AP358A

AP358A - Water dispersible gel formulations.

Info

Publication number: AP358A
Application number: APAP/P/1991/000300A
Authority: AP
Inventors: Leonard E Hodakowski; Chi-Yu Chen; Samuel Terry Gouge; 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: CA2066243A1; AU8097791A; OA09570A; BR9105834A; CN1058319A; ATE184747T1; FI921141A0; TR26120A; PL294075A1; NZ239003A; DE69131642D1; PT98353A; AU647154B2; EP0491916A1; FI921141A; RU2102881C1; CA2066243C; KR920702196A; AU8039791A; CS221791A3

Abstract

A water dispersible organic gel comprising a hazardous product

Description

A water dispersible organic gel comprising a hazardous product, a surfactant and a gelling agent. The gels are particularly useful in containers such as water soluble or water dispersible bags to render the hazardous product safer to handle and for the environment.

Patent Abstract of Japan VoJaNo.30 World Patent Ιβ£Β>ϋβΐθΠ<ΙΑΕ^η (56) Documents cited: GB - A - 2067407;

(C-2)(512) 150380;

INVENTORS CONTD

2. CHI-YU CHEN

10004 WHITESTONE ROAD RALEIGH, NORTH CAROLINA 27615 UNITED STATES OP AMERICA

3. SAMUEL T GOUGE

1708 PARKRIDGE WAY

RALEIGH, NORTH CAROLINA 27614

UNITED STATES OF AMERICA

4. PAUL J WEBER

3515-A CENTURY OAKS ROAD DURHAM, NORTH CAROLINA 27713 UNITED STATES OF AMERICA

BADORIGINAL A

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

These containerisation systems are suitable for containing hazardous products rendering them safer to handle and for the environment.

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

Hazardous compounds, especially agrochemical compounds, are formulated in various compositions. Liquid compositions are most convenient for farmers because of the relative ease vith vhich 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. Secure containers, resistant to shock, can be used. However, in the event of an accident, for example during transportation, the risk remains of spillage or leakage vith rapid loss of liquid, for example leaking onto the ground.

BAD ORIGINAL ft

AP3 5 8

- 2 It has been difficult to provide a formulation and 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 for everybody, and the environment.

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AP 2 5 9

The invention also seeks to provide a new formulation system foi agrochemicals which is easy to put in a containing system and vhich is easy to manipulate for the farmer.

The invention also 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 vhich is as much condensed as possible, using the least amount of space.

The invention also seeks to provide new formulation system to contain hazardous compounds, e.g.. agrochemicals vhich diminish 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. This causes spillage of the agrochemicals they contain and creates contamination problems.

In fact, there are a variety of defects which 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 points. 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 where containers may be subjected to rough or unsafe handling by distributors or farmers.

The invention also seeks to avoid leakage through pinholes when 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

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AP3 5 8 the liquid going through the pinhole contaminates all of its environment.

The invention also seeks to avoid • breakage of the container which 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 proposed to reduce the possibility of breakage by means 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 which dissipates, ^as »uch 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 known to use gel formulations for pharmaceutical or cosmetics, but there is practically no risk of pollution or contamination of the environment when handling such products, in contrast to pesticides and agrochemicals. Furthermore, the gels used for pharmaceutical or cosmetic purposes are generally vaterbased. Thus, it vas unobvious to obtain gels vhich are convenient for vater soluble sachets or bags, for pesticide containing vater soluble sachets or bags, or for shock absorption purposes for such bags.

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Another possibility ie to have agrochemicals in the form of wettable powders in a bag which may be water soluble. However, not all agrochemcials may be used under the form of a wettable powder. Even if these powders are wettable, the length of time to .get the powder wetted (wetting time) may cause some technical problems.

As already said, 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; 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 movement which causes the thixotropic liquid becomes 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 the bags breaking upon freezing.

The present invention seeks to provide a new formulation system for agrochemicals which quickly dissolves when put into water and which is not damaged bv normal freezing.

The invention also seeks to provide a formulation system vherein 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 which reduces the risks of clogging the spray nozzles or the filters of spray tanks.

