CA2066424C - Containerization system for agrochemicals and the like - Google Patents
Containerization system for agrochemicals and the likeInfo
- Publication number
- CA2066424C CA2066424C CA002066424A CA2066424A CA2066424C CA 2066424 C CA2066424 C CA 2066424C CA 002066424 A CA002066424 A CA 002066424A CA 2066424 A CA2066424 A CA 2066424A CA 2066424 C CA2066424 C CA 2066424C
- Authority
- CA
- Canada
- Prior art keywords
- gel
- containerization system
- bag
- containerization
- water
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
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
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/18—Semi-solid fertilisers, e.g. foams or gels
-
- 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)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Soil Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Packages (AREA)
- Wrappers (AREA)
- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
Abstract
This invention relates to a containerization system and to containers which are particularly suitable for storing, packaging and transporting toxic or hazardous products, such as agricultural chemicals. The containerization system comprises the chemical in the form of a gel which is contained within a water-soluble or water-dispersible bag.
Description
WO 9;!/01374 PCI`/EP9l/01348 "",`"~
2066~2~ ; `
CONTAINERIZATION SYSTEM FOR AG~OCHEMICALS AND THE LIXE
This invention relates to a containerization system and to ` ~-containers which are psrticularly suitable for storing, packaging ,~?~
and transporting to~cic or hazsrdous products, e.g., agricultural chemical compounds, such as pesticides.
At present, most hazardous and tosic liquids are stored in metal drums or, where smaller quantities are involved, in plastic .~ containers. Hazardous or to~cic compounds, such as agrochemical `;`- - `
compounds, are formulated in various compositions. `~
The expression to~ic or hazardous compounds as used herein `~
means an industrial chemical or agrochemical compound, which, if --~
released in the quantity or concentration normally present in ~X
15 storage and shipping containers, may cause damage to the environment or be injurious to a person contacted by it. ``;~
With respect to agricultural chemicals, liquid compositions, ~``~``
particularly in the form of concentrates, are most convenient for farmers because of the relative ease with which they can be ~O handled, formulated and used. However, there are significant ` `
difficulties in handlin~ such liquid compositions. } -~
There is a danger of spillage or leakage if holes develop in the containers or if containers are accidentally dropped and thereby crack or fail. Containers have been developed which `
2066~2~ ; `
CONTAINERIZATION SYSTEM FOR AG~OCHEMICALS AND THE LIXE
This invention relates to a containerization system and to ` ~-containers which are psrticularly suitable for storing, packaging ,~?~
and transporting to~cic or hazsrdous products, e.g., agricultural chemical compounds, such as pesticides.
At present, most hazardous and tosic liquids are stored in metal drums or, where smaller quantities are involved, in plastic .~ containers. Hazardous or to~cic compounds, such as agrochemical `;`- - `
compounds, are formulated in various compositions. `~
The expression to~ic or hazardous compounds as used herein `~
means an industrial chemical or agrochemical compound, which, if --~
released in the quantity or concentration normally present in ~X
15 storage and shipping containers, may cause damage to the environment or be injurious to a person contacted by it. ``;~
With respect to agricultural chemicals, liquid compositions, ~``~``
particularly in the form of concentrates, are most convenient for farmers because of the relative ease with which they can be ~O handled, formulated and used. However, there are significant ` `
difficulties in handlin~ such liquid compositions. } -~
There is a danger of spillage or leakage if holes develop in the containers or if containers are accidentally dropped and thereby crack or fail. Containers have been developed which `
2~) possess great resistance to impact and shock. 1 ```;
While such containers are secure under normal storage and -~
handling conditions, in the event of an accident, for example during transporting, there remains an appreciable risk of spillage or leakage with rapid loss of liquid. Leakage of to~ic and 30 hazardous chemicals can create damage to the environment.
The chemical and packaging industries have long sought a ` `
secure container which provides sufficient safeguards for those ;~
handling it, such as farmers and transpor~ers, as well as adequate ~ ~`
protection for the environment.
: . `'. '' ",`,".~'~: ' . .; . ~ -,::
WO 92/01374 PCI/EP9ltO1348 ~,o~i6~ 2 It is known, for e~cample, to package agrochemicals in soluble bags or sachets made from films. However, such films may crack and break and thus cause leakage of the agrochemical contents.
There are a variet~ of defects whic~ can occur in films, which a may lead to weal~nesses of the film and become a potential source - `of leakage. For esample, the presence of air bubbles, dust ~ - -particles or foreign bodies in gel particles or the eristence of thin `;
points on or in the film are all potential weak points- If a film with such a weak point is subjected to a lot of handling or ~() physical shock, the film may fail at 8 weak point.
This is especially a problem in the agrochemical industry where containers may be subjected to repeated and uncontrolled `~
handling by distributors, transporters or farmers.
Another possibility is to provide agrochemicals in the form 1.-, of wettable powders which can be contained within a bag which may be water soluble or water dispersible. ~Iowever, wettable `
powders are less and less used in agricultural farming. ~~
Also suggested have been containing systems for pesticides ~ -in which the liquid-containing active ingredient is enclosed within ' O soluble bags or sachets. However, the bags tend to develop -~ pinholes and the contained liquid leaks under such conditions causing potential injury to the environment. -`
It has also been proposed for pesticides ~ be packaged in `
soluble bags or sachets which contain an air space to absorb '~ shocks and to avoid leakage. This feature does tend to reduce bag failure. However, this does not avoid the problems of pinholes.
In other industries such as pharmaceuticals and cosmetics, gel formulations have been used as a means for packaging pharmaceutical or cosmetic products. However, such gel :~) formulations are often utilized for aesthetic and other reasons and not as par~ of a containerization system for holding and securing to~cic or hazardous chemicals. Furthermore, the gels used for pharmaceutical or cosmetic purposes are generally water- based.` ~;
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WO 92/01374 PCr/EP91/01348 ;~
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The present invention seeks to provide a new method and ; `
.. :
system for storing, containing and packaging to~cic and hazardous compositions such as agrochemicals which is ~fe for handling. `
The present invention further ~eeks to provide a new ~ ` s `
system to contain agrochemicals which is easy to manipulate for the farmer. ` --The present invention further seeks to provide a new -`
system for containing chemicals such as agrochemicals which -enables such chemicals to be readily, rapîdly and easily solubilized and/or dispersed in water, preferably in less than five minutes under normal agitation.
The present invention further seelcs to provide a new system for storing, containing and packaging chemicals such as agrochemicals, said system utilizing a minimum amount of i ~ volumetric space. .-'i~.i,.,. .~".,~
The present invention further seeks to provide a new container and a new system fcr containing hazardous compounds which diminishes the risks of leakage and pollution.
The present invention further seeks to avoid leakage through pinholes of a bag containing hazardous compositions. Only ;` ` ;`
one pinhole among thousands of bags is enough to cause a lot of `
trouble, because the liquid going through the pinhole contaminates ~ `;
all of its environment~ ` -The present invention further seeks to avoid breakage of the container with its contents. When the container is rigid, there `
is substantial possibility of simple breakage. ~ `
With a liquid in a bag this possibility is somewhat reduced, ~ -but the liquid still transmits the shocks and there is the problem of hydraulic hammer effect. The present invention seeks to àvoid ` `
this hydraulic hammer effect, or at least to reduce it. - ```~
The present invention further seeks to dissipate, as much as ~- `
possible, the force of a shock to a container. ~ ~~
The present invention further seeks to provide a shock absorbing system for containing agrochemicals, e.g., pesticides. ~
-, ' ' ..,",:,;,.
````" ~ '~ i' WO 92/01374 PCI/EP91/01348 `~
2 0 6 6 ~
The present invention further seeks to provide a containing system wherein less solvent is needed in the formulation of the - ~- `
chemical, which is a cost saving advantage both in shipping and ~ - -manufacturing. ` ~ ` `
An additional advantage of the present invention is that higher concentrations of active ingredient can be obtained when using gels rather than liquids.
The present invention seeks to provide a new container -~
system for agrochemicals which quickly dissolves when put into water. The invention further seeks to provide a new container system for agrochemicals which reduces the risk of clogging the spray nozzles or the filters of spray tanks.
Other objects and advantages of the invention will be apparent from the description which follows. Other objects of the 1:~ invention will better appear from the following description.
The objects of the invention can be achieved in full or in -~ -part by means of the invention.
The present invention accordingly provides a containerisation system for holding and securing i.e. containing `
~0 chemical compounds which comprises a water soluble and water dispersible bag which completely encloses a gel, said gel comprising a chemical compound.
The present invention provides a containerization system comprising a water soluble or water dispersible bag which 2~ contains, i.e. encloses, holds and secures a chemical compound ~ `
which can be a to~ic or ha ardous chemical; the chemical `-compound i5 present in a gel which is of essentially organic ~;
material. The present invention is slso directed to a containerization system that can seIf-dispènse the active ~;
30 ingredient contained therein when placed in an aqueous medium.
The present invention also concerns a method for containing, i.e. ` ``
bolding and securing, chemicals in a manner which reduces the ;
chances of the chemical spilling, leaking or con~acting with the ``~
environment during shipping and storage.
WO 92/01374 2 0 5 6 ~ 2 ~ Pcr/Enl/0l348 ~
- . ., . ~ .
The containerization system of the present invention ~'",'~.`"7,.~'''`'~'~
compri~es a bag comprising a water ~oluble or water-dispersible `~ 'h~
film w~ich envelcops and encloses a hazardous or to~cic chemical present in a gel. The gel provides its own discrete advantages and applications as a concentrate for the chemical compound. When the gel of the present invention is used in conjunction with the enveloping bag, a conta~nerization system is provided which is unique in its ability to maintain integrity and prevent leakage of ;
the subject chemical into the environment. !~''.,`'',',.~, The ultimate purpose of the containerization system iæ to ~
preserve a to~cic or hazardous chemical in a form which can be ~;
safely handled and which is secured in a mariner preventing its rapid leakage into the environment. The invenhon achieves these -~
objectives not merely by creating an enveloping barrier of l 3 protection but by employing a system integrally related to the subject chemical.
The present invention also includes a method for holding ~ ;
and securing chemical compounds, such as to~ic and ha~ardous compounds, in a manner to prevent their contact with the environment during shipment and storage, said method comprising~
(i~ mi~cing at an elevated temperature a chemical compound ` ~ -with other gel ingredients until the chemic 1 compound and ` ~``
ingredients are sufficiently dissolved or dispersed to appear visually as a substantially single phase, ~3 (ii) allowing the mi~cture to cool and to form a gel, and (iii) enclosing and sealing a predetermined amount of said gel within a bag of a water-soluble or water dispersible film.
In a preferred embodiment the chemical compound is an ~
agricultural chemical. ~`
In a further preferred embodiment the chemical compound is to~ic or hazardous to the en~rironment or to persons contacted by `:
it. ' Preferably the gel is composed substantially of organic :~,a~'`,`'`3~`.'`'' materials.
