Gel formulations for use in toxic or hazardous product containerisation systems

The present invention relates to novel compositions comprising dangerous products and which are nonetheless safe to handle and harmless to the environment.

Currently, most hazardous liquids are stored in metal kegs or, when smaller quantities are required, plastic containers.

Hazardous compounds, especially agrochemicals, are formulated in various compositions. Liquid compositions are the most convenient for farmers because of the relative ease with which they can be handled. However, there are difficulties in handling these liquid compositions. There is a risk of spillage or leakage if there are holes in containers previously used or if these containers fall. Although it is possible to use safe, impact-resistant containers in the event of an accident, for example during transport, there remains the risk of spillage or leakage with rapid loss of liquid, for example running on the floor.

It has proven difficult to provide a formulation and packaging system that is safe for the individuals handling them, including

<img file="MA22221A1_D0001.tif" />

MA 22221 US farmers and transporters, as well as for the environment.

It is known to present agrochemicals in soluble bags or sachets, but this does not completely eliminate the possibility of cracking and rupture of the bag and a problem of contamination by the liquid. Specifically, when water soluble bags are used, the agrochemical compositions present in the bag are organic compositions, i.e. compositions based on non-aqueous solvents, and the solvent has more or less the tendency to extract 1 'adjuvant and additives of the film and to make the wall' (the film) of the bag more fragile (in particular at low temperature and more precisely at a temperature below o ° c) or to reduce its duration of use.

It is known to use gel formulations for pharmaceutical or cosmetic products, but there is practically no risk of pollution or contamination of the environment when handling these products, as opposed to pesticides and agrochemicals. In addition, the gels used for pharmaceutical or cosmetic purposes are generally water-based gels, so that it was not obvious to obtain gels which are suitable for water-soluble sachets or bags or which are suitable for water-soluble sachets or bags. water-soluble sachets or bags containing agrochemicals or which are suitable for the purpose of absorbing shocks to which these bags are subjected.

In addition, and from a practical point of view, higher concentrations of active ingredient can be obtained when using gels instead of liquids.

An object of the present invention is to provide novel formulations and a novel formulation system containing agrochemicals which are safe for everyone, in particular.

<img file="MA22221A1_D0002.tif" />

MA 22221 US ا farmer and those who handle agrochemicals.

Another object of the present invention is to provide a novel formulation system for agrochemicals which is easy to place in a container and which is easy to handle by the farmer.

Another object of the present invention is to provide novel formulations and a novel formulation system for agrochemicals which are readily soluble and / or dispersible in water. This poses a problem which is particularly difficult to solve since the increase in viscosity is often linked to an increased difficulty of dispersion in water.

Another object of the present invention is to provide a novel formulation system for agrochemicals which is as condensed as possible, using as little volume as possible.

Another object of the present invention is to provide novel formulations and a novel formulation system intended to contain hazardous compounds, for example agrochemicals, which reduce the risk of contamination.

Another object of the present invention is to provide novel formulations and a novel formulation system for containing odorous or foul-smelling compounds, eg agrochemicals, which suppress odors or reduce odor problems.

Another object of the present invention is to prevent rupture of the container which contains an agrochemical formulation. When the container is brittle and rigid, there is a clear possibility of simple rupture, but the liquid still transmits the shocks and it seizes.

<img file="MA22221A1_D0003.tif" />

NIA 22221 US poses the problem of a hydraulic hammer effect. An objective of the present invention is to avoid, or at least partially reduce, this hydraulic hammer effect. Another object of the present invention is to provide a formulation or composition for hazardous compounds which dissipate, as much as possible, the energy of an external impact to which a container is subjected.

Another object of the present invention is to provide a shock absorbing formulation system for containing agrochemicals, eg pesticides, plant protection agents or plant growth regulators.

Another object of the present invention is to provide a formulation which further increases the longevity of the water soluble bag or sachet during storage, eg by preventing the film of the bag from becoming brittle at freezing temperature.

Another object of the present invention is to provide a novel formulation system for agrochemicals which dissolves rapidly when placed in water and which is not damaged by usual freezing.

Further, it is an object of the present invention to provide a novel formulation system for agrochemicals which reduces the risk of clogging of spray nozzles or filters of spray tanks.

Other objects and advantages of the present invention will become apparent from the following description.

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

The present invention provides formulations or compositions, including agrochemical compositions.

