EP0607316B1 - Sealed package - Google Patents
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- Publication number
- EP0607316B1 EP0607316B1 EP92921975A EP92921975A EP0607316B1 EP 0607316 B1 EP0607316 B1 EP 0607316B1 EP 92921975 A EP92921975 A EP 92921975A EP 92921975 A EP92921975 A EP 92921975A EP 0607316 B1 EP0607316 B1 EP 0607316B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- package
- seal
- package according
- seals
- contents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 230000000361 pesticidal effect Effects 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 22
- 230000035939 shock Effects 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 239000004009 herbicide Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 230000002363 herbicidal effect Effects 0.000 claims description 3
- NRXQIUSYPAHGNM-UHFFFAOYSA-N ioxynil Chemical compound OC1=C(I)C=C(C#N)C=C1I NRXQIUSYPAHGNM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical class OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 238000007789 sealing Methods 0.000 description 56
- 239000000499 gel Substances 0.000 description 13
- 239000000575 pesticide Substances 0.000 description 11
- -1 poly(3-morpholinylethylene) Polymers 0.000 description 10
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000007666 vacuum forming Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000254 damaging effect Effects 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002195 soluble material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000005489 Bromoxynil Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012050 conventional carrier Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002991 molded plastic Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- MTQKMPGBALVEDL-ZPCKWCKBSA-N (z,12r)-12-hydroxy-2-sulfooctadec-9-enoic acid Chemical class CCCCCC[C@@H](O)C\C=C/CCCCCCC(C(O)=O)S(O)(=O)=O MTQKMPGBALVEDL-ZPCKWCKBSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical class CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- SKBUTIDCIMIMFQ-UHFFFAOYSA-N CN1NC(=CC(=N1)C)C=C Chemical group CN1NC(=CC(=N1)C)C=C SKBUTIDCIMIMFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002732 Polyanhydride Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical group CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical class CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 229960000282 metronidazole Drugs 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000003750 molluscacide Substances 0.000 description 1
- 230000002013 molluscicidal effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012858 resilient material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000004550 soluble concentrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical class OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004546 suspension concentrate Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
Definitions
- This invention relates to a package particularly suitable for containing a pesticidal composition.
- Pesticides e.g. herbicides
- Such chemicals are typically supplied in a metal or blow-moulded plastics container.
- a quantity of the pesticide is measured out of the container in concentrated form and then mixed with a large volume of water before being sprayed onto a locus to be treated or onto plants.
- concentrated materials are frequently highly toxic so great care must be taken in measuring and mixing them to avoid spillage and to avoid human or animal contact with the concentrated pesticide.
- FR-A-1,088,598 discloses a package containing liquid suitable for dropping from an aeroplane without using a parachute.
- the package comprises a central pocket containing the liquid with a series of seals around the central pocket. Subjected to a mechanical shock starting from the innermost seal, seals can be ruptured successively leaving at least the outermost seal intact.
- GB-A-943,498 discloses a package in the form of an envelope of heat sealable material which comprises a seam comprising a rupturable area such that the seam area comprises either discrete bonded or unbonded areas. Typically, the rupturable seam area divides the packaging into compartments, the contents of which may be mixed by rupturing the seam.
- the present invention seeks to overcome the disadvantages of known packages and to provide a flexible package having an improved resistance to mechanical shock.
- the present invention provides a closed package comprising one or more flexible water dispersible or water soluble polymeric sheets sealed to form an outer non-breachable seal as known from EP-A-0 347 220 with, at least one inner breachable seal of lower peel strength than the non-breachable seal and optionally a space between the inner and outer seals containing substantially none of the contents of the package.
- the breachable seal When the package is subjected to mechanical shock the breachable seal may be breached dissipating the energy of the shock without damaging the outer seal.
- the package comprises a space between the inner and outer seals, the space contains substantially none of the contents of the package: if the inner seal is breached the extra volume accessible to the contents may help to dissipate shock.
- the breachable seal used in the package is one which may be breached when the package is subjected to mechanical shock for example when dropped from a height of 1 to 2m.
- the breachable seal can be breached by peeling apart the seal; additionally it can be breached by means of a gap in the seal.
- the package of the invention comprises one or more sheets of flexible material, preferably thermoformable material, sealed to form a closed package.
- sheets of flexible material preferably thermoformable material
- they are of the same material, but they may be different.
- the package is formed by two separate sheets of material sealed to form a closed package.