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WO92/01374 ~,~; PCI`/EP91/01348 ~ ~ ' In a further preferred embodiment the gel comprises the chemical compound and one or more ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelled or gelling agents.
In a furtber preferred embodiment gel comprises the ~
chemical compound and nonionic surfactant. The surfactant is preferably a nonionic emulsifier.
Preferably the nonionic emulsifier is a sulfonate.
In a further preferred embodiment the otganic solvent is a petroleum hydrocarbon selected from the group consisting of aromatic and aliphatic solvents.
In a further preferred embodiment th`e gel comprises the chemical compound and an organic solvent.
In a further preferred embodiment the gel comprises the ' compound, a gelling agent, a solvent and a surfactant. -i"
Preferably the gel has a water content which is less than 5%
by weight. ~ -Preferably the gel has a viscosity of between 1000 and - ~
30,000 centipoise. `
'0 In a further preferred embodiment the gel and the gel ~` `
within the bag have a density greater than 1. ; -~
In a further preferred embodiment the bag is made of a `
polymeric water soluble film having a thickness between about 10 ;
and 500 microns, and is not permeable to and not substantially `
^.~ soluble or dispersible in the organic components of the gel.
' .`' ',' "~
As already e~cplained, a tn~ic or hazardous chemical can be :;
any compound which can cause injury to persons e~posed to the chemical or which can damage the environment. One class of such ~n compounds is agricultural chemicals or agrochemicals such as pesticides (e.g., herbicides, fungicides, nematocides, insecticides, ` `
et~c.) and plant protect}on agents (e.g., plant growth regulators,`` `
nutrients, etc.). ~ -....
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W O 92/01374 PC~r/EP91/01348 ~ ~`
~6 1~
In practice, the gel material used in the invention comprises ~ ~
the active ingredient, which is the hazardous or to~cic chemical in ~ ;
association with ingredients that participate in or a-~sist in the ` "
formatlo~ of the gel, for e~cample, surfactants, dispersants, 5 thic~ceners, solvents and gelled or gelling agents.
A gel is generally a colloid in which the dispersed phase ``~
has combined with the continuous phase to produce a viscous, i :~
jelly-Like product. A gel can be a dispersed system consisti}lg typically of a high molecular weight campound or aggregate of - -small particles in very close association with a liquid. The gels ~ -used in the invention usua!ly have an organic continuous phase, in contrast to most e~isting gel materials which are water--based and have an aqueous continuous phase~
Furthermore, the gels used in the invention have essentially `
-~ one physical phase, at least as can be seen when visually observed. Gels that are preferred for the invention are Shose which can be divided by cutting and whose cut parts are able to merge together by simple ju~taposition. i Solvents useful in the gel of the present invention are ~ `
G organic solvents such as petroleum hydrocarbons which include aliphatic and arom~tic solvents. Surfactants that ~ n be used in ` "
the invention are nonionic and anionic surfactants and combinations thereof. Illustrative gelling agents that can be used ` ` ` ``
include mLlCtUreS of dioctyl sulfosuccinate salt and sodium ; ~ `
~, .
benzoate, tetramethyl decynediol etho~;ylated dialkylphenol, ~ `
combinations of modified clay and propylene carbonate, `
hydrogenated castor oil, etho~cylated veget~ble oil, dioctyl ester of sodium sulf~ocinate and sodium benzoate, diatomaceous earth, and mi~ctures of dimethyl hexane and he~yne diol~ ;
The gel material which is used in the invention is essentially a material which has a phase difference phi between the controUed ~ . }
shear stress and the resulting shear`~strain such ~hat tg(phi) is les~s than or equal to 1-5, pre~erably less ~han or equal to 1.2. `;`~
Tg(phi) is the LangenL of the phi an~e (or phase difference).
~-``~.
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S~JBSTITUTE SHEET `~ ~
. .
WO 92J01374 6Ç~ 4~14 PCI~/EP9l/0l348 The measurement of phi is made by means of a rheometer `
ha~ing a flat fi~ced 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 æpeed motor; the rotation is a sinusoidal one, i.e., the torque and the angular displacement change as a sine function with time. This angular displacement corresponds to the hereabove mentioned shear strain;
the torque of the controlled speed motor (which causes the angular displacement) corresponds to the hereabove mentioned
While such containers are secure under normal storage and -~
handling conditions, in the event of an accident, for example during transporting, there remains an appreciable risk of spillage or leakage with rapid loss of liquid. Leakage of to~ic and 30 hazardous chemicals can create damage to the environment.
The chemical and packaging industries have long sought a ` `
secure container which provides sufficient safeguards for those ;~
handling it, such as farmers and transpor~ers, as well as adequate ~ ~`
protection for the environment.
: . `'. '' ",`,".~'~: ' . .; . ~ -,::
WO 92/01374 PCI/EP9ltO1348 ~,o~i6~ 2 It is known, for e~cample, to package agrochemicals in soluble bags or sachets made from films. However, such films may crack and break and thus cause leakage of the agrochemical contents.
There are a variet~ of defects whic~ can occur in films, which a may lead to weal~nesses of the film and become a potential source - `of leakage. For esample, the presence of air bubbles, dust ~ - -particles or foreign bodies in gel particles or the eristence of thin `;
points on or in the film are all potential weak points- If a film with such a weak point is subjected to a lot of handling or ~() physical shock, the film may fail at 8 weak point.
This is especially a problem in the agrochemical industry where containers may be subjected to repeated and uncontrolled `~
handling by distributors, transporters or farmers.
Another possibility is to provide agrochemicals in the form 1.-, of wettable powders which can be contained within a bag which may be water soluble or water dispersible. ~Iowever, wettable `
powders are less and less used in agricultural farming. ~~
Also suggested have been containing systems for pesticides ~ -in which the liquid-containing active ingredient is enclosed within ' O soluble bags or sachets. However, the bags tend to develop -~ pinholes and the contained liquid leaks under such conditions causing potential injury to the environment. -`
It has also been proposed for pesticides ~ be packaged in `
soluble bags or sachets which contain an air space to absorb '~ shocks and to avoid leakage. This feature does tend to reduce bag failure. However, this does not avoid the problems of pinholes.
In other industries such as pharmaceuticals and cosmetics, gel formulations have been used as a means for packaging pharmaceutical or cosmetic products. However, such gel :~) formulations are often utilized for aesthetic and other reasons and not as par~ of a containerization system for holding and securing to~cic or hazardous chemicals. Furthermore, the gels used for pharmaceutical or cosmetic purposes are generally water- based.` ~;
'''`, `~';
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.
,~ '' .
WO 92/01374 PCr/EP91/01348 ;~
... ~, ~, .. ~
20664~
The present invention seeks to provide a new method and ; `
.. :
system for storing, containing and packaging to~cic and hazardous compositions such as agrochemicals which is ~fe for handling. `
The present invention further ~eeks to provide a new ~ ` s `
system to contain agrochemicals which is easy to manipulate for the farmer. ` --The present invention further seeks to provide a new -`
system for containing chemicals such as agrochemicals which -enables such chemicals to be readily, rapîdly and easily solubilized and/or dispersed in water, preferably in less than five minutes under normal agitation.
The present invention further seelcs to provide a new system for storing, containing and packaging chemicals such as agrochemicals, said system utilizing a minimum amount of i ~ volumetric space. .-'i~.i,.,. .~".,~
The present invention further seeks to provide a new container and a new system fcr containing hazardous compounds which diminishes the risks of leakage and pollution.
The present invention further seeks to avoid leakage through pinholes of a bag containing hazardous compositions. Only ;` ` ;`
one pinhole among thousands of bags is enough to cause a lot of `
trouble, because the liquid going through the pinhole contaminates ~ `;
all of its environment~ ` -The present invention further seeks to avoid breakage of the container with its contents. When the container is rigid, there `
is substantial possibility of simple breakage. ~ `
With a liquid in a bag this possibility is somewhat reduced, ~ -but the liquid still transmits the shocks and there is the problem of hydraulic hammer effect. The present invention seeks to àvoid ` `
this hydraulic hammer effect, or at least to reduce it. - ```~
The present invention further seeks to dissipate, as much as ~- `
possible, the force of a shock to a container. ~ ~~
The present invention further seeks to provide a shock absorbing system for containing agrochemicals, e.g., pesticides. ~
-, ' ' ..,",:,;,.
````" ~ '~ i' WO 92/01374 PCI/EP91/01348 `~
2 0 6 6 ~
The present invention further seeks to provide a containing system wherein less solvent is needed in the formulation of the - ~- `
chemical, which is a cost saving advantage both in shipping and ~ - -manufacturing. ` ~ ` `
An additional advantage of the present invention is that higher concentrations of active ingredient can be obtained when using gels rather than liquids.
The present invention seeks to provide a new container -~
system for agrochemicals which quickly dissolves when put into water. The invention further seeks to provide a new container system for agrochemicals which reduces the risk of clogging the spray nozzles or the filters of spray tanks.
Other objects and advantages of the invention will be apparent from the description which follows. Other objects of the 1:~ invention will better appear from the following description.
The objects of the invention can be achieved in full or in -~ -part by means of the invention.
The present invention accordingly provides a containerisation system for holding and securing i.e. containing `
~0 chemical compounds which comprises a water soluble and water dispersible bag which completely encloses a gel, said gel comprising a chemical compound.
The present invention provides a containerization system comprising a water soluble or water dispersible bag which 2~ contains, i.e. encloses, holds and secures a chemical compound ~ `
which can be a to~ic or ha ardous chemical; the chemical `-compound i5 present in a gel which is of essentially organic ~;
material. The present invention is slso directed to a containerization system that can seIf-dispènse the active ~;
30 ingredient contained therein when placed in an aqueous medium.
The present invention also concerns a method for containing, i.e. ` ``
bolding and securing, chemicals in a manner which reduces the ;
chances of the chemical spilling, leaking or con~acting with the ``~
environment during shipping and storage.
WO 92/01374 2 0 5 6 ~ 2 ~ Pcr/Enl/0l348 ~
- . ., . ~ .
The containerization system of the present invention ~'",'~.`"7,.~'''`'~'~
compri~es a bag comprising a water ~oluble or water-dispersible `~ 'h~
film w~ich envelcops and encloses a hazardous or to~cic chemical present in a gel. The gel provides its own discrete advantages and applications as a concentrate for the chemical compound. When the gel of the present invention is used in conjunction with the enveloping bag, a conta~nerization system is provided which is unique in its ability to maintain integrity and prevent leakage of ;
the subject chemical into the environment. !~''.,`'',',.~, The ultimate purpose of the containerization system iæ to ~
preserve a to~cic or hazardous chemical in a form which can be ~;
safely handled and which is secured in a mariner preventing its rapid leakage into the environment. The invenhon achieves these -~
objectives not merely by creating an enveloping barrier of l 3 protection but by employing a system integrally related to the subject chemical.
