CA2285202A1 - System and method for packaging a chemical composition - Google Patents
System and method for packaging a chemical composition Download PDFInfo
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- CA2285202A1 CA2285202A1 CA002285202A CA2285202A CA2285202A1 CA 2285202 A1 CA2285202 A1 CA 2285202A1 CA 002285202 A CA002285202 A CA 002285202A CA 2285202 A CA2285202 A CA 2285202A CA 2285202 A1 CA2285202 A1 CA 2285202A1
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- 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
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- 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
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- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
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Abstract
A system and method are provided for storing an active ingredient such as a pesticide or other type of agricultural chemical in a water soluble package. The active ingredient is incorporated in a storage formulation including a hydrophilic, non-aqueous solvent which is capable of dissolving the active ingredient but not the water soluble package. The storage formulation optionally includes additives such as gelling agents, surfactants and/or antifoaming agents.
Description
SYSTEM AND METHOD FOR PACKAGING A CHEMICAL COMPOSITION
BACKGROUND OF THE INVENTION
1. Technical Field The present invention relates to a system and method for packaging a chemical composition in a package which is water soluble.
BACKGROUND OF THE INVENTION
1. Technical Field The present invention relates to a system and method for packaging a chemical composition in a package which is water soluble.
2. Background of the Art Pesticides and other chemicals used as active ingredients in the agricultural industry ( "agrochemicals"), are often formulated in liquid compositions.
While liquid compositions are convenient because of the ease in which they can be handled and dispersed, they nevertheless present safety problems. For example, there is a danger of spillage or leakage if the package in which they are stored is punctured.
There is also a danger of splashing when the liquid is added to a tank of water.
It is known that chemical compositions may be contained in soluble bags.
For example, an agrochemical can be placed in a water soluble bag which, in turn, is placed within a non-water soluble container. In use, the water soluble bag is removed from the non-water soluble container and simply placed in the tank of water into which the agrochemical is to be diluted. The agrochemical can be in the form of a powder.
Alternatively, the agrochemical can be packaged in the form of a liquid solution or gel.
If a liquid or gel is employed the liquid solvent must be compatible with the water soluble package. By "compatible" is meant that the solvent will not dissolve the package material or cause noticeable deterioration of the package.
One solution to this problem is to use a hydrophobic solvent. For example.
U. S. Patent No. x,139,152 to Hodakowski et al. discloses a method for packaging an ?5 agrochemical by dispersing the hazardous chemical in a hydrophobic solvent an aromatic solvent. Surfactants and gelling agents are also employed to form a dispersable gel which can be packaged in a water soluble bag. The difficulty with this method is that a relatively high percentage of surfactants must be used to help disperse the hydrophobic gel in a water medium. Such surfactants can increase the phytotoxicity of the composition and thereby cause unintended damage to plant life.
Alternatively, water based gels are also known to be packageable in water soluble bags. For example, U.S. Patent No. 5,341,932 to Chen et al. discloses the use of an aqueous gel to package hazardous agrochemicals. In order to prevent the aqueous gel from damaging the water soluble bag electrolytes are included as a component of the gel composition to render the bag material insoluble in the gel. Nevertheless, use of electrolytes presents difficulties. Even a small amount of water in the gel system can soften or dissolve water soluble packaging. At elevated temperatures the solubility of electrolytes in water increases and the aqueous phase becomes unsaturated.
This leaves more water available to attack the water soluble packaging. At lower temperatures the electrolytes may crystallize out. Thus, the formulations which rely on electrolytes to make aqueous phases compatible with water soluble packaging can be rendered impractical because of their sensitivity to temperature variations.
It would be desirable to have hydrophilic solvent based compositions which can be stored in water soluble bags and which don't suffer from the disadvantages described above.
SUMMARY OF THE INVENTION
In accordance with the present invention a system and method are provided for storing an active ingredient in a water soluble package. The system comprises:
a) a first package fabricated from a water soluble material, and b) a storage formulation having the active ingredient as a first component and a hydrophilic non-aqueous solvent as a second component, the hydrophilic non-aqueous solvent being capable of dissolving the active ingredient but not the water soluble material from which the first package is fabricated, said storage formulation being contained in the first package.
The method comprises:
a) producing a storage formulation by forming a solution or dispersion of the active ingredient in a non-aqueous hydrophilic solvent:
b) placing the storage formulation in the water soluble package, wherein the water soluble package is fabricated from a material which is insoluble in the non-aqueous hydrophilic solvent; and c) sealing the water soluble package to enclose the storage formulation therein.
The storage formulation can optionally include other additives such as gelling agents, surfactants, and antifoaming agents. Preferably the water soluble package is stored in a non-water soluble package.
The method and system disclosed herein are particularly advantageous for the storage and dispensing of hazardous chemicals used in agriculture such as pesticides and plant growth regulators.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present method for packaging an active ingredient in packages which are water soluble includes the step of dissolving or dispersing the active ingredient in a non-aqueous hydrophilic solvent which is compatible with the water soluble package. The combination of the active ingredient and hydrophilic solvent provides a storage formulation which can optionally include gelling agents, surfactants, and other additives as described below. The storage formulation is placed in the water soluble package, which is then sealed by any suitable method known to those with skill in the art and preferably enclosed in a non-water soluble container. The non-water soluble container can be made from metal or plastic, and is preferably an outer envelope uabricated from polymers such as polyolefins and polyesters including, for example, polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, and the like.
In use, the outer envelope is manually opened and the water soluble package is removed and added to, for example, a tank of water in which the package dissolves and releases its contents. The water soluble package does not need to be opened and there is less danger of the user coming into manual contact with the active ineredient in the formulation. This is a great advantage with respect to the agricultural industry in which hazardous pesticides are routinely used.
While the present method is contemplated as being especially advantageous for use with agrochemicals and will be described and exemplified in terms of such chemicals, it should be understood that any type of water soluble or non-water soluble chemical may be packaged in accordance with the method described herein, for example, dyes, and water treating agents such as bactericides, tlocculants, surfactants and the like.
By way of example, the agrochemicals to be packaged can be insecticides.
nematicides, herbicides, fungicides, plant growth regulators, rodenticides, or a combination of these agents. Such agents include, but are not limited to, water soluble derivatives such as ammonium salts, monovalent or divalent metal salts, or amine salts of the following exemplary compounds: fungicides such as tebuconazole, metalaxyl, imazalil, thiabendazole, and 2-(thiocyanatomethylthio)benzothiazole:
herbicides (or defoliants) such as acetochlor, imazapyr, paraquat, 2,4-D, propachlor, and imazaquin;
insecticides or acaricides such as malathion, methylparathion, dieldrin, aldrin, amitraz, fenvalerate, and diazinon. Inorganic pesticides include sulfur, sodium chlorate, sodium tluoride, sodium fluoroacetate, and bordeaux mixture. Other pesticides which may be packaged in accordance with the method and system described herein may be found in The Pesticide Manual, Ninth Ed., British Crop Protection Council Pub. (1991).
Organic agrochemieals which are in the form of salts or water soluble salts can be simple amine derivatives or ammonium or monovalent metal or acid halide or sulfate derivatives. The active ingredients which are in a salt form, may be more particularly in the form of a salt of an amine or of ammonium, sodium, potassium, lithium, ammonium, alkanolamines, and simple alkyl or fatty amines.
The following derivatives of organic agrochemicals exemplify those found to be feasible: benzoate, phenate, mono-and di-carboxylate, alkylamine salt, quaternary ammonium salt, phosphonium salt, hydrogen sulfate salt, pyrazolium salts, arsinate.
guanidine, benzenediazosulfonate, acetamide, phosphonate, phosphinate, imidazole, piperidinium, carbamate, arsonate, vinyl phosphate, dithiocarbamate.
naphthylacetate.
bypyridinium, pyrophosphate, pyridyloxyacetate, phosphorothioate.
The water soluble package is preferably fabricated from a polymeric water soluble film, more preferably a cold water soluble film. Cold water soluble means soluble in water at temperature less than 35°C., generally between 5°C. and 35°C. The thickness of the film is generally between 1 and 2 mils.
Suitable materials for fabricating the water soluble package are water soluble (or possibly water dispersible) materials which are insoluble in the organic solvents used to dissolve or disperse the agrochemical active ingredient.