- the or every sheet comprising the package is of water soluble or water dispersible material.
- the use of such material which e.g. is known from EP-A-0 347 220 may allow one or more of the following advantageous features, particularly if the contents comprises a hazardous chemical, such as a pesticide:
- water soluble or water dispersible materials include polyvinylalcohol, polyethylene oxide; alkyl and hydroxyalkylcellulose, such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose; carboxymethylcellulose; polyvinyl ethers such as polymethylvinyl ether or poly(2-methoxy or ethoxy ethylene); poly(2,4-dimethyl-6-triazinylethylene; poly(3-morpholinylethylene); poly(N-1,2,4-triazonylethylene; poly(vinylsulfonic acid); polyanhydrides; low molecular weight urea-formaldehyde resins; low molecular weight melamine-formaldehyde resins; poly(2-hydroxyethyl methacrylate); polyacrylic acid and its homologs.
- Preferred materials are polyethylene oxide, methyl cellulose, or polyvinyl alcohol, most preferably polyvinyl alcohol.
- polyvinylalcohol will be used as a
- thermoformable eg Vinex, polyvinylalcohol resin
- such resins possess the advantages of being adaptable to deep draw molding without significant shrinkage problems.
- the material may be unoriented, momo-axially oriented or bi-axially oriented.
- Water soluble materials are preferred since they provide less disposal problems.
- the materials used will generally be cold water soluble; cold water soluble polyvinyl alcohol is preferred. In one specific embodiment, cold water soluble polyvinyl alcohol which is 40 to 99% hydrolysed or alcoholised is used. It will be understood that other materials may be used when the package is to be dissolved or dispersed in hot water.
- the maximum tensile strength of the water soluble or water dispersible material of the sheets comprising the package is preferably at least 20, more preferably from 30 to 80, N/mm 2 and the elongation at break is preferably 200 to 380%, more preferably from 220 to 350%. Testing for these values is generally carried out at 23°C and 50% relative humidity.
- the package of the invention should release its contents in less than about 10 minutes.
- the package will be placed in the spray tank of a conventional sprayer.
- the tank will generally be partly filled with water, and the package added.
- the contents of the bag will be released more rapidly. It is preferred that release it should take place in less than about a minute, for example in 30 to 40 seconds. It will be understood that the time taken to release the pesticide will depend upon a number of factors apart from the nature of the bag, including the temperature of the water and the level of agitation.
- the package may contain material in liquid, gel or granular form.
- the or each sheet may be a laminate, generally of two layers of different or the same material, as pinholes are unlikely to coincide in two layers of material.
- the sheets When the contents are in granular form, the sheets typically comprise a single layer of material. However, in cases where it is particularly desirable to avoid pinholes in the package, eg. to prevent the escape of unpleasant odours, a laminate material of the type described above may be used.
- the or each sheet comprising the package will generally be from 20 to 500 ⁇ m, preferably 50 to 250 ⁇ m, thick.
- the thickness of the sheets will be kept to the minimum needed to prevent rupture of the package, so that the water soluble or dispersible material is dissolved or dispersed as quickly as possible and the contents then released.
- the package is provided with an inner breachable seal or seals in the region of the package most likely to fail.
- the region of the package most likely to fail will vary according to a number of factors including the contents, shape and size of the package, the storage and usage conditions of the package and can be determined by routine experimentation.
- the package comprises an inner seal and an outer seal of a higher peel strength than the inner seal.
- the inner seal may itself comprise regions of varying peel strength, typically being of lower peel strength in the inner region of the seal, or it may be of uniform peel strength.
- the inner and outer seals may be joined to form a single continuous seal of varying peel strength or they may be separated by a space.
- peel strengths may be the same or different. Where the strength of the seals does vary, then typically the innermost breachable seal will be of lowest peel strength, the outermost breachable seal of highest peel strength and any intermediate seals will be of intermediate strength, progressively increasing towards the outermost seal.
- the inner and outer seals may be heat seals.
- the outer seal may be a conventional heat seal typically, 2 to 5 mm thick.
- the or each inner heat seal will typically have a thickness from 1 to 10mm, e.g. 2 to 5mm.
- each inner seal will be within 20 mm of the outer seal.
- the inner and outer seals may be widely separated with the proviso that the space between them does not contain any of the contents of the package.
- the inner seal or seals may seal the portion of the package containing the contents and the outer seal be formed around a handle portion of the package.