The present invention also includes a method for holding ~ ;
and securing chemical compounds, such as to~ic and ha~ardous compounds, in a manner to prevent their contact with the environment during shipment and storage, said method comprising~
(i~ mi~cing at an elevated temperature a chemical compound ` ~ -with other gel ingredients until the chemic 1 compound and ` ~``
ingredients are sufficiently dissolved or dispersed to appear visually as a substantially single phase, ~3 (ii) allowing the mi~cture to cool and to form a gel, and (iii) enclosing and sealing a predetermined amount of said gel within a bag of a water-soluble or water dispersible film.
In a preferred embodiment the chemical compound is an ~
agricultural chemical. ~`
In a further preferred embodiment the chemical compound is to~ic or hazardous to the en~rironment or to persons contacted by `:
it. ' Preferably the gel is composed substantially of organic :~,a~'`,`'`3~`.'`'' materials.
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WO92/01374 ~,~; PCI`/EP91/01348 ~ ~ ' In a further preferred embodiment the gel comprises the chemical compound and one or more ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelled or gelling agents.
In a furtber preferred embodiment gel comprises the ~
chemical compound and nonionic surfactant. The surfactant is preferably a nonionic emulsifier.
Preferably the nonionic emulsifier is a sulfonate.
In a further preferred embodiment the otganic solvent is a petroleum hydrocarbon selected from the group consisting of aromatic and aliphatic solvents.
In a further preferred embodiment th`e gel comprises the chemical compound and an organic solvent.
In a further preferred embodiment the gel comprises the ' compound, a gelling agent, a solvent and a surfactant. -i"
Preferably the gel has a water content which is less than 5%
by weight. ~ -Preferably the gel has a viscosity of between 1000 and - ~
30,000 centipoise. `
'0 In a further preferred embodiment the gel and the gel ~` `
within the bag have a density greater than 1. ; -~
In a further preferred embodiment the bag is made of a `
polymeric water soluble film having a thickness between about 10 ;
and 500 microns, and is not permeable to and not substantially `
^.~ soluble or dispersible in the organic components of the gel.
' .`' ',' "~
As already e~cplained, a tn~ic or hazardous chemical can be :;
any compound which can cause injury to persons e~posed to the chemical or which can damage the environment. One class of such ~n compounds is agricultural chemicals or agrochemicals such as pesticides (e.g., herbicides, fungicides, nematocides, insecticides, ` `
et~c.) and plant protect}on agents (e.g., plant growth regulators,`` `
nutrients, etc.). ~ -....
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W O 92/01374 PC~r/EP91/01348 ~ ~`
~6 1~
In practice, the gel material used in the invention comprises ~ ~
the active ingredient, which is the hazardous or to~cic chemical in ~ ;
association with ingredients that participate in or a-~sist in the ` "
formatlo~ of the gel, for e~cample, surfactants, dispersants, 5 thic~ceners, solvents and gelled or gelling agents.
A gel is generally a colloid in which the dispersed phase ``~
has combined with the continuous phase to produce a viscous, i :~
jelly-Like product. A gel can be a dispersed system consisti}lg typically of a high molecular weight campound or aggregate of - -small particles in very close association with a liquid. The gels ~ -used in the invention usua!ly have an organic continuous phase, in contrast to most e~isting gel materials which are water--based and have an aqueous continuous phase~
Furthermore, the gels used in the invention have essentially `
-~ one physical phase, at least as can be seen when visually observed. Gels that are preferred for the invention are Shose which can be divided by cutting and whose cut parts are able to merge together by simple ju~taposition. i Solvents useful in the gel of the present invention are ~ `
G organic solvents such as petroleum hydrocarbons which include aliphatic and arom~tic solvents. Surfactants that ~ n be used in ` "
the invention are nonionic and anionic surfactants and combinations thereof. Illustrative gelling agents that can be used ` ` ` ``
include mLlCtUreS of dioctyl sulfosuccinate salt and sodium ; ~ `
~, .
benzoate, tetramethyl decynediol etho~;ylated dialkylphenol, ~ `
combinations of modified clay and propylene carbonate, `
hydrogenated castor oil, etho~cylated veget~ble oil, dioctyl ester of sodium sulf~ocinate and sodium benzoate, diatomaceous earth, and mi~ctures of dimethyl hexane and he~yne diol~ ;
The gel material which is used in the invention is essentially a material which has a phase difference phi between the controUed ~ . }
shear stress and the resulting shear`~strain such ~hat tg(phi) is les~s than or equal to 1-5, pre~erably less ~han or equal to 1.2. `;`~
Tg(phi) is the LangenL of the phi an~e (or phase difference).
~-``~.
. . . :,~ , ~.
S~JBSTITUTE SHEET `~ ~
. .
WO 92J01374 6Ç~ 4~14 PCI~/EP9l/0l348 The measurement of phi is made by means of a rheometer `
ha~ing a flat fi~ced 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 æpeed motor; the rotation is a sinusoidal one, i.e., the torque and the angular displacement change as a sine function with time. This angular displacement corresponds to the hereabove mentioned shear strain;
the torque of the controlled speed motor (which causes the angular displacement) corresponds to the hereabove mentioned
3 ~) controlled shear stress.
The gel which may be used in the invention is primarily ~;
organic, which means that it has a low water content, generally less than 5% (by weight), preferably less than 3%, more preferably less than 1%.
i.-l Generally, the gel which may be used in the invention is a material having a viscosity from 500 centipoise (measurement made with a Brookfield viscometer at 23 C with a flat plate rotating at ~-20 round per minute) to 50000 centipoise, preferably from 1000 to `` `
30000 centipoise, and still more preferably from 1 000 to 5 000 :
7 () centipoise.
It is to be understood that all measurements and test procedures in this specification, unless otherwise stated, are taken `
at 23C ~room temperature).
According to one embodiment of the invention, the gels ` ``
., which are used in the invention are successful when submitted to `~ 3`.
the following puncture test 500 g of a material/gel are placed in `-a pol~inyl alcohol water soluble bag (having a 50 micron thick ~`
wall) and heat sealed. The bag is suspended using a binder clip ~ ` `
at which time a dissecting needle (the diameter of which i9 0.~
30 mm) is inserted into the lower third of the bag and withdrawn.
The material/gel is observed for 30 minutes to determine lea~age.
A gel which is successful in the present test shows no leakage and preferably may be used in the invention. A droplet of material `
~ `' . ..:
, . ~ ..-' ~.- `', ' `'~` `.
The gel which may be used in the invention is primarily ~;
organic, which means that it has a low water content, generally less than 5% (by weight), preferably less than 3%, more preferably less than 1%.
i.-l Generally, the gel which may be used in the invention is a material having a viscosity from 500 centipoise (measurement made with a Brookfield viscometer at 23 C with a flat plate rotating at ~-20 round per minute) to 50000 centipoise, preferably from 1000 to `` `
30000 centipoise, and still more preferably from 1 000 to 5 000 :
7 () centipoise.
It is to be understood that all measurements and test procedures in this specification, unless otherwise stated, are taken `
at 23C ~room temperature).
According to one embodiment of the invention, the gels ` ``
., which are used in the invention are successful when submitted to `~ 3`.
the following puncture test 500 g of a material/gel are placed in `-a pol~inyl alcohol water soluble bag (having a 50 micron thick ~`
wall) and heat sealed. The bag is suspended using a binder clip ~ ` `
at which time a dissecting needle (the diameter of which i9 0.~
30 mm) is inserted into the lower third of the bag and withdrawn.
The material/gel is observed for 30 minutes to determine lea~age.
A gel which is successful in the present test shows no leakage and preferably may be used in the invention. A droplet of material `
~ `' . ..:
, . ~ ..-' ~.- `', ' `'~` `.
4 PCr/EP91/01348 ~;
20S6424 ~... ,,`.-g . . .. .. _:
may appear on the hole, but no persistent flowing or leakage occurs.
Preferred characteristics of a gel which is appropriate for ;;
the invention are (alone or in combination): ~-* The viscosity should be generally from 500 to 50000 ` ` -centipoise, preferably from 1000 to 30000 centipoise, and still more preferably from 1 000 to 5 000 centipoise (measurement made with a Brookfield machine).
* The dispersibility in water should be substantially `-lt! complete when the gel is subjected to normal agitation in water after a 15 minutes interval, preferably after a 10 minutes interval.
The gel preferably contains an essentially non-aqueous solvent The chemical nature of the enveloping film constituting the - - `
., bag can vary quite widely. Suitable materials are water soluble (or possibly water dispersible) materia}s whieh are insoluble in the organic solvents used to dissolve or disperse the active ingredient (e.g., agrochemical). Specific suitable materials include `
polyethylene o~ide, such as polyethylene glycol; starch and -"`
modified starch; alkyl and hydro~cyalkylcellulose, such as `
hydro~ymethylcellulose, hydro~yethylcellulose, hydro~ypropyl cellulose; carbo~cymethylcellulose; polyvinylethers such as poly ``":~
methyl vinylether or poly(2-metho~cyetho~yethylene); poly(2,4 dimethyl-6-triazinylethylene; poly(3-morpholinyl ethylene); poly(N- `
'. 1,2,4-triazolylethylene); poly(vinylsulfonic acid); polyanhydr;des; ; ;~
low molecular weight melamine-formaldehyde resins; low molecular .~ ?
weight urea formaldehyde resins; poly(2-hydro~yethyl ;~
methacrylate); polyacrylic acid and its homologs.
A preferred enveloping film comprises or is made from v ~`
:30 poly~inylalcohol (PVA). When PVA is used, it is preferably partially or fully alcoholyzed or hydrolyzed, e.g., 40-100%, preferably 80- -~
~9SX alcoholyzed or hydrolyzed, as a polyvinyl acetate (or other `~
ester) film. Copolymers or other derivatives of such polymers can ` `
also be used.
. `',';``:~ `' ,-`, '.' '`" .
~ 1 0 :. ~
Additional preferred materials for constituting the bags in the invention are polyethylene o~cide, methylcellulose, and polyvinylalcohol.
The following features, alone or in combination, constitute additional preferred features of the invention: r~
According to another feature, the gels and the bag containing gel of the invention preferably have a specific grarity greater than 1, preferably greater than 1.1.
According to another feature the gels contained in the bags ~
0 of the invention preferably have spontaneity (as hereafter -~ `
. .
defined) less than 75, preferably less than 25.
According to another feature, the bags of the invention ~
generally have a capacity of from 0.01 to 12 litres; preferably ~ -they have a capacity of from 0.2 to 12 litres, more preferably from .
1:~ 0.45 to 6 litres.