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AP3 5 8

J

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;

a water soluble or water dispersible surfactant, or a mixture of such surfactants, such that:

if hazardous product in the organic solvent, if present, (50g) and the surfactant (5g) are added to an amount of water, at 50°C, which is sufficient to bring the volume of the mixture to 100 ml, the mixture is agitated so as to give a homogenous emulsion and this is left to stand for 30 minutes at 50°C, the amount of oily layer which has separated out, and forms a distinct liquid phase is less than 20 ml;

a gelling agent which is liquid or solid at 23°C and if solid has a particle size less than 100 microns, preferably less than 20 microns; and which is soluble at a concentration of at least 10% by weight in a liquid mixture^ preferably above 50°C, of the hazardous product, surfactant and organic solvent, if present, and;

less than 3% by weight of water, preferably less than

8ADOR/G/NAL

The surfactant or surfactants may be non-ionic or anionic or cationic or may be zwitterionic. Amphoteric surfactants may be used.

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

an organic solvent or a mixture of organic solvents in which the hazardous product is soluble (e.g. completely soluble) at the concentration present in the gel. a dispersant, a secondary thickener; and/or other additives, such as stabiliser(s), antifoaming agent(s), buffer(s), antifreezing agent(s).

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

to 95%, preferably 10 to 90% more preferably 25 to 80%, of hazardous product;

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AP 3 5 8 .y to SOI, core preferably 2 to 151, of turfactant;

0.1 to 501, cere preferably 2 to 101, oi gelling agent;

0.1 to 30V, Bore preferably 1 to 25V, of secondary thickener;

to 80% of solvent, more preferably 3 to

50%; and to 20% of other additives (as hereinbefore defined), preferably 0.1 to 10V.

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

Preferred gels are also those which contain a surfactant which is able to form a liquid mixture, preferably a liquid phase, with the hazardous product (i.e, the active ingredient) and organic solvent, if present, at a temperature above 70*C preferably above 50°C. This liquid mixture may be a single continuous phase of in the form of an emulsion.

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

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

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It is known that a gel is generally a colloid in which 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 or aggregate of small particles in very close association with a liquid. In the gels, the hazardous product (or active ingredient) may be in a soluble form, or in a dispersed form such as in a suspension.

According to one feature, the gels used in the invention preferably have a specific gravity greater than 1, preferably greater than 1.05, more preferably greater than l.i.

According to a particular feature of the invention, the components of the compositions are chosen in such a way that the gels 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 with 99ml vater are put into a 150ml 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^eC.

The surfactant which may be used in the invention may be selected from among those of the folloving list (vhich is non limitating; provided that the physical requirements of the surfactant are met) :

alkanolamides, poly condensates of ethylene oxide with fatty alcohols, fatty esters, or fatty amines, or substituted phenols (particularly alkylphenols or arylphenols) ; block

BAD ORIGINAL

Μ» copolymers vith 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; salts of lignosulphonic acids, salts of phenyl sulphonic or naphthalene sulphonic acids, diphenyl sulfonates; alkyaryl sulfonates; sulfonated fatty alcohols or amines or amides; poly condensates of ethylene oxide vith fatty acids and their sulfate or sulfonate derivatives; salts of sulphosuccinic or sulfosuccinamic acid esters; taurine derivatives (particularly alkyltaurates); betaine derivatives; phosphoric esters of alcohols 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 corresponding to the active ingredient in such a vay that, vhen mixed, at 50/50 v/v and 25*C, vith (and optionally grinded 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 different 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 or equal to 1.2. Tg(phi) is the tangent of the angle phi (or phase difference). 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· time. This angular displacement corresponds to the hereabove mentioned shear strain; the torque of the controlled speed motor

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O W (which causes the angular displacement) corresponds to the hereabove mentioned controlled shear stress.

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

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

' By the expression hazardous product as used herein is meant a product (material) vhich 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 nutrients).

