AP357A

AP357A - Gel formuatio for hazardous products.

Info

Publication number: AP357A
Application number: APAP/P/1991/000301A
Authority: AP
Inventors: Leonard E Hodakowski; Samuel Terry Gouge; Paul J Weber; Chi-Yu Chen
Original assignee: Rhone Poulenc Agrochimie
Priority date: 1990-07-18
Filing date: 1991-07-18
Publication date: 1994-09-03
Also published as: MY106541A; PT98352A; RO110894B1; CS221691A3; AU8039991A; BR9105836A; MA22217A1; NZ239002A; TR26104A; EP0491915B1; ATE184746T1; CA2066419C; FI921140A0; IL98805A0; WO1992001375A1; CN1058318A; FI921140A; JPH05501720A; PL294074A1; AU8200091A

Abstract

A water

Description

Title: GEL FORMULATIONS FOR HAZARDOUS PRODUCTS

Abstract

A water dispersible organic gel, which is a continuous system, comprising effective amounts of hazardous product, a water soluble or water dispersible surfactant which contains a non ionic surfactant and optionally an anionic or amphoteric surfactant, and a gelling agent having if solid, a particle size less than 100 microns. The gels are especially suitable for use in water soluble or water dispersible bags rendering the hazardous product safer to handle and for the environment.

(56)

Documents cited:

CA 659 675;

CA 1 005 660 ;

US 3 556 765;

US 3 660 071

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INVENTORS CONTD

2. SAMUEL T. GOUGE

1708 Parkridge Way Raleigh

North Carolina 27614

U.S.A.

3. PAUL J. WEBER

3515-A CENTURY OAKS ROAD DURHAM

NORTH CAROLINA 27713

U.S.A.

4. CHI-YU CHEN

10004 WHITESTONE ROAD RALEIGH

NORTH CAROLINA 27615

U.S.A.

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The invention relates to new containerisation systems containing water dispersible organic gels.

The containerisation systems are suitable for containing hazardous product rendering them safe to handle and for the environment.

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

Hazardous compounds, especially agrochemical 10 compounds, are formulated in various compositions.

Liquid compositions are

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AP3 5 7 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 has been difficult to provide a formulation and a containerisation system (i.e container) which safeguards those handling it, including farmers and transporters, and the environment.

The present invention seeks to provide a new formulation system to contain agrochemicals which is safe to handle, and for the environment.

The invention further seeks to provide a new formulation system for agrochemicals which is readily, rapidly and easily soluble and/or dispersible in water.

The invention also seeks to provide a new formulation system for agrochemicals which is as much condensed as possible, using the least amount of space.

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The invention also seeks to provide a new formulation system to contain hazardous compounds, e.g., agrochemicals vhich diminishes the risks of pollution.

It is also known that liquid agrochemicals may be contained in soluble bags or sachets made from films. However, such films may crack and break and thus, cause spillage of the agrochemicals they contain and create contamination problems. In fact, there are a variety of defects vhich may be present in films, which lead to weaknesses of film and consequently a potential source of leakage. The presence of air bubbles, or dust particles or foreign bodies, or gel particles or thin points on or in the film are all potential weak pointe. If a film with such a weak point is subjected to a lot of handling or physical shocks, the film may fail at that point. This is especially a problem in the agrochemical industry vhere containers may be m subjected to rough or unsafe handling by distributors or farmers.

The invention therefore seeks to avoid leakage through pinholes vhen an agrochemical containing bag is used. Such pinholes are rare, but 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 invention also seeks to avoid breakage of the container vhich contains an agrochemical formulation. 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.

An object of the instant invention is to avoid, or at least to partially reduce, this hydraulic hammer effect. It has been

- 3 BAD ORIGINAL £ mP 3 5 7 proposed to reduce the possibility of breakage by weans of an air space in the bag, but this represents some loss of storage space.

The invention also seeks to provide a formulation or composition for hazardous compounds vhich dissipates, as much as possible, the energy of a shock to a container from outside.

The invention also seeks to provide a shock absorbing formulation system for containing agrochemicals, e.g., pesticides or plant protection agents or plant grovth regulators.

It was knovn to use gel formulations for pharmaceuticals or cosmetics, but there is practically no risk of pollution or contamination of environment vhen handling such products, in contrast to pesticides and agrochemicals.