- either the or each inner peelable seal or the outer non-peelable seal may be sealed using an adhesive.
- Conventional polymeric adhesive may be used; the strength of the adhesive used may be adjusted to provide a peelable or a non-peelable seal as desired.
- Suitable adhesives include small amounts of water or low molecular weight solutions of polyvinyl alcohol, optionally mixed with polyvinyl acetate.
- the non-peelable and peelable seal or seals may constitute a double or multiple seal around the whole the package.
- the inner seals or seals may be used to reinforce the outer seal only in those regions of the package which are particularly vulnerable to damage by mechanical shock.
- the inner and outer seals may be joined to prevent the contents of the package entering the space between them, if present.
- the package of the invention may comprise an outer non-breachable seal and one or more inner seals having a narrow gap in or between them providing access to a space between the inner seal or seals and the outer seal which space contains substantially none of the contents of the package.
- Mechanical shock to the package may be dissipated by the entry of the contents of the package into the space between the inner and outer seals.
- the package may comprise a single inner seal with a narrow gap in it, or a pair of overlapping seals with narrow gaps between them, which gaps are in a portion of the interior of the package which does not contain any of the contents of the package when in its normal upright orientation.
- the same type of seals may be used as are described above: a combination of non-peelable outer seal and peelable inner seals will be used.
- the contents of the package may be in liquid, gel or granular form, preferably liquid or gel form. Where the contents are in liquid form they may be in the form of a solution or of a dispersion e.g. an emulsion or a suspension. Similarly in gel form, the contents may be a single phase gel or a dispersion
- the contents will be substantially dry. They may comprise any conventional carrier, diluent or surfactant.
- the water soluble or water dispersible material When the contents are in liquid or gel form and comprises an organic solvent, the water soluble or water dispersible material will be one which is insoluble in the organic solvent.
- the packages of the present invention generally contain from 0.1 grams to 7kg, preferably 1g to 5kg, where the composition is in granular form. Where the contents are in liquid or gel form, the package typically contains from 5ml to 10 litres, preferably from 50ml to 5 litres.
- the package will contain at least a small amount of unfilled space, eg at least about 5% by volume, so as to minimise the likelihood of spillage of the composition during the production of the package.
- the unfilled space further provides an area into which the contents of the package may move on exposure to mechanical shock which tends to dissipate the energy from the shock.
- the package of the invention may, in a particular embodiment contain a pesticidal composition.
- a pesticidal composition may be of conventional type.
- Suitable pesticides which may be used in the package of the present invention include fungicides, insecticides and herbicides (for example hydroxybenzonitrile herbicides, e.g. bromoxynil or ioxynil or derivatives thereof such as salts or esters, e.g. heptanoates or octanoates). Specifically a hydroxybenzonitrile herbicide comprising a mixture of ioxynil and bromoxynil ester may be used.
- Molluscicides suitable for addition to, for example, ponds or streams may also be employed.
- the package of the invention may contain chemicals which are potentially toxic or damaging or detrimental to health or to the environment.
- pesticides this includes chemicals which are to be dissolved or dispersed in a large volume of water or aqueous liquid, such as compounds, e.g. metronidazole, used to combat spoilage in industrial aqueous liquids, or compounds for addition to the aqueous circuits of e.g. domestic or industrial heating systems, compounds for addition to swimming pools, photographic materials, inks, dyestuffs, non-aqueous organic acids and cement additives.
- the contents should generally not comprise borates, chlorides or chlorates in amounts effective to lead to deterioration of the material unless the material is protected from them.
- suitable organic solvents which may be used as carriers include petroleum based solvents, e.g. petroleum ethers, mineral oils, aliphatic or aromatic hydrocarbons, e.g. hexane, octane, cyclohexane, benzene, xylene and naphthalene, halogenated aliphatic or aromatic hydrocarbons, e.g. carbon tetrachloride, chloroform, methylene chloride and chlorobenzene, esters e.g. amyl acetate, ketones, e.g.
- petroleum based solvents e.g. petroleum ethers, mineral oils, aliphatic or aromatic hydrocarbons, e.g. hexane, octane, cyclohexane, benzene, xylene and naphthalene, halogenated aliphatic or aromatic hydrocarbons, e.g. carbon tetrachloride, chloroform,
- cyclohexanone, ethers, or a higher alcohol lower alcohols may migrate through the water soluble or water dispersible materials described above: this can result in product appearing on the outside of the package.