According to another feature the bag is preferably made of a polymeric water soluble film. The thickness of this film is generally from 10 to about 500 microns, preferably from 20 to ~ --` }
about 100 microns. '-'"'"'':,~5 "O According to another feature, the bag of the invention is ` ~-not filled to capacity: the bag is then generally filled to at least 60% of capacity with the gel, which preferably comprises an i agricultural chemical, more preferably to at least 70X of capacity, ~`
stiLl more preferably 80% to 99X of capacity and most preferably - `
^~ 85% to 95X of capacitY. The bag is preferably not filled to i "
complete capacity because the unused capacity gives the bag ~ `-resistance to breakage when dropped, transported or stored. This , ```
unused capacity may or may not contain air or an inert gas. The ``;;
unused capacity, whether or not it contains air or gas improves shock resistance. Howe~er, in deciding how much unused capacity to pro~ride, the advantages of shock resistance and the cost of providing unused capacity must be balanced against the need, if ~```
any, for shock resistance and the cost of unuseà capacity. Thust ~ -if the bag is stored and/or transported in a shock absorbing --WO 92/01374 PCI`/EP9l/01348 1 1 2 0 5 6 4 2 ~
' ~''': ;:
container, then it may noS be as helpful to provide this unused capacity. ~ `' Also, the capacity to which the bag is filled, and whether ~ h`
the unused capacity does or does not contain air or a gas is `
affected by whether it is desirable to have the bag sink or float.
Also, whether the bag sinks or floats will depend not only on the unused capacity, but also the density of the bag contents.
The water soluble films which are used to make the water -soluble bags are known. In order to make a bag, the film needs to ` i~
n be shaped (possibly parti~lly sealed) and then filled with the gel.
Generally the gels are able to flow, even if it is a slow rate due :" '`'4'~
to high viscosity. ~f necessary the gel is propelled in to ~ .
. the bag with pressure. A container, which is used to contain a gel,has not been used up to now in agriculture.
1.~ When filled with the gel compositin hereinbefore ;~
described, the bag has to be finally sealed, generally heat sealed, So be closed. The sealing may be made according to known manner. '`. ~`~'''.!,`''~',':~, EXAMPl.ES
The following e2amples are given for illustrative purposes and should not be understood as restricting the invention. -`
''5 In these e~amples, the Brookfield viscosity was measured, as previously indicated, with a Brookfield viscosimeter which had a `~
flat plate rotating at 20 revolutions per minute. In all of the following e2amples, the prepared gels had a tg(phi) of between `~
0.75 and 1.5. ~ `~
0 The emulsion stability of the prepared gels is evaluated according to the following method: 1 ml of the gel is m~ed with ``
99 ml water in a 150 ml tube; the tube is inverted-10 times at the rate of 1 complete inversion per second. ~ating of the emulsion stability is made by reading the relative amount of phases after , : '.
., .,~,.
. ~ :' ' -.
WO 92~01374 PCr/EP91/01348 ~ -~ 96~ ' 12 ~ ~
24 hours. The emulsion stability is rated as follows: "e~tcellent" if the amount of emulsion (phase looking like mil}c) represents 98 to 100% (v/v) of the total, the balance being cream or thin; "good" if the amount of emulsion represents 90 to 98% (v/v) of the total, .; the balance being mainly cream with no more than S ml bein8 thin; ` ~ `"fair" if -the amount of emulsion represents 70 to 90X (vJv) of the -~-total, the balance being cream or thin; and "poor" if the total of emulsion represents 70 or less % (v/v) of the total.
The spontaneity is assessed according to the fo~lowing ~:
method: A mi~cture of 1 ml gel with 99 ml water are put into a 150 ml glass tube ( diameter 22mm) which is stoppered and inverted by 180 degrees (upside down). The number of inversions required to -completely disperse the gel is called the spontaneity. ~
,, ... , .-EXAMPLE 1 j-A gel is made by stirring and shaking at 50 C a misture of .-the following ingredients until they are each dissolved or` ` `
dispersed: i ~
, ~ ,.,~.. " . .
active ingredient: the herbicide 2,4-D; ;
pheno~y benzoic acid (isooctyl ester): 64.8X
solvent aromatic solvent with flash ` `~
point of 65 C: 24.2X
'' ;. adjuvants~
non ionic/sulfonate blended emulsifier: 4 X ~;
calcium alkylbenzene sulfonste: 1 X -mi~ture of dioctylsulfosuccinate salt and sodium benzoate ` 6 X. `~
3 t' - ;~
' ~:
'.'~' ";
WO 92/01374 PCI/EP91/01348 ~ ~
~ ~, ;^, 2Q56~24 ~
During stirring, a dissolution or dispersion appears, and ` `;
thereafter gelation. Gelation increases as the mL~ture cools to about ~0 C. ;
The Brookfield viscosity of the gel is 3000 centipoise. ` `
. The emulsion stability is "good" according to the above described test. ; `~
1100 g of this gel are put in a one-litre bag made of a film !'~
of PVA (88X hydrolyzed polyvinyl acetate; cold water soluble;
thickness: 55 microns). The bag, which is almost full (about 95%
;0 v/~r), is hot sealed. The specific gra~rity of the gel and of the bag containing the gel is 1.1. -~
The bag is dropped 10 times from 1.2 m above the ground.
No breaking or leakage is observed.
The bag is put into a tank containing water under gentle '., agitation (that is to say such as that obtained with pump recycling). The bag and its contents are dispersed within a 3 minute interYal. There is no clogging in the filter, which is a `~
screen ha~ing 0.28 mm openings.
EXAMPI.E 2 The procedure of E~ample 1 is repeated, using the same active ingredient in a mi~ture containing the following adju~rants~
non ionic/sulfonate blended emulsifier: 5.2 X
tetramethyl decynediol: 30 X.
The Brookfield viscosity of the gel is 3000 centipoise.
:~0 The emulsion stability is good using the above described `
test.
". ' '`~'' :'' ~
WO 92/01374 PC~/EP9l/01348 ~ ~ ~
66~ 14 1100 g of this gel are put in a 1 litre bag made of a film of `
PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; ` :~ ~
thicknçss: 55 microns). The bag, which is almost full (about 95% ;
v/v), is hot sealed. The specific gravity both of the gel and of ; ` -~`
:~ the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle " -agitation (that is to say such as that obtained with pump i~
ln recycling). It is dispersed within a 3 minute interval. There is no "` i clogging in She filter which is a screen having 0.28 mm openings.
The procedure of E%ample 1 is repeated, using the same l.. active ingredient in a mL~ture containing the following adjuvants:
non ionic/sulfonate blended emulsifier: 21.5X;
calcium alkylbenzene sulfonate 3.~X;
etho~ylated dialkylphenol: 10 X.
`~) The Brookfield viscosity of the gel is 3000 centipoise.
The emulsion stability is good using the above described test~ ~ ;
1100 g of this gel are put in a 1 litre bag made of a film of PVA (88X hydrolyzed pol~inyl acetate; cold water soluble; ~
";) thickness: 55 microns). The bag, which is almost full (about 95X - ~``
v/v), is hot sealed. The specific gravity both of the gel and of ~ `
the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the `
ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle ; ~ `
agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 3 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings. .
`~
WO 92/01374 PCI`/EP91/01348 2~S6~24 ~"''""'~''''~:'c 1 J ~; ~
'.', EXAMPLE 4 `
gel is made by stirring at 50 C a mi~ture of:
acti~e ingredient bromo~cynil acid in the form of an octanoate ester: 61.15%;
solvent aromstic solvent with a f}ash point of 3& C: 22.85X;
polyaryl phenoletho~ylated: 6 X;
}0 calcium alkylbenzene sulfonate: 2 %;
clay which has been modified by addition of methyl groups: t~ X;
propylene carbonate (activating the thickener): 2 X.
These materials are mi~ced together while shearing with an Attritor mi~cer. The product started to gel within a few minutes.
I`he Brookfield viscosity of the gel is 4200 centipoise.
The emulsion stability is good using the above described t; test~
The spontaneity is 38.
1100 g of this gel are put in a l litre bag made of a film of PVA (88% hydrolyzed polyvinyl acetate; cold water soluble;
thickness: 55 microns). The bag, which is almost full (about 95X `
`~ v/v), is hot sealed. The specific gra~ity both of the gel and of ``~
..
the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the -ground. No breaking or leakage is observed. `
The bag is placed in a tank containing water under gentle :~0 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.
; ,, ` ;' :~ ', ,', '~ :'`
WO 92/01374 PCr/EP9l/013"8 .~:. ~...;~
~,~,'1.~' 1 6 EXAMPLE
The procedure of E~cample 4 is repeated, using a mLl~ture ; -containing the following components~
J active ingredient ~ i~
bromo:cynil octanoate: 18.65%; -~
bromo~cynil heptanoste: 13.85%; -methyl chloropropionic acid (isooctyl ester) 37.4 X; ` `
solvent: aromatic solvent with a flash point of 38 C: 11.1 X;
hydrogenated castor oil: 3 X;
etho~ylated vegetable oil: 3 %;
non ionic/sulfonate blended emulsifier: 13 X.
: . . .'.' . '. . .',' ' 1~ These materials are mi~ed together while shearing with an - :-Attritor mi~cer. The product started to gel within a few minutes. .
The Brookfield viscosity of the gel is 3150 centipoise. `
The emulsion stability is good using the above described test.
^ 0 The spontaneity is 20.
1100 g of this gel are put in a l litre bag made of a film of PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; ~ `-thickness: 55 microns). The bag, which is almost full tabout 95' `~
v/v), is hot sealed. The specific gravity both of the gel and of `. the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 10 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings. ; `~
E~MPLE 6 `
The procedure of E~cample 6 is repeated using a mi~ture containing the following components:
' ., .
~.
~': ;`.
;. .
_ WO 92/01374 PCI`/EP91/01348 ~ ~
17 2QS~2~ ,'`,,",~,,~,1 active ingredient ~,~
bromo~ynil octanoate: 18~4X; ;~
bromo~ynil heptano~t~ 14 X;
~ethyl chlorophenoxy acetic acid (isooctyl ester) 36.6X;
non ionicJsulfonate blended emulsifier:9 %;
sodium sulfonate of naphthalene formaldehyde condensate: 3 Xi dioctyl ester of sodium sulfosuccinic acid ^, and sodium benzoate 2 X;
diatomaceous e rth: 17 X.
These materials are mi~ted together while shearing with`an Attritor mi cer. The product started to have the appearance of a ~ s i, smooth paste, and is a gel within a few minutes. -The Brookfield viscosity of the gei is 9000 centipoise. `
The emulsion stabilit~ is good using the above described tes t_ The spontaneity is 9. ` "
'`O 1100 g of this gel are put in a 1 litre bag made of a film of , `
P~'~ (88% hydrolyzed polyvinyl acetate; cold water soluble; `~
thickness: 55 microns). The bag, which is almost full (abaut 95% ~ -~
v/v), is hot sealed. The specific gravit~ bot'. of the gel and of ` ~ `
the bag containing the gel is 1.1.
` The bag is then dropped 10 times from 1.2~ m upon the ~ ` `
ground. No breaking or leakage is observed.
The bag is placed in a tanli containing water ~nder gentle agitation (~hat is to say such as that obtained with pump , ;~<~
recycling). It is dispersed within a 10 minute interval. There is no ' :`;'` clogoing in the filter which is a screen having 0.28 mm openings.