<img file="MA22221A1_D0004.tif" />

MA 22221 US which are particularly suitable for packaging in a water-soluble or water-dispersible bags containing a water-dispersible organic gel, which is a continuous medium comprising:

a hazardous product, for example an agrochemical or an active ingredient (including a pesticide, plant protection agent, or plant growth regulator), a water soluble or water dispersible surfactant, and a gelling agent or thickener (i.e. a compound which greatly increases the viscosity of a polymer in an organic solution.

The term “surfactant” refers to organic material which significantly reduces the surface tension of water.

Surfactants which are particularly suitable for the present invention are defined by the following test: In accordance with this test, the liquid active ingredient (50 g) and a surfactant builder (5 g) are added to an amount of water at 5O٠C in a graduated cylinder; the amount of oily phase which may have separated (and thus formed a distinct liquid phase) should then be less than 20 ml.

The surfactant which is used in the present invention can be nonionic, anionic or cationic, or can exhibit some or all of these characteristics, as for example in the case of mixtures of surfactants. Preferably, it is capable of forming, at a temperature above 50 ° C., preferably above 70 ° C., a liquid phase with the active ingredient. Another advantageous characteristic of the surfactant is that this surfactant contains at least 10% of a surfactant comprising hydroxy and / or alkoxy groups, such as polyethoxyl or polypropoxyl derivatives, in particular

MA 22221 US Derived from fatty amines, fatty acids, fatty alcohols or arylphenols.

Certain preferred surfactants are those which consist of a mixture which contains a nonionic surfactant and optionally an ionic surfactant, and which is capable of forming at a temperature above 5O٠C, preferably above 70 ° C, a liquid phase with the active ingredient.

The gel corresponding to the above definition may optionally contain the following additional constituents:

* an organic solvent in which the active ingredient is completely soluble at room temperature, * a secondary thickener; the thickeners which can be used are the following (non-limiting list): a polymer of acrylic acid, optionally in the form of a salt or a copolymer and optionally partially crosslinked, ٠ fused silica;

hydroxyethylcellulose, carboxymethylcellulose, ٠ organically modified attapulgite or montmorillonite clay, ٠ hardened castor oil; cetyl and stearyl alcohols or esters, polyethylene glycols; Glycerol hydroxystearate, a polymer of vinyl alcohol (low molecular weight), sodium dioctylsulfosuccinate and sodium benzoate; alkylbenzenesulfonates; xanthan gum, polyvinylpyrrolidone; a vinyl acetate polymer, * other additives such as anti-foam agents, stabilizers, buffers, anti-freeze agents.

Among the gels of the present invention corresponding to the aforementioned definition, certain particular gels are preferred, in particular those comprising:

<img file="MA22221A1_D0005.tif" />

MA 22221 US

<td></td><td>10 to</td><td> 90 %,</td><td>preferably</td><td>25 to 80</td><td>%, of</td>

<td colspan="2">The active ingredient.</td><td></td><td></td><td></td><td></td>

<td></td><td>1 to 50</td><td>%, of</td><td>preferably 2 to</td><td>20%, of</td><td>surface-</td>

<td>so much.</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>0.1 to</td><td> 50 %,</td><td>preferably</td><td>0.5 to 10</td><td>%, of</td>

<td>The agent</td><td>gelling agent.</td><td></td><td></td><td></td><td></td>

to 80% of the solvent, preferably 3 to 50%, to 20% of the bag softening agent.

preferably 0.1 to 10%, optionally 0.1 to 20%, preferably 2 to 8%, of a dispersant, 20% of other additives, preferably 0.1 to 10%.

The bag softening agent which can be used in the present invention is preferably a compound which is capable of reducing the glass transition temperature of the vinyl alcohol polymer to room temperature. Further, this bag softening agent is a compound which is water soluble or dispersible in water and is at least 0.1% soluble in the organic phase containing the active ingredient and the solvent or surfactant.