Furthermore, the gels used for pharmaceutical or cosmetical « purposes are generally water-based, so that it vas unobvious to obtain gels vhich are convenient for vater soluble sachets or bags, nor for pesticide containing vater soluble sachets or bags, nor for shock absorption purposes for such begs.

Another possibility is to have agrochemicals in the form of vet table powders in a bag vhich may be vater soluble. However, not all agrochemicals may be used under the form of a wettable powder, and even these powders are wettable, the length of the time to get the powder wetted (wetting time) may cause some technical problems.

As already stated, other containing systems for pesticides which are safe for the environment have been proposed in the past, especially those containing liquid in soluble bags or sachets. However, it may happen that the bags have pinholes;

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the contained liquid leaks in such conditions and may pollute the environment.

Even though thixotropic liquid may be used, this possibility of leakage through pinholes remains when shipping, because the shipping creates a move which causes the thixotropic liquid to become more fluid.

Furthermore, even the non aqueous liquid contained in the known water soluble bags may have a low, but non zero, content of water, and this content, even though it is low, may cause bag breakage upon freezing.

The present invention seeks to provide a new formulation system for agrochemicals vhich quickly dissolves vhen put into vater and vhich is not damaged by normal freezing.

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The invention also seeks to provide a formulation system wherein less solvent is needed* in the * formulation of the pesticide, which is cost saving both in shipping and manufacturing.

The invention further seeks to provide a new formulation system for agrochemicals vhich reduces the risks of clogging the spray nozzles or the filters of spray tanks.

The present invention provides a containerisation system comprising a water dispersible organic gel in a water soluble or water dispersible bag, wherein the gel is a continuous system having 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, which gel comprises effective amounts of:

a hazardous product; optionally organic solvent;

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- 6 a water soluble or water dispersible surfactant which comprises a non ionic surfactant and optionally an anionic or amphoteric surfactant, and which is able to form a liquid mixture with the hazardous product and organic solvent, if present, at a temperature above 70°C preferably above 50°C;

a gelling agent which is liquid or solid at 23°C and if solid has a particle size lower than 100 microns, and which is soluble at a concentration of at least 10% by weight in the liquid mixture of hazardous product, surfactant and organic solvent, if present; and less than 3% by weight of water, preferably less than

1%.

The liquid mixture of surfactant, hazardous product and optionally organic solvent may be a single continuous phase or it may be in the form of an emulsion.

The anionic or amphoteric surfactant may be zwitterionic.

The gel used in the present invention may optionally comprise one or more of the further following components:

an organic solvent or mixture of organic solvents in which the hazardous product is soluble (e.g. completely soluble) at the concentration present in the gel;

a dispersent;

a secondary thickener; and/or other additives, such as stabiliser(s), antifoaraing agent(s), buffer(s), antjfreezing agent(s).

Among the gels used in the invention as hereabove defined, some particular gels are preferred, especially those comprising by weight:

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AP3 5 7 to 951, preferably 10 to 90%, more preferably 25 to 80%, of hazardous product to 50%, more preferably 2 to 15%, of surfactant,

0.1 to 50%, more preferably 2 to 10%, of gelling agent

0.1 to 30%, more preferably 1 to 25% of secondary thickener,

0.80% of solvent, more preferably 3 to 50%, to 20% of other additives (as herein before defined), preferably, 0.1 to 10%.

When the gels contain a dispersant, they preferably comprise by weight 1 to 25%, more preferably 2 to 8% of dispersant.

According to a particular feature of the invention, the components of the compositions are chosen in such a way that the gels have a viscosity of 600 to 30,000 centipoises, more preferably of 1000 to 12000 centipoises (those viscosities are Brookfield viscosities measured vith a viscosimeter in form of a flat plate rotating at 20 revolutions per minute).

By the wording continuous system, it is meant a material which is visually homogeneous, that is to say which has the visual appearance to have only one physical phase; this does not exclude the possibility of having small solid particles dispersed therein, provided these particles are small enough not to constitute a visible separate physical phase.

It is known that a gel is generally a colloid in vhich the dispersed phase has combined with the continuous phase to produce a viscous, jelly-like product; it is also a dispersed System consisting typically of a high molecular weight compound

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AP3 5 7 or aggregate of small particles in very close association with a liquid. In the gels used in the invention, the hazardous product (or active ingredient) may be in a soluble form, or in a dispersed form such as in a suspension.