Specific suitable materials include polyethylene oxide, polyethylene glycol; starch and modified starch;
alkyl and hydroxyaikylcellulose, hydroxypropyl cellulose; methylcellulose.
carboxymethylceilulose; polyvinylethers such as poly methyl vinylether or poly(2-methoxyethoxyethylene); poly(2,4-dimethyl-6-triazinylethylene; poly(3-morpholinyl ethylene); poly(N-1,2,4-triazolylethylene); poly(vinylsulfonic acid);
polyanhydrides; low molecular weight melamine-formaldehyde resins; low molecular weight urea-formaldehyde resins; poly(2-hydroxyethyl methacrylate); polyacrylic acid and its homologs.
Most preferably the enveloping film comprises or is made from IS polyvinylalcohol ("PVA"). PVA is generally partially or fully alcoholysed or hydrolysed (e.g., 40-100%, preferably 80-99~b alcoholysed or hydrolysed). Polyvinyl acetate (or other ester) film or copolymers or other derivatives of such polymers can also be used.
PVA films found suitable for use in the present method are available under the designation M 8435 002 from Chris Craft Industrial Products, Ine. located at 450 West 169th Street, South Holland, IL 60473 and KC grade 2 mil PVA film from Mitsui Plastics. Inc. located at 11 Martine Avenue, White Plains, NY 10606.
As mentioned above, the non-aqueous hydrophilic solvent must be able to dissolve or at least form a dispersion with the active ingredient while being compatible with the construction material of the package. Such solvents are capable of dissolving or dispersing both hydrophilic and hydrophobic agents and include gamma-butyrolactone and dipropylenegiycol monomethylether, for example. By employing such solvents the storage formulation does not need to rely on the presence of electrolytes to preserve the integrity of the water soluble package.
Preferably one or more gelling agents are added to the storage formulation.
'The gelling agents must be dispersible in both water and the non-aqueous hydrophilic solvent. Gelling agents can include organic water soluble gums and resins such as:
alginates, carboxymethylcellulose, carrageenan, guar gum, agar, gum arabic, gum ghatti.
gum karaya, gum tragacanth, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropyI methylcellulose, locust bean gum, pectins, polyacrylamide, polyacrylic acid, polyethylene glycol, polyethylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone, starch, tamarind gum, and xanthan gum.
The gelling agents can be inorganic as well. Examples include, but are not limited to, the following: natural clays such as kaolins, Serpentines, smectites (montmorillonites), bentonites, illites, glauconite, chlorites, vermiculites.
mixed-layer clays, attapulgite, saponite and sepiolite, and synthetic clays such as synthetic smectic clays, silicates and fluorosilicates may also be used.
Especially preferred gelling agents for the method set forth herein include polyvinyl pyrrolidone, hydroxypropyl methylcellulose, polyethylene oxide, hydroxypropyl cellulose, and silica (as fumed silica). Gelling agents advantageously provide self sealing capability in the event that the water soluble package develops pin hole leaks.
The storage formulation can optionally include other additives such as antifoaming agents to help remove bubbles from the gel. An example of an antifoaming agent suitable for use in the method described herein is a modified polyether-polysiloxane containing more than 50 % polysiloxane, which is commercially available under the designation Tegosipon 3062 from the Goldschmidt Co. located at 914 East Randolph Road, Hopewell, VA 23860.
Surfactants can optionally be included in the storage formulation but are not required. Surfactants which can be used in the method described herein include, but are not limited to, the following: alkanolamides; poly condensates of ethylene oxide with fatty alcohols, fatty esters, or fatty amines, or substituted phenols (particularly alkyphenols or arylphenols); block copolymers with ethoxy and propoxy groups;
esters of fatty acids with polysols such as glycerol or glycol; polysaccharides:
organopolysiloxanes:
sorbitan derivatives: ethers or esters of sucrose or fructose, salts of lignosulphonic acids, salts of phenyl suiphonic or naphthalene sulphonic acids, diphenyl sulfonates;
alkyaryi sulfonates: sulfonated fatty alcohols or amines or amides: poly condensates of ethylene oxide with fatty acids and their sulfate or sulfonate derivatives: salts of sulphosuccinic or sulfosuccinamic acid esters: taurine derivatives (particularly alkyltaurates);
betaine derivatives: phosphoric esters of alcohols or of polycondensates of ethylene oxide with phenols: and sulphate, sulphonate and phosphate functional derivatives of the above compounds. A preferred concentration of surfactant in the storage formulation ranges from 0% up to about 50%, more preferably 1 %-20% .
The examples set forth below illustrate the method and materials of the present invention described more generally above. The packages used in the examples were fabricated from PVA film.
The following tests were employed in some of the examples:
In the pinhole test 20 grams of formulation was sealed in a PVA bag having a hole of about 1 mm in diameter. The bag was then hung up and the observation was made as to whether the formulation leaked or whether the formulation sealed the hole with its film forming property.
In the dispersion test 20 grams of the formulation were packaged in a PVA
bag and the bag was thrown into 200 grams of water (at room temperature if not otherwise specified). The observation was recorded.
All composition parts are by weight unless otherwise indicated. Viscosities are measured with a Brookfield LVT viscometer, spindle 3 at 30 rpm.
Example 1 A gel base was made by mixing 90 parts of gamma-butyrolactone and 10 parts polyvinyl pyrrolidone gelling agent at room temperature until the polyvinyl pyrrolidone was dissolved. The polyvinyl pyrrolidone was obtained under the designation PVP K-90 from International Specialty Products, located at 1361 Alps Road, Wayne. NJ
07470. The resulting product was a homogeneous, clear gel with a viscosity of 680 cps.
Example 2 A gel base was made by mixing 93 parts of gamma-butyrolactone and 7 parts polyvinyl pyrroiidone gelling agent at room temperature until the polyvinyl pyrrolidone was dissolved. The polyvinyl pyrrolidone was obtained under the designation PVP K-120 from International Specialty Products. The resulting product was a homogeneous, clear gel having a viscosity of 1360 cps.
-7_ Example 3 A gel base was made by mixing 91.5 pans gamma-butyrolactone and 8.5 parts hydroxypropyl methylcellulose gelling agent at room temperature until the gelling agent was completely dispersed. The hydroxypropyl methylceliulose gelling agent was obtained under the designation Methocel E5 from Dow Chemical Co. The resulting product was a homogeneous, semi-clear gel having a viscosity of 500 cps. A
pinhole test was performed and no dripping was observed.
Example 4 A gel base was made by mixing 90 parts gamma-butyrolactone and 10 parts hydroxypropyl methylcellulose gelling agent (Methocel E5) at room temperature until the gelling agent was completely dispersed. The resulting product was a homogeneous semi-clear gel having a viscosity of 1200 cps. A pinhole test was performed and no dripping was observed.
Example 5 A gel base was made by mixing 98 parts gamma-butyrolactone and 2 parts hydroxypropyi methylceliulose gelling agent and heating the mixture briefly to 70°C. Mixing was continued while cooling the mixture down until a homogeneous, semi-clear gel was obtained. The gelling agent was obtained under the designation Methocel E4M from Dow Chemical Co. The viscosity of the resulting gel was 1960 cps.
Example 6 A gel base was made by dispersing 6.5 parts hydroxypropyl methylcelluiose (Methocel E5) in 12 parts polyethylene glycol. This mixture was then added to 81.4 parts gamma-butyrolactone and then heated briefly to 60°C. Then 0.1 parts of Tegosipon 3062 antifoaming agent was then added to the mixture, which was then cooled with continued stirring until a homogeneous semi-clear gel was obtained. The resulting gel had a viscosity of 1220 cps.
_g_ Example 7 A gel base was made by dispersing 6.5 parts hydroxypropyl methyIcellulose ( Methocel ES) in 12 parts polyethylene glycol and adding this mixture to 81.4 parts gamma-butyrolactone. This mixture was then heated briefly to 80°C for 30 minutes while stirring. The mixture was then cooled and 0.1 parts of Tegosipon 3062 antifoaming agent was then added with continued stirring until a homogeneous semi-clear gel vas obtained. The resulting gel had a viscosity of 2320 cps.
Example 8 A gel base v~-as made by mixing 97 parts gamma-butyrolactone and 3 parts of polyethylene oxide gelling agent. The polyethylene oxide was obtained under the designation Polyox 1105 from Union Carbide Co. The mixture was briefly heated to 40°C with stirring and then cooled with continued stirring until a homogeneous, clear gel was formed. The gel had a viscosity of 2200 cps.