The softening agent for the bag can be chosen from the following liquids (this list is non-limiting): alcohols (linear or branched, saturated or unsaturated), in particular alkenols having 6 to 36 carbon atoms; alkenols having 10 to 30 carbon atoms; glycols and triols such as di- and tripentaerythritols, trimethylolethane, anhydroenneaheptitol, butanetriol, hexanetriol, erythritols, threitols, ribitol, arabinitols, xylitol, allitol, dulcitol, glucitol , sorbitol, mannitol, altritol, iditol, maltitol, lactitol, ethyleneglycol, diethylene glycol, triethyleneglycol, trimethyleneglycol, tetramethyleneglycol, pentamethyleneglycol, hexamethyleneglycol, propylene-

<img file="MA22221A1_D0006.tif" />

MA 22221 US glycol, glycerol, 2,3-butanedi01, 1-butanediol; mono-, di-, tetra- and polyamines, such as diethylenetriamine and ethanolamines; amides, for example acetamide and formamide, dimethylformamide, hexamethylphosphotriamide; sulfoxides, for example dimethylsulfoxide; piperazines.

Bag softening agents which can be used in the present invention as described above impart and maintain flexibility to the bag film, thereby preventing breakage of the bag during handling or storage. , especially at low freezing temperatures (for example below -2O ° C). Thus, there is a low probability that contamination or pollution will occur under these severe conditions.

In accordance with a particular characteristic of the present invention, the constituents of the compositions of the present invention are chosen such that one or more of the following characteristics are present:

* the resulting gels form a continuous medium, and / or * the resulting gels have a viscosity of 500 to 30,000 mPa.s, preferably 1,000 to 12,000 mPa.s (these viscosities are Brookfield viscosities measured with a viscometer under shape of a flat plate rotating at 20 revolutions per minute.

* the gel 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 angle phi (or phase difference). The phi measurement is carried out by means of a rheometer having a fixed flat plate and a rotating cone above this plate so that the angle between the plate and this cone is less than 10 ', of

<img file="MA22221A1_D0007.tif" />

MA 22221 US preferably less than 4 °. The cone is caused to rotate by means of a speed-regulated motor, rotation the rotation is a sinusoidal rotation, which means that the torque and the angular displacement vary as a sinusoidal function over time. This angular displacement corresponds to the shear deformation the torque of the motor at (which causes the angular displacement) controlled shear mentioned above re-jerked speed corresponds to the above born density tension

1.1 g / cm3.

higher gels advantageously have one to 1, preferably higher than gels have a spontaneity (as defined below) lower than 75, preferably lower than 25.

The expression continuous medium designates a material which is visually homogeneous, that is to say which has the visual appearance of a single physical phase; this does not exclude the possibility of the presence of small solid particles dispersed in this medium, provided that these particles are small enough not to constitute a distinct visible physical phase.

It is known that a gel is generally a colloid in which the dispersed phase is combined with the continuous phase to form a viscous, jelly-like product; it is also a dispersed medium typically consisting of a high molecular weight compound or an aggregate of small particles in very close association with a liquid.

The expression hazardous product, as used in the present invention, designates a product which can cause damage to the environment or be harmful to a person handling it.

In accordance with an essential characteristic

<img file="MA22221A1_D0008.tif" />

, NIA 22221US and preferred of the present invention, the hazardous material is an active ingredient which is an agrochemical, more specifically a pesticide or a plant protection agent (including plant growth regulators or plant nutrients) .

The present invention is not limited to certain particular agrochemicals; a list of most of the agrochemicals which can be used in the present invention includes:

fungicides such as triadimefon, tebuconazole, prochloraz, triforin, tridemorph, propiconazole, primicarb, iprodione, metalaxyl, bitertanol, iprobenfos, flusilazol, fosetyl, propyzonil, chlorothalide , dichlone, mancozebe, anthraquinone, manebe, vinclozolin, fenarimol, bendiocarb, captafol, benalaxyl, thiram, herbicides (or defoliants) such as quizalofop and its derivatives, 1 ا acetochlor, metolachlor , imazapur and imazapyr, glyphosate and gluphosinate, butachlor, acifluorfen, oxyfluorfene, butralin, fluazifop-butyl, bifenox, bromoxynil, ioxynil, diflufenican, phenmediphame, desmediphame , oxadiazone, mecoprop, MCPA, MCPB, MCPP, linuron, 1Iisoproturon, flamprop and its derivatives, ethofumesate, diallate, carbetamide, alachlor, metsulfuron, chlorsulfuron, chlorpyralid ; 2,4-D, tribufos, triclopyr, diclofορ-methyl, sethoxydim, pendimethalin, trifluralin, ametryne, chlorambene, amitrole, asulam, dicamba, bentazon,! ' atrazine, cyanazine, thiobencarb, prometryne, 2- (2chl0r0benzyl) -4,4-dimethyl-1,2-0xaz01idin-3-0ne, fluometuron, napropamide, paraguat, bentazole,