- mixtures of solvents e.g. mixtures of a hydrocarbon solvent with another solvent such as a ketone or a higher alcohol, may also be used.
- the organic liquid must be reasonably dry and typically contains less than 2 to 3% of water if the package is water soluble or water dispersible to ensure that it does not leak prematurely from the package.
- compositions may comprise a surfactant, in addition to, or in some cases instead of, an organic solvent as a carrier or diluent.
- a surfactant which is reasonably dry in that it contains less than 2 to 3% water.
- Suitable surfactants may be of the ionic or non-ionic types: for example sulphoricinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyaryl phenols, e.g.
- nonyl- or octyl-phenols or carboxylic acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxy groups by condensation with ethylene oxide, alkali and alkaline earth metal salts of sulphuric acid esters and sulphonic acids such as dinonyl- and dioctyl-sodium sulphonosuccinates and alkali and alkaline earth metal salts of high molecular weight sulphonic acid derivatives such as sodium and calcium lignosulphonates and sodium and calcium alkylbenzene sulphonates.
- the contents may comprise up to 10%, e.g. from 0.05% to 10% of surfactant but, if desired, may comprise higher proportions of surfactant for example up to 15% in liquid emulsifiable suspension concentrates and up to 25% in water soluble concentrates.
- the contents of the package may be thickened or rendered thixotropic to provide a gel.
- An increased viscosity in the contents can reduce the likelihood of the of rupture if the package is subjected to mechanical shock.
- the contents of the package may be rendered more viscous or thixotropic by the inclusion of additives, for example, a modified organophile, or bentonite, lecithin, polymethylene oxide or silica gel.
- concentrations of the chemical, such as pesticide, dissolved or dispersed in the organic liquid or in the gel will generally be those conventionally used: in order to reduce the bulk of each package, however, concentrations may be increased.
- Each package will preferably contain at least about 500 ml and will preferably contain a convenient standard volume, for example 500 ml or 1 litre, although it will be appreciated that any convenient standard volume may be chosen.
- this may comprise any conventional carrier or diluent which if the package is water soluble or dispersible is reasonably dry, in that it contains less than 2 to 3% of moisture.
- suitable solid diluents or carriers are aluminium silicate, talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent carbon black and clays such as kaolin and bentonite.
- Solid compositions may comprise surfactants, such as dispersing agents, for example those surfactants previously mentioned. In some cases such surfactants may also be used as diluents or carriers.
- the concentration of chemical such as pesticide in the solid pesticidal compositions may be as conventionally used: concentrations may however be increased to reduce the bulk of the package.
- the contents, such as pesticidal compositions, present in the package of the present invention may be prepared by conventional means.
- the packages of the present invention may be obtained by first forming a receptacle adapted to retain the contents, filling the open receptacle with contents and then sealing it.
- the open receptacle may be obtained by conventional means. For example, this may be achieved by a vacuum forming where material forming the receptacle is deformed to conform to the shape of a suitable mould and may, if desired, be a thermoforming process to cause the sheet to retain its shape after release from the mould.
- the mould may be equipped with pinholes through which the space between the mould and the sheet can be evacuated.
- the sheet may be driven against the mould by vacuum forming, or by applying a superatmospheric pressure to the other side of the sheet, or by mechanical displacement of the sheet (plug forming).
- the contents of the package are placed inside and the receptacle closed to form a sealed compartment.
- the sealing step may involve the sealing of two surfaces of the package together, the folding of a or the sheet of the material forming the receptacle onto itself and then sealing to itself or the sealing of an additional sheet of material to the open receptacle. It will be appreciated that the open receptacle may be partially sealed prior to filling it.
- the inner breachable seal and outer non-breachable seals of the package may be produced simultaneously or using separate sealing steps.
- Either seal may be produced, at least partially prior to filling the package.
- either seal may be produced by heat sealing or by an adhesive.
- the heat sealing may be carried out using conventional heat sealing equipment and conventional conditions.
- the parameters of sealing jaw temperature, jaw pressure and dwell time may be controlled to obtain an optimum heat seal.
- heat sealing is generally carried out at 15 to 85% relative humidity (measured at 18 to 22°C). The relative humidity is preferably 35 to 55%.
- Some routine experimentation may be required to obtain a suitable heat seal depending on the material forming the package, e.g. the particular grade and thickness of PVOH chosen.
