 150 ml glass tube (diameter 22mm) which is stoppered and inverted by 180 degrees (upside down). The number of inversions required to completely disperse the gel is called the spontaneity.

EXAMPLE 1

A gel is made by stirring and shaking at 50° C a mixture of the following ingredients until they are each dissolved or dispersed:

active ingredient: the herbicide 2,4-D;

phenoxy benzoic acid (isooctyl ester): 64.8% solvent: aromatic solvent with flash point of 65° C: 24.2%

5 adjuvants:

non ionic/sulf onate blended emulsifier: 4 % calcium alkylbenzene sulfonate: 1 % mixture of dioctylsulfosuccinate salt and sodium benzoate 6 %.

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During stirring, a dissolution or dispersion appears, and thereafter gelation. Gelation increases as the mixture cools to about 20° C.

The Brookfield viscosity of the gel is 3000 centipoise.

The emulsion stability is good according to the above described test.

1100 g of this gel are put in a one-litre bag made of a film of PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; thickness: 55 microns). The bag, which is almost full (about 95X v/v), is hot sealed. The specific gravity of the gel and of the bag containing the gel is 1.1.

The bag is dropped 10 times from 1.2 m above the ground. No breaking or leakage is observed.

The bag is put into a tank containing water under gentle 1 3 agitation (that is to say such as that obtained with pump recycling). The bag and its contents are dispersed within a 3 minute interval. There is no clogging in the filter, which is a screen having 0.28 mm openings.

EXAMPLE 2

The procedure of Example 1 is repeated, using the same active ingredient in a mixture containing the following adjuvants:

non ionic/sulfonate blended emulsifier: tetramethyl decynediol:

5.2 X

X.

The Brookfield viscosity of the gel is 3000 centipoise.

The emulsion stability is good using the above described test.

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1100 g of this gel are put in a 1 litre bag made of a film of PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; thickness: 55 microns). The bag, which is almost full (about 95% v/v), is hot sealed. The specific gravity both of the gel and of the bag containing the gel is 1.1.

The bag is then dropped 10 times from 1.2 m upon the ground. No breaking or leakage is observed.

The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 3 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings.

EXAMPLE 3

The procedure of Example 1 is repeated, using the same

5 active ingredient in a mixture containing the following adjuvants:

non ionic/sulf onate blended emulsifier: 21.5%;

calcium alkylbenzene sulfonate: 3.¾ ethoxylated dialkylphenol: 10 %.

The Brookfield viscosity of the gel is 3000 centipoise.

The emulsion stability is good using the above described test.

1100 g of this gel are put in a 1 litre bag made of a film of PVA (88% hydrolyzed polyvinyl acetate; cold water soluble;

5 thickness: 55 microns). The bag, which is almost full (about 95% v/v), is hot sealed. The specific gravity both of the gel and of the bag containing the gel is 1.1.

The bag is then dropped 10 times from 1,2 m upon the ground. No breaking or leakage is observed.

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EXAMPLE 4

A gel is made by stirring at 50° C a mixture of: active ingredient:

bromoxynil acid in the form of an octanoate ester: 61.15%;

solvent: aromatic solvent with a flash point of 38° C: 22.85%;

polyaryl phenolethoxylated: 6 %;

calcium alkylbenzene sulfonate: 2 %;

clay which has been modified by addition of methyl groups: 6 %;

propylene carbonate (activating the thickener): 2 %.

These materials are mixed together while shearing with an Attritor mixer. The product started to gel within a few minutes.

The Brookfield viscosity of the gel is 4200 centipoise.

The emulsion stability is good using the above described test.

The spontaneity is 38.

The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 10 minute interval. There is no clogging in the filter which is a 50 mesh screen.

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EXAMPLE 5

The procedure of Example 4 is repeated, using a mixture containing the following components:

active ingredient:

bromoxynil octanoate: 18.65%;

bromoxynil heptanoate: 13.85%;

methyl chloropropionic acid (isooctyl ester) 37.4 %;

solvent: aromatic solvent with a flash ¹0 point of 38° C: 11,1 %;

hydrogenated castor oil: 3 %;

ethoxylated vegetable oil: 3 %;

non ionic/sulfonate blended emulsifier: 13 %.

5 These materials are mixed together while shearing with an

Attritor mixer. The product started to gel within a few minutes.

The Brookfield viscosity of the gel is 3150 centipoise.

The emulsion stability is good using the above described test.

£0 The spontaneity is 20.

1100 g of this gel are put in a 1 litre bag made of a film of

PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; thickness: 55 microns). The bag, which is almost full (about 95% v/v), is hot sealed. The specific gravity both of the gel and of £3 the bag containing the gel is 1.1.

