AP325A - Gel formulations for use in toxic or hazardous product containerisation systems. - Google Patents

Gel formulations for use in toxic or hazardous product containerisation systems. Download PDF

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Publication number
AP325A
AP325A APAP/P/1991/000297A AP9100297A AP325A AP 325 A AP325 A AP 325A AP 9100297 A AP9100297 A AP 9100297A AP 325 A AP325 A AP 325A
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AP
ARIPO
Prior art keywords
gel
containerisation system
bag
surfactant
hazardous product
Prior art date
Application number
APAP/P/1991/000297A
Other versions
AP9100297A0 (en
Inventor
Leonard E Hodakowski
Chi-Yu Chen
Samuel Terry Gouge
Paul J Weber
Original Assignee
Rhone Poulenc Agrochimie
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/554,615 external-priority patent/US5080226A/en
Application filed by Rhone Poulenc Agrochimie filed Critical Rhone Poulenc Agrochimie
Publication of AP9100297A0 publication Critical patent/AP9100297A0/en
Application granted granted Critical
Publication of AP325A publication Critical patent/AP325A/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01C—PLANTING; SOWING; FERTILISING
    • A01C15/00—Fertiliser distributors
    • A01C15/003—Bulk fertiliser or grain handling in the field or on the farm
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A01N39/04—Aryloxy-acetic acids; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B29/00—Packaging of materials presenting special problems
    • B65B29/10—Packaging two or more different substances isolated from one another in the package but capable of being mixed without opening the package, e.g. forming packages containing a resin and hardener isolated by a frangible partition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B9/00—Enclosing successive articles, or quantities of material, e.g. liquids or semiliquids, in flat, folded, or tubular webs of flexible sheet material; Subdividing filled flexible tubes to form packages
    • B65B9/02—Enclosing successive articles, or quantities of material between opposed webs
    • B65B9/04—Enclosing successive articles, or quantities of material between opposed webs one or both webs being formed with pockets for the reception of the articles, or of the quantities of material
    • B65B9/042—Enclosing successive articles, or quantities of material between opposed webs one or both webs being formed with pockets for the reception of the articles, or of the quantities of material for fluent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/40—Fertilisers incorporated into a matrix
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/45—Form not covered by groups C05G5/10 - C05G5/18, C05G5/20 - C05G5/27, C05G5/30 - C05G5/38 or C05G5/40, e.g. soluble or permeable packaging

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Zoology (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Soil Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Wrappers (AREA)
  • Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Colloid Chemistry (AREA)

Abstract

A water dispersible organic gel which is a

Description

GEL FORMULATIONS FOR USE IN TOXIC OR HAZARDOUS . PRODUCT COKTAINERISATIOH SYSTEMS
These containerisation systems are suitable for containing hazardous products to render them safer to handle and for the environment.
At present, most hazardous liquids are stored in metal drumfe or, where smaller quantities are required, plastic containers.
Hazardous compounds, especially agrochemical compounds are formulated in various compositions. Liquid * * 4 composition are » most convenient for farmers because of the relative ease vith vhich they can be handled. There are, nevertheless, difficulties in handling such liquid coapositions. 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 exaaple during transportation, the risk remains of spillage or leakage vith 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) vhich safeguards those handling it, including farmers and transporters, and the environment.
- 2 It is known to have agrochemicals in soluble bags or sachets, but that does not avoid completely the possibility of , the bag cracking and breaking and the liquid creating a contamination problem. More specifically, when water soluble bags are used, the agrochemical compositions contained in the bag are organic ones, that is to say nonaqueous solvent-based i
compositions and, more or,less, the solvent has the tendency to extract the adjuvant and additives of the film and to render the wall (film) of the bag more brittle (especially at low temperature and more specifically at temperature below 0*C) or to reduce its service life.
It was known to use gel formulations for pharmaceuticals or cosmetics, but there is practically no risk of pollution or contamination of environment when handling such products, in contrast to pesticides and agrpchemicais.
Furthermore the gels used for pharmaceutical or cosmetical» purposes are generally water-based, so that it was unobVious to obtain gels, which are convenient for water soluble sachets or bags, nor for agrochemicals containing water soluble sachets or 'hags, nor for 3hock absorption purposes for such bags.
z
Furthermore, and in a practical point of view, higher concentrations of active ingredient may be obtainable when using gels instead of liquids.