_ The procedure Or E~ample 5 is repcatcà1 using a mi~cture con~ining ~1lc ~ollowin~ component~:
"i'~ ',;".
S'~ J'T_ S~-!=T
WO 92/0l374 PCI`/EP9l/0l348 ~ ~
,., -.. .,, ",.
18 ~ ~
active ingredient -~-bromo~tynil octanoate: 18.89X; ;~
~romo~cynil heptanoate: 12.59%; ;~
atrazine: 44.58%; ~r,~
., solvent same as in esample 5: 18.54%; ~:~
polyethylene glycol: 2.7 %. `~
These materials are mi~ed together while shearing with an ~;
Attritor mixer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes. ~ -l ^ The Brookfield viscosity of the gel is 7300 centipoise.
The emulsion`stability is good using the above described ` :~`
test.
The spontaneity is 15. `~
1100 g of this gel are put in a l litre bag made of a film of . `
.~; PVA (88Z hydrolyzed polyvinyl acetate; cold water soluble;
thickness: 55 microns). The bag, which is almost full (about 95 vjv), is hot sealed. The specific gravity both of the gel and of - h` ~
the bag containing the gel is 1.l. ~ `
The bag is then dropped 10 times from 1.2 m upon the `~ ground. No breakmg or leakage is observed.
The bag is pla~ed in a tank containing water under gentle j `s agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 10 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings.
The procedure of E~cample 7 is repeated, using a mixture ;~
containing the following components using: -active ingredient ;` '` bromo:cynil octanoate: 33.7X;
methyl chloropropionic acetic acid `~
(isooctyl ester) 36.2%;
solvent solvent ~romatic solvent with a ~,-WO 92/01374 PCI`/EP9l/0l348 ~ `
-- '9 20S642~
flash point of 65 C: 3 X; ``i~
non ionic~sulfonate blended emulsifier: B.5X;
calcium dodecyl benzene sulfonate: 1 X;
tetramethyl decyne diol: 17.6%. `~
These materials are mi ~ed together while shearing with an '~
Attritor mixer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes. ~- .
The Brookfield viscosity of the gel is 2200 centipoise~
The emulsion stability is good using the above described test.
The spon~aneity is l~
1100 g of this gel are pu~ in a 1 litre baa made of a film of PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; -thicl;ness: ~5 microns~. The bag, which is ~lmost full (about 95%
v/v), is hot sealed. The speci~ic gravity both of the gel and of the bag conl aining the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the ground. No breaking or leaksge is observed.
The bag is placed in a tank containing water under gentle `;~
agit~tion (that is to say such as that obtained with pump -~ ~
recycling). It is dispersed within a 5 minutes interval. There is no - ~`
clogginLO~ in the filter which is a screen having 0.28 mm openings. `- `~
`.-. :`'~-E.~MPLE 9 ` `~ ~`
.
The procedure of Example 8 is repeated, using a mL~ture , containing the following components~
acSive ingredient and solvent are the same ~s in e~ample 8, and amounl of acti~re ingredient is the same;
solvent is the same but the amount is 10.6 calcium do<lecyl benzene sulfonate: 2 %;
mi~ture of dimethyl he~cane and he~yne diol: 11.5%;
calcium alkylaryl sulîon~tc and a ~--`
polyarylphenol ethoxylate:
~:;~' . `'.
'`t S~ ITU~E SHEE~ ~"
WO 92/01374 PCI/EP9l/01348 - ~-,66~ 2 0 These materials are mi~ced together at 90 C while shearing with an Attritor mi~cer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes. ;
.. The Brookfield viscosity of the gel is 2500 centipoise.
The emulsion stability is good using the above described ~ ~
test. ~ ~ s The spontaneity is 5.
1100 g of this gel are put in a 1 litre bag made of a film of i` ` `~
;0 PVA (88% hydrolyzed polYvinyl acetate; cold water soluble; ;~
thickness: 55 microns). The bag, which is almost full (about 95X
v/v), is hot sealed. The specific gravity both of the gel and of the bag containing the gel is 1.1. ~ `~;
The bag is then dropped 10 times from 1.2 m upon the ' 5 ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle ~;~
agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 5 minutè in~er~ral.There is no `~
clogging in the filter which is a screen having 0.28 mm openings.
The procedure of E~cample 5 is repeated, using a mi~cture .; . . ~ .
containing the following components using~
active ingredient .; bromo~cynil octanoate: 33.5%;
bromo~ynil heptanoate: 33.5%; ^~
solvent aromatic sol~rent with a flash ` -~-~
point of 65 C: 22.75X; `;~f"`~
non ionic~sulfonate blended emulsifier: 4.5%;
~ . ~,, ~, .
calcium dodecyl benzene sulfonate: 1%; ~ ~`
and sodium benzoate: 4.25%; ~"
tetramethyl decyne diol: ` 0.5X.
.''-.'~ :' . ~ , ,.. ....
, " ` ,' '`'`` '~',~ ',`", WO 92/01374 2 ~ S ~ 4 2 ~ PCI/EP9l/01348 ~ ;
;.. -.;.
These materials are mi~ed together at 50O C while shearing `
with an Attritor mi~cer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes. ;;
The Brookfield viscosity of the gel is 4850 centipoise.
The emulsion stability is e~ccellent using the above described test.
The spontaneity is 10.
1100 g of this gel are put in a l litre bag made of a film of -~
PVA (88% hydrolyzed pol~rinyl wetate; cold water soluble;
1 !) thickness: 5~ microns~. The bag, which is almost full ~about 95X
v/v), is hot sealed. The specific gravity both of the gel and of the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the .
ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump -~
recycling). It is dispersed within a 3 minute interv~l. There is no clogging in the filter which is a screen having 0.28 mm openings.
' .`;" '."~ ' `
`'; " '''`
.. ..
~. .
20S6424 ~... ,,`.-g . . .. .. _:
may appear on the hole, but no persistent flowing or leakage occurs.
Preferred characteristics of a gel which is appropriate for ;;
the invention are (alone or in combination): ~-* The viscosity should be generally from 500 to 50000 ` ` -centipoise, preferably from 1000 to 30000 centipoise, and still more preferably from 1 000 to 5 000 centipoise (measurement made with a Brookfield machine).
* The dispersibility in water should be substantially `-lt! complete when the gel is subjected to normal agitation in water after a 15 minutes interval, preferably after a 10 minutes interval.
The gel preferably contains an essentially non-aqueous solvent The chemical nature of the enveloping film constituting the - - `
., bag can vary quite widely. Suitable materials are water soluble (or possibly water dispersible) materia}s whieh are insoluble in the organic solvents used to dissolve or disperse the active ingredient (e.g., agrochemical). Specific suitable materials include `
polyethylene o~ide, such as polyethylene glycol; starch and -"`
modified starch; alkyl and hydro~cyalkylcellulose, such as `
hydro~ymethylcellulose, hydro~yethylcellulose, hydro~ypropyl cellulose; carbo~cymethylcellulose; polyvinylethers such as poly ``":~
methyl vinylether or poly(2-metho~cyetho~yethylene); poly(2,4 dimethyl-6-triazinylethylene; poly(3-morpholinyl ethylene); poly(N- `
'. 1,2,4-triazolylethylene); poly(vinylsulfonic acid); polyanhydr;des; ; ;~
low molecular weight melamine-formaldehyde resins; low molecular .~ ?
weight urea formaldehyde resins; poly(2-hydro~yethyl ;~
methacrylate); polyacrylic acid and its homologs.
A preferred enveloping film comprises or is made from v ~`
:30 poly~inylalcohol (PVA). When PVA is used, it is preferably partially or fully alcoholyzed or hydrolyzed, e.g., 40-100%, preferably 80- -~
~9SX alcoholyzed or hydrolyzed, as a polyvinyl acetate (or other `~
ester) film. Copolymers or other derivatives of such polymers can ` `
also be used.
. `',';``:~ `' ,-`, '.' '`" .
~ 1 0 :. ~
Additional preferred materials for constituting the bags in the invention are polyethylene o~cide, methylcellulose, and polyvinylalcohol.
The following features, alone or in combination, constitute additional preferred features of the invention: r~
According to another feature, the gels and the bag containing gel of the invention preferably have a specific grarity greater than 1, preferably greater than 1.1.
According to another feature the gels contained in the bags ~
0 of the invention preferably have spontaneity (as hereafter -~ `
. .
defined) less than 75, preferably less than 25.
According to another feature, the bags of the invention ~
generally have a capacity of from 0.01 to 12 litres; preferably ~ -they have a capacity of from 0.2 to 12 litres, more preferably from .
1:~ 0.45 to 6 litres.
According to another feature the bag is preferably made of a polymeric water soluble film. The thickness of this film is generally from 10 to about 500 microns, preferably from 20 to ~ --` }
about 100 microns. '-'"'"'':,~5 "O According to another feature, the bag of the invention is ` ~-not filled to capacity: the bag is then generally filled to at least 60% of capacity with the gel, which preferably comprises an i agricultural chemical, more preferably to at least 70X of capacity, ~`
stiLl more preferably 80% to 99X of capacity and most preferably - `
^~ 85% to 95X of capacitY. The bag is preferably not filled to i "
complete capacity because the unused capacity gives the bag ~ `-resistance to breakage when dropped, transported or stored. This , ```
unused capacity may or may not contain air or an inert gas. The ``;;
unused capacity, whether or not it contains air or gas improves shock resistance. Howe~er, in deciding how much unused capacity to pro~ride, the advantages of shock resistance and the cost of providing unused capacity must be balanced against the need, if ~```
any, for shock resistance and the cost of unuseà capacity. Thust ~ -if the bag is stored and/or transported in a shock absorbing --WO 92/01374 PCI`/EP9l/01348 1 1 2 0 5 6 4 2 ~
' ~''': ;:
container, then it may noS be as helpful to provide this unused capacity. ~ `' Also, the capacity to which the bag is filled, and whether ~ h`
the unused capacity does or does not contain air or a gas is `
affected by whether it is desirable to have the bag sink or float.
Also, whether the bag sinks or floats will depend not only on the unused capacity, but also the density of the bag contents.
The water soluble films which are used to make the water -soluble bags are known. In order to make a bag, the film needs to ` i~
n be shaped (possibly parti~lly sealed) and then filled with the gel.
Generally the gels are able to flow, even if it is a slow rate due :" '`'4'~
to high viscosity. ~f necessary the gel is propelled in to ~ .
. the bag with pressure. A container, which is used to contain a gel,has not been used up to now in agriculture.
1.~ When filled with the gel compositin hereinbefore ;~
described, the bag has to be finally sealed, generally heat sealed, So be closed. The sealing may be made according to known manner. '`. ~`~'''.!,`''~',':~, EXAMPl.ES
The following e2amples are given for illustrative purposes and should not be understood as restricting the invention. -`
''5 In these e~amples, the Brookfield viscosity was measured, as previously indicated, with a Brookfield viscosimeter which had a `~
flat plate rotating at 20 revolutions per minute. In all of the following e2amples, the prepared gels had a tg(phi) of between `~
0.75 and 1.5. ~ `~
0 The emulsion stability of the prepared gels is evaluated according to the following method: 1 ml of the gel is m~ed with ``
99 ml water in a 150 ml tube; the tube is inverted-10 times at the rate of 1 complete inversion per second. ~ating of the emulsion stability is made by reading the relative amount of phases after , : '.