Example 9 A gel base was made by mixing 98 pans gamma-butyrolactone with 2 parts hydroxypropyl cellulose gelling agent. The hydroxypropyl cellulose was obtained under the designation Klucel G from Aqualon Co. of Hopeweil, VA. The mixture was heated to 50°C and cooled with continued stirring until a homogeneous semi-clear gel was obtained having a viscosity of 4300 cps.
?0 Example 10 A gel base was made by mixing 98 parts gamma-butyrolactone with 2 pans Klucel G. The mixture was heated to 70°C and cooled with continued stirring until a homogeneous semi-clear gel was obtained having a viscosity of 10,400 cps.
Example 11 ?5 A gel base was made by mixing 90 parts gamma-butyrolactone and 10 parts hydroxypropyl cellulose gelling agent obtained under the designation Klucel L
from _g_ Aqualon Co. The mixture was heated to 70°C and then cooled with stirring until a homogeneous semi-clear gel was obtained having a viscosity of 7200 cps.
Example 12 A gel base was obtained by mixing 86 pans gamma-butyrolactone and 14 parts hydroxypropyl cellulose gelling agent obtained under the designation Klucel E from Aqualon Co. The mixture was heated to 60°C and then cooled with stirring until a homogeneous semi-clear gel was obtained having a viscosity of 2900 cps.
Example 13 A gel base was made by mixing 80 parts gamma-butyrolactone and 20 parts fumed silica obtained under the designation HiSil 233 from PPG Industries.
Inc., located at one PPG Place, Pittsburgh, PA 15272. The components were stirred together at room temperature until a homogeneous semi-clear gel was obtained having a viscosity of 4000 cps.
Example 14 A gel base made in accordance with the method of Example 3 was provided and 25 parts metalaxyl were added to 75 parts of the gel 'at room temperature with stirring until the Metalaxyl was completely dissolved. The resulting storage formulation was amber colored, homogeneous and semi-clear.
A pinhole test was performed and no dripping through the pinhole of the PVA bag was observed. Moreover, the formulation exhibited film-forming property, i.e., the pinhole was sealed by the formulation after a period of time.
A dispersion test was performed and the formulation was observed to disperse in water in less than 1.5 minutes to form a stable homogeneous clear solution without precipitation.
Also. a sample of the storage formulation in a 2.0 miI PVA bag was kept at -10°C to test for storage stability. The sample remained homogeneous and clear for more than two years.
Example 15 A gel base made in accordance with the method of Example 4 was provided and 25.7 parts of metalaxyl were added to 74.3 pans of the gel at room temperature with stirring until the Metalaxyl was completely dissolved. The resulting storage formulation S was amber colored, homoseneous, and semi-clear.
A pinhole test was performed and very slow dripping initially occurred.
However, gel was self sealing and after a period of time no further dripping was observed.
A dispersion test was performed and the formulation was observed to disperse in water in less than 2 minutes to form a stable, homogeneous, clear solution without precipitation.
Example 16 A gel base made in accordance with the method of Example 2 was provided and 25 parts of metalaxyl were added to 75 parts of the gel at room temperature with stirring until the Metalaxyl was completely dissolved. The resulting storage formulation was an amber colored, homogeneous, clear gel having a viscosity of 1680 cps.
A pinhole test was performed and very slow dripping was observed with subsequent self sealing of the pinhole by the gel.
A dispersion test was performed and the formulation was observed to disperse in less than about 5 minutes to form a clear solution without precipitation.
Example 17 A gel base made in accordance with the method of Example 7 was provided and 25.7 parts of metalaxyf were added to 74.3 parts of the gel base at room temperature with stirring until the Metalaxyl was completely dissolved. The resulting storage formulation was an amber colored, homogeneous, clear gel having a viscosity of cps.
A pinhole test was performed and no dripping was observed. The gel was self sealing.
A dispersion test was performed and the formulation was observed to disperse in less than 2 minutes to form a stable clear solution with no precipitation.
A sample of the storage formulation in a 2.0 mil PVA bag was packaged in a second non-soluble plastic bag and stored for more than one year under ambient conditions. No leakage was observed. The bags remained flexible.
Example 18 A gel base made in accordance with the method of Example 11 was provided and 25.7 parts of metalaxyl were added to 74.3 parts of the gel base at room temperature with stirring until the Metalaxyl was completely dissolved, The resulting storage formulation was an amber colored homogeneous, semi-clear gel having a viscosity of 4800 cps.
A pinhole test was performed and no dripping was observed. The gel was self seating.
A dispersion test was performed and the formulation was observed to disperse in less than 2 minutes to form a stable clear solution with no precipitation.
Samples of the storage formulation were sealed in PVA bags which were then contained in non water soluble plastic bags. The packaged samples were then stored at 40°C for about 21 months. No leakage occurred and the PVA bags remained flexible.
Example 19 Three parts of polyethylene polypropylene glycol. obtained under the designation Pluronic P 104 from BASF Corp., and 25.6 parts mewlaxyl were added to 62.2 parts of gamma-butyrolactone at room temperature with stirring until the metalaxyl was completely dissolved. Then 9 pans of fumed silica, obtained under the designation Aerosil 300 from Degussa Co., and 0.2 parts of Tegosipon 3062 were added to the mixture with continued stirring until an amber colored, homogeneous, semi-clear gel was obtained having a viscosity of 2500 cps.
Example 20 A gel base made in accordance with the method of Example 3 was provided, and 54 parts of imazalil were added to 26 parts of gel base at room temperature with stirring until the imazalil was completely dissolved. Then 20 pans of polyethylene glycol, obtained under the designation Witconol 5906 from Witco Corporation, located at One American Lane, Greenwich, CT 06831, were added to the mixture. The resulting storage formulation was an amber colored, homogeneous, semi-clear gel.
A pinhole test was performed and very slow dripping initially occurred.
However, the gel was self sealing and after a period of time no further dripping was observed.
A dispersion test was performed and the formulation was observed to disperse in less than 1.5 minutes to form a milky emulsion. The milky emulsion exhibited some precipitation after 24 hours but returned to emulsion after agitation.
A sample of the storage formulation was sealed in a PVA bag and stored at -10°C for one week. The gel remained homogeneous and clear.
Example 21 A geI base made in accordance with the method of Example 7 was provided, and 59.5 parts of imazalil were stirred into 20.5 parts of the gel base at room temperature until completely dissolved. Then 20 parts of Witconol 5906 were added with continued stirring until an amber colored homogeneous, semi-clear gel was obtained having a viscosity of 660 cps.
A pinhole test was performed and very slow dripping was initially observed. However. the gel was self sealing and after a period of time no further dripping was observed.
A dispersion test was performed and the formulation was observed to disperse in less than 2 minutes to form a milky emulsion.
Example 22 A gel base made in accordance with the method of Example 3 was provided and 10 parts of tebuconazole were stirred into 88 parts of gel base at room temperature until the tebuconazole was completely dissolved. Then 2 parts Witconol 5906 were added to the mixture with stirring. The resulting storage formulation was a colorless, homogeneous, semi-clear gel.
A pinhole test was performed. No dripping was observed. The gel was self sealing after a period of time.
A dispersion test was performed, and the storage formulation was observed to disperse in less then 1 minute to form a milky tine suspension. The suspension showed some precipitation after 24 hours but returned to suspension after agitation.
A sample of storage formulation was sealed in a PVA bag and was observed to remain homogeneous and clear after one week storage at -10°C.
Example 23 A gel base made in accordance with the method of Example 5 was provided and 10 parts of tebuconazole were stirred into 88 parts of gel base at room temperature until the tebuconazole was completely dissolved. Then 2 parts Witconol 5906 were added to the mixture with stirring. The resulting storage formulation was a colorless, homogeneous, semi-clear gel.
A sample of storage formulation was sealed in a PVA bag and was observed to remain homogeneous and clear after six months of storage.
Example 24 A gel base made in accordance with the method of Example 7 was provided and 10 parts of tebuconazole were stirred into 87.6 parts of gel base at room temperature until the tebuconazole was completely dissolved. Then 2 parts Witconol 5906 were added to the mixture with stirring. The resulting storage formulation was a colorless, homogeneous, semi-clear gel.
A pinhole test was performed. No dripping was observed. The gel was self sealing after a period of time.