The present invention seeks to provide Mew-f | femulations ond^a new formulation system containing &
agrochemicals which safe for everybody, specially the farmer and those who handle the agrochemicals.
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AP Ο Ο Ο 3 2 5
- 3 The invention also seeks to provide new formulation‘system for agrochemicals which is easy to put in a containing system and which is easy to manipulate by the farmer.
The invention also seeks to provide praw f ofwuI ei tions-end| a new formulation^ system for agrochemicals which fewf readily soluble and/or dispersible in vater. This is a problem vhich is especially difficult to overcome because the increase in viscosity is often connected vith an increased difficulty to disperse in vater.
The invention ^lso seeks to provide a new formulation system for agrochemicals which is as condensed as possible, usin<j the least amount of space.
The invention also seeks to provide piew Aeimuigtisns eedfa new formulation system to contain • « <
hazardous compounds, e.g., agrochemicals vhich reduce thet risk of contamination. . .... '
The invention also seeks to provide formalafelons-aod^a new formulation system to contain smelling or stinking compounds, e.g., agrochemicals which remove the odors y
or reduce odor problems.
'f The invention also seeks to avoid breakage of the container that contains an agrochemical formulation. When the container is brittle and rigid, there is a distinct possibility of simple breakage, but the liquid still |transmits the shocks and there is the problem of hydraulic hammer effect. The invention seeks to avoid, or at least partially reduce, this hydraulic hammer effect. The invention also seeks to provide a formulation)^—for hazardous compounds that dissipat i as much as possible, the energy of an external shock to a container.
BAD ORiqiNal A
- 4 The invention also seeks to provide a shock absorbing formulation system for containing agrochemicals, e.g., pesticides or plant protection agents or plant protection agents or plant growth regulators.
The invention also seeks to provide a formulation system which further extends the service life of the water soluble bag or sachet during storage, such as preventing the bag film from becoming brittle at freezing temperature.
The invention further seeks to provide a new formulation system for agrochemicals which quickly dissolves when put into water and which is not damaged by normal freezing.
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.
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:
a hazardous product, as active ingredient, e.g. an agrochemical (especially a pesticide, a plant protection agent, a plant growth regulator or plant nutrient);
optionally organic solvent;
a water soluble or water dispersible surfactant; a gelling agent; and a plasticising agent.
The gels are especially suitable to be contained in a water soluble or water dispersible bag.
The gelling agent or thickener is a compound that substantially increases the viscosity of an organic solution.
The gelling agent which is used in the present invention may be liquid or preferably solid. The gelling agent is preferably soluble at a concentration of at least
BAD ORIGINAL &
AP 0 0 0 3 2 5
-ί 10% by weight in a liquid mixture of the hazardous product, surfactant and organic solvent, if present, at a temperature above 50°C. If solid, it generally has a particle size of less than 100 microns, preferably less than 40 microns, more preferably less than 20 microns and most preferably less than 10 microns.
Preferred gelling agents include tetramethyl decyne diol, ethoxylated dialkylphenol, methylated clay, propylene carbonate, hydrogenated castor oil, ethoxylated vegetable oil, diatomaceous earth, mixtures of dioctyl sodium sulfosuccinate and sodium benzoate, mixtures of hexanediol and hexynediol, and a polyacrylic acid polymer or copolymer, optionally in the form of a salt and optionally crosslinked (e.g. partially crosslinked).
By the word surfactant, it is meant an organic material which substantially reduces the surface tension of water.
Surfactants which are particularly suitable for the invention are defined by the following test: according to this test, the liquid active ingredient in organic solvent, if present in the gel, (50g in total) and surface-active adjuvant (5g) are added to an amount of water, at 50®C, which is sufficient to bring the volume of the mixture to 100ml; the mixture is agitated so as to give a homogeneous emulsion and this is left to stand for 30 mintues at 50eC 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 ml.