- the quality of the seal can be checked, for example by visual inspection for areas of opacity or for bubbles. Imperfections in the seal may give rise to a lack of water solubility or water dispersibility of the seal where this is desired.
- an inner peelable seal and an outer non-peelable seal may be produced simultaneously using the same heat sealing platen.
- the strength of the heat seal produced may be varied for example by varying the sealing jaw temperature over the heat seal platen.
- a slightly lower jaw temperature may be used on the inner portion of the sealing surface which produces a peelable seal: a variation in sealing jaw temperature may be obtained using a stepped sealing jaw having a first sealing surface closer to a heating element and at a higher temperature than a second sealing surface.
- a contoured jaw may alternatively be used and there may be a space between the inner and outer sealing surface corresponding to a space between the seals.
- a sealing jaw comprising more than two sealing surfaces may be used to produce a package comprising more than one inner breachable seal.
- such variation may be obtained by varying sealing jaw pressure or dwell time.
- a stepped jaw may also be used in conjunction with a planar member of resilient material.
- a seal of variable strength may then be obtained by the variation in jaw pressure which is produced by the stepped jaw.
- Figure 1 illustrates a package formed by thermoforming or vacuumforming a sheet 1 of water-soluble material into a mould 2, a pesticidal composition 3 being contained in the recess thus formed.
- a second sheet 4 of water-soluble material is heat sealed to the first sheet on the flange 5 of the mould 2.
- the heat seal comprises an outer non-breachable seal 6 and an inner breachable seal 7.
- Figure 2 illustrates a package having an integral handle 8.
- the package contains a quantity, for example 1 to 5 litres, of a liquid 9.
- the heat seal comprises an outer non-breachable seal 10 and an inner breachable seal 11 and may also comprise an additional breachable seal 12 at the bottom of the container.
- the breachable seals 11 and 12 may have different peel strengths.
- the handle may have an area 13 of non-breachable seal.
- Figure 3 shows two heat sealing jaw arrangements which may be used to provide a variation in peel strength across the seal by varying the jaw pressure applied during the sealing process.
- Figure 3(a) shows a resilient planar sealing jaw 14 which is heated and a non-heated stepped sealing jaw 15 having a sealing surface a portion of which 16 is closer to the jaw 14 and a portion 17 further from jaw 14.
- variation in jaw pressure is produced by the difference in the distance x between 14 and 16 and the distance x + y between 14 and 17, bearing in mind the jaw 14 will resile on closing.
- Figure 3(b) shows an alternative arrangement in which the sealing surface of the non-heated jaw has a portion 18 parallel to the heated jaw and a further portion 19 which slopes away from the heated jaw providing a continuous variation in the jaw pressure.
- Jaw 14 may be resilient.
- Figure 4 shows that two heat sealing jaw arrangements which may be used to provide a variation in peel strength by varying the jaw temperature across the seal during the sealing process.
- Figure 4(a) shows a stepped heated sealing jaw 20 and a corresponding stepped non-heated sealing jaw 21. The distance between the corresponding sealing surface of the jaws is a constant x. Variation in the temperature at the steps of the sealing jaw, which is due to variation in the distance of the sealing surface from a heating element, produces a variation in peel strength. Either of the jaws 20 and 21 may be resilient.
- Figure 4(b) shows an alternative arrangement in which two planar sealing jaws are employed, a non-heated jaw 22 and a heated jaw 23 in which a variation in temperature is produced by the presence in the jaw of insulating material 24. Due to the insulating material the portions 25 and 26 of the heated jaw are at lower temperatures than the portion 27 when in operation. Either of the jaws 20 and 21 may be resilient.
- Figure 5 shows a heat sealing arrangement which may be used to provide a variation in peel strength by varying the dwell time.
- a heated jaw 28 is employed together with two separately removable non-heated jaws 29 and 30. In operation the heated and non-heated jaws are separated by a constant distance x and variation in dwell time is achieved by withdrawing one of the jaws 29 and 30 while continuing to seal against the other.
- a jaw, preferably jaw 28, may be resilient.
- Figure 6 shows a heat sealing jaw arrangement in which variation in peel strength is produced by a combination of variation in jaw pressure and temperature.
- the arrangement shown is similar to that shown in Figure 3b save that the non-heated jaw 31 is planar and the heated jaw 32 has a portion 33 of its sealing surface parallel to 31 and a portion 34 which slopes away from 31.