A dispersion test was performed, and the storage formulation was observed to disperse in less then 2 minutes to form a milky tine suspension. The suspension showed some precipitation after 24 hours but returned to suspension after agitation.
:~ 100 gram sample of storas~e formulation was sealed in a PVA bag 2.0 mils thickness. which was then packaged in a non-water soluble plastic bag.
after more than one year of storage at ambient conditions the whole system remained intact. No leakage occurred and the PVA bag remained filexibie.
Example 25 At room temperature 10.7 parts of Pluronic P 104 were mixed with 73.2 parts gamma-butyrolactone. Then 10.8 parts tebuconazole were stirred into the mixture until completely dissolved. Then 5.3 parts Aerosil 300 were added with stirrins~. The resulting storage formulation was a colorless homogeneous, semi-clear gel having a viscosity of 900 cps.
A dispersion test was performed. In 22°C water the formulation was completely dispersed in 2.5 minutes. In 1 °C water the formulation was completely dispersed in less than 4'h minutes. The diluted sample showed some sedimentation after 24 hours but could be easily resuspended with agitation.
Example 26 A gel base made in accordance with the method of Example 7 was provided and 2 parts of Witconol 5909 were added to 78 parts of gel base. Then 20 parts of thiabendazole were stirred into the gel. The resulting storage formulation was a homogeneous white gel having a viscosity of 7800 cps.
A pinhole test was performed. No dripping was observed. The gel was self sealing.
A dispersion test was performed and the formulation was observed to disperse in less than 2 minutes to form a milky suspension.
Example 27 At room temperature 2.1 parts Pluronic P 104 were mixed with 73.3 parts gamma-butyrolactone. Then 20.9 parts of thiabendazole were stirred into the mixture.
Then 3.7 parts Aerosil 300 were added with stirring. The resulting storage formulation was a milky homogeneous gel having a viscosity of 1200 cps.
A dispersion test was performed. The formulation was completely dispersed in 22°C water in a little over 2 minutes. In 1 °C
water the formulation was completely dispersed in a little over 3.5 minutes. The diluted sample showed some sedimentation after 24 hours but could easily be resuspended with agitation.
Example 28 At room temperature, 10.7 parts Pluronic P104, 10.7 parts metalaxyl, and 10.7 parts tebuconazole were mixed with 62.5 pans gamma-butyrolactone. Then 4.9 parts Aerosil 300 and 0.5 parts Tegosipon were stirred into the mixture. The resulting storage formulation was an amber colored, homogeneous, semi-clear gel having a viscosity of 1300 cps.
Example 29 50 pans of 2-(thiocyanatomethylthio)benzothiazole ( "TCMTB") and 2 parts Pluronic 104 were heated together at 40°C until completely molten. To this mixture was added 48 parts of a gel base made in accordance with the method of Example 8.
The mixture was stirred while cooling down and the resulting storage formulation was an amber colored homogeneous and clear gel having a viscosity of 1000 cps.
While liquid compositions are convenient because of the ease in which they can be handled and dispersed, they nevertheless present safety problems. For example, there is a danger of spillage or leakage if the package in which they are stored is punctured.
There is also a danger of splashing when the liquid is added to a tank of water.
It is known that chemical compositions may be contained in soluble bags.
For example, an agrochemical can be placed in a water soluble bag which, in turn, is placed within a non-water soluble container. In use, the water soluble bag is removed from the non-water soluble container and simply placed in the tank of water into which the agrochemical is to be diluted. The agrochemical can be in the form of a powder.
Alternatively, the agrochemical can be packaged in the form of a liquid solution or gel.
If a liquid or gel is employed the liquid solvent must be compatible with the water soluble package. By "compatible" is meant that the solvent will not dissolve the package material or cause noticeable deterioration of the package.
One solution to this problem is to use a hydrophobic solvent. For example.
U. S. Patent No. x,139,152 to Hodakowski et al. discloses a method for packaging an ?5 agrochemical by dispersing the hazardous chemical in a hydrophobic solvent an aromatic solvent. Surfactants and gelling agents are also employed to form a dispersable gel which can be packaged in a water soluble bag. The difficulty with this method is that a relatively high percentage of surfactants must be used to help disperse the hydrophobic gel in a water medium. Such surfactants can increase the phytotoxicity of the composition and thereby cause unintended damage to plant life.
Alternatively, water based gels are also known to be packageable in water soluble bags. For example, U.S. Patent No. 5,341,932 to Chen et al. discloses the use of an aqueous gel to package hazardous agrochemicals. In order to prevent the aqueous gel from damaging the water soluble bag electrolytes are included as a component of the gel composition to render the bag material insoluble in the gel. Nevertheless, use of electrolytes presents difficulties. Even a small amount of water in the gel system can soften or dissolve water soluble packaging. At elevated temperatures the solubility of electrolytes in water increases and the aqueous phase becomes unsaturated.
This leaves more water available to attack the water soluble packaging. At lower temperatures the electrolytes may crystallize out. Thus, the formulations which rely on electrolytes to make aqueous phases compatible with water soluble packaging can be rendered impractical because of their sensitivity to temperature variations.
It would be desirable to have hydrophilic solvent based compositions which can be stored in water soluble bags and which don't suffer from the disadvantages described above.
SUMMARY OF THE INVENTION
In accordance with the present invention a system and method are provided for storing an active ingredient in a water soluble package. The system comprises:
a) a first package fabricated from a water soluble material, and b) a storage formulation having the active ingredient as a first component and a hydrophilic non-aqueous solvent as a second component, the hydrophilic non-aqueous solvent being capable of dissolving the active ingredient but not the water soluble material from which the first package is fabricated, said storage formulation being contained in the first package.
The method comprises:
a) producing a storage formulation by forming a solution or dispersion of the active ingredient in a non-aqueous hydrophilic solvent:
b) placing the storage formulation in the water soluble package, wherein the water soluble package is fabricated from a material which is insoluble in the non-aqueous hydrophilic solvent; and c) sealing the water soluble package to enclose the storage formulation therein.
The storage formulation can optionally include other additives such as gelling agents, surfactants, and antifoaming agents. Preferably the water soluble package is stored in a non-water soluble package.
The method and system disclosed herein are particularly advantageous for the storage and dispensing of hazardous chemicals used in agriculture such as pesticides and plant growth regulators.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present method for packaging an active ingredient in packages which are water soluble includes the step of dissolving or dispersing the active ingredient in a non-aqueous hydrophilic solvent which is compatible with the water soluble package. The combination of the active ingredient and hydrophilic solvent provides a storage formulation which can optionally include gelling agents, surfactants, and other additives as described below. The storage formulation is placed in the water soluble package, which is then sealed by any suitable method known to those with skill in the art and preferably enclosed in a non-water soluble container. The non-water soluble container can be made from metal or plastic, and is preferably an outer envelope uabricated from polymers such as polyolefins and polyesters including, for example, polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, and the like.
In use, the outer envelope is manually opened and the water soluble package is removed and added to, for example, a tank of water in which the package dissolves and releases its contents. The water soluble package does not need to be opened and there is less danger of the user coming into manual contact with the active ineredient in the formulation. This is a great advantage with respect to the agricultural industry in which hazardous pesticides are routinely used.
While the present method is contemplated as being especially advantageous for use with agrochemicals and will be described and exemplified in terms of such chemicals, it should be understood that any type of water soluble or non-water soluble chemical may be packaged in accordance with the method described herein, for example, dyes, and water treating agents such as bactericides, tlocculants, surfactants and the like.
By way of example, the agrochemicals to be packaged can be insecticides.
nematicides, herbicides, fungicides, plant growth regulators, rodenticides, or a combination of these agents. Such agents include, but are not limited to, water soluble derivatives such as ammonium salts, monovalent or divalent metal salts, or amine salts of the following exemplary compounds: fungicides such as tebuconazole, metalaxyl, imazalil, thiabendazole, and 2-(thiocyanatomethylthio)benzothiazole:
herbicides (or defoliants) such as acetochlor, imazapyr, paraquat, 2,4-D, propachlor, and imazaquin;
insecticides or acaricides such as malathion, methylparathion, dieldrin, aldrin, amitraz, fenvalerate, and diazinon. Inorganic pesticides include sulfur, sodium chlorate, sodium tluoride, sodium fluoroacetate, and bordeaux mixture. Other pesticides which may be packaged in accordance with the method and system described herein may be found in The Pesticide Manual, Ninth Ed., British Crop Protection Council Pub. (1991).