<img file="MA22221A1_D0009.tif" />

MA 22221 US molinate, propachlor, imazaquin, metribuzin, tebuthiuron, oryzalin, insecticides OR nematicides such as lebufos, carbosulfan, amitraz, vamidothion, lethion, triazophos, propoxur, phosalone , permethrin, cypermethrin, parathion, parathionmethyl, diazinon, methomyl, malathion, lindane, fenvalerate, ethoprophos, endrin, endosulfan, dimethoate, dieldrin, dicrotophos, dichlorprop, dichlorvos, azinphos and its derivatives, aldrin, cyfluthrin, deltamethrin, disulfoton, chlordimeforme, chlorpyrifos, carbaryl, dicolfol, thiodicarb, propargite, demeton, phosalone, plant growth regulators such as gibberellic acid, ethephon, cycocel, chlormequat, mepiquat.

Among these numerous agrochemicals, the following are particularly interesting: organophosphorus insecticides and herbicides of the hydroxybenzonitrile type such as bromoxynil or ioxynil, in the form of a salt or an ester.

In order to assess whether a surface-active adjuvant has dispersing properties and can constitute a dispersant according to the present invention, the following test is carried out: an aqueous solution (100 ml) containing kaolin or atrazine (50 g ), in the form of solid particles having a diameter of 1 to 10 micrometers.

and a surfactant (5 g) is left to stand at 2O٠C for 30 minutes in a graduated cylinder (kaolin is used when the dispersing agent is capable of dispersing a hydrophilic solid. Atrazine is used. when the dispersing agent is capable of dispersing a hydrophobic solid substance). After rest, 9 / lOth (nine-tenth) of the volume of the suspension.

<img file="MA22221A1_D0010.tif" />

MA 22221 US upper part of the suspension, are taken, without stirring, and the solids content (residue after evaporation of water) 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 spontaneity is evaluated according to the following method: a mixture of 1 ml of gel with 99 ml of water is introduced into a 150 ml glass tube which is sealed and returns 180 '(the upper part down). The number of inversions required for complete dispersion of the gel is referred to as spontaneity.

A thickener is a compound that increases the viscosity of a gel or liquid.

The surfactant which can be used in the present invention can be chosen from those forming part of the following list (which is not limiting): salts of lignosulfonic acids, salts of phenylsulfonic or naphthalesulfonic acids; polycondensation products of ethylene oxide with fatty alcohols, fatty acids, fatty esters or fatty amines, or substituted phenols (in particular alkylphenols or arylphenols); salts of esters of sulfosuccinic acids, ٠ taurine derivatives (in particular alkyl taurates), * phosphoric esters of alcohols or of polycondensation products of ethylene oxide with phenols; esters of fatty acids with polyols; and sulphate, sulphonate and phosphate derivatives of the aforementioned compounds.

The dispersants which can be used in the present invention can be chosen from those of the following list (which is not limiting): a condensed naphthal esulfonic acid; polyacrylic acid, sodium sulfosuccinate, calcium lignosulfonate, glycerol stearate, a polycondensation product of

<img file="MA22221A1_D0011.tif" />

MA 22221 US ethylene oxide and propylene oxide.

The present invention also includes a packaging system which is a water soluble or water dispersible bag which contains a gel as defined above.

-The chemical nature of the packaging film constituting the bags which may contain the compositions or gels of the present invention can vary considerably. Suitable materials are water soluble (or optionally water dispersible) materials which are insoluble in the organic solvents used for the dissolution or dispersion of the agrochemically active ingredient. Particular suitable materials include a polymer of ethylene oxide, such as polyethylene glycol, ٠ starch and modified starch, ٠ alkyl- and hydroxyalkyl cellulose, such as

Hydroxymethylcellulose, hydroxyethylcellulose.

hydroxypropylcellulose; carboxymethylcellulose, ٠ polyvinyl ethers such as polymethylvinyl ether; p01y (2,4-dimethyl-6-triazinylethylene); poly (vinylsulfonic acid); polyanhydrides; low molecular weight uree-formaldehyde resins; low molecular weight melamine-formaldehyde resins; poly (2-hydroxyethyl methacrylate); a polymer of acrylic acid and its homologues; but the packaging film preferably comprises or is made of polyvinyl alcohol (PVA). PVA generally consists of a film of polyvinyl acetate which is fully alcoholized or hydrolyzed, by 100%, preferably 80 to 99%.