- Variation in the jaw pressure is provided by variation in the distance between the jaws and variation in the temperature of the heated jaw 32 is provided by the variation in the distance of the sealing surface of 32 from a heating element.
- Either of the jaws may be resilient.
- Figure 7 shows a heat sealing jaw arrangement in which variation in peel strength is produced by a combination of variation in jaw pressure and dwell time.
- a planar sealing jaw 34 is employed with a non-heated jaw 35 having a stepped sealing surface.
- the portion of the stepped surface of 35 which is closer to 34 is mounted on a spring 37 and is movable relative to the remainder of 35.
- a variation in jaw pressure is produced by the variation in the separation of the jaws.
- the spring 37 extends increasing the dwell time of the sealing surface 36 in contact with the preferably resilient jaw 34.
- jaw 35 is resilient but jaw 34 and member 36 are not, or are more rigid, the contact pressure at the interface 34/36 will be higher than that at the interface 34/35 when the jaws are fully closed together.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Packages (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9121984 | 1991-10-16 | ||
GB919121984A GB9121984D0 (en) | 1991-10-16 | 1991-10-16 | Sealed package |
PCT/GB1992/001898 WO1993008091A2 (en) | 1991-10-16 | 1992-10-16 | Sealed package |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0607316A1 EP0607316A1 (en) | 1994-07-27 |
EP0607316B1 true EP0607316B1 (en) | 1997-02-26 |
Family
ID=10703041
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92921975A Expired - Lifetime EP0607316B1 (en) | 1991-10-16 | 1992-10-16 | Sealed package |
Country Status (18)
Country | Link |
---|---|
EP (1) | EP0607316B1 (xx) |
JP (1) | JPH07502003A (xx) |
CN (1) | CN1030831C (xx) |
AP (1) | AP374A (xx) |
AT (1) | ATE149131T1 (xx) |
AU (1) | AU2783692A (xx) |
BR (1) | BR9206762A (xx) |
DE (1) | DE69217665T2 (xx) |
EG (1) | EG19530A (xx) |
GB (1) | GB9121984D0 (xx) |
IL (1) | IL103426A (xx) |
MA (1) | MA22678A1 (xx) |
MX (1) | MX9205918A (xx) |
NZ (1) | NZ244732A (xx) |
PT (1) | PT100971A (xx) |
TW (1) | TW226321B (xx) |
WO (1) | WO1993008091A2 (xx) |
ZA (1) | ZA928012B (xx) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1421010B2 (en) † | 2001-08-16 | 2012-01-18 | Warner-Lambert Company LLC | Water soluble packaging |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5645169A (en) * | 1992-07-17 | 1997-07-08 | Ciba-Geigy Corporation | Package for use in the transport of water-soluble bags of agricultural chemicals in gel or liquid form |
US6499597B2 (en) | 1994-02-01 | 2002-12-31 | Aquasol Limited | Skin package |
GB9401893D0 (en) * | 1994-02-01 | 1994-03-30 | Aquasol Ltd | New packages |
GB2361686A (en) * | 2000-04-28 | 2001-10-31 | Procter & Gamble | Water-soluble, multi-compartment pouch for detergent product |
EP1276846A2 (en) * | 2000-04-28 | 2003-01-22 | The Procter & Gamble Company | Method for treating stained materials |
US6812199B2 (en) | 2000-04-28 | 2004-11-02 | The Procter & Gamble Company | Method for treating stained materials |
US6995126B2 (en) | 2000-04-28 | 2006-02-07 | The Procter & Gamble Company | Pouched compositions |
GB2380463B (en) * | 2001-10-03 | 2003-09-24 | Reckitt Benckiser Nv | A Process for Producing a Sealed Water-Soluble Package |
PL1678037T3 (pl) | 2003-10-31 | 2010-04-30 | Henkel Ag & Co Kgaa | Sposób pakowania |
JP2007533560A (ja) * | 2003-10-31 | 2007-11-22 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | サポートプレートを用いる包装方法 |