Organic agrochemieals which are in the form of salts or water soluble salts can be simple amine derivatives or ammonium or monovalent metal or acid halide or sulfate derivatives. The active ingredients which are in a salt form, may be more particularly in the form of a salt of an amine or of ammonium, sodium, potassium, lithium, ammonium, alkanolamines, and simple alkyl or fatty amines.
The following derivatives of organic agrochemicals exemplify those found to be feasible: benzoate, phenate, mono-and di-carboxylate, alkylamine salt, quaternary ammonium salt, phosphonium salt, hydrogen sulfate salt, pyrazolium salts, arsinate.
guanidine, benzenediazosulfonate, acetamide, phosphonate, phosphinate, imidazole, piperidinium, carbamate, arsonate, vinyl phosphate, dithiocarbamate.
naphthylacetate.
bypyridinium, pyrophosphate, pyridyloxyacetate, phosphorothioate.
The water soluble package is preferably fabricated from a polymeric water soluble film, more preferably a cold water soluble film. Cold water soluble means soluble in water at temperature less than 35°C., generally between 5°C. and 35°C. The thickness of the film is generally between 1 and 2 mils.
Suitable materials for fabricating the water soluble package are water soluble (or possibly water dispersible) materials which are insoluble in the organic solvents used to dissolve or disperse the agrochemical active ingredient.
Specific suitable materials include polyethylene oxide, polyethylene glycol; starch and modified starch;
alkyl and hydroxyaikylcellulose, hydroxypropyl cellulose; methylcellulose.
carboxymethylceilulose; polyvinylethers such as poly methyl vinylether or poly(2-methoxyethoxyethylene); poly(2,4-dimethyl-6-triazinylethylene; poly(3-morpholinyl ethylene); poly(N-1,2,4-triazolylethylene); poly(vinylsulfonic acid);
polyanhydrides; low molecular weight melamine-formaldehyde resins; low molecular weight urea-formaldehyde resins; poly(2-hydroxyethyl methacrylate); polyacrylic acid and its homologs.
Most preferably the enveloping film comprises or is made from IS polyvinylalcohol ("PVA"). PVA is generally partially or fully alcoholysed or hydrolysed (e.g., 40-100%, preferably 80-99~b alcoholysed or hydrolysed). Polyvinyl acetate (or other ester) film or copolymers or other derivatives of such polymers can also be used.
PVA films found suitable for use in the present method are available under the designation M 8435 002 from Chris Craft Industrial Products, Ine. located at 450 West 169th Street, South Holland, IL 60473 and KC grade 2 mil PVA film from Mitsui Plastics. Inc. located at 11 Martine Avenue, White Plains, NY 10606.
As mentioned above, the non-aqueous hydrophilic solvent must be able to dissolve or at least form a dispersion with the active ingredient while being compatible with the construction material of the package. Such solvents are capable of dissolving or dispersing both hydrophilic and hydrophobic agents and include gamma-butyrolactone and dipropylenegiycol monomethylether, for example. By employing such solvents the storage formulation does not need to rely on the presence of electrolytes to preserve the integrity of the water soluble package.
Preferably one or more gelling agents are added to the storage formulation.
'The gelling agents must be dispersible in both water and the non-aqueous hydrophilic solvent. Gelling agents can include organic water soluble gums and resins such as:
alginates, carboxymethylcellulose, carrageenan, guar gum, agar, gum arabic, gum ghatti.
gum karaya, gum tragacanth, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropyI methylcellulose, locust bean gum, pectins, polyacrylamide, polyacrylic acid, polyethylene glycol, polyethylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone, starch, tamarind gum, and xanthan gum.
The gelling agents can be inorganic as well. Examples include, but are not limited to, the following: natural clays such as kaolins, Serpentines, smectites (montmorillonites), bentonites, illites, glauconite, chlorites, vermiculites.
mixed-layer clays, attapulgite, saponite and sepiolite, and synthetic clays such as synthetic smectic clays, silicates and fluorosilicates may also be used.
Especially preferred gelling agents for the method set forth herein include polyvinyl pyrrolidone, hydroxypropyl methylcellulose, polyethylene oxide, hydroxypropyl cellulose, and silica (as fumed silica). Gelling agents advantageously provide self sealing capability in the event that the water soluble package develops pin hole leaks.
The storage formulation can optionally include other additives such as antifoaming agents to help remove bubbles from the gel. An example of an antifoaming agent suitable for use in the method described herein is a modified polyether-polysiloxane containing more than 50 % polysiloxane, which is commercially available under the designation Tegosipon 3062 from the Goldschmidt Co. located at 914 East Randolph Road, Hopewell, VA 23860.
Surfactants can optionally be included in the storage formulation but are not required. Surfactants which can be used in the method described herein include, but are not limited to, the following: alkanolamides; poly condensates of ethylene oxide with fatty alcohols, fatty esters, or fatty amines, or substituted phenols (particularly alkyphenols or arylphenols); block copolymers with ethoxy and propoxy groups;
esters of fatty acids with polysols such as glycerol or glycol; polysaccharides:
organopolysiloxanes:
sorbitan derivatives: ethers or esters of sucrose or fructose, salts of lignosulphonic acids, salts of phenyl suiphonic or naphthalene sulphonic acids, diphenyl sulfonates;
alkyaryi sulfonates: sulfonated fatty alcohols or amines or amides: poly condensates of ethylene oxide with fatty acids and their sulfate or sulfonate derivatives: salts of sulphosuccinic or sulfosuccinamic acid esters: taurine derivatives (particularly alkyltaurates);
betaine derivatives: phosphoric esters of alcohols or of polycondensates of ethylene oxide with phenols: and sulphate, sulphonate and phosphate functional derivatives of the above compounds. A preferred concentration of surfactant in the storage formulation ranges from 0% up to about 50%, more preferably 1 %-20% .
The examples set forth below illustrate the method and materials of the present invention described more generally above. The packages used in the examples were fabricated from PVA film.
The following tests were employed in some of the examples:
In the pinhole test 20 grams of formulation was sealed in a PVA bag having a hole of about 1 mm in diameter. The bag was then hung up and the observation was made as to whether the formulation leaked or whether the formulation sealed the hole with its film forming property.
In the dispersion test 20 grams of the formulation were packaged in a PVA
bag and the bag was thrown into 200 grams of water (at room temperature if not otherwise specified). The observation was recorded.
All composition parts are by weight unless otherwise indicated. Viscosities are measured with a Brookfield LVT viscometer, spindle 3 at 30 rpm.
Example 1 A gel base was made by mixing 90 parts of gamma-butyrolactone and 10 parts polyvinyl pyrrolidone gelling agent at room temperature until the polyvinyl pyrrolidone was dissolved. The polyvinyl pyrrolidone was obtained under the designation PVP K-90 from International Specialty Products, located at 1361 Alps Road, Wayne. NJ
07470. The resulting product was a homogeneous, clear gel with a viscosity of 680 cps.
Example 2 A gel base was made by mixing 93 parts of gamma-butyrolactone and 7 parts polyvinyl pyrroiidone gelling agent at room temperature until the polyvinyl pyrrolidone was dissolved. The polyvinyl pyrrolidone was obtained under the designation PVP K-120 from International Specialty Products. The resulting product was a homogeneous, clear gel having a viscosity of 1360 cps.
-7_ Example 3 A gel base was made by mixing 91.5 pans gamma-butyrolactone and 8.5 parts hydroxypropyl methylcellulose gelling agent at room temperature until the gelling agent was completely dispersed. The hydroxypropyl methylceliulose gelling agent was obtained under the designation Methocel E5 from Dow Chemical Co. The resulting product was a homogeneous, semi-clear gel having a viscosity of 500 cps. A
pinhole test was performed and no dripping was observed.
Example 4 A gel base was made by mixing 90 parts gamma-butyrolactone and 10 parts hydroxypropyl methylcellulose gelling agent (Methocel E5) at room temperature until the gelling agent was completely dispersed. The resulting product was a homogeneous semi-clear gel having a viscosity of 1200 cps. A pinhole test was performed and no dripping was observed.