According to a particular feature of the invention, the components of the compositions are chosen in such a way that the gels used in the invention have a specific gravity greater than 1, preferably greater than 1.05, more preferably greater than 1.1.

According to another particular feature of the invention, the components of the compositions are chosen in such a way that the gels contained in the bags of the invention preferably 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 gel vith 99 ml water are -put into a 150 ml glass tube which is stoppered and inverted through 180· (upside down). The number of times required to completely disperse the gel is called the spontaneity.

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 vhich are particularly suitable for the invention are defined by the following test: according to this test, the liquid active ingredient, in the organic solvent if present in the gel, (50g in total) and surface-active adjuvant (5 g) are added to an amount of water, at 50°C, which is sufficient to bring the volume of the mixture to 100 cl; the mixture is agitated so as to give a homogenous emulsion and this is left to stand for 30 minutes at 50^eC in a graduated cylinder; the amount of oily layer which may have separated out (and thus formed a distinct liquid phase) must then be less than 20 cl.

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The surfactant vhich say be used in the invention nay be selected iron among those of the folloving list (vhich is non limitative):

non ionic surfactant: alkanolamides, poly condensates of ethylene oxide vith fatty alcohols, fatty esters, or fatty amines, or substituted phenols (particularly alkylphenols or arylphenols); block copolymers with ethoxy and propoxy groups esters of fatty acids vith polyols such as glycerol or glycol; polysaccharides; organopolysiloxanes; sorbitan derivatives; ethers or esters of sucrose or glucose;

anionic or amphoteric surfactants: salts of lignosulphonic acids, salts of phenyl sulphonic or naphthalene sulphonic acids, diphenyl sulfonates; alkylaryl sulfonates; sulfonated fatty alcohols or amines or amides; poly condensates of ethylene oxide vith fatty acids and their sulfate or sulfonates derivatives; salts of sulphosuccinic or sulfosuccinamic acid esters; taurine derivatives (particularly alkyltaurates); betaine derivatives; phosphoric esters of ialcohols or of polycondensates of ethylene oxide vith phenols; and sulphate, sulphonate and phosphate functional derivatives of the above compounds.

By the vording gelling agent, it is meant a material

I (corresponding to the active ingredient in such a vay that, vhen mixed, at 50/50 v/v and 25*C, vith (and optionally ground vith) an organic solvent vherein the active ingredient is soluble, a gel is obtainable. According to the present invention, a gel is essentially a material vhich has a phase difference phi betveen the controlled shear stress and the resulting shear strain such that tg(phi) is less than or equal to 1.5, preferably less than >r egual to 1.2. Tg(phi) is the tangent of the angle phi (or

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AP3 5 7 phase difference). The measurement of phi is made by Beans of a «

rheometer having a flat fixed plate and a rotating cone above 'this plate such that 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 controlled shear stress.

Gelling agents which may be used in the invention are tetramethyl decyne diol, ethoxylated dialkylphenol, methylated clay, propylene carbonate, hydrogenated caster oil, ethoxylated vegetable oil, diatomaceous earth, mixture of dioctyl sodium sulfosuccinate and sodium benzoate, and mixtures of hexanediol and hexynediol.

Preferably if the gelling agent is solid it has a particle size of less than 40 microns, more preferably less than 10 microns.

The expression hazardous product as used herein is defined as a product which may cause damage to the environment or be injurious to a person handling it.

According to one main and preferred feature of the invention, the hazardous product is an active ingredient which is an agrochemical, and more precisely a pesticide or a plant protection agent (including plant growth regulators or plant nutrient).

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

in the invention includes:

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Fungicides such as Triadimefon, Tebuconazole,

Prochloraz, Triforine, Tridemorph, Propiconazole, Pirimicarb, Iprodione, Metalaxyl, Bitertanol, Iprobenfos, Flusilazol,

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Fosetyl, Propyzanide, Chlorothalonil, Dichlone, Mancozeb,

Anthraquinone, Maneb, Vinclozolin, Fenariaol, Bendiocarb,

Captafol, Benalaxyl, Thiram;

Herbicides (or defoliants) such as quizalofop and its derivatives, Acetochlor, Metolachlor, Iaazapur And laazapyr, Glyphosate And Gluphosinate, Butachlor, Acifluorfen, Oxyfluorfen, Butralin, Fluazifop-butyl, Bifenox, Broaoxynil, loxynil,

Diflufenican, Phenaediphaa, Deeaediphaa, Oxadiazon, Mecopropo, MCPA, MCPB, MCPP, Linuron, Isoproturon, Flaaprop And Its Derivatives, Ethofuaesate, Diallate, Carbetamide, Alachlor, Metsulfuron, Chlorsulfuron, Chlorpyralid, 2,4-d, Tribufos, Triclopyr, Diclofop-aethyl, Sethoxydia, Pendiaethalin, Trifluralin, Ametryn, Chloraaben, Aaitrole, Asulaa, Dicaaba, Bentazone, Atrazine, Cyanazine, Thlobencarb, Proaetryn, 2-(2chlorobenzyl)-4,4-dijnethyl-l,2-oxazolidin-3-©ne, Fluometuron, Hapropaaide, Paraquat, Bentazole, Molinate, Propachlor,

Iaazaquin, Metribuzin, Tebuthiuron, and Oryzalin;

Insecticides or neaaticides such as Ebufos,

Carbosulfan, Aaitraz, Vaaidothion, Ethion, Triazophos, Propoxur, Phosalonc, Peraethrin, Cyperaethrin, Parathion, Methylparathion, Diazinon, Kethoayl, Malathion, Lindane, Fenvalerate, Ethoprophos, Endrin, Endosulfan, Dimethoate, Dieldrin, Dicrotophos, Dichlorprop, Dichlorvos, Azinphos And Its Derivatives, Aldrin, Cyfluthrin, Deltaaethrin, Disulfoton, Chlordiaefora,

Chlorpyrifos, Carbaryl, Dicofol, Thiodicarb, Propargite, Deneton, and Phosalone;

Plant grovth regulators such as gibberllic acid, ethrel or ethephon, cycocel, Chloraequat, Ethephon, and Mepiquat.

In order to assess whether a surface-active adjuvant possesses dispersing properties and may be a dispersant according

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AP3 5 7 to the invention, the following test is carried out: an aqueous suspension (100 al) containing kaolin or atrazine .(50 g), in the form of solid particles having a particle size between 1 and 10 microns, and surface-active adjuvant (5 g) is left to stand at 20*C for 30 minutes in a graduated cylinder (kaolin is used when the dispersing agent is able to disperse a hydrophilic solid. Atrazine is used when the dispersing agent is able to disperse a hydrophobic solid). After standing, 9/10th (nine-tenths) of the volume of the suspension, situated in the upper part of the suspension, is removed, without agitation, and the solids content (residue after evaporation of the vater) of the remaining tenth is measured; this solids content must not exceed 12% by weight of the solids content of 100 ml of the suspension on which the test is carried out.

The dispersant vhich may be used in the invention may be selected from among those of the following list (vhich is non limitative): salts of lignosulphonic acids such as calcium lignossulfonate, salts of phenyl sulphonic or naphthalene sulphonic acids, condensed naphthalene sulfonic acid; poly condensates of ethylene oxide vith fatty alcohols or fatty acids or fatty esters or fatty amines, or substituted phenols (particularly alkyphenols or arylphenole); salts of sulphosuccinic acid esters, such as sodium sulfosuccinate; taurine derivatives (particularly alkyltaurates); phosphoric esters of alcohols or of polycondensates of ethylene oxide with phenols; esters of polyols and of fatty acids or sulphuric acid or sulphonic acids or phosphoric acids; glyceryl esters, especially esters with fatty acids such as glyceryl stearate; ethylene glycols; and the like.

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The secondary thickener is a compound which increases the viscosity of a gel or a liquid.

The secondary thickener which may be used in the invention may be selected from among the following list (which is non limitative) : fumed silica; hydroxyethyl cellulose, carboxymethylcellose; organically modified attapulgite or montmorillonite clay; hardened castor oil; cetyl and stearyl alcohols or esters; polyethylene glycols; glyceryl hydroxystearate, polyvinylalcohol; salts of sulphosuccinic acid esters such as the dioctyl sodium sulfosuccinate; salts of benzoic acid such as sodium benzoate; and alkyl sulphates.

The gels used in the invention can be prepared or manufactured by any knovn 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. Sometimes it is easier to operate with a slow addition of the constituents of the composition and it might be also useful if the gelling agent is added last.