The surfactant that is used in the invention may be nonionic, anionic or |^tionic, or may be zwitterionic . Amphoteric surfactants may be used. A mixture of surfactants may also be used. Preferably the surfactant is able to form a liquid mixture, preferably a liquid phase, with hazardous product and organic solvent, if present, at a temperature above 70’C, preferably above 50eC. This liquid
ORIGINAL mixture may be in the form of a single continuous phase or of an emulsion. Another preferable feature of the surfactant is ‘that it contains at least 10% of a surfactant having hydroxy and/or alcoxy groups, such as polyethoxylated or polyproxylated derivatives. Especially preferred are derivatives of fatty amine or fatty acids or fatty alcohols or aryl phenols.
Preferred surfactants include noninonic surfactants, optionally mixed with an ionic surfactant, and which are able to form a liquid mixture with the hazardous product and organic solvent, if present, at a temperature above 50°C, preferably above 70’C.
The hereinbefore defined gel may optionally contain the further following components:
an organic or mixture of organic' solvents in which therein the hazardous product is solubleze.g. completely .( soluble, at room temperature/‘ a dispersant; a secondary thickener;
such as a polyacrylic acid polymer, optionally in the form of a salt or a copolymer and optionally cross-linked (eg.
partially cross-linked), fumed silica; hydroxyethyl cellulose carboxy-nethylcelltflose; organically modified attapulglte or aontaorill6nite clay; hardened castor oil; cetyl and stearyl alcohols or esters; polyethylene glycols; glycerol hydroxystearate, polyvlnylalcohol (of low naolecular veight), dloctyl sodiua sulfosuccinate and sodiua benzoate; alkyl benzene sulfonates; xanthua gua, polyvinylpyrrolidone; or polyvinyl acetate;
' other additives such as antifoaa agents.
stabilizers, buffers, antifreezing agents.
ΟΓΜαλγΧμtt WKbr·™*
Aaong thek^+sfor the invention as hereabove defined, £ · <
some particular gels are preferred, especially those Jr-™npr-i«;inr^hy weight:
to 95%, preferably 10 to 90%, more preferably 25 to 80%, of hazardous product;
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AP0OO325 to 50%, more preferably 2 to 201:, of surfactant;
0.1 to, 50%,' preferably 0.5 to 10% of gelling agent;
to 80%, preferably 3 to 50%, of solvent;
to 20% preferably o.l to 10% of plasticising agent; optionally 0.1 to 20%, preferably 2 to 8%, of a dispersant; and to 20%, preferably 0.1 to 10%, of other additives.
The plasticising agent vhich nay be used in the invention is preferably a compound that is able to reduce the glass transition temperature of polyvinyl alcohol to below room temperature.
Furthermore this plasticising agent is preferably a. compound that is water soluble or water dispersible and is soluble at a concentration of at least 0.1% by weight in a liquid mixture of the hazardous product, the surfactant and optionally organic solvent,, .if present.
The plasticising agent, for example selected-from: alcohols compounds (linear or branched, saturated or unsaturated), especially alcenols having from 6 to 36 carbon atoms; alcenols having from 10 to 30 carbon atoms/ glycols and triols such as di- and tripentaerythritol, trimethylolethane, anhydroenneaheptitol, butanetriol, hexanetriol, erythritols, threitols, ribitol, arabinitols, xylitol, allitol, dulcitol, glucitol, sorbitol mannitol, altritol, iditol, maltitol, lactitol, ethyleneglycol, diethyleneglycol, triethyleneglycol, trimethyleneglycol, !
tetramethyleneglycol, pentamethyleneglycol, hexamethyleneglycol, propyleneglycol, glycerol, 2,3-butanediol, 1,3-butanediol,;_mono, di-, tri-, tetra-, and poly-amines, such as diethylenetriamine and ethanolamines; asides, e.g., acetamide and formamide,
bad origiNal dimethylformamide, hexamethylphosphotriaraide; sulfoxides, e.g., dimethylsulfoxide; piperazines.
The plasticising agents (or bag softener) that may be used in invention as described above inpart and maintain softness to a container such as a bag containing the gel.
They thus help to prevent the container from breaking during handling.or storage, especially at low freezing temperatures (e.g., under -20*C).
Thus there is little chance for contamination or pollution to occur under these severe conditions.