Example 5 A gel base was made by mixing 98 parts gamma-butyrolactone and 2 parts hydroxypropyi methylceliulose gelling agent and heating the mixture briefly to 70°C. Mixing was continued while cooling the mixture down until a homogeneous, semi-clear gel was obtained. The gelling agent was obtained under the designation Methocel E4M from Dow Chemical Co. The viscosity of the resulting gel was 1960 cps.
Example 6 A gel base was made by dispersing 6.5 parts hydroxypropyl methylcelluiose (Methocel E5) in 12 parts polyethylene glycol. This mixture was then added to 81.4 parts gamma-butyrolactone and then heated briefly to 60°C. Then 0.1 parts of Tegosipon 3062 antifoaming agent was then added to the mixture, which was then cooled with continued stirring until a homogeneous semi-clear gel was obtained. The resulting gel had a viscosity of 1220 cps.
_g_ Example 7 A gel base was made by dispersing 6.5 parts hydroxypropyl methyIcellulose ( Methocel ES) in 12 parts polyethylene glycol and adding this mixture to 81.4 parts gamma-butyrolactone. This mixture was then heated briefly to 80°C for 30 minutes while stirring. The mixture was then cooled and 0.1 parts of Tegosipon 3062 antifoaming agent was then added with continued stirring until a homogeneous semi-clear gel vas obtained. The resulting gel had a viscosity of 2320 cps.
Example 8 A gel base v~-as made by mixing 97 parts gamma-butyrolactone and 3 parts of polyethylene oxide gelling agent. The polyethylene oxide was obtained under the designation Polyox 1105 from Union Carbide Co. The mixture was briefly heated to 40°C with stirring and then cooled with continued stirring until a homogeneous, clear gel was formed. The gel had a viscosity of 2200 cps.
Example 9 A gel base was made by mixing 98 pans gamma-butyrolactone with 2 parts hydroxypropyl cellulose gelling agent. The hydroxypropyl cellulose was obtained under the designation Klucel G from Aqualon Co. of Hopeweil, VA. The mixture was heated to 50°C and cooled with continued stirring until a homogeneous semi-clear gel was obtained having a viscosity of 4300 cps.
?0 Example 10 A gel base was made by mixing 98 parts gamma-butyrolactone with 2 pans Klucel G. The mixture was heated to 70°C and cooled with continued stirring until a homogeneous semi-clear gel was obtained having a viscosity of 10,400 cps.
Example 11 ?5 A gel base was made by mixing 90 parts gamma-butyrolactone and 10 parts hydroxypropyl cellulose gelling agent obtained under the designation Klucel L
from _g_ Aqualon Co. The mixture was heated to 70°C and then cooled with stirring until a homogeneous semi-clear gel was obtained having a viscosity of 7200 cps.
Example 12 A gel base was obtained by mixing 86 pans gamma-butyrolactone and 14 parts hydroxypropyl cellulose gelling agent obtained under the designation Klucel E from Aqualon Co. The mixture was heated to 60°C and then cooled with stirring until a homogeneous semi-clear gel was obtained having a viscosity of 2900 cps.
Example 13 A gel base was made by mixing 80 parts gamma-butyrolactone and 20 parts fumed silica obtained under the designation HiSil 233 from PPG Industries.
Inc., located at one PPG Place, Pittsburgh, PA 15272. The components were stirred together at room temperature until a homogeneous semi-clear gel was obtained having a viscosity of 4000 cps.
Example 14 A gel base made in accordance with the method of Example 3 was provided and 25 parts metalaxyl were added to 75 parts of the gel 'at room temperature with stirring until the Metalaxyl was completely dissolved. The resulting storage formulation was amber colored, homogeneous and semi-clear.
A pinhole test was performed and no dripping through the pinhole of the PVA bag was observed. Moreover, the formulation exhibited film-forming property, i.e., the pinhole was sealed by the formulation after a period of time.
A dispersion test was performed and the formulation was observed to disperse in water in less than 1.5 minutes to form a stable homogeneous clear solution without precipitation.
Also. a sample of the storage formulation in a 2.0 miI PVA bag was kept at -10°C to test for storage stability. The sample remained homogeneous and clear for more than two years.
Example 15 A gel base made in accordance with the method of Example 4 was provided and 25.7 parts of metalaxyl were added to 74.3 pans of the gel at room temperature with stirring until the Metalaxyl was completely dissolved. The resulting storage formulation S was amber colored, homoseneous, and semi-clear.
A pinhole test was performed and very slow dripping initially occurred.
However, gel was self sealing and after a period of time no further dripping was observed.
A dispersion test was performed and the formulation was observed to disperse in water in less than 2 minutes to form a stable, homogeneous, clear solution without precipitation.
Example 16 A gel base made in accordance with the method of Example 2 was provided and 25 parts of metalaxyl were added to 75 parts of the gel at room temperature with stirring until the Metalaxyl was completely dissolved. The resulting storage formulation was an amber colored, homogeneous, clear gel having a viscosity of 1680 cps.
A pinhole test was performed and very slow dripping was observed with subsequent self sealing of the pinhole by the gel.
A dispersion test was performed and the formulation was observed to disperse in less than about 5 minutes to form a clear solution without precipitation.
Example 17 A gel base made in accordance with the method of Example 7 was provided and 25.7 parts of metalaxyf were added to 74.3 parts of the gel base at room temperature with stirring until the Metalaxyl was completely dissolved. The resulting storage formulation was an amber colored, homogeneous, clear gel having a viscosity of cps.
A pinhole test was performed and no dripping was observed. The gel was self sealing.
A dispersion test was performed and the formulation was observed to disperse in less than 2 minutes to form a stable clear solution with no precipitation.
A sample of the storage formulation in a 2.0 mil PVA bag was packaged in a second non-soluble plastic bag and stored for more than one year under ambient conditions. No leakage was observed. The bags remained flexible.
Example 18 A gel base made in accordance with the method of Example 11 was provided and 25.7 parts of metalaxyl were added to 74.3 parts of the gel base at room temperature with stirring until the Metalaxyl was completely dissolved, The resulting storage formulation was an amber colored homogeneous, semi-clear gel having a viscosity of 4800 cps.
A pinhole test was performed and no dripping was observed. The gel was self seating.
A dispersion test was performed and the formulation was observed to disperse in less than 2 minutes to form a stable clear solution with no precipitation.
Samples of the storage formulation were sealed in PVA bags which were then contained in non water soluble plastic bags. The packaged samples were then stored at 40°C for about 21 months. No leakage occurred and the PVA bags remained flexible.
Example 19 Three parts of polyethylene polypropylene glycol. obtained under the designation Pluronic P 104 from BASF Corp., and 25.6 parts mewlaxyl were added to 62.2 parts of gamma-butyrolactone at room temperature with stirring until the metalaxyl was completely dissolved. Then 9 pans of fumed silica, obtained under the designation Aerosil 300 from Degussa Co., and 0.2 parts of Tegosipon 3062 were added to the mixture with continued stirring until an amber colored, homogeneous, semi-clear gel was obtained having a viscosity of 2500 cps.
Example 20 A gel base made in accordance with the method of Example 3 was provided, and 54 parts of imazalil were added to 26 parts of gel base at room temperature with stirring until the imazalil was completely dissolved. Then 20 pans of polyethylene glycol, obtained under the designation Witconol 5906 from Witco Corporation, located at One American Lane, Greenwich, CT 06831, were added to the mixture. The resulting storage formulation was an amber colored, homogeneous, semi-clear gel.
A pinhole test was performed and very slow dripping initially occurred.
However, the gel was self sealing and after a period of time no further dripping was observed.
A dispersion test was performed and the formulation was observed to disperse in less than 1.5 minutes to form a milky emulsion. The milky emulsion exhibited some precipitation after 24 hours but returned to emulsion after agitation.
A sample of the storage formulation was sealed in a PVA bag and stored at -10°C for one week. The gel remained homogeneous and clear.
Example 21 A geI base made in accordance with the method of Example 7 was provided, and 59.5 parts of imazalil were stirred into 20.5 parts of the gel base at room temperature until completely dissolved. Then 20 parts of Witconol 5906 were added with continued stirring until an amber colored homogeneous, semi-clear gel was obtained having a viscosity of 660 cps.
A pinhole test was performed and very slow dripping was initially observed. However. the gel was self sealing and after a period of time no further dripping was observed.
A dispersion test was performed and the formulation was observed to disperse in less than 2 minutes to form a milky emulsion.