GB2415163A (en) * | 2004-06-19 | 2005-12-21 | Reckitt Benckiser Nv | A process for preparing a water-soluble container |
EP3859767B1 (en) * | 2020-02-03 | 2022-06-15 | Hitachi Energy Switzerland AG | Method for forming an ohmic contact to p-type silicon carbide |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1088598A (fr) * | 1953-08-13 | 1955-03-08 | Outre à liquide pour largage par avion | |
GB922317A (en) * | 1958-05-05 | 1963-03-27 | Associated Fumigators Ltd | Improvements in or relating to means for packaging pesticides |
NL111984C (xx) * | 1958-12-22 | |||
US3716369A (en) * | 1967-04-14 | 1973-02-13 | S Perlman | Process for cooking foods in polyalkylene teraphalate film bag |
DE1786019A1 (de) * | 1968-08-06 | 1971-11-11 | Spiess C F & Sohn | Verfahren zur Herstellung eines Beutels,insbesonders Standbeutel aus thermoplastischem Kunststoff |
DE1934749A1 (de) * | 1969-07-09 | 1971-01-14 | Spiess C F & Sohn | Beutel aus thermoplastischer Kunststoff- oder Verbundfolie |
DE2652454A1 (de) * | 1976-11-17 | 1978-05-18 | Unilever Nv | Standfaehiger faltbeutel |
FR2573391B1 (fr) * | 1984-11-16 | 1990-03-23 | Unisystems Private Ltd | Poche de conditionnement d'un produit liquide |
IL90587A (en) * | 1988-06-15 | 1996-05-14 | May & Baker Ltd | Package releases software by touching with water |
-
1991
- 1991-10-16 GB GB919121984A patent/GB9121984D0/en active Pending
-
1992
- 1992-01-14 AP APAP/P/1992/000437A patent/AP374A/en active
- 1992-10-13 TW TW081108120A patent/TW226321B/zh active
- 1992-10-14 IL IL10342692A patent/IL103426A/en not_active IP Right Cessation
- 1992-10-14 MA MA22965A patent/MA22678A1/fr unknown
- 1992-10-14 NZ NZ244732A patent/NZ244732A/en unknown
- 1992-10-15 PT PT100971A patent/PT100971A/pt not_active Application Discontinuation
- 1992-10-15 EG EG62492A patent/EG19530A/xx active
- 1992-10-15 MX MX9205918A patent/MX9205918A/es unknown
- 1992-10-16 EP EP92921975A patent/EP0607316B1/en not_active Expired - Lifetime
- 1992-10-16 AT AT92921975T patent/ATE149131T1/de not_active IP Right Cessation
- 1992-10-16 CN CN92111694A patent/CN1030831C/zh not_active Expired - Fee Related
- 1992-10-16 BR BR9206762A patent/BR9206762A/pt not_active Application Discontinuation
- 1992-10-16 DE DE69217665T patent/DE69217665T2/de not_active Expired - Fee Related
- 1992-10-16 JP JP5507541A patent/JPH07502003A/ja active Pending
- 1992-10-16 ZA ZA928012A patent/ZA928012B/xx unknown
- 1992-10-16 AU AU27836/92A patent/AU2783692A/en not_active Abandoned
- 1992-10-16 WO PCT/GB1992/001898 patent/WO1993008091A2/en active IP Right Grant
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1421010B2 (en) † | 2001-08-16 | 2012-01-18 | Warner-Lambert Company LLC | Water soluble packaging |
Also Published As
Publication number | Publication date |
---|---|
TW226321B (xx) | 1994-07-11 |
IL103426A0 (en) | 1993-03-15 |
ATE149131T1 (de) | 1997-03-15 |
NZ244732A (en) | 1995-07-26 |
AU2783692A (en) | 1993-05-21 |
IL103426A (en) | 1995-12-31 |
EG19530A (en) | 1995-06-29 |
WO1993008091A3 (en) | 1993-06-24 |
AP9200437A0 (en) | 1992-10-14 |
ZA928012B (en) | 1993-07-28 |
DE69217665T2 (de) | 1997-10-02 |
CN1071636A (zh) | 1993-05-05 |
JPH07502003A (ja) | 1995-03-02 |
MX9205918A (es) | 1993-04-01 |
CN1030831C (zh) | 1996-01-31 |
GB9121984D0 (en) | 1991-11-27 |
WO1993008091A2 (en) | 1993-04-29 |
AP374A (en) | 1994-11-27 |
BR9206762A (pt) | 1995-10-24 |
DE69217665D1 (de) | 1997-04-03 |
MA22678A1 (fr) | 1993-07-01 |
PT100971A (pt) | 1994-05-31 |
EP0607316A1 (en) | 1994-07-27 |
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