., .,~,.
. ~ :' ' -.
WO 92~01374 PCr/EP91/01348 ~ -~ 96~ ' 12 ~ ~
24 hours. The emulsion stability is rated as follows: "e~tcellent" if the amount of emulsion (phase looking like mil}c) represents 98 to 100% (v/v) of the total, the balance being cream or thin; "good" if the amount of emulsion represents 90 to 98% (v/v) of the total, .; the balance being mainly cream with no more than S ml bein8 thin; ` ~ `"fair" if -the amount of emulsion represents 70 to 90X (vJv) of the -~-total, the balance being cream or thin; and "poor" if the total of emulsion represents 70 or less % (v/v) of the total.
The spontaneity is assessed according to the fo~lowing ~:
method: A mi~cture of 1 ml gel with 99 ml water are put into a 150 ml glass tube ( diameter 22mm) which is stoppered and inverted by 180 degrees (upside down). The number of inversions required to -completely disperse the gel is called the spontaneity. ~
,, ... , .-EXAMPLE 1 j-A gel is made by stirring and shaking at 50 C a misture of .-the following ingredients until they are each dissolved or` ` `
dispersed: i ~
, ~ ,.,~.. " . .
active ingredient: the herbicide 2,4-D; ;
pheno~y benzoic acid (isooctyl ester): 64.8X
solvent aromatic solvent with flash ` `~
point of 65 C: 24.2X
'' ;. adjuvants~
non ionic/sulfonate blended emulsifier: 4 X ~;
calcium alkylbenzene sulfonste: 1 X -mi~ture of dioctylsulfosuccinate salt and sodium benzoate ` 6 X. `~
3 t' - ;~
' ~:
'.'~' ";
WO 92/01374 PCI/EP91/01348 ~ ~
~ ~, ;^, 2Q56~24 ~
During stirring, a dissolution or dispersion appears, and ` `;
thereafter gelation. Gelation increases as the mL~ture cools to about ~0 C. ;
The Brookfield viscosity of the gel is 3000 centipoise. ` `
. The emulsion stability is "good" according to the above described test. ; `~
1100 g of this gel are put in a one-litre bag made of a film !'~
of PVA (88X hydrolyzed polyvinyl acetate; cold water soluble;
thickness: 55 microns). The bag, which is almost full (about 95%
;0 v/~r), is hot sealed. The specific gra~rity of the gel and of the bag containing the gel is 1.1. -~
The bag is dropped 10 times from 1.2 m above the ground.
No breaking or leakage is observed.
The bag is put into a tank containing water under gentle '., agitation (that is to say such as that obtained with pump recycling). The bag and its contents are dispersed within a 3 minute interYal. There is no clogging in the filter, which is a `~
screen ha~ing 0.28 mm openings.
EXAMPI.E 2 The procedure of E~ample 1 is repeated, using the same active ingredient in a mi~ture containing the following adju~rants~
non ionic/sulfonate blended emulsifier: 5.2 X
tetramethyl decynediol: 30 X.
The Brookfield viscosity of the gel is 3000 centipoise.
:~0 The emulsion stability is good using the above described `
test.
". ' '`~'' :'' ~
WO 92/01374 PC~/EP9l/01348 ~ ~ ~
66~ 14 1100 g of this gel are put in a 1 litre bag made of a film of `
PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; ` :~ ~
thicknçss: 55 microns). The bag, which is almost full (about 95% ;
v/v), is hot sealed. The specific gravity both of the gel and of ; ` -~`
:~ the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle " -agitation (that is to say such as that obtained with pump i~
ln recycling). It is dispersed within a 3 minute interval. There is no "` i clogging in She filter which is a screen having 0.28 mm openings.
The procedure of E%ample 1 is repeated, using the same l.. active ingredient in a mL~ture containing the following adjuvants:
non ionic/sulfonate blended emulsifier: 21.5X;
calcium alkylbenzene sulfonate 3.~X;
etho~ylated dialkylphenol: 10 X.
`~) The Brookfield viscosity of the gel is 3000 centipoise.
The emulsion stability is good using the above described test~ ~ ;
1100 g of this gel are put in a 1 litre bag made of a film of PVA (88X hydrolyzed pol~inyl acetate; cold water soluble; ~
";) thickness: 55 microns). The bag, which is almost full (about 95X - ~``
v/v), is hot sealed. The specific gravity both of the gel and of ~ `
the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the `
ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle ; ~ `
agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 3 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings. .
`~
WO 92/01374 PCI`/EP91/01348 2~S6~24 ~"''""'~''''~:'c 1 J ~; ~
'.', EXAMPLE 4 `
gel is made by stirring at 50 C a mi~ture of:
acti~e ingredient bromo~cynil acid in the form of an octanoate ester: 61.15%;
solvent aromstic solvent with a f}ash point of 3& C: 22.85X;
polyaryl phenoletho~ylated: 6 X;
}0 calcium alkylbenzene sulfonate: 2 %;
clay which has been modified by addition of methyl groups: t~ X;
propylene carbonate (activating the thickener): 2 X.
These materials are mi~ced together while shearing with an Attritor mi~cer. The product started to gel within a few minutes.
I`he Brookfield viscosity of the gel is 4200 centipoise.
The emulsion stability is good using the above described t; test~
The spontaneity is 38.
1100 g of this gel are put in a l litre bag made of a film of PVA (88% hydrolyzed polyvinyl acetate; cold water soluble;
thickness: 55 microns). The bag, which is almost full (about 95X `
`~ v/v), is hot sealed. The specific gra~ity both of the gel and of ``~
..
the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the -ground. No breaking or leakage is observed. `
The bag is placed in a tank containing water under gentle :~0 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.
; ,, ` ;' :~ ', ,', '~ :'`
WO 92/01374 PCr/EP9l/013"8 .~:. ~...;~
~,~,'1.~' 1 6 EXAMPLE
The procedure of E~cample 4 is repeated, using a mLl~ture ; -containing the following components~
J active ingredient ~ i~
bromo:cynil octanoate: 18.65%; -~
bromo~cynil heptanoste: 13.85%; -methyl chloropropionic acid (isooctyl ester) 37.4 X; ` `
solvent: aromatic solvent with a flash point of 38 C: 11.1 X;
hydrogenated castor oil: 3 X;
etho~ylated vegetable oil: 3 %;
non ionic/sulfonate blended emulsifier: 13 X.
: . . .'.' . '. . .',' ' 1~ These materials are mi~ed together while shearing with an - :-Attritor mi~cer. The product started to gel within a few minutes. .
The Brookfield viscosity of the gel is 3150 centipoise. `
The emulsion stability is good using the above described test.
^ 0 The spontaneity is 20.
1100 g of this gel are put in a l litre bag made of a film of PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; ~ `-thickness: 55 microns). The bag, which is almost full tabout 95' `~
v/v), is hot sealed. The specific gravity both of the gel and of `. the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 10 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings. ; `~
E~MPLE 6 `
The procedure of E~cample 6 is repeated using a mi~ture containing the following components:
' ., .
~.
~': ;`.
;. .
_ WO 92/01374 PCI`/EP91/01348 ~ ~
17 2QS~2~ ,'`,,",~,,~,1 active ingredient ~,~
bromo~ynil octanoate: 18~4X; ;~
bromo~ynil heptano~t~ 14 X;
~ethyl chlorophenoxy acetic acid (isooctyl ester) 36.6X;
non ionicJsulfonate blended emulsifier:9 %;
sodium sulfonate of naphthalene formaldehyde condensate: 3 Xi dioctyl ester of sodium sulfosuccinic acid ^, and sodium benzoate 2 X;
diatomaceous e rth: 17 X.
These materials are mi~ted together while shearing with`an Attritor mi cer. The product started to have the appearance of a ~ s i, smooth paste, and is a gel within a few minutes. -The Brookfield viscosity of the gei is 9000 centipoise. `
The emulsion stabilit~ is good using the above described tes t_ The spontaneity is 9. ` "
'`O 1100 g of this gel are put in a 1 litre bag made of a film of , `
P~'~ (88% hydrolyzed polyvinyl acetate; cold water soluble; `~
thickness: 55 microns). The bag, which is almost full (abaut 95% ~ -~
v/v), is hot sealed. The specific gravit~ bot'. of the gel and of ` ~ `
the bag containing the gel is 1.1.
` The bag is then dropped 10 times from 1.2~ m upon the ~ ` `
ground. No breaking or leakage is observed.
The bag is placed in a tanli containing water ~nder gentle agitation (~hat is to say such as that obtained with pump , ;~<~
recycling). It is dispersed within a 10 minute interval. There is no ' :`;'` clogoing in the filter which is a screen having 0.28 mm openings.
_ The procedure Or E~ample 5 is repcatcà1 using a mi~cture con~ining ~1lc ~ollowin~ component~:
"i'~ ',;".
S'~ J'T_ S~-!=T
WO 92/0l374 PCI`/EP9l/0l348 ~ ~
,., -.. .,, ",.
18 ~ ~
active ingredient -~-bromo~tynil octanoate: 18.89X; ;~
~romo~cynil heptanoate: 12.59%; ;~
atrazine: 44.58%; ~r,~
., solvent same as in esample 5: 18.54%; ~:~
polyethylene glycol: 2.7 %. `~
These materials are mi~ed together while shearing with an ~;
Attritor mixer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes. ~ -l ^ The Brookfield viscosity of the gel is 7300 centipoise.
The emulsion`stability is good using the above described ` :~`
test.
The spontaneity is 15. `~
1100 g of this gel are put in a l litre bag made of a film of . `
.~; PVA (88Z hydrolyzed polyvinyl acetate; cold water soluble;
thickness: 55 microns). The bag, which is almost full (about 95 vjv), is hot sealed. The specific gravity both of the gel and of - h` ~
the bag containing the gel is 1.l. ~ `
The bag is then dropped 10 times from 1.2 m upon the `~ ground. No breakmg or leakage is observed.
The bag is pla~ed in a tank containing water under gentle j `s agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 10 minute interval. There is no clogging in the filter which is a screen having 0.28 mm openings.
The procedure of E~cample 7 is repeated, using a mixture ;~
containing the following components using: -active ingredient ;` '` bromo:cynil octanoate: 33.7X;
methyl chloropropionic acetic acid `~
(isooctyl ester) 36.2%;
solvent solvent ~romatic solvent with a ~,-WO 92/01374 PCI`/EP9l/0l348 ~ `
-- '9 20S642~
flash point of 65 C: 3 X; ``i~
non ionic~sulfonate blended emulsifier: B.5X;
calcium dodecyl benzene sulfonate: 1 X;
tetramethyl decyne diol: 17.6%. `~
These materials are mi ~ed together while shearing with an '~
Attritor mixer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes. ~- .