The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump 3 0 recycling). It is dispersed within a 10 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings. EXAMPLE 6

The procedure of Example 5 is repeated using a mixture containing the following components:

AP3 56 active ingredient:

bromoxynil octanoate: 18.4%;

bromoxynil hegtanoate: 14 %;

ι^y · 2 t*· / methyl chloroprepaenic/acetic acid C : (isooctyl ester) ,^z 36.6%;

non ionic/sulfonate blended emulsifier: 9 %;

sodium sulfonate of naphthalene formaldehyde condensate: 3 %;

dioctyl ester of sodium sulfosuccinic acid

0 and sodium benzoate 2 %;

diatomaceous earth: 17 %.

These materials are mixed together while shearing with an Attritor mixer. The product started to have the appearance of a

1smooth paste, and is a gel within a few minutes.

The Brookfield viscosity of the gel is 9000 centipoise.

The emulsion stability is good using the above described test.

The spontaneity is 9.

1100 g of this gel are put in a 1 litre bag made of a film of

PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; thickness: 55 microns). The bag, which is almost full (about 95% v/v), is hot sealed. The specific gravity both of the gel and of the bag containing the gel is 1.1.

2. The bag is then dropped 10 times from 1.2 m upon the ground. No breaking or leakage is observed.

The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 10 minute interval. There is no

0 clogging in the filter which is a screen having 0.28 mm openings.

EXAMPLE 7

The procedure of Example 5 is repeated, using a mixture containing the following components:

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active ingredient:
bromoxynil octanoate:	18.89%;
bromoxynil heptanoate:	12.59%;
atrazine:	44.58%;
solvent: same as in example 5:	18.54%;
polyethylene glycol:	2.7 %.
These materials are mixed together while	shearing with an

Attritor mixer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes.

The Brookfield viscosity of the gel is 7300 centipoise.

The emulsion stability is good using the above described test.

The spontaneity is 15.

The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 10 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings.

EXAMPLE 8

The procedure of Example 7 is repeated, using a mixture containing the following components using:

active ingredient:

bromoxynil octanoate: 33.7%;

methyl chloropropionic acetic acid (isooctyl ester) solvent: solventxaromatic solvent with a

36.2%;

ΛΡ3Ιβ flash point of 65° C:

non ionic/sulfonate blended emulsifier: calcium dodecyl benzene sulfonate: tetramethyl decyne diol:

X; 8.5%;

%; 17.6%.

These materials are mixed together while shearing with an Attritor mixer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes.

The Brookfield viscosity of the gel is 2200 centipoise.

The emulsion stability is good using the above described test.

The spontaneity is 14.

The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 5 minutes interval. There is no clogging in the filter which is a screen having 0.28 mm openings.

EXAMPLE 9

The procedure of Example 8 is repeated, using a mixture containing the following components:

active ingredient and solvent are the same as in example 8, and amount of active ingredient is the same;

solvent is the same but the amount is 10.6%;

calcium dodecyl benzene sulfonate: 2 %;

mixture of dimethyl hexane and hexyne diol: calcium alkylaryl sulfonate and a polyarylphenol ethoxylate:

11.5%;

%.

These materials are mixed together at 90° C while shearing with an Attritor mixer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes.

The Brookfield viscosity of the gel is 2500 centipoise.

The emulsion stability is good using the above described test.

The spontaneity is 5.

1100 g of this gel are put in a 1 litre bag made of a film of 10 PVA (88% hydrolyzed polyvinyl acetate; cold water soluble;

thickness: 55 microns). The bag, which is almost full (about 95% v/v), is hot sealed. The specific gravity both of the gel and of the bag containing the gel is 1.1.

The bag is then dropped 10 times from 1.2 m upon the 1 ground. No breaking or leakage is observed.

The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 5 minute interval.There is no clogging in the filter which is a screen having 0.28 mm openings.

EXAMPLE 10

The procedure of Example 5 is repeated, using a mixture containing the following components using:

active ingredient:
bromoxynil octanoate:	33.5%;
bromoxynil heptanoate:	33.5%;
solvent: aromatic solvent with a flash
point of 65° C:	22.75%;
non ionic/sulfonate blended emulsifier:	4.5%;
calcium dodecyl benzene sulfonate:	IX;
and sodium benzoate:	4.25%;
tetramethyl decyne diol:	0.5%.

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These materials are mixed together at 50° C while shearing with an Attritor mixer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes.

The Brookfield viscosity of the gel is 4850 centipoise.

The emulsion stability is excellent using the above described test.

The spontaneity is 10.

The bag is placed in a tank containing water under gentle agitation (that is to say such aa that obtained with pump recycling). It is dispersed within a 3 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings.

Claims

1. A containerization system for holding and securing agricultural chemical compounds which comprises a water soluble or water dispersible bag which completely encloses a water dispersible gel, said gel comprising an agricultural chemical compound and being such as to avoid leakage of the gel through pinholes which may develop in the bag.

2 . A containerization system according to claim 1 wherein the chemical compound is a pesticide or a plant protection agent.