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

Fungicides such as Triadimefon, Tebuconazole, Prochlaraz, Triforine, Tridemorph, Propiconazole, Pirimicarb, Iprodioine, Ketalaxyl, Bitertanol, Iprobenfos, Flusilazol, Fosetyl, Propyzamide, Chlorothalonil, Dichlone, Mancozeb, Anthraquinone, Maneb, Vinclozolin, Fenarimol, Bendiocarb, Captafol, Benalaxyl, Thiram;

Herbicides (or defoliants) such as guizalofop and its derivatives, Acetochlor, Metolachlor, Imazapur and Imazapyr, Glyposate and Gluphosinate, Butachlor, Aciflourfen, Oxyfluorfen, Butralin, Fluazifop-butyl, Bifenox, Bromoxynil, Ioxynil, Diflufenican, Phenroediphan, Desmedipham, Oxadiazon, Mecopropo,

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AP3 5 8

MCPA, MCPB, MCPP, Linuron, Isoproturon, Flamprop and its derivatives, Ethofumesate, Diallate, Carbetamide, Alachlor, Hetsulfuron, Chlorsulfuron, Chlorpyralid, 2,4-d, Tribufos, Triclopyr, Diclofop-methyl, Sethoxydim, Pendimethalin, Trifluralin, Ametryn, Chloramben, Amitrole, Asulam, Dicaaba, Bentazone, Atrazine, Cyanazine, Thiobencarb, Prometryn, 2-(2chlorobenzyl)-4, 4-dimethyl-l,2-oxazolidin-3-one, Fluometuron, Napropamide, Paraquat, Bentazole, Molinate, Propachlor, Imizaquin, Metribuzin, Tebuthiuron, Oryzalin; and

Insecticides or nematicides such as Ebufos, Carbosulfan, Amitraz, Vaaidothion, Ethion, Triazophos, Propoxur, Phosalone, Permethrin, Cypermethrin, Parathion, Methylparathion, Diazinon, Metomyl, Malathion, Lindane, Fenvalerate, Ethoprophos, Endrin, Endosulfan, Dimethoate, Dieldrin, Dicrotophos,

Dichloroprop, Dichlorvos, Azinpohs and its derivatives, Aldrin, Cyfluthrin, Deltamethrin, Disulfoton, Chlordimeform,

Chlropyrifos, Carbaryl, Dicofol, Thiodicarb, Propargite, Demeton, Phosalone.

Plant growth regulators such as gibberellic acid, ethrel or ethephon, cycoccl, Chlormequat, Ethephon, Mephiquat.

In order to assess whether a surface-active adjuvant possesses dispersing properties and may be a dispersant according to the invention, the following test is carried out: an aqueous suspension (100 ml) containing kaolin or atrazine (50 g), in the form of solid particles having a particle size between 1 and 10 microns, and the 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, 9/10ths (nine- 12 BAD ORIGINAL

AP3 5 8 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 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 dispersant vhich may be used in the invention may be selected among those of the following list (which is non limiting): salts of lignosulphonic acids such as calcium lignosulfonate, salts of phenyl sulphonic or naphthalene sulphonic acids, condensed naphthalene sulfonic acid; poly condensates of ethylene oxide with fatty alcohols or fatty acids or fatty esters or fatty amines, or substituted phenols (particularly alkyphenols or arylphenols); salt of sulphonsuccinic acid esters, such as spdium sulfosuccinate; taurine derivatives (particularly alkyltauarates); phosphoric esters of alcohols or polycondensates of ethylene oxide with phenols; esters of polyols and of fatty acids or sulfuric acid or sulphonic acids or phosphoric acids; glyceryl esters, especially esters vith fatty acids such as glyceryl stearate; ethylene glycols; and the like.

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 those of the following list (which is non limiting): fumed silica; hydroxyethyl cellulose, carboxy-methylcellulose; organically modified attapulgite or montmorillonite clay; hardened castor oil; cetyl and stearyl alcohols or esters; polyethylene glycols; glyceryl hydroxystearate, polyvinylalcohol; salts of sulphosuccinic acid

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AP3 5 8 esters such as the dioctyl sodium sulfosuccinate; salts of benzoic acid such as sodiun benzoate; alkyl sulphates.

The preparation or manufacturing of the gels of the invention can be made by any knovn method. A convenient vay is to mix together the different constituents of the mixture/ composition and to stir them, optionally vith grinding or milling and/or heating. Sometimes it is easier to operate vith a slow addition of the constituents of the composition. It might also be useful that the gelling agent is added .last.

The chemical nature of the enveloping film constituting the bags vhich may contain the composition/gels of the invention can vary quite widely. Suitable materials are vate^ soluble (or possibly vater dispersible) materials vhich are insoluble in the organic Solvents used to dissolve or disperse the agrochemical active ingredient. Specific suitable materials include polyethylene oxide, such as polyethylene glycol; starch and modified starch; alkyl and hydroxyalkylcellulose, such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxyethylcellulose, polyvinylethers such as poly methyl vinylether; poly(2,4-dimethyl-6triazolyethelene); poly(vinylsulfonic acid); polyanhydrides; low molecular weight urea-formaldehyde resins; low molecular weight nelamine-fornadehyde 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 poly ethyleneoxide or methylcellulose,

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AP3 5 8 or polyvinylalcohol. When polyvinylalcohol is used, it is advantageously a 40-100%, preferably 80-99% alcoholized or hydrolysed, polyvinyl acetate file.

The water soluble films vhich are used to make the vater soluble bags are knovn. To make a bag, the film needs to be shaped (possibly partially sealed) and then filled vith the gel. Generally, the gels are able to flov, even if it is a slow rate due to the high viscosity, λ container vhich is used to contain the gels cannot be easily emptied due to this high gel viscosity (that a reason vhy the gels vere 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 folloving copending applications, the disclosures of vhich are incorporated herein by reference: application of Leonard E. Hodakovski,

Chi-Yu 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 Samuel T. Gouge, Leonard E. Hodakovski, Chi-Yu R. Chen and Paul J. Weber for Gel Formulations for Hazardous Products 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.

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I

AP3 5 8 ·,

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

In those examples, tg(phi) is less than 1.5 and the surfactant satisfies to the test requirement hereabove defined.

EXAMPLE,-1

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

Active ingredient:

2,4-D phenoxy benzoic acid isooctyl ester: 64.8%

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 shaked until each component is dissolved or dispersed.

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AP3 5 8

During stirring, a dissolution appears, and thereafter a gelation. Gelation is Increased during the 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.

llOOg 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 (specific gravity) both of the gel and of the bag containing the gel is 1.1 gm/cc.

The bag is then dropped 10 times from 1.2 m upon the ground. Ko 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 with pump recycling). It is dispersed within a 3 min. interval. There is no clogging in the filter which is a 100 mesh screen.

Another bag, made in the same way as the previous one, is tested for pinhole protection. A needle (diameter: 0.6 mm) is passed through the bag. A small droplet is observed which forms at the locus where the needle passed. However, this droplet vas small enough not to drop from the bag and not to flov along the bag.

EXAMPLE 2

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

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AP3 5 8

Surfactant:

non ionic/sulfonate blended emulsifier: 5.21

Gelling agent:

tetramethyl decynediol: 30%

The Brookfield viscosity of the gel is 3000 centipoises.

The emulsion stability is good in the above described test.

HOOg 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 gm/cc.

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 gentle agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 3 min. interval. There is no clogging in the filter which is a 100 mesh screen.

EXAMPLE 1

The procedure for Example 1 vas repeated, except that a mixture containing the folloving adjuvants is used:

Surfactant:

non ionic/sulfonate blended emulsifier:

21.5%

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AP3 5 8 and calcium alkylbenzene sulfonate:

3.7¾

Gelling agent:

ethoxylated dialkyphenol: 10¾

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 (88¾ 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 gm/cc.

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

EXAMPLE 4

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

Active ingredient:

bromoxynil acid (octanoate ester): 18.65¾ bromoxynil acid (heptanoate ester): 13.85¾

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AP3 5 8 methylchloropropionic acid (isooctyl ester):

37.4¾

Solvent:

aromatic solvent vith a flash point of 38*C: 11.1¾

Surfactant:

non ionic/sulfonate blender emulsifier: 13¾

Gelling agent mixture:

hydrogenated caster oil: 3¾ ethoxylated vegetable oil: 3¾

These materials are mixed together while shearing vith an attritor mixer. The product started to gel in a few minutes.

The Brookfield viscosity of the gel is 3150 centipoises.

The emulsion stability is good in the above described test.

The spontaneity is 20.

llOOg 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, which 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 gm/cc.

The bag is put in a tank containing water under gentle agitation (that is to say such as that obtained with pump

- 20 BADORIGINAL ft recycling). It ie dispersed within a 10 minute interval. There is no clogging in the filter which is a 50 mesh screen.

EXAMPLE 5

The procedure for Example 4 vas repeated, except that a mixture containing the folloving components is 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 churning with an 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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ΑΡ3|β

The emulsion stability is good in the above described test.

The spontaneity is 9.

llOOg 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 (about 95% v/v), is heat sealed. The density both of the gel and of the bag containing the gel is 1.1 gm/cc.

The bag is put 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.

EXAMPLE 6

The procedure of Exaaple 5 vas repeated, except that a mixture containing the following components is used:

Active ingredient:

bromoxynil octanoate: 31.5% bromoxynil heptanoate: 31.5% atrazine: 44.58%

Solvent:

same as in Example 1: 23.25%

Gelling agent:

mixture of dioctyl sodium sulfosuccinic acid and sodium benzoate: 2.0%

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AP3 5 8

Surfactants:

ethoxylated/propoxylated block copolymer with alkyphenol: 3.6% alkylarysulfonate of an aaine: 5%

Antifreeze agent:

polyethylene glycol: 1%

Antifoam agent:

polyorganosiloxane: 0.5%

These materials are mixed together and passed through a bead mill. The product gets the appearance of gelatinous 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.

llOOg 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 gm/cc.

The bag is put 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 100 mesh screen.

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AP3 ο 8

EXAMPLE ,.2

The procedure of Example 6 vas repeated, except that a mixture containing the following components is used:

Active ingredient:

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

Solvent:

aromatic solvent with a flash point of 65*C: 3.0%

Surfactant:

non-ionic/sulfonate blended emulsifier: 8.5% and calcium dodecyl benzene sulfonate: 1.0%

Gelling agent:

tetraaethyl decyne diol: 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 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.

llOOg of this gel are put in a 1 liter bag made of a film of PVA (88% hydrolysed polyvinyl acetate; cold water

BAD ORIGINAL

- 24 AP3 5 8 soluble; thickness: 55 Microns). The beg, which is alfflost 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 froa 1.2 a upon the ground. No breaking or leakage is observed.

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

EX&MELS-l

The procedure of Example 7 was repeated, except that a mixture containing the following components is used:

Active ingredient and solvent are the same as in Example 7, and amount of active ingredient is the same, solvent is the same but the amount is 10.6%.

Surfactant mixture:

polyarylphenol ethoxylated: 6% and calcium dodecyl benzene sulfonate: 2%

Gelling agent:

mixture of hexane and hexyne diol: 11.5%

The Brookfield viscosity of the gel is 2500 centipoises.

- 25 BAD ORIGINAL s.

£ⁿ5 ·< fl

The emulsion stability is good in the above described test.

The spontaneity is 5.

. llOOg 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 (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 (that is to say such as that obtained vith pump recycling). It is dispersed vithin a 5 minute interval. There is no clogging in the filter vhich is a 100 mesh screen.

EXAMPLE 9

The procedure of Example 4 vas repeated, except that a mixture containing the folloving components is used:

Active ingredient:

bromoxynil octanoate: 33.5% bromoxynil heptanoate: 33.5%

Solvent:

aromatic solvent vith a flash point of 65· C:

17.5%

Surfactant:

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

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- 26 AP3 5 8

Gelling agent:

mixture of dioetyl sodium sulfosuccinate and sodium benzoate: 4.25%

Antifoam agent:

tetramethyl decyne diol: 0.5%

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 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.

llOOg 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 gm/cc.

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

EXAMPLE., Ifl

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

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AP3 5 8

Active ingredient:

bromoxynil acid (as the octanote ester):

30.15% bromoxynil acid (as the heptanoate ester):

31.15%

Solvent:

aromatic solvent with a flash pont of 38*C:

22.85%

Surfactant:

polyaryl phenolethoxylated: 6.0% calcium alkylbenzene sulfonate: 2.0%

Gelling agent mixture:

a clay which has been modified by addition of methyl groups: 6.0% and propylene carbonate: 2.0%

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

The Brookfield viscosity of the gel is 4200 centipoises.

The emulsion stability is good in the above described test.

The spontaneity is 38.

llOOg 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 bad ORIGINAL $

- 28 AP3 5 8 (about 95 % v/v), is heat sealed. The density both of the gel and of the bag containing the gel is 1.1 gm/cc.

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

5 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;

10 optionally organic solvent;

if hazardous product in the organic solvent, if present, (50g) and the surfactant (5g) are

15 added to an amount of water, at 50°C, which is sufficient to bring the volume of the mixture to 100 ml, the mixture is agitated so as to give a homogenous emulsion and this is left to stand for 30 minutes at 50°C, the amount of

20 oily layer which has separated out, and forms a distinct liquid phase is less than 20 ml;

a gelling agent vhich is liquid or solid at 23°C and if solid has a particle size less than 100 microns, and which is soluble at a concentration of at least

25 10% by weight in a liquid mixture of the hazardous product, surfactant and organic solvent, if present, and ;

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AP3 5 8

- 31 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 l or 2, wherein the hazardous product is a plant protection agent, a plant growth regulator, a pesticide or a plant nutrient.

4. A containerisation system according to claim 1,

2 or 3, wherein the gelling agent is liquid or is solid and has a particle size less than 20 microns and the gel has a water content less than 1% by weight.

5. 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.

6. A containerisation system according to any one of the preceding claims wherein the gel comprises a surfactant which is able to form a liquid mixture with the hazardous product and organic solvent if present, at a temperature above 70°C.

7. A containerisation system according to claim 6,

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APJ 5 8

- 32 wherein the gel comprises a surfactant which is able to form a liquid phase with the hazardous product and organic solvent, if present, at a temperature above 50°C.

8. A containerisation system according to any one of the preceding claims, wherein the gel comprises by weight:

5 to 95% of hazardous product,

1 to 50% of surfactant,

0.1 to 50% of gelling agent, and

0 to 80% of solvent.

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

25 to 80% of hazardous product,

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, and

0.1 to 30% of secondary thickener,

11. A containerisation system according to claim 10 wherein the gel further 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 5.

12. A containerisation system according to any one of the preceding claims wherein the gel has a viscosity of

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AP 3 5 8

- 33 600 to 30,000 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 gravity greater than 1.05.

16. A containerisation system according to any one of the preceding claims wherein 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 1.2.

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-dimethy1-6-triazolylethylene) ; poly(vinylsulfonic acid); a polyanhydride; a low molecular weight urea-formaldehyde resin; a low molecular weight

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AP 3 5 8

- 34 melamine-formaldehyde resin; a polyacrylate, a polymethacrylate or polyacrylic acid or a homolocue thereof.

20. A containerisation system according to claim

5 19, wherein the bag comprises a polyethylene oxide which is polyethylene glycol; a hydroxyalkylcellulose which is hydroxymethyl-, hydroxyethyl- or hydroxypropyl-cellulose; a carboxyalkyl-cellulose which is carboxymethyl-cellulose; a polyvinylether which is polymethylvinylether; or a

10 polymethacrylate which is poly(2-hydroxyethyl methacrylate).

21. A containerisation system according to any one of the preceding claims wherein the bag comprises polyethylene oxide, methylcellulose, or polyvinyl alcohol.

15 22. A containerisation system according to claim

21, wherein the bag comprises polyvinyl alcohol which is 40 to 100% alcoholysed or hydrolysed polyvinyl acetate.

23. A containerisation system according to claim

22, wherein the polyvinyl alcohol is 80 to 99% alcoholysed 20 or hydrolysed polyvinyl acetate.