The Brookfield viscosity of the gel is 2200 centipoise~
The emulsion stability is good using the above described test.
The spon~aneity is l~
1100 g of this gel are pu~ in a 1 litre baa made of a film of PVA (88% hydrolyzed polyvinyl acetate; cold water soluble; -thicl;ness: ~5 microns~. The bag, which is ~lmost full (about 95%
v/v), is hot sealed. The speci~ic gravity both of the gel and of the bag conl aining the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the ground. No breaking or leaksge is observed.
The bag is placed in a tank containing water under gentle `;~
agit~tion (that is to say such as that obtained with pump -~ ~
recycling). It is dispersed within a 5 minutes interval. There is no - ~`
clogginLO~ in the filter which is a screen having 0.28 mm openings. `- `~
`.-. :`'~-E.~MPLE 9 ` `~ ~`
.
The procedure of Example 8 is repeated, using a mL~ture , containing the following components~
acSive ingredient and solvent are the same ~s in e~ample 8, and amounl of acti~re ingredient is the same;
solvent is the same but the amount is 10.6 calcium do<lecyl benzene sulfonate: 2 %;
mi~ture of dimethyl he~cane and he~yne diol: 11.5%;
calcium alkylaryl sulîon~tc and a ~--`
polyarylphenol ethoxylate:
~:;~' . `'.
'`t S~ ITU~E SHEE~ ~"
WO 92/01374 PCI/EP9l/01348 - ~-,66~ 2 0 These materials are mi~ced together at 90 C while shearing with an Attritor mi~cer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes. ;
.. The Brookfield viscosity of the gel is 2500 centipoise.
The emulsion stability is good using the above described ~ ~
test. ~ ~ s The spontaneity is 5.
1100 g of this gel are put in a 1 litre bag made of a film of i` ` `~
;0 PVA (88% hydrolyzed polYvinyl acetate; cold water soluble; ;~
thickness: 55 microns). The bag, which is almost full (about 95X
v/v), is hot sealed. The specific gravity both of the gel and of the bag containing the gel is 1.1. ~ `~;
The bag is then dropped 10 times from 1.2 m upon the ' 5 ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle ~;~
agitation (that is to say such as that obtained with pump recycling). It is dispersed within a 5 minutè in~er~ral.There is no `~
clogging in the filter which is a screen having 0.28 mm openings.
The procedure of E~cample 5 is repeated, using a mi~cture .; . . ~ .
containing the following components using~
active ingredient .; bromo~cynil octanoate: 33.5%;
bromo~ynil heptanoate: 33.5%; ^~
solvent aromatic sol~rent with a flash ` -~-~
point of 65 C: 22.75X; `;~f"`~
non ionic~sulfonate blended emulsifier: 4.5%;
~ . ~,, ~, .
calcium dodecyl benzene sulfonate: 1%; ~ ~`
and sodium benzoate: 4.25%; ~"
tetramethyl decyne diol: ` 0.5X.
.''-.'~ :' . ~ , ,.. ....
, " ` ,' '`'`` '~',~ ',`", WO 92/01374 2 ~ S ~ 4 2 ~ PCI/EP9l/01348 ~ ;
;.. -.;.
These materials are mi~ed together at 50O C while shearing `
with an Attritor mi~cer. The product started to have the appearance of a smooth paste, and is a gel within a few minutes. ;;
The Brookfield viscosity of the gel is 4850 centipoise.
The emulsion stability is e~ccellent using the above described test.
The spontaneity is 10.
1100 g of this gel are put in a l litre bag made of a film of -~
PVA (88% hydrolyzed pol~rinyl wetate; cold water soluble;
1 !) thickness: 5~ microns~. The bag, which is almost full ~about 95X
v/v), is hot sealed. The specific gravity both of the gel and of the bag containing the gel is 1.1.
The bag is then dropped 10 times from 1.2 m upon the .
ground. No breaking or leakage is observed.
The bag is placed in a tank containing water under gentle agitation (that is to say such as that obtained with pump -~
recycling). It is dispersed within a 3 minute interv~l. There is no clogging in the filter which is a screen having 0.28 mm openings.
' .`;" '."~ ' `
`'; " '''`
.. ..
~. .
Claims (98)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A containerization system for holding and securing agricultural chemical compounds which comprises a water soluble or water dispersible bag which completely encloses a gel, said gel comprising an agricultural chemical compound, wherein said gel possesses non-flowability characteristics to substantially prevent persistent flow or leakage of the agricultural chemical compound from the bag in the event the bag develops pinholes.
2. A containerization system according to claim 1, wherein the agricultural chemical compound is a pesticide or a plant protection agent.
3. A containerization system according to claim 1, wherein the gel is water soluble or water dispersible.
4. A containerization system according to claim 1, wherein the agricultural chemical compound is toxic or hazardous to the environment or to persons contacted thereby.
5. A containerization system according to any one of claims 1 to 4, wherein the gel has a viscosity of from 500 to 50,000 centipoise.
6. A containerization system according to claim 5, wherein the gel has a viscosity of from 1,000 to 5,000 centipoise.
7. A containerization system according to any one of claims 1 to 4, wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.5.
8. A containerization system according to claim 7, wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.2.
9. A containerization system according to any one of claims 1 to 4, wherein the gel substantially completely disperses in water after agitation in water during at most 15 minutes.
10. A containerization system according to any one of claims 1 to 4, wherein the gel contained in the bag has a spontaneity less than 75.
11. A containerization system according to any one of claims 1 to 4, wherein the gel is a composition which has essentially one visually observable physical phase.
12. A containerization system according to any one of claims 1 to 4, wherein the gel has a specific gravity greater than 1.
13. A containerization system according to any one of claims 1 to 4, wherein said gel comprises the agricultural chemical compound and a nonionic surfactant.
14. A containerization system according to claim 13, wherein said surfactant is a nonionic emulsifier.
15. A containerization system according to claim 14, wherein said nonionic emulsifier is a sulfonate.
16. A containerization system according to any one of claims 1 to 4, wherein the gel has a water content which is less than 5% by weight.
17. A containerization system according to any one of claims 1 to 4, wherein said gel comprises the agricultural chemical compound and one or more ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelled or gelling agents.
18. A containerization system according to any one of claims 1 to 4, wherein the bag has a capacity of from 0.01 to 12 litres.
19. A containerization system according to any one of claims 1 to 4, wherein the bag is not filled to capacity and has more than 50% of its volume capacity filled with gel.
20. A containerization system according to claim 19, wherein the bag is filled to from 80% to 99%.
21. A containerization system according to any one of claims 1 to 4, wherein the bag comprises a polymeric water soluble film.
22. A containerization system according to any one of claims 1 to 4, wherein the bag comprises a film whose thickness is from 10 to 500 microns.
23. A containerization system according to claim 21, wherein the bag comprises polyethylene oxide, methylcellulose or polyvinylalcohol.
24. A containerization system according to any one of claims 1 to 4, wherein the bag comprises a 40-100% alcoholized or hydrolysed polyvinyl acetate film.
25. A self-dispensing containerization system for agricultural chemical compounds that are used in aqueous compositions, said system comprising a water-soluble or water-dispersible bag which encloses a gel of substantially organic material comprising an agricultural chemical compound and other gel ingredients wherein the gel has a viscosity of from 1,000 to 30,000 centipoise, the specific gravity of the bag with the gel container therein is greater than 1 and the bag and gel are sufficiently water dispersible so that they are substantially completely dispersed in agitated water within 15 minutes.
26. A containerization system according to claim 25, wherein the agricultural chemical compound is a pesticide or a plant protection agent.
27. A containerization system according to claim 25, wherein the gel is water soluble or water dispersible.
28. A containerization system according to claim 25, wherein the agricultural chemical compound is toxic or hazardous to the environment or to persons contacted thereby.
29. A containerization system according to any one of claims 25 to 28, wherein the gel has a viscosity of from 500 to 50,000 centipoise.
30. A containerization system according to claim 29, wherein the gel has a viscosity of from 1,000 to 5,000 centipoise.
31. A containerization system according to any one of claims 25 to 28, wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.5.
32. A containerization system according to claim 31, wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.2.
33. A containerization system according to any one of claims 25 to 28, wherein the gel substantially completely disperses in water after agitation in water during at most 15 minutes.
34. A containerization system according to any one of claims 25 to 28, wherein the gel contained in the bag has a spontaneity less than 75.
35. A containerization system according to any one of claims 25 to 28, wherein the gel is a composition which has essentially one visually observable physical phase.
36. A containerization system according to any one of claims 25 to 28, wherein the gel has a specific gravity greater than 1.
37. A containerization system according to any one of claims 25 to 28, wherein said gel comprises the agricultural chemical compound and a nonionic surfactant.
38. A containerization system according to claim 37, wherein said surfactant is a nonionic emulsifier.
39. A containerization system according to claim 38, wherein said nonionic emulsifier is a sulfonate.
40. A containerization system according to any one of claims 25 to 28, wherein the gel has a water content which is less than 5 % by weight.
41. A containerization system according to any one of claims 25 to 28, wherein said gel comprises the agricultural chemical compound and one or more ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelled or gelling agents.
42. A containerization system according to any one of claims 25 to 28, wherein the bag has a capacity of from 0.01 to 12 litres.
43. A containerization system according to any one of claims 25 to 28, wherein the bag is not filled to capacity and has more than 50% of its volume capacity filled with gel.
44. A containerization system according to claim 43, wherein the bag is filled to from 80% to 99%.
45. A containerization system according to any one of claims 25 to 28, wherein the bag comprises a polymeric water soluble film.
46. A containerization system according to any one of claims 25 to 28, wherein the bag comprises a film whose thickness is from 10 to 500 microns.
47. A containerization system according to claim 45, wherein the bag comprises polyethylene oxide, methylcellulose or polyvinylalcohol.
48. A containerization system according to any one of claims 25 to 28, wherein the bag comprises a 40-100% alcoholyzed or hydrolysed polyvinyl acetate film.
49. A system according to claim 25, wherein the bag and gel are dispersed within 10 minutes of agitation in water and are usable in agricultural spraying devices.
50. A containerization system for holding and securing pesticides which comprises a water soluble or water dispersible bag which completely encloses a gel, said gel comprising a pesticide, wherein said gel possesses non-flowability characteristics to substantially prevent persistent flow or leakage of the pesticide from the bag in the event the bag develops pinholes.
51. A containerization system according to claim 50, wherein the pesticide is toxic or hazardous to the environment or to persons contacted thereby.
52. A containerization system according to claim 50, wherein the gel is water soluble or water dispersible.
53. A containerization system according to any one of claims 50 to 52, wherein the gel has a viscosity of from 500 to 50,000 centipoise.
54. A containerization system according to claim 53, wherein the gel has a viscosity of from 1,000 to 5,000 centipoise.
55. A containerization system according to any one of claims 50 to 52, wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.5.