The preferred material for the partially or example 40 in the constitution of the bags intended for the gels of the present invention is polyethylene oxide or methylcellulose, or else polyvinyl alcohol. When polyvinyl alcohol is used, it advantageously consists of an acetate film of

<img file="MA22221A1_D0012.tif" />

NIA 22221 US polyvinyl alcoholizes or hydrolyzes 40 to 100%, preferably 80-99%.

The gels of the present invention are generally very easy to produce, simply by mixing the components, optionally with grinding or kneading.

In order to produce a bag, the film must be shaped (possibly partially sealed) and then filled with the gel. In general, the gels are flowable, even if it is a slow speed flow due to the high viscosity. A container which is used for packaging gels cannot be easily emptied due to this high viscosity of the gel (this is one reason why gels have not heretofore been used in agriculture). When it is filled, the bag must finally be sealed, in general heat-sealed, for its closure.

Additional information can be found in the following concurrently pending applications, the descriptions of which are incorporated by reference herein: David Edwards and William McCarthy Application for Laminated Bags for Containerization of Toxic or Hazardous Materials filed April 4, 1991; asked by Samuel T. Gouge, Leonard E. Hodakowski, Chi-Yu R. Chen and Paul J. Weber for Gel Formulations for Hazardous Products filed April 4, 1991; Leonard E. Hodakowski, Chi-Yu R. Chen, Samuel T. Gouge and Paul J. Weber application for Water Dispersible Gel Formulations filed April 4, 1991; asks Leonard E. Hodakowski, Ricky w. Couch, Samuel T. Gouge and Robert v. Ligon for Gel Formulations filed April 4, 1991; and request from 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.

<img file="MA22221A1_D0013.tif" />

MA 22221 US

The following examples are included for the purpose of illustration and should not be construed as limiting the present invention.

In these examples, tg (phi) is less than 1.5. EXAMPLE'1

A gel is prepared by stirring at 50 ° C of a mixture:

of an active ingredient: the isooctyl ester of 2,4-D-phenoxybenz0ic acid: 64.8% of a solvent: an aromatic solvent having a flash point of 65٠c: 23.2% of a surfactant: a mixture of an emulsifier consisting of a mixture of nonionic emulsifier / sulfonate: 4% and of a calcium alkylbenzenesulfonate: 1% of a gelling agent: a mixture of a dioctylsulfosuccinate and sodium benzoate: 6% a bag softening agent: ethyleneglycol: 1%

The mixture is stirred and stirred by shaking until dissolution or dispersion of each component.

During agitation, dissolution occurs, followed by gelation. Gelation is increased during cooling to room temperature (20 ° C.).

The Brookfield viscosity of the gel is equal to 3000 mPa.s.

The stability of the emulsion is good in the test described above.

1100 g of this gel are introduced into a liter bag made up of a film of PVA (88% hydrolyzed polyvinyl acetate; soluble in cold water; thickness:

<img file="MA22221A1_D0014.tif" />

MA 22221 US micrometers). The bag, which is almost full (about% v / v), is heat sealed. The density

<td>frost and 1.1 g / cm3.</td><td>that</td><td>of</td><td>bag containing</td><td>the freeze</td><td>are</td><td>equal to</td>

<td></td><td>Then</td><td>we</td><td>Drop it</td><td>10 times</td><td>the</td><td>bag of a</td>

<td>Hight of</td><td>1.2 m</td><td>sure</td><td>ground. Any</td><td>breaking up</td><td colspan="2">or leak is</td>

<td>observed.</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td colspan="2">Another</td><td colspan="2">sample bag</td><td>is</td><td>also</td>

prepare and store at -2O٥C for 3 days. Then the bag is dropped 5 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

The bag is placed in a tank containing water with moderate agitation (i.e. agitation obtained by recycling with a pump). It is dispersed over a period of 3 minutes. There is no plugging of the filter, which consists of a 0.149 mm mesh screen.

EXAMPLE 2

The procedure of Example 1 is repeated, except that a mixture containing the following adjuvants is used:

Surfactant: an emulsifier consisting of a nonionic emulsifier / sulfonate mixture:

5,2 %

Gelling agent: tetramethyldecynediol: 30%

The Brookfield viscosity of the gel is equal to 3000 mPa.s.

The stability of the emulsion is good in the test described above.

1100 g of this gel are introduced into a liter bag made up of a PVA film (88% hydrolyzed polyvinyl acetate; soluble in cold water; thickness: 55 micrometers). The bag, which is almost full (about 95% v / v), is heat sealed. The density of the gel and that of the bag containing the gel are equal to

PP

MA 22221 US

<td></td><td></td><td></td><td> 17</td><td></td><td></td><td></td><td></td><td></td>

<td>1.1 g / cm³.</td><td>Then</td><td>we</td><td>leash</td><td>fall</td><td>the bag</td><td> 10</td><td>time</td><td>of a</td>

<td>Hight of</td><td>1.2 m</td><td>sure</td><td>ground.</td><td>Any</td><td>breaking up</td><td>or</td><td>escape</td><td>is not</td>

<td>observed.</td><td colspan="2">Another</td><td>bag of</td><td colspan="2">this sample</td><td colspan="3">is also</td>

prepare and store at -2 0 ٠ c for 3 days. Then the bag is dropped 5 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

The bag is placed in a tank containing water with moderate agitation (ie that obtained by recycling by means of a pump). It is dispersed over a period of 3 minutes. There is no plugging of the filter, which consists of a 0.149mm mesh screen. EXAMPLE 3

The procedure of Example 1 is repeated, except that a mixture containing the following adjuvants is used:

Surfactant: an emulsifier consisting of a nonionic emulsifier / sulfonate mixture:

21.5% and a calcium alkylbenzenesulfonate:

١ 3,1

Gelling agent: dialkylphenol ethoxyl 10%

Bag softening agent: a mixture

<td colspan="2">ethylene glycol</td><td>and water</td><td>in</td><td>a</td><td>report</td>

<td>weight of 9</td><td>to 1.</td><td></td><td></td><td></td><td></td>

<td>The viscosity</td><td colspan="2">Brookfield from</td><td>gel</td><td>is</td><td>equal to</td>

<td>3500 mPa.s.</td><td></td><td></td><td></td><td></td><td></td>

<td>Stability</td><td>of</td><td>emulsion</td><td>is</td><td colspan="2">good in</td>

<td>the test described above.</td><td></td><td></td><td></td><td></td><td></td>

1100 g of this gel are introduced into a liter bag made up of a PVA film (88% hydrolyzed polyvinyl acetate; soluble in cold water; thickness:

micrometers). The bag, which is almost full (about% v / v), is heat sealed. The density

<img file="MA22221A1_D0015.tif" />

MA 22221 US of the gel and that of the bag containing the gel are equal to

1.1 g / cm³.

Then the bag is dropped 10 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

-The bag is introduced into a tank containing water with moderate agitation (that obtained by recycling with a pump). It is dispersed over a period of 3 minutes. There is no obstruction of the filter, which consists of a 0.149mm mesh screen.

EXAMPLE 4

A gel is prepared by stirring at 50 ° C of a mixture:

active ingredients:

bromoxynil (in the form of octanoic ester): 30.15% bromoxynil (in the form of heptanoic ester): 31.15% of a solvent: an aromatic solvent having a flash point of 38 ° c: 21 , 85% of a surfactant: a polyarylphnl ethoxy: 6.0%, and a calcium alkylbenzenesulfonate: 2.0% of a mixture of gelling agents: a clay which has been modified by addition of methyl groups: 6, 0%, and propylene carbonate: 2.0% of a bag softener: ethyleneglycol: 1%

These materials are mixed together while subjecting them to shear by means of a friction wear mixer. The product begins to gel within minutes.

<img file="MA22221A1_D0016.tif" />

MA 22221 US

<td>The</td><td>viscosity</td><td>Brookfield from</td><td>gel is equal to</td>

<td>4200 mPa.s.</td><td></td><td></td><td></td>

<td>The</td><td>stability</td><td>emulsion</td><td>is good in</td>

<td>! 'described test</td><td>above.</td><td></td><td></td>

<td>The</td><td>spontaneity</td><td>is equal to 38</td><td> ٠</td>

-1100 g of this gel are introduced into a 1 liter bag consisting of a film of PVA (88% hydrolyzed polyvinyl acetate; soluble in cold water; thickness: 55 micrometers). The bag, which is almost full (approximately

95 % v / v) is heat sealed. The density of the gel and that of the bag containing the gel are equal to

1.1 g / cm3.

Then the bag is dropped 10 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

Another bag of this sample is also prepared and stored at -2O٠C for 3 days. Then the bag is dropped 5 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

The bag is introduced into a tank containing water with moderate agitation (ie that obtained by recycling with a pump). It is dispersed over a period of 3 minutes. There is no obstruction of the filter, which consists of a 25 mesh 0.149 mm grid.

EXAMPLE 5

The procedure of Example 4 is repeated, except that a mixture containing the following constituents is used:

Active ingredients:

bromoxinyl (octanoic ester): 18.65% bromoxinyl (heptanoic ester): 13.85% methylchloropropionic acid (isooctyl ester): 37.4%

Solvent: an aromatic solvent having a point

<img file="MA22221A1_D0017.tif" />

MA 22221 US flash of 38 ° c: 10.1%

Surfactant: an emulsifier consisting of a mixture of nonionic emulsifier / sulfonate: 13%

Mixture of gelling agents:

hydrogenated castor oil: 3% ethoxylated vegetable oil: 3%

Bag softening agent: ethylene glycol: 1%

These materials are mixed with each other while subjecting them to shear using a friction wear mixer. The product begins to gel within minutes.

The Brookfield viscosity of the gel is equal to 3150 mPa.s.

The stability of the emulsion is good in the test described above.

Spontaneity is equal to 20.

1100 g of this gel are introduced into a 1 liter bag made up of a film of PVA (polyvinyl acetate hydrolyzed at 88%; soluble in cold water, ٠ thickness: 55 micrometers). The bag, which is almost full (about% v / v) is heat sealed. The density of the gel and that of the bag containing the gel are equal to

1.1 g / cm3.

Then the bag is dropped 10 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

Another bag of this sample is also prepared and stored at -2O ° C for 3 days. Then the bag is dropped 5 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

The bag is introduced into a tank containing water under moderate agitation (that is to say that obtained by recycling with a pump). It is

<img file="MA22221A1_D0018.tif" />

MA 22221 US disperses in a period of 3 minutes. There is no obstruction of the filter, which consists of a 0.149mm mesh screen.

EXAMPLE 6

The procedure of Example 5 is repeated, except that a mixture containing the following constituents is used:

Active ingredients:

bromoxinyl (as octanoic ester): 18.4% bromoxinyl (as heptanoic ester): 14.0%

Methylchloropropionic-acetic acid (isooctyl ester): 36.6%

Mixture of surfactants: emulsifier consisting of a mixture of nonionic emulsifier / sulfonate: 9.0% and dioctyl ester of the sodium salt of sulfosuccinic acid and sodium benzoate

<td></td><td>sodium:</td><td></td><td></td><td> 2,0 %</td>

<td>Agent</td><td>gelling agent: earth</td><td>diatoms</td><td> :</td><td> 17,0 %</td>

<td colspan="2">Dispersant: product of</td><td>condensation</td><td>of</td><td>naphtha-</td>

<td></td><td>lenesulfonate</td><td>sodium and</td><td>of</td><td>trained</td>

<td></td><td>dehyde:</td><td></td><td></td><td> 3,0 %</td>

<td>Agent</td><td colspan="2">bag softening:</td><td>a</td><td>mixed</td>

<td></td><td>ethylene glycol</td><td>and water in</td><td>a</td><td>report</td>

<td></td><td>9 to 1 weight</td><td> :</td><td></td><td> 1%</td>

These materials are mixed together while subjecting them to shear by means of a friction wear mixer. The product begins to look like a smooth paste and is in gel form within minutes.

The Brookfield viscosity of the gel is equal to 9000 mPa.s.

The stability of the emulsion is good in

<img file="MA22221A1_D0019.tif" />

MA 22221 US the test described above.

Spontaneity is equal to 9.

1100 g of this gel are introduced into a 1 liter bag made up of a film of PVA (polyvinyl acetate hydrolysed at 88%; soluble in cold water; thickness: 55 micrometers). The bag, which is almost full (about 95% v / v) is heat sealed. The density of the gel and that of the bag containing the gel are equal to

1.1 g / cm3.

Then the bag is dropped 10 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

Another bag of this sample is also prepared and stored at -2O ° C for 3 days. Then the bag is dropped 5 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

The bag is introduced into a reservoir containing water with moderate agitation (ie that obtained by recycling with a pump). It is dispersed over a period of 3 minutes. There is no obstruction of the filter, which consists of a 0.149mm mesh screen.