Example 22 A gel base made in accordance with the method of Example 3 was provided and 10 parts of tebuconazole were stirred into 88 parts of gel base at room temperature until the tebuconazole was completely dissolved. Then 2 parts Witconol 5906 were added to the mixture with stirring. The resulting storage formulation was a colorless, homogeneous, semi-clear gel.
A pinhole test was performed. No dripping was observed. The gel was self sealing after a period of time.
A dispersion test was performed, and the storage formulation was observed to disperse in less then 1 minute to form a milky tine suspension. The suspension showed some precipitation after 24 hours but returned to suspension after agitation.
A sample of storage formulation was sealed in a PVA bag and was observed to remain homogeneous and clear after one week storage at -10°C.
Example 23 A gel base made in accordance with the method of Example 5 was provided and 10 parts of tebuconazole were stirred into 88 parts of gel base at room temperature until the tebuconazole was completely dissolved. Then 2 parts Witconol 5906 were added to the mixture with stirring. The resulting storage formulation was a colorless, homogeneous, semi-clear gel.
A sample of storage formulation was sealed in a PVA bag and was observed to remain homogeneous and clear after six months of storage.
Example 24 A gel base made in accordance with the method of Example 7 was provided and 10 parts of tebuconazole were stirred into 87.6 parts of gel base at room temperature until the tebuconazole was completely dissolved. Then 2 parts Witconol 5906 were added to the mixture with stirring. The resulting storage formulation was a colorless, homogeneous, semi-clear gel.
A pinhole test was performed. No dripping was observed. The gel was self sealing after a period of time.
A dispersion test was performed, and the storage formulation was observed to disperse in less then 2 minutes to form a milky tine suspension. The suspension showed some precipitation after 24 hours but returned to suspension after agitation.
:~ 100 gram sample of storas~e formulation was sealed in a PVA bag 2.0 mils thickness. which was then packaged in a non-water soluble plastic bag.
after more than one year of storage at ambient conditions the whole system remained intact. No leakage occurred and the PVA bag remained filexibie.
Example 25 At room temperature 10.7 parts of Pluronic P 104 were mixed with 73.2 parts gamma-butyrolactone. Then 10.8 parts tebuconazole were stirred into the mixture until completely dissolved. Then 5.3 parts Aerosil 300 were added with stirrins~. The resulting storage formulation was a colorless homogeneous, semi-clear gel having a viscosity of 900 cps.
A dispersion test was performed. In 22°C water the formulation was completely dispersed in 2.5 minutes. In 1 °C water the formulation was completely dispersed in less than 4'h minutes. The diluted sample showed some sedimentation after 24 hours but could be easily resuspended with agitation.
Example 26 A gel base made in accordance with the method of Example 7 was provided and 2 parts of Witconol 5909 were added to 78 parts of gel base. Then 20 parts of thiabendazole were stirred into the gel. The resulting storage formulation was a homogeneous white gel having a viscosity of 7800 cps.
A pinhole test was performed. No dripping was observed. The gel was self sealing.
A dispersion test was performed and the formulation was observed to disperse in less than 2 minutes to form a milky suspension.
Example 27 At room temperature 2.1 parts Pluronic P 104 were mixed with 73.3 parts gamma-butyrolactone. Then 20.9 parts of thiabendazole were stirred into the mixture.
Then 3.7 parts Aerosil 300 were added with stirring. The resulting storage formulation was a milky homogeneous gel having a viscosity of 1200 cps.
A dispersion test was performed. The formulation was completely dispersed in 22°C water in a little over 2 minutes. In 1 °C
water the formulation was completely dispersed in a little over 3.5 minutes. The diluted sample showed some sedimentation after 24 hours but could easily be resuspended with agitation.
Example 28 At room temperature, 10.7 parts Pluronic P104, 10.7 parts metalaxyl, and 10.7 parts tebuconazole were mixed with 62.5 pans gamma-butyrolactone. Then 4.9 parts Aerosil 300 and 0.5 parts Tegosipon were stirred into the mixture. The resulting storage formulation was an amber colored, homogeneous, semi-clear gel having a viscosity of 1300 cps.
Example 29 50 pans of 2-(thiocyanatomethylthio)benzothiazole ( "TCMTB") and 2 parts Pluronic 104 were heated together at 40°C until completely molten. To this mixture was added 48 parts of a gel base made in accordance with the method of Example 8.
The mixture was stirred while cooling down and the resulting storage formulation was an amber colored homogeneous and clear gel having a viscosity of 1000 cps.
Claims (29)
1. A system for storing an active ingredient which comprises:
a) a first package fabricated from a water soluble material; and, b) a storage formulation having the active ingredient as a first component and a hydrophilic non-aqueous solvent as a second component, the hydrophilic non-aqueous solvent being capable of dissolving the active ingredient but not the water soluble material from which the first package is fabricated, said storage formulation being contained in the first package.
a) a first package fabricated from a water soluble material; and, b) a storage formulation having the active ingredient as a first component and a hydrophilic non-aqueous solvent as a second component, the hydrophilic non-aqueous solvent being capable of dissolving the active ingredient but not the water soluble material from which the first package is fabricated, said storage formulation being contained in the first package.
2. The system of Claim 1 wherein the active ingredient is a pesticide and/or plant growth regulator.
3. The system of Claim 2 wherein the active ingredient is a chemical selected from the group consisting of tebuconazole, metalaxyl, imazalil, thiabendazole, 2-(thiocyanatomethylthio)benzothiazole, acetochlor, imazapyr, paraquat, 2,4-D, propachlor, imazaquin, malathion, methylparathion, dieldrin, aldrin, amitraz, fenvalerate, diazinone, sulfur, sodium chlorate, sodium fluoride, sodium fluoroacetate, and bordeaux mixture.
4. The system of Claim 1 wherein the hydrophilic non-aqueous solvent is selected from the group consisting of gamma-butyrolactone and dipropyleneglycol monomethyl ether.
5. The system of Claim 1 wherein the storage formulation contains a gelling agent.
6. The system of Claim 5 wherein the gelling agent is selected from the group consisting of polyvinyl pyrrolidone, hydroxypropyl methylcellulose, polyethylene oxide, hydroxypropyl cellulose, carboxymethylcellulose, carrageenan, guar gum, agar, gum arabic, gum ghatti, gum karaya, gum tragacanth, hydroxyethylcellulose, hydroxypropylcellulose, locust bean gum, pectins, polyacrylamide, polyacrylic acid, polyethylene glycol, polyvinyl alcohol, starch, tamarind gum, xanthan gum, kaolins, serpentines, smectites (montmorillonites), bentonites, illites, glauconite, chlorites, vermiculites, mixed-layer clays, attapulgite, saponite, sepiolite, silicates, fluorosilicates.
and fumed silica.
and fumed silica.
7. The system of Claim 1 wherein the storage formulation further contains up to about 50 % of a surfactant.
8. The system of Claim 7 wherein the surfactant is selected from the group consisting of polyethylene glycol, polyethylene polypropylene glycol, alkanolamides, polycondensates of ethylene oxide with fatty alcohols, polycondensates of ethylene oxide with fatty esters, polycondensates of ethylene oxide with fatty amines, polycondensates of ethylene oxide with substituted phenols, block copolymers with ethoxy and propoxy groups, esters of fatty acids with polyols, polysaccharides, organopolysiloxanes, sorbitan derivatives, ethers or esters of sucrose or fructose, salts of lignosulphonic acids, salts of phenyl sulphonic or naphthalene sulphonic acids, diphenyl sulfonates, alkyaryl sulfonates, sulfonated fatty alcohols, sulfonated fatty amines, sulfonated fatty amides, poly condensates of ethylene oxide with sulfonated fatty acids, salts of sulphosuccinic acid esters, salts of sulfosuccinamic acid esters, taurine derivatives, alkyltaurates, betaine derivatives, phosphoric esters of alcohols, and phosphoric esters of polycondensates of ethylene oxide with phenols:
9. The system of Claim 7 wherein the storage formulation further contains an antifoaming agent.
10. The system of Claim 1 wherein the first package is fabricated from a material selected from the group consisting of poly vinyl alcohol, polyethylene oxide, polyethylene glycol, starch, hydroxypropyl cellulose, methylcellulose, carboxymethylcellulose, polymethyl vinylether, poly(2-methoxyethoxyethylene), poly(2,4-dimethyl-6-triazinylethylene, poly(3-morpholinyl ethylene), poly(N-1,2,4-triazolylethylene), poly(vinylsulfonic acid), soluble melamine-formaldehyde resin, soluble urea-formaldehyde resin, poly(2-hydroxyethyl methacrylate), and polyacrylic acid.