56. A containerization system according to claim 55, wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.2.
57. A containerization system according to any one of claims 50 to 52, wherein the gel substantially completely disperses in water after agitation in water during at most 15 minutes.
58. A containerization system according to any one of claims 50 to 52, wherein the gel contained in the bag has a spontaneity less than 75.
59. A containerization system according to any one of claims 50 to 52, wherein the gel is a composition which has essentially one visually observable physical phase.
60. A containerization system according to any one of claims 50 to 52, wherein the gel has a specific gravity greater than 1.
61. A containerization system according to any one of claims 50 to 52, wherein said gel comprises the pesticide and a nonionic surfactant.
62. A containerization system according to claim 61, wherein said surfactant is a nonionic emulsifier.
63. A containerization system according to claim 62, wherein said nonionic emulsifier is a sulfonate.
64. A containerization system according to any one of claims 50 to 52, wherein the gel has a water content which is less than 5% by weight.
65. A containerization system according to any one of claims 50 to 52, wherein said gel comprises the pesticide and one or more ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelled or gelling agents.
66. A containerization system according to any one of claims 50 to 52, wherein the bag has a capacity of from 0.01 to 12 litres.
67. A containerization system according to any one of claims 50 to 52, wherein the bag is not filled to capacity and has more than 50% of its volume capacity filled with gel.
68. A containerization system according to claim 67, wherein the bag is filled to from 80% to 99%.
69. A containerization system according to any one of claims 50 to 52, wherein the bag comprises a polymeric water soluble film.
70. A containerization system according to any one of claims 50 to 52, wherein the bag comprises a film whose thickness is from 10 to 500 microns.
71. A containerization system according to claim 69, wherein the bag comprises polyethylene oxide, methylcellulose or polyvinylalcohol.
72. A containerization system according to any one of claims 50 to 52, wherein the bag comprises a 40-100% alcoholyzed or hydrolysed polyvinyl acetate film.
73. A self-dispensing containerization system for pesticides that are used in aqueous compositions, said system comprising a water-soluble or water-dispersible bag which encloses a gel of substantially organic material comprising a pesticide and other gel ingredients wherein the gel has a viscosity of from 1,000 to 30,000 centipoise, the specific gravity of the bag with the gel container therein is greater than 1 and the bag and gel are sufficiently water dispersible so that they are substantially completely dispersed in agitated water within 15 minutes.
74. A containerization system according to claim 73, wherein the pesticide is toxic or hazardous to the environment or to persons contacted thereby.
75. A containerization system according to claim 73, wherein the gel is water soluble or water dispersible.
76. A containerization system according to any one of claims 73 to 75, wherein the gel has a viscosity of from 500 to 50,000 centipoise.
77. A containerization system according to claim 74, wherein the gel has a viscosity of from 1,000 to 5,000 centipoise.
78. A containerization system according to any one of claims 73 to 75, wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.5.
79. A containerization system according to claim 78, wherein the gel is a material which has a phase difference phi between the controlled shear stress and the resulting shear strain such that tg(phi), the tangent of the phi angle or phase difference, is less than or equal to 1.2.
80. A containerization system according to any one of claims 73 to 75, wherein the gel substantially completely disperses in water after agitation in water during at most 15 minutes.
81. A containerization system according to any one of claims 73 to 75, wherein the gel contained in the bag has a spontaneity less than 75.
82. A containerization system according to any one of claims 73 to 75, wherein the gel is a composition which has essentially one visually observable physical phase.
83. A containerization system according to any one of claims 73 to 75, wherein the gel has a specific gravity greater than 1.
84. A containerization system according to any one of claims 73 to 75, wherein said gel comprises the pesticide and a nonionic surfactant.
85. A containerization system according to claim 84, wherein said surfactant is a nonionic emulsifier.
86. A containerization system according to claim 85, wherein said nonionic emulsifier is a sulfonate.
87. A containerization system according to any one of claims 73 to 75, wherein the gel has a water content which is less than 5% by weight.
88. A containerization system according to any one of claims 73 to 75, wherein said gel comprises the pesticide and one or more ingredients selected from the group consisting of surfactants, dispersants, thickeners, solvents and gelled or gelling agents.
89. A containerization system according to any one of claims 73 to 75, wherein the bag has a capacity of from 0.01 to 12 litres.
90. A containerization system according to any one of claims 73 to 75, wherein the bag is not filled to capacity and has more than 50% of its volume capacity filled with gel.
91. A containerization system according to claim 90, wherein the bag is filled to from 80% to 99%.
92. A containerization system according to any one of claims 73 to 75, wherein the bag comprises a polymeric water soluble film.
93. A containerization system according to any one of claims 73 to 75, wherein the bag comprises a film whose thickness is from 10 to 500 microns.
94. A containerization system according to claim 92, wherein the bag comprises polyethylene oxide, methylcellulose or polyvinylalcohol.
95. A containerization system according to any one of claims 73 to 75, wherein the bag comprises a 40-100% alcoholyzed or hydrolysed polyvinyl acetate film.
96. A system according to claim 73, wherein the bag and gel are dispersed within 10 minutes of agitation in water and are usable in agricultural spraying devices.
97. A containerization system for holding and securing plant growth agents which comprises a water soluble or water dispersible bag which completely encloses a gel, said gel comprising a plant growth agent, wherein said gel possesses non-flowability characteristics to substantially prevent persistent flow or leakage of the plant growth agents from the bag in the event the bag develops pinholes.
98. A self-dispensing containerization system for plant growth agents that are used in aqueous compositions, said system comprising a water-soluble or water-dispersible bag which encloses a gel of substantially organic material comprising a plant growth agent and other gel ingredients wherein the gel has a viscosity of from 1,000 to 30,000 centipoise, the specific gravity of the bag with the gel container therein is greater than 1 and the hag and gel are sufficiently water dispersible so that they are substantially completely dispersed in agitated water within 15 minutes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US554,615 | 1990-07-18 | ||
| US07/554,615 US5080226A (en) | 1990-07-18 | 1990-07-18 | Containerization system for agrochemicals and the like |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2066424C true CA2066424C (en) | 1994-09-20 |
Family
ID=24214021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002066424A Expired - Fee Related CA2066424C (en) | 1990-07-18 | 1991-07-18 | Containerization system for agrochemicals and the like |
Country Status (30)
| Country | Link |
|---|---|
| US (2) | US5080226A (en) |
| EP (1) | EP0493553B1 (en) |
| JP (1) | JP2518759B2 (en) |
| KR (1) | KR920702194A (en) |
| CN (1) | CN1029107C (en) |
| AP (1) | AP356A (en) |
| AT (1) | ATE150253T1 (en) |
| AU (2) | AU8039691A (en) |
| BR (1) | BR9105833A (en) |
| CA (1) | CA2066424C (en) |
| CZ (1) | CZ283327B6 (en) |
| DE (1) | DE69125261T2 (en) |
| DK (1) | DK0493553T3 (en) |
| ES (1) | ES2099163T3 (en) |
| FI (1) | FI921139A (en) |
| GR (1) | GR3023459T3 (en) |
| HU (1) | HU212035B (en) |
| IE (1) | IE912504A1 (en) |
| IL (1) | IL98806A (en) |
| MA (1) | MA22216A1 (en) |
| MY (1) | MY106818A (en) |
| NZ (1) | NZ239001A (en) |
| OA (1) | OA09693A (en) |
| PL (1) | PL294073A1 (en) |
| PT (1) | PT98351A (en) |
| RO (1) | RO110895B1 (en) |
| RU (1) | RU2067547C1 (en) |
| TR (1) | TR26257A (en) |
| WO (1) | WO1992001374A1 (en) |
| ZA (5) | ZA915645B (en) |
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-
1990
- 1990-07-18 US US07/554,615 patent/US5080226A/en not_active Expired - Lifetime
-
1991
- 1991-07-11 IL IL98806A patent/IL98806A/en active IP Right Grant
- 1991-07-11 MA MA22491A patent/MA22216A1/en unknown
- 1991-07-15 AU AU80396/91A patent/AU8039691A/en not_active Withdrawn
- 1991-07-17 IE IE250491A patent/IE912504A1/en not_active IP Right Cessation
- 1991-07-17 PT PT98351A patent/PT98351A/en not_active Application Discontinuation
- 1991-07-17 MY MYPI91001290A patent/MY106818A/en unknown
- 1991-07-17 CZ CS912215A patent/CZ283327B6/en unknown
- 1991-07-18 CN CN91104959A patent/CN1029107C/en not_active Expired - Fee Related
- 1991-07-18 DK DK91912408.1T patent/DK0493553T3/da active
- 1991-07-18 DE DE69125261T patent/DE69125261T2/en not_active Expired - Fee Related
- 1991-07-18 RO RO92-200356A patent/RO110895B1/en unknown
- 1991-07-18 ZA ZA915645A patent/ZA915645B/en unknown
- 1991-07-18 ES ES91912408T patent/ES2099163T3/en not_active Expired - Lifetime
- 1991-07-18 CA CA002066424A patent/CA2066424C/en not_active Expired - Fee Related
- 1991-07-18 RU SU915011669A patent/RU2067547C1/en active
- 1991-07-18 AP APAP/P/1991/000302A patent/AP356A/en active
- 1991-07-18 TR TR91/0720A patent/TR26257A/en unknown
- 1991-07-18 HU HU9200880A patent/HU212035B/en not_active IP Right Cessation
- 1991-07-18 ZA ZA915641A patent/ZA915641B/en unknown
- 1991-07-18 ZA ZA915644A patent/ZA915644B/en unknown
- 1991-07-18 AT AT91912408T patent/ATE150253T1/en not_active IP Right Cessation
- 1991-07-18 EP EP91912408A patent/EP0493553B1/en not_active Expired - Lifetime
- 1991-07-18 ZA ZA915642A patent/ZA915642B/en unknown
- 1991-07-18 ZA ZA915643A patent/ZA915643B/en unknown
- 1991-07-18 NZ NZ239001A patent/NZ239001A/en unknown
- 1991-07-18 PL PL29407391A patent/PL294073A1/en unknown
- 1991-07-18 WO PCT/EP1991/001348 patent/WO1992001374A1/en active IP Right Grant
- 1991-07-18 BR BR919105833A patent/BR9105833A/en not_active IP Right Cessation
- 1991-07-18 JP JP3511866A patent/JP2518759B2/en not_active Expired - Fee Related
- 1991-07-18 KR KR1019920700614A patent/KR920702194A/en not_active Application Discontinuation
- 1991-07-18 AU AU81052/91A patent/AU651981B2/en not_active Ceased
-
1992
- 1992-03-17 FI FI921139A patent/FI921139A/en not_active Application Discontinuation
- 1992-03-18 OA OA60169A patent/OA09693A/en unknown
-
1994
- 1994-03-03 US US08/205,924 patent/US5358103A/en not_active Expired - Lifetime
-
1997
- 1997-05-16 GR GR970401108T patent/GR3023459T3/en unknown
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |