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IE911004A1 - Liquid pesticide concentrates - Google Patents

Liquid pesticide concentrates

Info

Publication number
IE911004A1
IE911004A1 IE100491A IE100491A IE911004A1 IE 911004 A1 IE911004 A1 IE 911004A1 IE 100491 A IE100491 A IE 100491A IE 100491 A IE100491 A IE 100491A IE 911004 A1 IE911004 A1 IE 911004A1
Authority
IE
Ireland
Prior art keywords
pesticide concentrate
concentrate according
water
pesticide
soluble
Prior art date
Application number
IE100491A
Other versions
IE66492B1 (en
Inventor
Guy Dez
Jacques Lerivrey
Rene Schneider
Alexander Zurkinden
Carolyn Moore
Original Assignee
Novartis Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=4200366&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=IE911004(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Novartis Ag filed Critical Novartis Ag
Publication of IE911004A1 publication Critical patent/IE911004A1/en
Publication of IE66492B1 publication Critical patent/IE66492B1/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/46Applications of disintegrable, dissolvable or edible materials
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/26Biocides, 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 in coated particulate form
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/34Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

There are described pesticidal active substance concentrates in packaged form which consist of a water-soluble packaging and a liquid, non-aqueous pesticidal concentrate.

Description

Liquid pesticide concentrates The present invention relates to liquid pesticide concentrates on a non-aqueous basis, which are sealed in a bag made of water-soluble plastic film.
Pesticides are normally marketed in the form of concentrates which, before use, are diluted with water to spray mixtures. When handling the concentrates, the toxicity of the active ingredients makes it necessary to take steps to prevent the user coming in contact with the concentrates. In particular, the user must be protected from inhaling the dust arising from handling solid formulations such as powders and granules, and from skin contact with liquid formulations such as emulsifiable concentrates. The manufacturers of pesticide concentrates therefore recommend taking a number of precautions, such as wearing protective masks, suits and gloves.
To secure further improved protection for the user, the proposal has already been made to avoid the dust formation associated with handling solid pesticide concentrates and skin contact with liquid concentrates by packaging these concentrates in a bag made from water-soluble plastic film. The spray mixture is prepared from such concentrates packed in water-soluble material by putting the concentrate and its packaging into the amount of water necessary for preparing the spray mixture. The spray mixture forms immediately after dissolution of the packaging and dispersion of the contents. Direct contact of the user with the concentrate is thereby avoided. Moreover, packaging concentrates in water-soluble packaging materials has the advantage that the concentrates can be removed from the containers in which they are transported and stored to protect them from moisture without leaving any residues which would make it necessary to clean the containers. In addition, it is much easier to control the dosage of the active ingredient, as each bag contains a defined amount of active ingredient.
The water-soluble bags of liquid active ingredient concentrates of the prior art have, however, a relatively high susceptibility to shock and impact, so that, when subjected to sudden mechanical stress, for example on falling to the ground, the bags burst. Not only do these unfavourable properties lead in the transportation and handling of such bags to -2constant loss and to contamination of the environment and/or of the user, but also to the loss of the advantages referred to above of the use of water-soluble packaging materials.
Hence it is the object of this invention to provide pesticide concentrates in packaged form which comprise a water-soluble packaging material and a liquid, non-aqueous pesticide concentrate, and which have increased stability to impact and shock.
Specifically, the invention provides pesticide concentrates in packaged form comprising a water-soluble packaging material and a liquid, non-aqueous pesticide concentrate, wherein the viscosity of said liquid pesticide concentrate is 1000-20 000 cp.
In the simplest case, the pesticide concentrates of this invention are solutions of one or more active ingredients in a non-aqueous solvent, the viscosity of which concentrates has been adjusted to 1000-20 000 cp by addition of a viscosity increasing substance. The pesticide concentrates may also, however, be solutions of one or more active ingredients in a non-aqueous solvent, in which additionally one or more active ingredients which are insoluble in said solvent are suspended, the viscosity of which suspensions have also been adjusted to 1000-20 000 cp by addition of a viscosity increasing substance. Finally, the concentrates of the invention may also be suspensions of one or more active ingredients in a non-aqueous solvent, the viscosity of which suspensions have been adjusted to 1000-20 000 cp by addition of a viscosity increasing substance.
In addition to comprising one or more active ingredients, the solvent and the viscosity increasing substance, the concentrates of this invention may advantageously contain one or more dispersants. The addition of one or more dispersants is especially expedient if the active ingredient and/or the solvent and/or the viscosity increasing substance are insoluble in water and it is necessary to form a dispersion after diluting the concentrate with water.
Suitable non-aqueous solvents are the solvents which are customarily used in pesticide formulation and which are inert to the water-soluble packaging material, viz. those solvents which neither dissolve the water-soluble packaging material nor in which it swells or otherwise adversely affect it. With respect to this limitation, it must be borne in mind that solvents generally tend all the less to dissolve or cause the packaging material to swell the greater the concentration of the substances dissolved therein is. Suitable solvents are alcohols, alkanediols (glycols), diethylene glycol monoethers, ketones, esters, aliphatic and aromatic hydrocarbons, as well as mineral and vegetable oils. Particularly suitable -3alcohols are Cj-Cgalkanols, preferably C3-C6alkanols and C5-C6cycloalkanols. Particularly suitable alkanediols are ethylene glycol and propylene glycol. Particularly suitable diethylene glycol monoethers are diethylene glycol monomethyl ether und dipropylene glycol monomethyl ether. Particularly suitable ketones are C4-C8alkanones and C5-C6cycloalkanones. Suitable esters are preferably C3-C6alkylacetates and lactones of C4-C5hydroxyalkanecarboxylic acids. Particularly suitable aliphatic and aromatic hydrocarbons are hexane, cyclohexane, toluene, xylene, as well as mixtures of the alkylbenzenes which are commercially available under the registered trademarks ®Solvesso and ®Shellsol. Particularly suitable mineral oils are higher boiling petroleum fractions. Suitable vegetable oils are castor oil, rape oil, rape oil esters, cotton seed oil and soybean oil. Particularly suitable solvents are cyclohexanol, diacetone alcohol, cyclohexanone, butyrolactone, amyl acetate, toluene, xylene, as well as mixtures of alkylbenzenes having a boiling range of 130-170°C.
Suitable viscosity increasing substances for the putposes of the invention are preferably water-soluble polymers and hydrophilic silicic acid. Suitable water-soluble polymers are typically cellulose derivatives, proteins (gelatin) and polyvinylpyrrolidone having a molecular weight of 600 000-1000 000. In individual cases it is also possible to use surfactants, such as ethylene oxide-propylene oxide block polymers or dodecylbenzenesulfonates, as viscosity increasing substances. Preferred viscosity increasing substances are cellulose derivatives, such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose.
The dispersants which may be suitably used are basically all nonionic, anionic and cationic dispersants customarily used in the art of pesticide formulation. It is preferred to use nonionic or anionic dispersants or mixtures of nonionic and anionic dispersants. Particularly suitable nonionic dispersants are ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers, as well as fatty acid and fatty alcohol polyglycol ethers. Particularly suitable anionic dispersants are salts of alkylbenzenesulfonic acids, for example calcium dodecylbenzenesulfonate, and also salts of mono- and diphenol polyglycol ether phosphates, as well as salts of monophenol polyglycol ether sulfates. Particularly suitable mixtures of anionic and nonionic dispersants are mixtures of alkylphenol polyglycol ethers and salts of mono- and diphenol polyglycol ether phosphates.
By water-soluble packaging materials are meant in the context of this invention preferably -4films made of water-soluble polymers, for example of polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of vinyl alcohol and vinyl pyrrolidone, copolymers of vinyl alcohol and vinyl acetate, as well as cellulosic films, for example carboxymethyl cellulose films. Polyvinyl alcohol films are the preferred packaging materials.
The active ingredient concentrates of this invention may in principle contain any agrochemical control agents, for example insecticides, acaricides, fungicides, herbicides and plant growth regulating substances.
The pesticide concentrates of this invention can be prepared by dissolving or suspending one or more active ingredients in a solution of the dispersant in a non-aqueous solvent, and then incorporating the viscosity increasing substance in the resultant mixture. The preparation of the concentrates can be carried out in a conventional mixing apparatus. If the individual components of the mixture are water-soluble, the addition of dispersant can be dispensed with, for in this case an aqueous solution is obtained direct from the concentrate upon dilution with water. If, however, one or more components of the concentrate are water-insoluble, then it is advantageous to add one or more dispersants in order to ensure the rapid and homogeneous dispersion of the components in water. The concentrate can then be filled immediately in equal portions into bags which can be made in known manner from films consisting of the polymers cited above. After they have been filled with the concentrate, the bags are sealed. The bags so obtained contain a defined amount of active ingredient per unit dose package. The individual bags can then be packed for transportation and storage individually or collectively in containers, for example cardboard, polyethylene, polypropylene or polyvinyl chloride containers, from which they can be readily removed immediately before use.
The bags of this invention are conveniently prepared by continuously feeding a web of water-soluble material 100-300 mm wide and 30-40 pm thick to a filling machine in which the web is first welded with a straight bead to a tubular film which is sealed at its end by a transverse weld. After being filled with the desired amount of active ingredient concentrate, the bag is then sealed with a severing weld, so as to obtain, on the one hand, a ready-for-use bag containing the active ingredient concentrate and, on the other, a new bag preformed from the tubular film into which the next portion of active ingredient concentrate can be filled. The welds can be made by heat welding at a temperature of ca. 300°C as well as by pulse welding or high-frequency welding.
IE 9ΐ1θθ4 -5The handling and application of the pesticide concentrates of this invention is exceedingly simple. One or more bags are taken from the container and put into a spray tank filled with water in which the bag made of water-soluble packaging material dissolves in a few minutes, and the concentrate disperses in the water to form a spray mixture. Not only are the previously known advantages of water-soluble bags thereby attained, namely avoidance of direct contact of the user with the concentrate, ready metering of the active ingredients without using graduated jars, and avoidance of contamination of the packing containers, but, in addition, the mechanical stability of the bags, especially the stability to sudden mechanical stress, is substantially increased in comparison with prior art bags of this kind containing liquid pesticide concentrates. Only by increasing the stability to sudden mechanical stresses is it possible to utilise fully the advantages accruing from the use of water-soluble packaging material.
The following Examples illustrate the invention in more detail.
A number of typical formulations of pesticide concentrates of this invention are illustrated below, without thereby implying any restriction of the present invention. Percentages are by weight. The preparation of the packs is also described.
Example 1 Propiconazole techn. 62.5 % calcium dodecylbenzenesulfonate 4.5 % castor oil polyglycol ether (EO36) 4.0 % isooctylphenol polyglycol ether (EO 8) 2.0 % alkylbenzene C10-03, to make up 100 % viscosity: 11000 cp Example 2 Propiconazole techn. 65.0 % PO-EO block polymer (80 % EO; MG: 8550) 4.5 % castor oil polyglycol ether (EO 36) 8.8 % sodium diamylsulfosuccinate 4.6 % n-butanol, to make up viscosity: 5000 cp 100 % Example 3 Propiconazole techn. 62.5 % calcium dodecylbenzenesulfonate 3.0 % isotridecyl alcohol polyglycol ether (EO 6) 3.0 % EO-PO block polymer (20 % EO; MG: 5000) 4.0 % silicone oil 0.2 % hydroxypropyl cellulose 1.0 % cyclohexanone, to make up 100 % viscosity: 2000 cp Example 4 Propiconazole techn. 62.5 % calcium dodecylbenzenesulfonate 3.0 % isotridecyl alcohol polyglycol ether (EO 6) 3.0 % EO-PO block polymer (20 % EO; MG: 5000) 4.0 % silicone oil 0.2 % hydroxypropyl cellulose 1.0 % dipropylene glycol monomethyl ether, to make up 100 % viscosity: 2000 cp Example 5 Propiconazole techn. 62.5 % tristyrylphenol polyglycol ether (EO 20) 8.0 % nonylphenol polyglycol ether (EO8) 8.0 % nonylphenol polyglycol ether (EO 8-10) phosphate 2.0 % ¢911004 silicone oil 0.2 % hydroxypropylcellulose 0.72 % cyclohexanone, to make up viscosity: 2400 cp 100 % Example 6 Penconazole techn. 25.0 % propylene glycol isotridecyl alcohol polyglycol 7.0 % ether (EO 6) 3.0 % calcium dodecylbenzenesulfonate EO-PO block polymer 4.0 % (20 % EO; MG: 5000) 10.0 % silicone oil 0.05 % hydrophilic silicic acid 3.5 % castor oil, to make up viscosity: 5000 cp 100 % Example 7 Phosphamidon techn. 65.6 % calcium dodecylbenzenesulfonate 1.6 % polyglycerol phthalate oleyl alcohol polyglycol ether 1.6 % (10 EO) 3.0 % silicone oil 0.08 % hydroxypropyl cellulose dipropylene glycol monomethyl 0.82 % ester, to make up viscosity: 3000 cp 100 % Beispiel 8 Monocrotophos techn. 60.6 % hydroxypropylcellulose dipropylene glycol methyl ether, 4.0 % to make up viscosity: 3000 cp 100 % -8Example 9 propargyl 2- [4- (5-c h loro-5-fl uoropyrid-2-yloxy)phenoxy] - propioniate 24.0 % 5-chloro-8-( 1 -methylhexyloxycarbonylmethoxy)- quinoline 6.0 % N-methylpyrrolidone 5.0 % calcium dodecylbenzoate 7.0 % nonylphenol polypropylene( 13)polyethylene(20)- glycol 13.0 % hydrophilic silicic acid 2.1 % ethyl cellulose 2.1 % anisole, to make up 100 % viscosity: 2000 cp Example 10: A web of polyvinyl alcohol (manufacturer: Syntana Handelsgesellschaft GmbH, Millheim-Ruhr, FRG), 200 mm wide and 35 pm thick, is fed continuously to a filling machine (manufacturer: NEDI S.A., Saint-Mammes, France) in which it is welded by pulse welding with a straight bead to a tube which is sealed at its end with a transverse weld. After being filled with 100 g of active ingredient according to Example 3, the preformed bags so obtained are then separated so as to give sealed bags 135 mm in length which contain the active ingredient concentrate.
The bags so obtained dissolve in 25-2001 of water of 15-20°C in ca. 1 minute to give a ready-for-use spray mixture.

Claims (13)

What is claimed is:
1. A pesticide concentrate in packaged form, which comprises a water-soluble bag and a liquid, non-aqueous pesticide concentrate, the viscosity of said liquid pesticide concentrate being 1000-20 000 cp.
2. A pesticide concentrate according to claim 1, which contains one or more active ingredients selected from the group consisting of insecticides, acaricides, fungicides, herbicides and plant growth regulating substances.
3. A pesticide concentrate according to claim 1, which contains a solvent which is inert to the water-soluble packaging material.
4. A pesticide concentrate according to claim 3, which contains a solvent selected from the group consisting of alcohols, alkanediols (glycols), diethylene glycol monoethers, ketones, esters, aliphatic and aromatic hydrocarbons, and mineral or vegetable oils.
5. A pesticide concentrate according to claim 3, which contains a solvent selected from the group consisting of cyclohexanol, diacetone alcohol, cyclohexanone, butyrolactone, amyl acetate, toluene, xylene, and mixtures of alkylbenzenes having a boiling range of 130-170°C.
6. A pesticide concentrate according to claim 1, which contains one or more dispersants.
7. A pesticide concentrate according to claim 1, which contains a water-soluble polymer or hydrophilic silicic acid as viscosity increasing substance.
8. A pesticide concentrate according to claim 7, which contains a viscosity increasing substance selected from the group consisting of cellulose derivatives, proteins (gelatin) or polyvinyl pyrrolidine having a molecular weight of 600 000-1000 000.
9. A pesticide concentrate according to claim 8, which contains a viscosity increasing substance selected from the group consisting of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose or hydroxypropyl cellulose. - 1010.
10.A pesticide concentrate according to claim 1, wherein the packaging material consists of a film made from a water-soluble polymer.
11. A pesticide concentrate according to claim 10, wherein the water-soluble packaging material is a film made from polyvinyl alcohol, polyvinyl pyrrolidone, a copolymer vinyl alcohol and vinyl pyrrolidone, a copolymer of vinyl alcohol and vinyl acetate, or is a cellulosic film.
12. A pesticide concentrate according to claim 10, wherein the packaging material is a polyvinyl alcohol film.
13. A pesticide concentrate according to any preceding claim, substantially as hereinbefore described and exemplified.
IE100491A 1990-03-27 1991-03-26 Liquid pesticide concentrates IE66492B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH101190 1990-03-27

Publications (2)

Publication Number Publication Date
IE911004A1 true IE911004A1 (en) 1991-10-09
IE66492B1 IE66492B1 (en) 1996-01-10

Family

ID=4200366

Family Applications (1)

Application Number Title Priority Date Filing Date
IE100491A IE66492B1 (en) 1990-03-27 1991-03-26 Liquid pesticide concentrates

Country Status (15)

Country Link
EP (1) EP0449773B1 (en)
KR (1) KR0168059B1 (en)
AT (1) ATE121903T1 (en)
AU (1) AU646440B2 (en)
BR (1) BR9101192A (en)
CA (1) CA2039001C (en)
CZ (1) CZ284551B6 (en)
DE (1) DE59105355D1 (en)
DK (1) DK0449773T3 (en)
ES (1) ES2071963T3 (en)
HU (1) HU217519B (en)
IE (1) IE66492B1 (en)
IL (1) IL97669A (en)
SK (1) SK280182B6 (en)
ZA (1) ZA912257B (en)

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US5395616A (en) * 1988-06-15 1995-03-07 May & Baker Ltd. Packaging for liquid products
AU653519B2 (en) * 1990-05-02 1994-10-06 Rhone-Poulenc Agriculture Limited Soluble sachets
US5080226A (en) * 1990-07-18 1992-01-14 Rhone-Poulenc Ag Company Containerization system for agrochemicals and the like
IL98801A (en) * 1990-07-18 1997-07-13 Rhone Poulenc Agrochimie Water dispersible gel formulations
IL98803A (en) * 1990-07-18 1996-06-18 Rhone Poulenc Agrochimie Gel formulations
IL98805A0 (en) * 1990-07-18 1992-07-15 Rhone Poulenc Agrochimie Gel formulations for hazardous products
US5248038A (en) * 1990-07-18 1993-09-28 Rhone-Poulenc Inc. Containerization system for agrochemicals and the like
MA22221A1 (en) * 1990-07-18 1992-04-01 Rhone Poulenc Agrochimie GEL FORMULATIONS FOR USE IN TOXIC PRODUCT PACKAGING SYSTEMS
AU655282B2 (en) * 1991-06-14 1994-12-15 Rhone-Poulenc Agro New aqueous formulations
IL104187A (en) * 1991-12-27 1996-05-14 Rhone Poulenc Agrochimie Containerization systems and composition suitable to be contained
DE4417555A1 (en) * 1994-05-19 1995-11-23 Bayer Ag Use of gel formulations as a mordant
CN1108098C (en) 1994-08-03 2003-05-14 曾尼卡有限公司 Gel formulation
DE19633271A1 (en) 1996-08-19 1998-02-26 Basf Ag Liquid formulation of ethyl (Z) -2-chloro-3- [2-chloro-5- (4,5,6,7-tetrahydro-1,3-dioxoisoindoldion-2-yl) phenyl] acrylate
AU3292299A (en) * 1998-02-25 1999-09-15 Uniroyal Chemical Company, Inc. System and method for packaging a chemical composition
US6727219B2 (en) 2002-07-01 2004-04-27 E. I. Du Pont De Nemours And Company Single dosage oxidizing treatment
CN114271272A (en) * 2022-01-21 2022-04-05 李汉承 Pesticide coagulated beads and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB922317A (en) * 1958-05-05 1963-03-27 Associated Fumigators Ltd Improvements in or relating to means for packaging pesticides
US3695989A (en) * 1970-08-12 1972-10-03 Robert E Albert Cold water soluble foam plastic package
IL90587A (en) * 1988-06-15 1996-05-14 May & Baker Ltd Package releasing its contents on contact with water

Also Published As

Publication number Publication date
HUT56690A (en) 1991-10-28
CZ284551B6 (en) 1999-01-13
ES2071963T3 (en) 1995-07-01
SK280182B6 (en) 1999-09-10
IL97669A (en) 1996-01-19
EP0449773A1 (en) 1991-10-02
AU646440B2 (en) 1994-02-24
KR0168059B1 (en) 1999-01-15
CA2039001C (en) 2001-04-24
KR910016250A (en) 1991-11-05
ZA912257B (en) 1991-12-24
EP0449773B1 (en) 1995-05-03
DE59105355D1 (en) 1995-06-08
ATE121903T1 (en) 1995-05-15
DK0449773T3 (en) 1995-07-17
IE66492B1 (en) 1996-01-10
IL97669A0 (en) 1992-06-21
BR9101192A (en) 1991-11-05
CA2039001A1 (en) 1991-09-28
CS9100809A2 (en) 1991-11-12
HU217519B (en) 2000-02-28
AU7385691A (en) 1991-10-03

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