According to a particular feature of the invention, the components of the compositions of the invention are chosen in such a way that one or more of the following feature are present:
* the resulting gels have a viscosity of 500 to
30,000 centipoise, more preferably of 1000 to 12000 centipoise % (these viscosities are Brookfield viscosities measured with a viscosimeter in the fora or a flat plat 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) ls/iess Xhan oi-mqnaQ to-l 5, prefcregr/ less than or 'equal to 1.2. Tg(phi) is the tangent of the angle phi (or phase z
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 that the angle betveen them is less than 10·, preferably less than 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 bao
AP Ο Ο Ο 3 2 5 speed motor (which causes the angular displacement) corresponds to the hereabove mentioned controlled shear stress ___ * _ · «
♦ the gels preferably have a specific gravity greater than 1, preferably greater than 1.05, more preferably greater than 1.1.
• the gels have a spontaneity (as hereafter defined) less than 75, preferably less than 25.
By the expression continuous system, it is meant a material which is visually homogeneous, that is to say vhich has the visual appearance of having 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 which the dispersed phase has combined vith 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 vith a liquid.
By the expression hazardous product as used herein is meant a product that may cause damage to the environment or be z .injurious to a person handling it.
·’
According to one main and preferred feature of the invention, the hazardous product is an active ingredient vhich 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 many agrochemicals which can be used in the invention includes:
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- 9 Fungicides such as Triadimefon, Tebuconazole,
Prochloraz, Triforine, Trideaorph, Propiconazole, Priaicarb, Iprodione, Metalazyl, bitertanol, Iprobenfos, Flusilazol, fosetyl, Propyzaaide, Chlorothalonil, Oichlone, Mancozeb, Antraquinone, Maneb, Vinclozolin, Fenariaol, Bendiocarb, Captafol, Benalaxyl, Thiraa,
Herbicides (or defoliants) such as quizalofop and its derivatives, Acetochlor, Hetolachlor, Iaazapur And Iaazapyr,
Glyphosate And Gluphosinate, Butachlor, Acifluorfen, Oxyfluofen,
Butralin, Fluazifop-butyl, Bifenox, Broaoxynil, Ioxynil,
Diflufenican, Phenaediphaa, Desaediphaa, Oxadiazon, Mccopropo.
MCPA, HCPB, HCPP, Linuron, Isoproturon, Flanprop And Its
Derivatives, Ethofusesate, Diallate, Carbetaaide, Alachlor,
Metsulfuron, Chlorsulfuron, Chlorpyralid, 2,4-d) Tribufos,
Triclopyr, Diclofop-aethyl, Sethoxydia, Pendimethalin, .» • <
Trifluralin, Aaetryn, Chloraaben, Aaitrole, Asulaa, Dicaaba, Bentazone, Atrazine, Cyanazine, Thiobencarb, Proaetryn-, 2-(2chlorobenzyl)-4, 4-diaethyl-l, 2-oxazolidine-3-one, Fluoaeturon, Napropaaide, Paraquat, Bentazole, Molinate, Propachlor, Iaazaquin, Metribuzin, Tebuthiuron, Oryzalin,
Insecticides or neaaticides such a Ebufos, Carbosulfan,
Aaitraz, Vaaidothion, Ethion, Triazophos, Propoxur, Phosalone, Peraethrin, Cyperaethrin, Parathion, Hethylparathion, Diazinon, Methomyl, Malathion, Lindane, Fenvalerate, Ethoprophos, Endrin, Endosulfan, Dimethoate, Dieldrin, Dicrotophos, Dichlorprop, Dichlorvos, Azinphos And Its Derivatives, Aldrin, Cyfluthrin, Deltaaethrin, Disulfonton, Chordiaefora, Chlorpyrifos, Carbaryl, Dicolfol, Thiodicarb, Propargite, Demeton, Phosalone,
Plant growth regulator such a gibberellic acid, ethyl or ethephon, cycocel, Chloraequat, Ethephon, Mepiquat.
AP Ο Ο Ο 3 2 5
Among those many agrochemicals, the folloving are of particular interest: the organophosphorus insecticides and the hydorxybenzonitriles herbicides such as bromoxynil or ioxynil either in the form of a salt or an ester.
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 (100ml) containing kaolin or atrazine (50g), in the form of solid particles having a particle size betveen 1 and 10 microns, and surface-active adjuvant (5g, 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 vhen the dispersing agent is able to disperse a hydrophobic solid). After standing, 9/l0ths (nine-tenths) of the volume of the suspension, situated in the, upper part of the suspension, is removed, vithout 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 vhich the test is carried out.
The spontaneity is assessed according to the folloving method: A mixture of 1 ml gel vith 99 ml water are put into a 150 ml glass tube vhich is stoppered and inverted through 180* (upside down). The number of times required to completely disperse the gel is called the spontaneity.
A thickener is a compound which increases the viscosity of a gel or a liquid.
The surfactant that may be used in the invention may be selected from those of the folloving list (vhich is nonlimitative): salts of lignosulphonic acids, salts of phenyl
BAD ORIGINAL t >
sulphonic or naphthalene sulphonic acids; poly condensates of ethylene oxide with fatty alcohols, fatty acids, fatty esters, or fatty amines, or substituted phenols (particularly alkyphenols or arylphenols); salts of sulphosuccinic acid esters; taurine derivatives (particularly alkyltaurates); phosphoric esters of alcohols or of polycondensates of ethylene oxide with phenols; esters of fatty acids vith polyols; and sulphate, s,ulphonate and phosphate functional derivatives of the above compounds.
The dispersants that may be used in the invention may be selected from those of the^following list (vhich is nonlimitative; condensed naphthalene sulfonic acid; polyacrylic * acid; sodium sulfosuccinate, Calcium lignosulfonate, glycerol stearate, poly condensate of ethylene oxide and propylene oxide.
'- *
The presc nt invention also provides a containerisation j ystem (i.e. a container) comprising a water soluble or i ater dispersible bag containing a gel of the present invent ion.
, The chemical nature of the enveloping film constituting ,m MM the bags vhich may contain the composition/gels pefcf fcheq invention can vary quite widely. Suitable materials are vater soluble (or ΐ ·, (possibly vatfer^dispersible) materials which 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 hydroxyalky lcellulose, such as hydroxyme thy lcellulose, hydroxyethylcellulose, hydroxypropylcellulose; carboxymethylcellulose; polyvinylethers such as poly methy vinylether; poly(2,4-dimethyl-6triazinylethylene; poly(vinylsulfonic acid); polyanhydrides; low molecular weight urea-formaldehyde resins; low molecular weight melamine-formaldehyde resins; poly(2-hydroxyethyl methacrylate);
AP Ο Ο Ο 3 2 5 polyacrylic acid and its homologs; but preferably the enveloping film comprises or is made from polyvinylalcohol (PVA). PVA is „ generally partially or fully alcoholysed or hydrolysed, e.g., 40 100%, preferably 80-99% alcoholysed or hydrolysed, polyvinyl acetate film.
. Preferred material for constituting the bags for the IK KM. pKUM
X | gels invent ion are polyethylene oxide or methylcellulose, !or polyvinylalcohol. When polyvinylalcohol ls used, it is advantageously a 40-100%, preferably 80-99% alcoholysed or hydrolysed, polyvinyl acetate film.
λ The gels/of the inventionsfare generally very easy to make, simply by mixing the components, optionally vith grinding or milling.
In order to made a bag, the film must'be shaped (possibly partially sealed) and then filled vith the gel. Generally the gels are able to flov, even if it is a slov rate due to the high viscosity, a container vhich is used to contain the gels cannot be easily emptied due to this high gel viscosity (that is a reason why the gels have not been used up to nov in agriculture). When filled, the bag must 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 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, Chi-Yu R. Chen,
Samuel T. Gouge and Paul J. Weber for Water Dispersible Gel
- 13 BAD ORIGINAL
I
Formulations filed April 4, 1991; application of Leonard E. Hodakowski, 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.
In these examples, tg(phi) is less than 1.5
EXAMPLE 1
A gel is 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:
23.2%
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% plasticising agent: ethylene glycol 1%.
The mixture is stirred and shaked until each component is dissolved or dispersed.
AP000325
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 ie 3000 centipoise.
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 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 ie then dropped 10 times from 1.2 m onto the ground. No breaking or leakage is observed.
Another bag of the sample is also made and stored at -20*C for 3 days. The bag is then dropped 5 times from 1.2 m onto 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 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 2
The procedure of example 1 is repeated, except that a mixture containing the following adjuvants is used:
Surfactant: non ionic/sulfonate blended emulsifier: 5.2%
Gelling agent: tetramethyl decynediol 30%
The bookfield viscosity of the gel is 3000 centipoises.
- 15 bad °biginal t r r\ .·, <·
The emulsion stability is good in the above described test.
1100 q of this gel are put in a 1 liter bag made of a film of PVA (881 hydrolysed polyvinly 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 onto the ground. No breaking or leakage is observed.
Another bag of this sample is also made and stored at -20*C for 3 days. The bag is then dropped 5 times from 1.2 m onto 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 with pump recycling). It is dispersed within a 3 minute interval. There < 4 r is no clogging in the filter, vhich is a 100 mesh screen.
EXAMPLE 3
The procedure of example 1 is repeated, except that a mixture containing the following adjuvants is used:
Surfactant: non ionic/sulfonate blended emulsifier: 21.5% and calcium alkylbenzene sulfonate: 3.7%
Gelling agent: ethoxylated dialkyphenol 10% plasticising agent: a mixture of ethylene glycol and water at 9 to 1 weight ratio 1%
The brookfield viscosity of the gel is 3500 centipoise.
The emulsion stability is good in the above described test.
- 16 BAD ORIGINAL &
AP Ο Ο Ο 3 2 5
1100 g of this gel are put in a 1 liter bag made of 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 a onto 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, vhich is a 100 mesh screen.
EXAMPLE 4
A gel is made by stirring at 50*C a mixture of: active ingredient:
bromoxynil acid (as the octanoate ester): 30.15% bromoxynil acid (as the heptanoate ester): 31.15%
Solvent: aromatic solvent vith a flash point of 38*C: 21.85%
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% plasticising agent: ethylene glycol 1%
These materials are mixed together while shearing with attritor mixer. The product started to gel in a few minutes.
The brookfield viscosity of the gel is 4200 centipoise.
BAD ORIGINAL C
- 17 described test.
The emulsion stability is good in the above
The spontaneity is 3β.
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.
The bag is then dropped 10 times from 1.2 m onto the ground. No breaking or leakage is observed.
Another bag of this sample is also made and stored at -20*C for 3 days. The bag is then dropped 5 times from 1.2 m onto 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 with pump recycling). It is dispersed within a 3min interval. There is no clogging in the filter, which is a 100 mesh screen.
EXAMPLE 5
The procedure of example 4 is repeated, except that a mixture containing the following components is used:
active ingredient:
bromoxynil acid (octanoate ester): 18.65% bromoxynil acid (heptanoate ester): 13.85% methylchloropropionic acid (isoctyl ester): 37.4%
Solvent: Aromatic solvent with a flash point of 38»C:
10.1%
Surfactant: non ionic/sulfonate blender emulsifier:
13%
Gelling agent mixture:
AP Ο Ο Ο 3 2 5 hydrogenated castor oil 3% ethoxylated vegetable oil 3% plasticising agent: ethylene glycol l%
These materials are mixed together while shearing with attritor mixer. The product started to gel in a few minutes.
The brookfield viscosity of the gel is 3150 centipoise.
The emulsion stability is good in the above described test.
The spontaneity is 20.
1100 g of this gel are put in a 1 liter bag made of a filo 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 onto the * *· ground. No breaking or leakage is observed.
Another bag of this sample is also made and stored at -20*C for 3 days. The bag is then dropped 5 times from 1.2 m onto 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 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 6
The procedure of example 5 is repeated except that a mixture containing the following components is used:
active ingredient:
bromoxynil octanoate: 18.4% bromoxynil heptanoate: 14.0%
- 19 'BAD ORIGINAL ύ ν (Η
methyl chloropropionic acetic acid (isocytl ester):
Surfactant mixture: non ionic/sulfonate blended
36.6» emulsifier: 9.0» and dioctyl ester of sodium sulfosuccinic acid and sodium benzoate: 2.0»
Gelling agent: diatomaceous earth: 17.0»
Dispersant: sodium sulfonic of naphthalene formaldehyde condensate: 3.0» plasticising agent: a,, mixture of ethylene glycol and water at 9 to 1 weight ratio: H
These materials are mixed together while shearing with attritor mixture. The product started to have the appearance of a smooth paste, and is a gel in few minutes.
The Brookfield viscosity of the gel is 9000 centipoises. ., /
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 (88» hydrolyzed 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 onto the ground. No breaking or leakage is observed.
Another bag of sample is also made and stored at -20*C for 3 days. The bag is then dropped 5 times from 1.2 m onto the ground. No breaking or leakage is observed.
SAT ORIGINAL
AP Ο Ο Ο 3 2 5
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 an interval. There is no clogging in the filter which is a 100 mesh screen.
EXAMPLE 7
The procedure of example 1 is repeated, except that a mixture containing the following adjuvants is used:
plasticising agent: tetrahydrofurfural alcohol 1%
The mixture is stirred and shaken until each component is dissolved or dispersed.
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 centipoise, the emulsion stability is good in the above described test.
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 vater 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 onto the ground. No breaking or leakage is observed.
Another bag of this sample is also made and stored at -20*C for 3 days. The bag is then dropped 5 times from 1.2 m onto 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 with pump
- 21 original recycling). It is dispersed within a 3mn interval. There is no clogging in the filter, which is a 100 mesh screen.
EXAMPLE 8 , The procedure of example 1 is repeated, except that a mixture containing the following material is used:
active ingredient bromoxynil'acid (as the octanoate ester): 30.15% bromoxynil acid (as the heptanoate ester): 31.15%
Solvent: aromatic solvent with a flash point of 38*C: 23.7%
Surfactant: polyaryl phenolethoxylated 6.0% calcium alkylbenzene sulfonate 2.0%
Gelling agent: mixture of dioctylsulfosuccinate.
salt and sodium benzoate 6% .1 t plasticising agent: ethylene glycol i%
The Brookfield viscosity of the gel is 3000 centipoises. The emulsion stability is good in the above described test.
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 water soluble; thickness: 55 microns). (about 95% v/v), is heat sealed, of the bag containing the gel is
The bag is the dropped ground. No breaking or leakage
The bag, which is almost full The density both of the gel and
1.1.
times from 1.2 m onto the s observed.
©AO qbiginMAP Ο Ο Ο 3 2 5
Another bag of sample is also made and stored at -20C for 3 days. The bag is' then dropped 5 times from 1.2 a onto the ground. No breaking or leakage is observed.
The bag is put in a tank containing water under gentile agitation {that is to say such as that obtained with puap recycling). It is dispersed within a 3 an interval. There is no clogging in the filter which is a 100 aesh screen.
EXAMPLE 9
The procedure of example 1 is repeated, except that a mixture containing the following material is used:
active ingredient:
bromoxynil acid (as the octanoate ester): 33.4% aethylchloropropionic acetic acid (isooctyl ester)
35.6%
Solvent: aromatic solvept with -flash point of 38*C: 20.5%
Surfactant: polyaryl phenolethoxylated 4.5% • calcium alkylbenzene sulfonate 0.5%
Gelling agent: mixture of dioctylsulfosuccinate salt , ., and sodium benzoate 5% z ' f plasticising agent: ethylene glycol 0.25%
Defoamer: substituted acetylenic diol 0.25%
The brookfield viscosity of the gel is 3000 centipoise.
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 water soluble; thickness: 55 microns,. The bag, which is almost full ffAO ORIGINAL
- 23 (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 onto the ground. No breaking or leakage is observed.
Another bag of this sample is also made and stored at -20sc for 3 days. The bag is then dropped 5 tines from 1.2 n onto 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 punp recycling). It is dispersed within a 3 min interval. There is no clogging in the filter, which is a 100 mesh screen.
BAD ORIGINAL

Claims (23)

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:
a hazardous product, optionally organic solvent, a water soluble or water dispersible surfactant, a gelling agent and a plasticising agent.
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 pesticide, a plant protection agent, a plant growth regulator or a plant nutrient.
4. A containerisation system according to claim 1, 2 or 3 wherein the gelling agent is a solid soluble at a concentration of at least 10% by weight in water and at least 10% by weight in a liquid mixture of hazardous product, surfactant and organic solvent, if present, at a temperature above 50°C.
5. A containerisation system according to claim 4 wherein the gelling agent has a particle size less than 40 microns.
BAD ORIGINAL
9 Ο Η 9
- 26
6. A containerisation system according to claim 5 wherein the gelling agent has a particle size less than 10 microns.
7. A containerisation system according to any one of the preceding claims wherein the plasticising agent is a compound which is able to reduce the glass transition temperature of polyvinyl alcohol to below room temperature.
8. A containerisation system according to claim 7 wherein the plasticising agent is a compound which is water soluble or water dispersible and is soluble at a concentration of at least 0.1% by weight in the liquid mixture of hazardous product, the surfactant and organic solvent, if present.
9. A containerisation system according to any one of the preceding claims wherein the surfactant is able to form a liquid mixture with the hazardous product in organic solvent, if present, at a temperature above 70°C.
10. A containerisation system according to claim 9 wherein the surfactant is able to form a liquid mixture with the hazardous product in organic solvent, if present, at a temperature above 50°C.
11. A containerisation system according to any one of the preceding claims wherein the gel further comprises one or more of the following:
an organic solvent or a mixture of solvents in which the hazardous product is soluble at the concentration in the gel;
bad origin*1AP Ο Ο Ο 3 2 5
- 27 a dispersant;
a thickener which is water soluble or water dispersible and which is soluble at a concentration of at least 5% by weight in a liquid mixture of the hazardous product in organic solvent, if present and surfactant; and/or another additive which is an antifoara agent, a stabiliser, a buffer, or an antifreezing agent.
12. A containerisation system according to any one of the preceding claims wherein the gel comprises by weight:
10 to 90% of hazardous product;
1 to 50% of surfactant;
0.1 to 50% of gelling agent;
0 to 80% of solvent;
0 to 20% of plasticising agent;
0 to 20% of other additives as defined in claim 11.
13. A containerisation system according to claim 12 wherein the gel comprises by weight:
25 to 80% hazardous product;
2 to 20% of surfactant;
0.5 to 10% of gelling agent;
3 to 50% of solvent;
0.1 to 10% of plasticising agent, and
0.1 to 10% of other additives as defined in claim 11.
14. A containerisation system according to any one of the preceding claims wherein the gel has a viscosity of ‘o(*
- 28 500 to 30,000 centipoise.
15. A containerisation system according to claim 14 wherein the gel has a viscosity of 1000 to 12,000 centipoise.
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 and 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 in which the bag comprises a polyethylene oxide which is polyethylene glycol; a hydroxyalkyl-cellulose which is ,0 ORIGINAL
AP Ο Ο Ο 3 2 5
- 29 hydroxymethyl-, hydroxyethyl- or hydroxypropyl-cellulose; a carboxyalkylcellulose which is carboxy-methylcellulose; a polyvinyl ether which is polymethylvinyl ether; or a polymethacrylate which is poly(2-hydroxyethylmethacrylate).
21. A containerisation system according to claim 19 wherein the bag comprises polyethylene oxide, methylcellulose or polyvinyl alcohol.
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 polyvinylalcohol is 80 to 99% alcoholysed or hydrolysed polyvinylacetate.
APAP/P/1991/000297A 1990-07-18 1991-07-18 Gel formulations for use in toxic or hazardous product containerisation systems. AP325A (en)

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EP0493558A1 (en) 1992-07-08
IL98804A0 (en) 1992-07-15
IE912508A1 (en) 1992-01-29
JPH05501722A (en) 1993-04-02
TR26253A (en) 1995-02-15
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HU9200887D0 (en) 1992-05-28
HU212036B (en) 1996-01-29
RU2094987C1 (en) 1997-11-10
AU8039891A (en) 1992-01-23
PL170084B1 (en) 1996-10-31
PT98355A (en) 1992-06-30
EP0493558B1 (en) 1999-09-22
DE69131643D1 (en) 1999-10-28
CZ221991A3 (en) 1994-01-19
DE69131643T2 (en) 2000-05-04
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AU647155B2 (en) 1994-03-17
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CN1058320A (en) 1992-02-05
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PT98355B (en) 1999-01-29
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AU8097891A (en) 1992-02-18

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