3. A containerization system according to any one of the preceding claims wherein the agricultural chemical is toxic or hazardous to the environment or to persons contacted by it.

4. A containerization system according to any one of the preceding claims wherein the gel. has a viscosity of from 500 to 50,000 centipoises.

5. A containerization system according to claim 4 wherein the gel has a viscosity of from 1,000 to 5,000 centipoises.

6. A containerization system according to any one of the preceding claims wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.5.

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- 23

7. A containerization system according to claim 6 wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.2.

8. A containerization system according to any one of the preceding claims wherein the gel substantially completely disperses in water after agitation in water during at most 15 minutes.

9. A containerization system according to claim 8, wherein the gel substantially completely disperses in water after agitation in water within 10 minutes.

10. A containerization system according to any one of the preceding claims wherein the gel has a spontaneity, as herein defined, less than 75.

11. A containerization system according to claim 10, wherein the gel has a spontaneity, as herein defined, less than 25.

12. A containerization system according to any one of the preceding claims wherein the gel is a composition which has essentially one visually observable physical phase.

13. A containerization system according to any one of the preceding claims wherein the gel can be divided by cutting and the cut parts are able to merge by simple juxtaposition.

14. A containerization system according to any one

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AP3 5 6 of the preceding claims wherein the gel has a specific gravity greater than 1.

15. A containerization system according to claim 14, wherein the gel has a specific gravity grater than 1.1.

5

16. A containerization system according to any one of the preceding claims wherein the gel comprises the agricultural chemical and one or more ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelling agents.

10

17. A containerization system according to claim 16 wherein the gel comprises agricultural chemical and a nonionic surfactant.

18. A containerization system according to claim 17 wherein the surfactant is a nonionic emulsifier.

15

19. A containerisation system according to claim 18 wherein the nonionic emulsifier is a sulfonate.

20. A containerization system according to any one of the preceding claims wherein the gel has a water content which is less than 5% by weight.

20

21. A containerization system according to any one of the preceding claims wherein the bag has a capacity of from 0.01 to 12 litres.

22. A containerization system according to claim 21 wherein the bag has a capacity of from 0.2 to 12 litres

25

23. A containerization system according to claim 22 wherein the bag has a capacity of from 0.045 to 6 litres.

24. A containerization system according to any one bad original s

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- 2 5 of the preceding claims wherein the bag is not filled to capacity and has more than 60% of its volume capacity filled with gel.

25. A containerization system according to claim 24 wherein the bag is filled to from 80% to 99% of capacity.

26. A containerization system according to any one of the preceding claims wherein the bag comprises a film whose thickness is from 10 to 500 microns.

27 . A containerization system according to claim 26, wherein the bag comprises a film whose thickness is from 20 to 100 microns.

28. A containerization system according to any one of the preceding claims wherein the bag comprises a polymeric water soluble film.

29. A containerization system according to system according to claim 28 wherein the bag comprises polyethylene oxide, methylcellulose or polyvinylalcohol.

30. A containerization system according to claim 29 wherein.,the bag comprises a 40-100% alcoholyzed or hydrolysed polyvinyl acetate film.

31. A containerization system according to claim 30, wherein the bag comprises a 80-99% alcoholyzed or hydrolysed polyvinyl acetate film.

32. A self-dispensing containerization system for agricultural chemical compounds that are used in aqueous compositions, said system comprising a water-soluble or water-dispersible bag which encloses a water dispersible

BiWaORlCSWWL

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- 26 gel of substantially organic material comprising an agricultural chemical compound and one or more other gel ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelling agents wherein the gel has a viscosity of from 1,000 to 30,000 centipoises, the specific gravity of the bag with the gel contained therein is greater than 1 and the bag and gel are sufficiently water dispersible so that they are substantially completely dispersed in agitated water within 15 minutes.

33. A system according to claim 32 wherein the agricultural chemical is as defined in claim 2 or 3; and/or the gel is as defined in any one of claims 5 to 20; and/or the bag is as defined in any one of claims 21 to 31.

34. A method for holding and securing agricultural chemical compounds in a manner to prevent their contact with the environment during shipment and storage, said method comprising:

(i) mixing at an elevated temperature an agricultural chemical compound with one or more other gel ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelling agents, until sufficiently dissolved or dispersed to appear visually as substantially a single phase, (ii) allowing the mixture to cool and to form a water-dispersible gel, and (iii) enclosing and sealing a predetermined amount of

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- 27 said gel within a bag of a water-soluble or water-dispersible film, the gel being such as to avoid leakage through pinholes

5 which may develop in the bag.

35. A method according to claim 34 wherein the chemical compound is as defined in claim 2 or 3.

36. A method according to claim 34 or 35 wherein the gel is as defined in any one of claims 4 to 20.

37. A method according to any one of claims 34 to 36 wherein the bag is as defined in any one of claims 21 to 31.