The chemical nature of the enveloping film constituting the bags in the containerisation systems of the invention can vary quite widely. Suitable materials are water soluble (or possibly vater dispersible) materials which are insoluble in the organic solvents used to dissolve or disperse the agrocherical active ingredient. Specific suitable materials include polyethylene oxide, such as polyethylene glycol; starch ar.d modified starch; alkyl and hydroxyalkylcellulose, such as hydroxymethy Ice 1 lu lose, hydroxyethylcellulose,

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AP3 5 7 hydroxypropylcellulose; carboxymethylcellulose; polyvinylethers such as poly methyl vinylether; poly(2,4-dimethy1-6triazolyethylene); 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).

Preferred material for constituting the bags for the gels are polyethylene oxide or methylcellulose, or polyvinylalcohol. When polyvinylalcohol is used, it is advantageously a 40-100%, preferably 80-99%, alcoholysed or hydrolysed, polyvinyl acetate film.

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 the high viscosity. A container which is used to contain the gels cannot be easily emptied due to this high gel viscosity (a reason why the gels were not used up to now in the agriculture). When filled, the bag has to be finally sealed, generally heat sealed, to be closed.

Further information may be found in the following copending applications, the disclosures of which are incoprorated herein by reference: application of Leonard E. Hodakowski, ChiYu R. Chen, Samuel T. Gouge, Paul J. Weber for Gel Formulations for Use in Toxic or Hazardous Product Containerization Systems filed April 4, 1991; application of David Edvards and William McCarthy for Laminated Bags for Containerization of Toxic or Hazardous Materials filed April 4, 1991; application of Leonard it. Hodakowski, Chi-Yu R. Chen, Samuel T. Gouge, and Paul J. Weber

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AP3 5 7 for Water Dispersible Cel Formulations filed April 4, 1991; application of Leonard E. Hodakovski, Ricky W. Couch, Samuel T. Gouge and Robert C. Ligon for Gel Formulations filed April 4, 1991; and application of Samuel T. Gouge, David P. Downing, Spencer B. Cohen, Allan J. Luke, Robert D. McLaughlin and James E. Shue for Bag In A Bag for Containerization of Toxic or Hazardous Material filed April 4, 1991.

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

EXAMPLE 1

A gel vas made by stirring at 50*C a mixture of:

Active ingredient: 2,4-D phenoxy benzole acid lsooctyl ester: 64.81

Solvent: aromatic solvent with flash point of 65*C:

24.2%

Surfactant: a mixture of a non ionic/sulfonate blended emulsifier 4% and calcium alkylbenzene sulfonate 1%

Gelling agent: mixture of dioctylsulfosuccinate salt and sodium benzoate: 6%.

The mixture is stirred and shaken until each component is dissolved or dispersed.

During stirring, a dissolution appears, and thereafter a gellation. Gellation is increased during cooling at room temperature (20*C).

The Brookfield viscosity of the gel is 3000 centipoises.

The emulsion stability is good in the above described test.

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1100 g of this gel are put in a 1 liter bag made of a film of PVA (88% hydrolysed polyvinyl acetate; cold water soluble; thickness: 55 Bicrons). The beg, vhich is almost full (about 95% v/v), is heat sealed. The density both of the gel and of the bag containing the gel is l.l.

The bag is then dropped 10 times froa 1.2 a upon the ground. Ho breaking or leakage ie observed.

The bag ie put in a tank containing vater under gentle agitation (such as that obtained vith puap recycling). It ie dispersed within a 3 ainute interval. There is no clogging in ' the filter vhich is a 100 aesh screen.

Another bag aade in the ease way as the previous one is tested for pinhole protection. A needle (diaaeter: 0.6 aa) is passed through the bag. It is observed a snail droplet vhich forns at the locus where the needle passed, but this droplet vas small enough not to drop froa the bag and not to flow along the bag.

EXAMPLE 2

The procedure of example 1 vas repeated, except a mixture containing the folloving adjuvants was used:

Surfactant: non ionic/sulfonate blended emulsifier:5.2%

Gelling agent: tetramethyl decynediol 30%.

The Brookfield viscosity of the gel is 3000 centipoises.

The emulsion stability is good in the above described test.

1100 g of this gel are put in a 1 liter bag made of a film of PVA (88% hydrolysed polyvinyl acetate; cold vater soluble; thickness: 55 microns). The bag, vhich is almost full bad original

AP3 5 7 (about 95% v/v), is heat sealed. The density 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 put in a tank containing vater under gently agitation (such as that obtained vith pump recycling). It is dispersed within a 3 minute interval. There is no clogging in the filter which is a 100 mesh screen.

EXAMPLE 3

The procedure of example 1 vas repeated, except a mixture containing the folloving adjuvants vas used:

Surfactant: non ionic/sulfonate blended emulsifier:

21.5%.

and calcium alkylbenzene sulfonate: 3.7%

Gelling agent: ethoxylated dialkyphenol: 10%

The Brookfield viscosity of the gel is 3000 centipoises.

The emulsion stability is good in the abovedescribed test.

1100 g of this gel are put in a l liter bag made of a film of PVA (88% hydrolysed polyvinyl acetate; cold vater soluble; thickness: 55 microns). The bag, vhich is almost full (about 95% v/v), is heat sealed. The density both of the gel and of the bag containing the gel is 1.1

The bag is put in a tank containing vater under gentle agitation (such as that obtained vith pump recycling). It

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AP3 5 7 is dispersed within a 3 Minute interval. There ia no clogging in the filter vhich ia a 100 mesh screen.

EXAMPLE 4A gel vas nade by stirring at 50*C a Mixture of: active ingredient:

broaoxynil acid (octanoate aster): 18.65% broaoxynil acid (heptanoata aster): 13.85% aethylchloropropionic acid (iaooctyl ester): 37.4%

Solvent: aroaatic solvent vith a flash point of 38*C:

11.1%

Surfactant: non ionic/sulfonate blender eaulsifier: 13%

Gelling agent aixture:

hydrogenated castor oil 3% ethoxylated vegetable oil 3%

These aaterials are aixed together while shearing vith attritor sixer. The product started to gel in a few minutes.

The Brookfield viscosity of the gel is 3150 centipoises.

The eaulsion stability is good in the above described test.

The spontaneity is 20.

1100 g of this gel are put in a 1 liter bag aade of a film of PVA (88% hydrolysed polyvinyl acetate; cold vater soluble; thickness: 55 microns). The bag, vhich is almost full (about 95% v/v), is heat eealed. The density both of the gel and of the bag containing the gel is 1.1.

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The bag is put in a tank containing vater under gentle agitation (such as that obtained vith pump recycling). It is dispersed vithin a 10 minute interval. There is no clogging in the filter vhich is a 50 mesh screen.

EXAMPLE 5

The procedure of example 4 vas repeated, except a mixture containing the following components was used:

Active ingredient:

bromoxynil octanoate 18.4% bromoxynil heptanoate: 14.0% methyl chloropropionic acetic acid (isooctyl ester)

36.6%

Surfactant mixture: non ionic/sulfonate blended emulsifier 9.0%

Gelling agent: diatomaceous earth 17.0% and dioctyl ester of sodium sulfosuccinic acid and sodium benzoate 2.0%

Dispersant: sodium sulfonate of naphthalene formaldehyde condensate 3.0%

These materials are mixed together while shearing vith attritor mixer. The product started to have the appearance of a smooth paste, and is a gel in a few minutes.

The Brookfield viscosity of the gel is 9000 centipoises.

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The emulsion stability is good in the above described test.

The spontaneity is 9.

' 1100 g of this gel are put in a 1 liter bag made of a film of PVA (88¾ hydrolysed polyvinyl acetate; cold water soluble; thickness: 55 microns). The bag, vhich is almost full (about 95¾ v/v), is heat sealed. The density both of the gel and of the bag containing the gel is 1.1.

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

EXAMPLE 6

The procedure of example 5 was repeated, except a mixture containing the folloving components was used:

Active ingredient:

bromoxynil octanoate 31.5¾ bromoxynil heptanoate 31.5¾ atrazine 44.58¾

Solvent: same as in example 1 23.25¾

Gelling agent: mixture of dioctyl sodium sulfosuccinate and sodium benzoate. 1.5¾ Stabilizer: alkyl sulfate 2.15¾

Surfactants:

ethoxylated/propoxylated block copolymer with alkylphenol 3.6¾ alkylarylsulfonate of an amine 5¾ bad ORIGINAL $

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Antifreeze agent: polyethylene glycol it

Antifoam: polyorganosiloxane 0.5¾

These materials are mixed together and passed through a bead mill. The product gets the appearance of a gelatineous mixture; after about 5 hours, it becomes much more viscous.

The Brookfield viscosity of the gel is 9100 centipoises and is 5200 after stirring for 4 minutes.

The emulsion stability is good in the above described test.

The spontaneity is 11.

1100 g of the gel are poured into a 1 liter bag made of a film of PVA (88¾ hydrolysed polyvinyl acetate; cold vater soluble; thickness: 75 microns). The bag, vhich is almost full (about 95% v/v), la heat sealed. The density both of the gel and of the bag containing the gel is 1.2.

The bag is then dropped 10 times from 1.2 m upon the ground. Ko breaking or leakage is observed.

The bag ia put in a tank containing vater under gentle agitation (such as that obtained vith pump recycling). It is dispersed within a 5 minute interval. There ia no clogging in the filter vhich ia a 100 mesh screen.

EXAMPLE 7

The procedure of example 6 vas repeated, except a mixture containing the following components was used:

Active ingredient:

bromoxynil octanoate 33.7% methyl chloropropionic acetic acid (isooctyl ester): ester 36.2%

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Solvent: aromatic solvent with flash point of 65*C: 3.0¾

Surfactant:

non ionic/sulfonate blended emulsifier 8.5¾ and calcium dodecyl benzene sulfonate 1.0¾

Gelling agent: tetramethyl decyne diol 17.6¾

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

The Brookfield viscosity of the gel is 2200 centipoises.

The emulsion stability is good in the above described test.

The spontaneity is 14.

1100 g of this gel are put in a 1 liter bag made of a film of PVA (88% hydrolysed polyvinyl acetate; cold water soluble; thickness: 55 microns). The bag, which is almost full (about 95% v/v), is heat sealed. The density 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. Ho breaking or leakage is observed.

The bag is put in a tank containing vater under gentle agitation (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 100 mesh screen.

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EXAMPLE 8

The procedure of example 7 vas repeated, except a mixture containing the folloving components vas used:

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 10.61

Surfactant mixture:

polyarylphenol ethoxylated and 61 calcium dodecyl benzene sulfonate 21

Gelling agent: mixture of hexane diol and hexyne diol: 11.5%

These materials are mixed together at 90*C vhila shearing vith attritor mixer. The product started to have the appearance of a smooth paste, and is a gel in a fev minutes.

The Brookfield viscosity of the gel is 2500 centipoises.

The emulsion stability is good in the above described test.

The spontaneity is 5.

1100 g of this gel are put in a 1 liter bag made of a fila of PVA (88% hydrolysed polyvinyl acetate; cold vater soluble; thickness: 55 microns). The bag, vhich is almost full (about 95% v/v), is heat sealed. The density both of the gel and of the bag containing the gel is 1.1.

The bag is put in a tank containing vater under gentle agitation (such as that obtained vith pump recycling). It is

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AP3 5 7 dispersed within a 5 minute interval. There is no clogging in the filter vhich is a 100 mesh screen.

EXAMPLE 9

The procedure of example 4 vaa repeated, except a mixture containing the following components was used:

Active ingredient:

bromoxynil octanoate 33.5% bromoxynil heptanoate 33.51

Solvent:

aromatic solvent vith a flash point of 65*C: 17.5%

Surfactant:

non ionic/sulfonate blended emulsifier 4.5% and calcium dodecyl benzene sulfonate 1.0%

Gelling agent: mixture of dioctyl sodium sulfosuccinate and sodium benzoate 4.25%

Antifoam: tetramethyl decyne diol o.5%

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

The Brookfield viscosity of the gel is 4850 centipoises.

The emulsion stability is excellent in the above described test.

The spontaneity is 10.

1100 g of this gel are put in a 1 liter bag made of a film of PVA (88% hydrolysed polyvinyl acetate; cold water soluble; thickness: 55 microns). The bag, which is almost full

- 24 BAD ORIG_!NAL

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

The bag is put in a tank containing water under gentle agitation (that is to say such as that obtained vith puap recycling). It is dispersed within a 3 minute interval. There is no clogging in the filter which is a 100 mesh screen.

Claims

1. A containerisation system comprising a water dispersible organic gel in a water soluble or water dispersible bag, wherein the gel is a continuous system having 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, which gel comprises effective amounts of:

a hazardous product; optionally organic solvent;

a water soluble or water dispersible surfactant which comprises a non ionic surfactant and optionally an anionic or amphoteric surfactant, and which is able to form a liquid mixture with the hazardous product and organic solvent, if present, at a temperature above 70°C;

a gelling agent which is liquid or solid at 23°C and if solid has a particle size lower than 100 microns, and which is soluble at a concentration of at least 10% by weight iij the liquid mixture of hazardous product, surfactant and organic solvent, if present; and less than 3% by weight of water.

2. A containerisation system according to claim 1 wherein the hazardous product is an agrochemical.

3. A containerisation system according to claim 1 or 2 wherein the hazardous product is a plant protection agent, a plant growth regulator, a pesticide or a plant nutrient.

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- 27

4. A containerisation system according to claim l, 2 or 3, wherein the water soluble or water dispersible surfactant is able to form a liquid mixture with the hazardous product and organic solvent if present at a temperature above 50°C.

5. A containerisation system according to any one of the preceding claims wherein the gelling agent is liquid or a solid with a particle size lower than 20 microns.

6. A containerisation system according to any one of the preceding claims wherein the gel comprises less than 1% by weight of water.

7. A containerisation system according to any one of the preceding claims wherein the gel further comprises one or more of the following components:

an organic solvent or a mixture of organic solvents in which the hazardous product is soluble at the concentration present in the gel;

a dispersant; a secondary thickener; or another additive which is a stabilizer, an antifoaming agent, a buffer or an antifreezing agent.

8. A containerisation system according to claim 7, wherein the gel comprises by weight;

5 to 95¾ of hazardous product,

1 to 50¾ of surfactant,

0.1 to 50% of gelling agent, and

0 to 80% of solvent.

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AP3 5 7 “ 2 3

9. A containerisation system according to claim 8

wherein the gel comprises by we ight: product 25 to 80% of hazardous 2 to 15% of surfactant, 2 to 10% of gelling agent, and 3 to 50% of solvent.

10. A containerisation system according to claim 8 or 9 wherein the gel further comprises by weight:

1 to 25% of dispersant,

0.1 to 30% of secondary thickener, and

0 to 20% of other additives as defined in claim 7.

11. A containerisation system according to claim 10 wherein the gel comprises by weight:

2 to 8% of dispersant,

1 to 25% of secondary thickener, and

0.1 to 10% of other additives as defined in claim 7.

12. A containerisation system according to any one of the preceding claims wherein the gel has a viscosity of 600 to 3.Q,000 centipoises.

13. A containerisation system according to claim 12, wherein the gel has a viscosity of 1,000 to 12,000 centipoises.

14. A containerisation system according to any one of the preceding claims wherein the gel has a specific gravity greater than 1.

15. A containerisation system according to claim 14, wherein the gel has a specific activity greater than

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1.05.

16. A containerisation system according to any one of the preceding claims wherein the gel has a phase different (phi) between the controlled shear stress and the resulting shear strain such that tg(phi) is less than or equal to 1.2.

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

18. A containerisation system according to claim 17, wherein the gel has a spontaneity less than 25.

19. A containerisation system according to any one of the preceding claims wherein the bag comprises a polyethylene oxide; a starch or modified starch; an alkyl or hydroxyalkylcellulose; a carboxyalkylcellulose; a polyvinylether; poly (2,4-dimethyl-6-triazolylethylene) ; poly(vinylsulfonic acid); a polyanhydride; a low molecular weight urea-formaldehyde resin; a low molecular weight melamine-formaldehyde resin; a polyacrylate, a polymethacrylate or polyacrylic acid or a homologue thereof .

20. A containerisation system according to claim 19, wherein the bag comprises a polyethylene oxide which is polyethylene glycol; a hydroxyalkylcellulose which is hydroxymethyl-, hydroxyethyl- or hydroxypropy1-cellulose; a carboxyalkyl-cellulose which is carboxymethyl-cellulose; a polyvinyl ether which is polymethylvinylether; or a

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- 30 polyrethacrylate which is poly (2-hydroxyethy1 methacrylate) .

21. A containerisation system according to any one of the preceding claims wherein the bag comprises

5 polyethylene oxide, methylcellulose, or polyvinyl alcohol.

22. A containerisation system according to claim 21, where the bag comprises polyvinyl alcohol which is 40 to 100% alcoholysed or hydrolysed polyvinyl acetate.

23. A containerisation system according to claim

10 22, wherein the polyvinyl alcohol is 80 to 99% alcoholysed or hydrolysed polyvinyl acetate.