EXAMPLE 7

The procedure of Example 1 is repeated, except that a mixture containing the following adjuvants is used:

Bag softening agent: tetrahydrofurfuryl alcohol 1%

The mixture is stirred and stirred by shaking until dissolution or dispersion of each component.

gelation occurs at room temperature

During stirring, dissolution, then gelation, increased during cooling to (2O٥C).

The Brookfield viscosity of the gel is equal

<img file="MA22221A1_D0020.tif" />

MA 22221 US

3000 mPa.s.

The stability of the emulsion is good in the test described above.

1100 g of this gel are placed in a 1 liter bag made from a film of PVA (88% hydrolyzed polyvinyl acetate, cold water soluble ٠; thickness: -55 micrometers). The bag, which is almost full (about% v / v) is heat sealed. The density of the gel and that of the bag containing the gel are equal to 1.1 g / cm3.

Then the bag is dropped 10 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

Another bag of this sample is also prepared and stored at -2O٠C for 3 days. Then the bag is dropped 5 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

The bag is introduced into a tank containing water with moderate agitation (i.e. that obtained by recycling with a pump). It is dispersed over a period of 3 minutes. There is no obstruction of the filter, which consists of a 0.149mm mesh screen.

EXAMPLE 8

The procedure of Example 1 is repeated, except that a mixture containing the following substances is used:

Active ingredients:

bromoxinyl (as octa30 noic ester): 30.15% bromoxinyl (as heptanoic ester): 31.15%

Solvent: an aromatic solvent with a flash point of 38٠c: 23.7%

Surfactant: polyarylphenol ethoxylated 6.0%

<img file="MA22221A1_D0021.tif" />

MA 22221 US calcium alkylbenzenesulfonate: 2.0%

Gelling agent: mixture of a dioctylsulfosuccinate and 6% sodium benzoate

Softening agent: ethyleneglycol 1%

The Brookfield viscosity of the gel is equal to 3000 mPa.s.

The stability of the emulsion is good in the test described above.

1100 g of this gel are introduced into a 1 liter bag made up of a film of PVA (polyvinyl acetate hydrolysed at 88%; soluble in cold water; thickness: 55 micrometers). The bag, which is almost full (about% v / v) is heat sealed. The density of the gel and that of the bag containing the gel are equal to

1.1 g / cm³.

Then the bag is dropped 10 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

Another bag of this sample is also prepared and stored at -2O ° C for 3 days. Then the bag is dropped 5 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

The bag is introduced into a tank containing water with moderate agitation (ie that obtained by recycling with a pump). It is dispersed over a period of 3 minutes. There is no obstruction of the filter, which consists of a 0.149mm mesh screen.

EXAMPLE 9

The procedure of Example 1 is repeated, except that a mixture containing the following substances is used:

Active ingredients:

bromoxinyl (as octanoic ester): 33.4%

<img file="MA22221A1_D0022.tif" />

MA 22221 US methylchloropropionic-acetic acid (isooctyl ester): 35.6%

Solvent: an aromatic solvent with a flash point of 38٠c: 20.5%

Surfactant: polyarylphenol ethoxyl 4.5% calcium alkylbenzenesulfonate 0.5%

Gelling agent: a mixture of dioctylsulfosuccinate and sodium benzoate 5%

Bag softening agent: ethyleneglycol

0,25 %

Anti-foaming agent: an acetylenic diol substitutes 0.25%

The Brookfield viscosity of the gel is equal to 3000 mPa.s.

The stability of the emulsion is good in the test described above.

1100 g of this gel are introduced into a 1 liter bag made up of a PVA film (88% hydrolyzed polyvinyl acetate; soluble in cold water; thickness: 55 micrometers). The bag, which is almost full (about% v / v) is heat sealed. The density of the gel and that of the bag containing the gel are equal to

1.1 g / cm3.

Then the bag is dropped 10 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

Another bag of this sample is also prepared and stored at -2O ° C for 3 days. Then the bag is dropped 5 times from a height of 1.2 m on the ground. No rupture or leakage is observed.

The bag is introduced into a tank containing water under moderate agitation (that is to say that obtained by recycling with a pump). It is dispersed over a period of 3 minutes. It does not happen

<img file="MA22221A1_D0023.tif" />

MA 22221 US No obstruction of the filter, which consists of a 0.149mm mesh screen.

It goes without saying that the present invention has been described for explanatory purposes only, but in no way limiting, and that numerous modifications can be made to it without departing from its scope.