11. The system of Claim 1 further including a second package fabricated from a non-water soluble material, wherein the first package is contained within the second package.
12. The system of Claim 11 wherein the second package is fabricated from a material selected from polyethylene, polypropylene, polyethylene terephthalate and polyvinyl chloride.
13. A system for storing an active ingredient which comprises:
a) a water soluble first package fabricated from a material selected from the group consisting of polyvinyl alcohol, polyethylene oxide and methylcellulose;
and, b) a solution of the active ingredient in a solvent selected from the group consisting of gamma-butyrolactone and dipropyleneglycol monomethylether, said solution being contained within the first package.
a) a water soluble first package fabricated from a material selected from the group consisting of polyvinyl alcohol, polyethylene oxide and methylcellulose;
and, b) a solution of the active ingredient in a solvent selected from the group consisting of gamma-butyrolactone and dipropyleneglycol monomethylether, said solution being contained within the first package.
14. The system of Claim 13 wherein the solution further includes a gelling agent selected from the group consisting of polyvinyl pyrrolidinone, hydroxypropyl methylcellulose, hydroxypropyl cellulose, polyethylene oxide, and silica.
15. The system of Claim 14 wherein said solution further contains a surfactant selected from the group consisting of polyethylene glycol and polyethylene polypropylene glycol.
16. The system of Claim 15 wherein the solution further includes an antifoaming agent.
17. The system of Claim 13 wherein the first package is contained within a non-water soluble outer package.
18. A method of packaging an active ingredient in a water soluble package comprising the steps of:
a) producing a storage formulation by forming a solution or dispersion of the active ingredient in a non-aqueous hydrophilic solvent:
b) placing the storage formulation in the water soluble package, wherein the water soluble package is fabricated from a material which is insoluble in the non-aqueous hydrophilic solvent; and c) sealing the water soluble package to enclose the storage formulation therein.
a) producing a storage formulation by forming a solution or dispersion of the active ingredient in a non-aqueous hydrophilic solvent:
b) placing the storage formulation in the water soluble package, wherein the water soluble package is fabricated from a material which is insoluble in the non-aqueous hydrophilic solvent; and c) sealing the water soluble package to enclose the storage formulation therein.
19. The method of Claim 18 wherein the non-aqueous hydrophilic solvent is selected from the group consisting of gamma-butyrolactone and dipropyleneglycol monomethyl ether.
20. The method of Claim 18 wherein the water soluble package is fabricated from a material selected from the group consisting of polyvinyl alcohol, polyethylene oxide, polyethylene glycol, starch, hydroxypropyl cellulose, methylcellulose, carboxymethylcellulose, polymethyl vinylether, poly(2-methoxyethoxyethylene), poly(2,4-dimethyl-6-triazinylethylene, poly(3-morpholinyl ethylene), poly(N-1,2,4-triazolylethylene), poly(vinylsulfonic acid), soluble melamine-formaldehyde resin, soluble urea-formaldehyde resin, poly(2-hydroxyethyl methacrylate), and polyacrylic acid.
21. The method of Claim 18 wherein the active ingredient is a pesticide and/or plant growth regulator.
22. The method of claim 18 wherein the active ingredient is a water soluble or water dispersible derivative of one or more of chemicals selected from the group consisting of tebuconazole, metalaxyl, imazalil, thiabendazole, 2-(thiocyanatomethylthio)benzothiazole, acetochlor, imazapyr, paraquat, 2,4-D, propachlor, imazaquin, malathion, methylparathion, dieldrin, aldrin, amitraz, fenvalerate, diazinone, sulfur, sodium chlorate, sodium fluoride, sodium fluoroacetate, and bordeaux mixture.
23. The method of Claim 18 further including the step of incorporating a gelling agent in the storage formulation.
24. The method of Claim 23 wherein the gelling agent is selected from the group consisting of polyvinyl pyrrolidone, hydroxypropyl methylcellulose, polyethylene oxide, hydroxypropyl cellulose, carboxymethylcellulose, carrageenan, guar gum, agar, gum arabic, gum ghatti, gum karaya, gum tragacanth, hydroxyethylcellulose, hydroxypropylcellulose, locust bean gum, pectins, polyacrylamide, polyacrylic acid, polyethylene glycol, polyvinyl alcohol, starch, tamarind gum, xanthan gum, kaolins, serpentines, smectites (montmorillonites), bentonites, illites, glauconite, chlorites, vermiculites, mixed-layer clays, attapulgite, saponite, sepiolite, silicates, fluorosilicates, and fumed silica.
25. The method of Claim 18 further including the step incorporating a surfactant in the storage formulation.
26. The method of Claim 25 wherein the surfactant is selected from the group consisting of polyethylene glycol, polyethylene polypropylene glycol, alkanoiamides, polycondensates of ethylene oxide with fatty alcohols, polycondensates of ethylene oxide with fatty esters, polycondensates of ethylene oxide with fatty amines, polycondensates of ethylene oxide with substituted phenols, block copolymers with ethoxy and propoxy groups, esters of fatty acids with polyols, polysaccharides, organopolysiloxanes, sorbitan derivatives, ethers or esters of sucrose or fructose, salts of lignosulphonic acids, salts of phenyl sulphonic or naphthalene sulphonic acids, diphenyl sulfonates, alkyaryl sulfonates, sulfonated fatty aicohols, sulfonated fatty amines, sulfonated fatty amides, polycondensates of ethylene oxide with sulfonated fatty acids, salts of sulphosuccinic acid esters, salts of sulfosuccinamic acid esters, taurine derivatives, alkyltaurates, betaine derivatives, phosphoric esters of alcohols, and phosphoric esters of polycondensates of ethylene oxide with phenols.
27. The method of Claim 18 further including the step of incorporating an antifoaming agent in the storage formulation.
28. The method of Claim 18 further including the step of placing the sealed water soluble package in a non-water soluble outer package.
29. The method of Claim 28 wherein the outer package is fabricated from a material selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate and polyvinyl chloride.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3028798A | 1998-02-25 | 1998-02-25 | |
| US09/030,287 | 1998-02-25 | ||
| PCT/US1999/003102 WO1999043206A1 (en) | 1998-02-25 | 1999-02-12 | System and method for packaging a chemical composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2285202A1 true CA2285202A1 (en) | 1999-09-02 |
Family
ID=21853474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002285202A Abandoned CA2285202A1 (en) | 1998-02-25 | 1999-02-12 | System and method for packaging a chemical composition |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU3292299A (en) |
| CA (1) | CA2285202A1 (en) |
| WO (1) | WO1999043206A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11634272B2 (en) | 2016-12-19 | 2023-04-25 | Upl Ltd | Moisture barrier package |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2011003720A (en) * | 2008-10-08 | 2011-04-28 | Wyeth Llc | Benzimidazole anthelmintic compositions. |
| US9296878B2 (en) * | 2012-03-28 | 2016-03-29 | Lanxess Deutschland Gmbh | Fungicide formulations for plasticized PVC |
| CN118021628B (en) * | 2024-01-23 | 2024-08-27 | 深圳市羽素生物科技有限公司 | Easily-dispersible sulfur microcapsule and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL90584A (en) * | 1988-06-15 | 1994-12-29 | May & Baker Ltd | Package releasing its contents on contact with water |
| KR0168059B1 (en) * | 1990-03-27 | 1999-01-15 | 베르너 발데크, 발트라우트 베케레 | Liquid pesticide concentrates |
| IE921037A1 (en) * | 1991-04-02 | 1992-10-07 | Rhone Poulenc Agrochimie | Containerization system |
-
1999
- 1999-02-12 WO PCT/US1999/003102 patent/WO1999043206A1/en active Application Filing
- 1999-02-12 AU AU32922/99A patent/AU3292299A/en not_active Abandoned
- 1999-02-12 CA CA002285202A patent/CA2285202A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11634272B2 (en) | 2016-12-19 | 2023-04-25 | Upl Ltd | Moisture barrier package |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3292299A (en) | 1999-09-15 |
| WO1999043206A1 (en) | 1999-09-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |