WO2002100733A1 - Use of oxygen absorbing substances for making flexible tubes - Google Patents
Use of oxygen absorbing substances for making flexible tubes Download PDFInfo
- Publication number
- WO2002100733A1 WO2002100733A1 PCT/FR2002/001923 FR0201923W WO02100733A1 WO 2002100733 A1 WO2002100733 A1 WO 2002100733A1 FR 0201923 W FR0201923 W FR 0201923W WO 02100733 A1 WO02100733 A1 WO 02100733A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxygen
- tube according
- microcapsules
- envelope
- tube
- Prior art date
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000001301 oxygen Substances 0.000 title claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 18
- 239000000126 substance Substances 0.000 title claims abstract description 12
- 239000003094 microcapsule Substances 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000006096 absorbing agent Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001817 Agar Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000008272 agar Substances 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000005670 electromagnetic radiation Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229960004667 ethyl cellulose Drugs 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000002826 nitrites Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000002775 capsule Substances 0.000 claims 4
- 206010011732 Cyst Diseases 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- 208000031513 cyst Diseases 0.000 claims 1
- -1 ferrous salt cobalt salt Chemical class 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 21
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000003570 air Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000001143 conditioned effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- UKVYVZLTGQVOPX-IHWYPQMZSA-N (z)-3-aminobut-2-enoic acid Chemical compound C\C(N)=C\C(O)=O UKVYVZLTGQVOPX-IHWYPQMZSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940045110 chitosan Drugs 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229940014259 gelatin Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 235000020944 retinol Nutrition 0.000 description 1
- 229960003471 retinol Drugs 0.000 description 1
- 239000011607 retinol Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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
- B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
- B65D35/02—Body construction
- B65D35/10—Body construction made by uniting or interconnecting two or more components
-
- 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
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
- B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
- B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
Definitions
- the invention relates to metal containers such as aluminum alloy tubes for storing and dispensing pasty liquid products. These tubes have an excellent barrier to gas diffusion and are particularly suitable for containing products sensitive to oxidation
- the aluminum alloy tubes are obtained by impact spinning of a pin. They have a cylindrical or conical skirt having an open end and another end connected to a dispensing head. Said dispensing head, or collar, comprises a neck. dispensing generally delimiting an orifice not yet uncapped and a shoulder connecting the neck to the
- the interior surface of the tube is covered with a varnish and, near the open end, an annular seal constitutes a "latex-based" resin, typically an adhesive resin based on synthetic rubber or an acrylic type resin, said resins being in suspension in an aqueous solution
- the tubes are packed upside down and the orifice is sealed and / or closed by a plug and then sent to the conditioner.
- the latter fills them by introducing the product to be conditioned by the open end.
- the portion of the skirt close to the open end, coated with the annular seal is flattened along a diameter so that the parts of the wall which are facing each other can come into contact over their entire surface and joining one to the other
- This flattened end is then folded on itself several times (in general 2 or three folds are produced) then compressed. In this way, thanks to the adhesive seal trapped in the folds thus produced, a seal is obtained.
- end of the tube by which the product is contained so waterproof in said tube
- the seal is self-adhesive or thermoadhesive
- the object according to the invention is a metal tube, comprising a cylindrical or conical skirt having an open end and another end connected to a dispensing head, the interior surface of said cylindrical skirt being covered, near said open end, an adhesive annular seal, characterized in that said adhesive seal comprises an oxygen-absorbing agent which is released during the final sealing of the tube
- the tube is metallic because its wall has a barrier property to the diffusion of excellent oxygen, clearly superior to that of any wall made of polymeric material.
- this tube is made of aluminum alloy
- the Applicant has found it advantageous to release in the vicinity of said pocket an oxygen-absorbing agent contained up to there in the joint
- the oxygen-absorbing agent can be incorporated directly into the so-called "latex-based" resin used to make the joint, in a chemical form which remains passive as long as it does not is not brought into contact with the product to be packaged.
- latex-based resin used to make the joint
- the oxygen-absorbing agent can also be simply contained in an envelope or, preferably, in a large quantity of microcapsules incorporated in the so-called "latex-based" resin used for making the joint, this envelope or these microcapsules in front be destroyed after filling and / or final sealing of the tube Conditioned inside microcapsules, the oxygen-absorbing agent is easy to mix in a liquid resin such that the resin used to make the seal the microcapsules are simply incorporated and mixed in this aqueous suspension then said resin "latex-based” is deposited on the inner wall of the tube when it is still in liquid form In general, this wall is already covered with a layer of varnish, generally of the phenolic epoxy type
- the drying of the resin "to latex base can optionally be provided at room temperature (self-adhesive seal) or at a higher temperature (heat-adhesive seal) The microbeads remain trapped in the hardened seal after drying
- microcapsules can be destroyed mechanically by taking advantage of the operations necessary for the final sealing (crushing then folding of the edges of the open end, compression of the final joint, etc.)
- the envelope of these microcapsules can also be destroyed - or made permeable to oxygen - under another type of mechanical action (ultrasound for example), or by external energy supply (heat supply, electromagnetic radiation of the microwave, ultra-violet or infrared types), or also by chemical route (supply of a solvent, water, lipids, pH of the packaged product,)
- the substance released during the final sealing absorbs the residual oxygen from the air pocket trapped in the container after filling of the product to be packaged and closing of the container.
- this substance is provided in an amount sufficient to also absorb the oxygen capable to diffuse during all the use of the product through the interface between the flattened, joined and folded joint parts
- This substance is chosen according to the conditions of use of the product packaged in the tube. It can be any oxidizable compound compatible with the use of the product to be dispensed, ter powder, a metal salt such as a salt. earthy or a cobalt salt, an oxidizable compound chosen from the group comprising reduced forms of quinone, or alternatively an oxidizable composition comprising an activated oxygen-absorbing compound chosen from the group comprising organic antioxidants, phosphites, phosphines and organic phosphates, hydroquinone, substituted hydroquinone, sulfates, sulfites, phosphites and nitrites of metals, thiodipropinoic acid and its esters and salts, thio-bis (ethylene glycol beta-aminocrotonate) , cysteine, cystine, methionine, primary, secondary and tertiary amines and their derivatives.
- a metal salt such as a salt. earthy or
- the microcapsules have a diameter between 1 and 50 ⁇ m.
- the envelopes are produced by drying, spraying ("spray-cooling", “prilling"), by coating in molten polymers, in gel polymers, by coating in a fluidized bed. in water-soluble polymers, by phase separation (simple or complex coacervation), by elimination of solvent, polymerization, crosslinking, polycondensation, etc.
- the envelopes of the microcapsules can be hydro or liposoluble with polymers of various natures: agar, alginate, wax, collagen, polylactate, polyglycolate, gelatin, chitosan, ethyl-cellulose, carboxymethyl-cellulose, polysaccharide, polyvinyl alcohol , polyethyleneimine, vinyl acetate or mixtures thereof.
Abstract
The invention concerns a metal tube, typically made of aluminium alloy, comprising a cylindrical or truncated skirt having one open end and another end linked to a dispensing head, the inner surface of said cylindrical skirt being covered, proximate to said open end, with an adhesive annular seal. The invention is characterised in that said adhesive seal comprises an oxygen absorbing agent which is released when the tube is finally sealed. To ensure that it is released only when the tube is finally sealed, the oxygen absorbing agent can be directly incorporated in the resin used for producing the seal, in a chemical form which remains passive as long as it is not contacted with the product to be packaged. The oxygen absorbing agent can also be simply comprised in an envelope or, preferably, in a large amount of microcapsules incorporated in said resin, said envelope or said microcapsules being destroyed after the tube is filled and/or sealed.
Description
UTI LISATION DE SUBSTANCES ABSORBANT L'OXYGENE DANS LA FABRICATION DE TUBES SOUPLES USE OF OXYGEN ABSORBING SUBSTANCES IN THE MANUFACTURE OF FLEXIBLE TUBES
DOMAINE TECHNIQUETECHNICAL AREA
L' invention concerne des récipients métalliques tels que les tubes en alliage d'aluminium destinés a stocker et distribuer des produits liquides a pâteux De tels tubes présentent une excellente barrière à la diffusion des gaz et sont particulièrement aptes a contenir des produits sensibles à l 'oxydationThe invention relates to metal containers such as aluminum alloy tubes for storing and dispensing pasty liquid products. These tubes have an excellent barrier to gas diffusion and are particularly suitable for containing products sensitive to oxidation
ETAT DE LA TECHNIQUESTATE OF THE ART
Les tubes en alliage d'aluminium sont obtenus par filage par choc d'un pion I ls comportent une jupe cylindrique ou conique ayant une extrémité ouverte et une autre extrémité reliée a une tête de distribution Ladite tête de distribution, ou collet, comporte un goulot de distribution délimitant en général un orifice non encore désoperculé et une épaule rel iant le goulot a la |upe La surface intérieure du tube est recouverte d'un vernis et, a proximité de l 'extrémité ouverte, d'un joint annulaire constitue d'une résine "a base de latex", typiquement une résine adhesive a base de caoutchouc synthétique ou encore une résine de type acrylique, lesdites résines étant en suspension dans une solution aqueuseThe aluminum alloy tubes are obtained by impact spinning of a pin. They have a cylindrical or conical skirt having an open end and another end connected to a dispensing head. Said dispensing head, or collar, comprises a neck. dispensing generally delimiting an orifice not yet uncapped and a shoulder connecting the neck to the | The interior surface of the tube is covered with a varnish and, near the open end, an annular seal constitutes a "latex-based" resin, typically an adhesive resin based on synthetic rubber or an acrylic type resin, said resins being in suspension in an aqueous solution
Une fois réalisés, les tubes sont emballés tête en bas et orifice opercule et/ou obture par un bouchon puis envoyés au conditionneur Ce dernier les remplit en introduisant le produit à conditionner par l'extrémité ouverte Lorsque le remplissage est fini, la portion de la jupe proche de l'extrémité ouverte, revêtue du joint annulaire, est aplatie suivant un diamètre de telle sorte que les parties de la paroi qui se trouvent au regard l'une de l'autre puissent entrer en contact sur toute leur surface et s'accoler l'une a l'autre Cette extrémité aplatie est ensuite pliée sur elle même plusieurs fois (en général 2 ou tris plis sont réalisés) puis comprimée De la sorte, grâce au joint adhésif piégé dans les plis ainsi réalisés, on obtient un scellage final du tube grâce auquel le produit est contenu de façon
étanche dans ledit tube Suivant la matière utilisée, le joint est auto-adhésif ou thermoadhésifOnce made, the tubes are packed upside down and the orifice is sealed and / or closed by a plug and then sent to the conditioner. The latter fills them by introducing the product to be conditioned by the open end. When the filling is finished, the portion of the skirt close to the open end, coated with the annular seal, is flattened along a diameter so that the parts of the wall which are facing each other can come into contact over their entire surface and joining one to the other This flattened end is then folded on itself several times (in general 2 or three folds are produced) then compressed. In this way, thanks to the adhesive seal trapped in the folds thus produced, a seal is obtained. end of the tube by which the product is contained so waterproof in said tube Depending on the material used, the seal is self-adhesive or thermoadhesive
Jusqu'à une époque récente, une telle pratique donnait entière satisfaction puisque l'on s recherchait essentiellement une étanchéité aux liquides, pour éviter une fuite du produit contenu dans le tube A l'heure actuelle, les tubes en alliage d'aluminium sont moins utilisés pour conditionner des produits de consommation courante (de type pâte dentifrice) mais ils restent particulièrement recherches lorsqu'il s'agit de conditionner des produits sensibles a une dégradation par l'air ambiant, notamment des produits facilement w oxydables Ainsi, parmi les produits cosmétiques, on peut citer les teintures pour cheveux ou les crèmes "anti-âge" contenant des produits tels que du rétinol ou de la vitamine CUntil recently, such a practice was entirely satisfactory since we were essentially looking for liquid tightness, to avoid leakage of the product contained in the tube. At present, aluminum alloy tubes are less used to package everyday consumer products (such as toothpaste) but they are still particularly sought after when it comes to packaging products sensitive to degradation by ambient air, in particular products that are easily w oxidizable. Thus, among the products cosmetics, there may be mentioned hair dyes or "anti-aging" creams containing products such as retinol or vitamin C
Or les formulations proposées par les fabricants de cosmétiques évoluent elles sont de plus en plus efficaces mais deviennent également de plus en plus sensibles a l 'oxydationNow the formulations proposed by cosmetic manufacturers are evolving they are more and more effective but also become more and more sensitive to oxidation.
15 Le joint d'étanchéité réalisé dans les conditions décrites précédemment répondait parfaitement aux exigences d'étanchéité vis-a-vis des liquides, mais pas aux exigences plus sévères d'étanchéité aux gaz, notamment à l'oxygène On constate donc maintenant que le scellage final du tube décrit plus haut ne permet plus de préserver le produit conditionné, le produit étant immédiatement altéré par l 'oxygène contenu dans l 'air piégé 0 au cours du scellage du tube ou étant progressivement oxydé par l'air qui arrive a diffuser au travers du joint adhésif15 The seal produced under the conditions described above perfectly met the requirements for sealing with respect to liquids, but not for the more stringent requirements for sealing against gases, in particular with oxygen. final sealing of the tube described above no longer makes it possible to preserve the conditioned product, the product being immediately altered by the oxygen contained in the trapped air 0 during the sealing of the tube or being progressively oxidized by the air which arrives to diffuse through the adhesive seal
PROBLEME POSE 5PROBLEM POSE 5
La demanderesse a donc cherché a résoudre les problèmes poses par l 'apparition de ces nouveaux produits particulièrement sensibles a l 'oxydation
OBJET DE L'INVENTIONThe Applicant has therefore sought to solve the problems posed by the appearance of these new products which are particularly sensitive to oxidation. OBJECT OF THE INVENTION
L'objet selon l 'invention est un tube métallique, comportant une jupe cylindrique ou conique ayant une extrémité ouverte et une autre extrémité reliée a une tête de distribution, la surface intérieure de ladite jupe cylindrique étant recouverte, a proximité de ladite extrémité ouverte, d'un joint annulaire adhésif, caractérisé en ce que ledit joint adhésif comporte un agent absorbeur d'oxygène qui est libéré au cours du scellage final du tubeThe object according to the invention is a metal tube, comprising a cylindrical or conical skirt having an open end and another end connected to a dispensing head, the interior surface of said cylindrical skirt being covered, near said open end, an adhesive annular seal, characterized in that said adhesive seal comprises an oxygen-absorbing agent which is released during the final sealing of the tube
Le tube est métallique car sa paroi a une propriété barrière a la diffusion de l 'oxygène excellente, nettement supérieure à celle de toute paroi en matériau polyméπque De préférence, pour des raisons pratiques de mise en forme, ce tube est en alliage d'aluminium Pour absorber l 'oxygène contenu dans la poche d'air résiduel subsistant au contact du produit après le scellage du tube, la demanderesse a trouvé avantageux de libérer au voisinage de ladite poche un agent absorbeur d'oxygène contenu jusque la dans le jointThe tube is metallic because its wall has a barrier property to the diffusion of excellent oxygen, clearly superior to that of any wall made of polymeric material. Preferably, for practical reasons of shaping, this tube is made of aluminum alloy To absorb the oxygen contained in the pocket of residual air remaining in contact with the product after the sealing of the tube, the Applicant has found it advantageous to release in the vicinity of said pocket an oxygen-absorbing agent contained up to there in the joint
Pour être libéré uniquement au moment du scellage final, l 'agent absorbeur d'oxygène peut être incorporé directement dans la résine dite "à base de latex" utilisée pour la réalisation du joint, sous une forme chimique restant passive tant qu'elle n 'est pas mise en contact avec le produit à conditionner Par exemple, on peut incorporer des produits tes que ceux divulgués dans US 4 536 409 & US 4 702 966, qui, en raison de leur sensibi lité a l'humidité, deviennent réducteurs après réaction avec l 'eau contenue dans le produit avec lequel ils sont mis en contactTo be released only at the time of final sealing, the oxygen-absorbing agent can be incorporated directly into the so-called "latex-based" resin used to make the joint, in a chemical form which remains passive as long as it does not is not brought into contact with the product to be packaged. For example, it is possible to incorporate products such as those disclosed in US 4,536,409 & US 4,702,966, which, due to their sensitivity to humidity, become reducing after reaction. with the water contained in the product with which they are brought into contact
L'agent absorbeur d'oxygène peut également être simplement contenu dans une enveloppe ou, de préférence, dans une grande quantité de microcapsules incorporées dans la résine dite "à base de latex" utilisée pour la réalisation du joint, cette enveloppe ou ces microcapsules devant être détruites après le remplissage et/ou le scellage final du tube
Conditionné à l' intérieur de microcapsules, l'agent absorbeur d'oxygène est facile a mélanger dans une résine liquide telle que la résine servant à réal iser le joint d'étanchéité les microcapsules sont simplement incorporées et mélangées dans cette suspension aqueuse puis ladite résine "à base de latex" est déposée sur la paroi interne du tube lorsqu'elle est encore sous forme liquide En général, cette paroi est déjà recouverte d'une couche de vernis, en général de type époxy phénohque Le séchage de la résine "à base de latex" peut éventuellement être assuré à température ambiante (joint auto-adhésif) ou à une température supérieure (joint thermo-adhésif) Les microbilles restent piégées dans le joint durci après séchageThe oxygen-absorbing agent can also be simply contained in an envelope or, preferably, in a large quantity of microcapsules incorporated in the so-called "latex-based" resin used for making the joint, this envelope or these microcapsules in front be destroyed after filling and / or final sealing of the tube Conditioned inside microcapsules, the oxygen-absorbing agent is easy to mix in a liquid resin such that the resin used to make the seal the microcapsules are simply incorporated and mixed in this aqueous suspension then said resin "latex-based" is deposited on the inner wall of the tube when it is still in liquid form In general, this wall is already covered with a layer of varnish, generally of the phenolic epoxy type The drying of the resin "to latex base "can optionally be provided at room temperature (self-adhesive seal) or at a higher temperature (heat-adhesive seal) The microbeads remain trapped in the hardened seal after drying
On peut détruire ces microcapsules par voie mécanique en profitant des opérations nécessaires au scellage final (écrasement puis pliage des bords de l'extrémité ouverte, compression du joint final, etc ) L'enveloppe de ces microcapsules peut également être détruite - ou rendue perméable à l'oxygène - sous un autre type d'action mécanique (des ultrasons par exemple), ou encore par apport énergétique externe (apport de chaleur, radiations électromagnétiques de types micro-ondes, ultra-violets ou infra-rouges), ou encore par voie chimique (apport d'un solvant, d'eau, de lipides, pH du produit conditionné, )These microcapsules can be destroyed mechanically by taking advantage of the operations necessary for the final sealing (crushing then folding of the edges of the open end, compression of the final joint, etc.) The envelope of these microcapsules can also be destroyed - or made permeable to oxygen - under another type of mechanical action (ultrasound for example), or by external energy supply (heat supply, electromagnetic radiation of the microwave, ultra-violet or infrared types), or also by chemical route (supply of a solvent, water, lipids, pH of the packaged product,)
La substance libérée au cours du scellage final absorbe l'oxygène résiduel de la poche d'air piégée dans le récipient après remplissage du produit à conditionner et fermeture dudit récipient De préférence, cette substance est prévue en quantité suffisante pour également absorber l'oxygène susceptible de diffuser au cours de toute l'util isation du produit à travers l' interface compris entre les parties de joint aplaties, accolées et pliéesThe substance released during the final sealing absorbs the residual oxygen from the air pocket trapped in the container after filling of the product to be packaged and closing of the container. Preferably, this substance is provided in an amount sufficient to also absorb the oxygen capable to diffuse during all the use of the product through the interface between the flattened, joined and folded joint parts
Cette substance est choisie en fonction des conditions d'utilisation du produit conditionné dans le tube I I peut s'agir de tout composé oxydable compatible avec l'emploi du produit a distribuer, de la poudre de ter, un sel métallique tel qu'un sel terreux ou un sel de cobalt, un composé oxydable choisi dans le groupe regroupant des formes réduites de quinone, ou encore une composition oxydable comprenant un composé absorbeur d'oxygène activé choisi parmi le groupe regroupant des antioxydants organiques, des
phosphites, phosphines et phosphates organiques, de l'hydroquinone, de l'hydroquinone substituée, des sulfates, sulfites, phosphites et nitrites de métaux, de l 'acide thiodipropinoïque et ses esters et sels, thio-bis (ethylène glycol beta-aminocrotonate), cystéine, cystine, méthionine, des aminés primaires, secondaires et tertiaires et leurs dérivés.This substance is chosen according to the conditions of use of the product packaged in the tube. It can be any oxidizable compound compatible with the use of the product to be dispensed, ter powder, a metal salt such as a salt. earthy or a cobalt salt, an oxidizable compound chosen from the group comprising reduced forms of quinone, or alternatively an oxidizable composition comprising an activated oxygen-absorbing compound chosen from the group comprising organic antioxidants, phosphites, phosphines and organic phosphates, hydroquinone, substituted hydroquinone, sulfates, sulfites, phosphites and nitrites of metals, thiodipropinoic acid and its esters and salts, thio-bis (ethylene glycol beta-aminocrotonate) , cysteine, cystine, methionine, primary, secondary and tertiary amines and their derivatives.
Les microcapsules ont un diamètre compris entre 1 et 50 μm. Suivant la nature de l'agent absorbeur d'oxygène, les enveloppes sont réalisées par séchage, pulvérisation ("spray- cooling", "prilling"), par enrobage dans des polymères fondus, dans des polymères gél ifiés, par enrobage en lit fluidisé dans des polymères hydrosolubles, par séparation de phase (coacervation simple ou complexe), par élimination de solvant, polymérisation, réticulation, polycondensation, etc...The microcapsules have a diameter between 1 and 50 μm. Depending on the nature of the oxygen-absorbing agent, the envelopes are produced by drying, spraying ("spray-cooling", "prilling"), by coating in molten polymers, in gel polymers, by coating in a fluidized bed. in water-soluble polymers, by phase separation (simple or complex coacervation), by elimination of solvent, polymerization, crosslinking, polycondensation, etc.
Les enveloppes des microcapsules, selon leur composition, peuvent être hydro ou liposolubles avec des polymères de natures diverses: agar, alginate, cire, collagène, polylactate, polyglycolate, gélatine, chitosane, éthyle-cellulose, carboxyméthyle-cellulose, polysaccharide, alcool de polyvinyle, polyéthylène-imine, vinyle acétate ou leurs mélanges.
The envelopes of the microcapsules, depending on their composition, can be hydro or liposoluble with polymers of various natures: agar, alginate, wax, collagen, polylactate, polyglycolate, gelatin, chitosan, ethyl-cellulose, carboxymethyl-cellulose, polysaccharide, polyvinyl alcohol , polyethyleneimine, vinyl acetate or mixtures thereof.
Claims
REVENDICATIONS
1 ) Tube métallique, comportant une jupe cylindrique ou conique ayant une extrémité ouverte et une autre extrémité reliée à une tête de distribution, la surface intérieure de1) Metal tube, comprising a cylindrical or conical skirt having one open end and another end connected to a dispensing head, the inner surface of
5 ladite jupe cylindrique étant recouverte, à proximité de ladite extrémité ouverte, d'un joint annulaire adhésif, caractérisé en ce que ledit joint adhésif comporte un agent absorbeur d'oxygène qui est libéré au cours du scellage final du tube5 said cylindrical skirt being covered, near said open end, with an adhesive annular seal, characterized in that said adhesive seal comprises an oxygen-absorbing agent which is released during the final sealing of the tube
2) Tube selon la revendication 1 dans lequel ledit agent absorbeur d'oxygène est w incorporé directement dans la résine utilisée pour réaliser le joint adhésif, sous une forme chimique restant passive tant qu'elle n'est pas mise en contact avec le produit a conditionner2) Tube according to claim 1 wherein said oxygen absorbing agent is w incorporated directly into the resin used to make the adhesive joint, in a chemical form remaining passive as long as it is not brought into contact with the product a condition
3) Tube selon la revendication 1 dans lequel ledit agent absorbeur d'oxygène est contenu is dans au moins une enveloppe incorporée dans la résine utilisée pour réaliser ledit joint adhésif3) Tube according to claim 1 wherein said oxygen absorbing agent is contained is in at least one envelope incorporated in the resin used to make said adhesive joint
4) Tube selon la revendication 3 dans lequel ledit agent absorbeur d'oxygène est contenu dans des microcapsules, de diamètre compris entre 1 et 50 . m, incorporées dans la 0 résine uti l isée pour réal iser ledit joint adhésif4) Tube according to claim 3 wherein said oxygen-absorbing agent is contained in microcapsules, of diameter between 1 and 50. m, incorporated into the 0 resin used to make said adhesive joint
5) Tube selon la revendication 3 ou 4 dans lequel l'enveloppe ou les microcapsules sont choisies parmi les capsules aptes a être détruites par voie mécanique au cours du scellage final, par écrasement puis pliage des bords de l'extrémité ouverte de la jupe 55) Tube according to claim 3 or 4 wherein the envelope or the microcapsules are chosen from capsules capable of being destroyed mechanically during the final sealing, by crushing then folding of the edges of the open end of the skirt 5
6) Tube selon la revendication 3 ou 4 dans lequel l'enveloppe ou les microcapsules sont choisies parmi les capsules aptes à être détruites à l 'aide d'ultrasons6) Tube according to claim 3 or 4 wherein the envelope or the microcapsules are chosen from capsules capable of being destroyed using ultrasound
7) Tube selon la revendication 3 ou 4 dans lequel l 'enveloppe ou les microcapsules sont 0 choisies parmi les capsules aptes à être détruites ou rendues perméables a l 'oxygène
par apport énergétique externe, tel que apport de chaleur, radiations électromagnétiques de types micro-ondes, ultra-violets ou infra-rouges7) Tube according to claim 3 or 4 wherein the envelope or the microcapsules are 0 chosen from capsules capable of being destroyed or made permeable to oxygen by external energy supply, such as heat supply, electromagnetic radiation of the microwave, ultraviolet or infrared types
8) Tube selon la revendication 3 ou 4 dans lequel l'enveloppe ou les microcapsules sont choisies parmi les capsules aptes a être détruites ou rendues perméables à l'oxygène par voie chimique, telle que apport d'un solvant, d'eau, de lipides, modification due au pH du produit conditionné8) Tube according to claim 3 or 4 wherein the envelope or the microcapsules are chosen from capsules capable of being destroyed or made permeable to oxygen by chemical means, such as supply of a solvent, water, lipids, modification due to the pH of the packaged product
9) Tube selon l'une quelconque des revendications 1 à 8 dans lequel ladite substance absorbant l'oxygène est prévue en quantité suffisante pour également absorber l 'oxygène susceptible de diffuser au cours de toute l'utilisation du produit a travers l 'interface compris entre les parties de joint aplaties, accolées et pliées9) Tube according to any one of claims 1 to 8 wherein said oxygen absorbing substance is provided in an amount sufficient to also absorb oxygen capable of diffusing during the entire use of the product through the interface included between the flattened, joined and folded joint parts
1 0) Tube selon l ' une quelconque des revendications 1 a 9 dans lequel lad ite substance absorbant l 'oxygène appartient au groupe regroupant la poudre de fer, les sels métalliques tel que sel ferreux sel de cobalt, les composés oxydables choisis dans le groupe regroupant des formes réduites de quinone, ou encore les compositions oxydables comprenant un composé absorbeur d'oxygène activé choisi parmi le groupe regroupant des antioxydants organiques, des phosphites, phosphines et phosphates organiques, de l'hydroquinone, de l 'hydroquinone substituée, des sulfates, sulfites, phosphites et nitrites de métaux, de l 'acide thiodipropmoique et ses esters et sels, thio- bis (ethylène glycol beta-ammocrotonate), cystéme, cystme, méthionme, des ami nés primaires, secondaires et tertiaires et leurs dérivés1 0) Tube according to any one of claims 1 to 9 wherein the said oxygen-absorbing substance belongs to the group comprising iron powder, metal salts such as ferrous salt cobalt salt, oxidizable compounds selected from the group grouping together reduced forms of quinone, or alternatively oxidizable compositions comprising an activated oxygen-absorbing compound chosen from the group grouping together organic antioxidants, phosphites, phosphines and organic phosphates, hydroquinone, substituted hydroquinone, sulfates , sulfites, phosphites and nitrites of metals, thiodipropmoic acid and its esters and salts, thio-bis (ethylene glycol beta-ammocrotonate), cystem, cyst, methionme, primary, secondary and tertiary born friends and their derivatives
1 1 ) Tube selon l ' une quelconque des revendications 3 a 9 dans lequel l 'enveloppe ou les microcapsules sont en un matière appartenant au groupe regroupant agar, alginate, cire, col lagène, polylactate, polyglycolate, gélatine, chitosane, éthyle-cel lulose, carboxyméthyle-cel lu lose, polysacchaπde, alcool de polyvinyle, polyéthylène-imi ne, vinyle acétate ou leurs mélanges
1 1) Tube according to any one of claims 3 to 9 wherein the envelope or the microcapsules are made of a material belonging to the group comprising agar, alginate, wax, neck lagene, polylactate, polyglycolate, gelatin, chitosan, ethyl-cel lulose, carboxymethyl-cel lu lose, polysacchaπde, polyvinyl alcohol, polyethylene-imine, vinyl acetate or mixtures thereof
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02745489A EP1392573A1 (en) | 2001-06-08 | 2002-06-06 | Use of oxygen absorbing substances for making flexible tubes |
| US10/478,688 US20040206774A1 (en) | 2001-06-08 | 2002-06-06 | Use of oxygen absorbing substances for making flexible tubes |
| PL02364375A PL364375A1 (en) | 2001-06-08 | 2002-06-06 | Use of oxygen absorbing substances for making flexible tubes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0107526A FR2825689B1 (en) | 2001-06-08 | 2001-06-08 | USE OF OXYGEN ABSORBING SUBSTANCES IN THE MANUFACTURE OF FLEXIBLE TUBES |
| FR01/07526 | 2001-06-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002100733A1 true WO2002100733A1 (en) | 2002-12-19 |
Family
ID=8864105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR2002/001923 WO2002100733A1 (en) | 2001-06-08 | 2002-06-06 | Use of oxygen absorbing substances for making flexible tubes |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20040206774A1 (en) |
| EP (1) | EP1392573A1 (en) |
| CZ (1) | CZ20033297A3 (en) |
| FR (1) | FR2825689B1 (en) |
| PL (1) | PL364375A1 (en) |
| WO (1) | WO2002100733A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011101260B4 (en) * | 2011-04-01 | 2015-08-06 | Linhardt Gmbh & Co. Kg | tube package |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB869742A (en) * | 1958-03-17 | 1961-06-07 | Domestos Ltd | Squeeze container |
| US4907393A (en) * | 1987-10-16 | 1990-03-13 | Omori Machinery Co., Ltd. | Packaging method and apparatus |
| WO1996011861A1 (en) * | 1994-10-12 | 1996-04-25 | Chevron Chemical Company | Oxygen scavenging article for use in packages |
| US6089404A (en) * | 1998-05-16 | 2000-07-18 | Wella Aktiengesellschaft | Tube with a metallic casing and a label and method of making same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4776458A (en) * | 1986-08-11 | 1988-10-11 | Sashco, Inc. | Materials container |
| JPH04339772A (en) * | 1991-05-09 | 1992-11-26 | Toyo Seikan Kaisha Ltd | Container lid with liner and production thereof |
| NZ272780A (en) * | 1994-08-23 | 1998-02-26 | Grace W R & Co | Food package comprising an oxygen-sensitive article enclosed in polymeric film |
| US5628429A (en) * | 1995-11-22 | 1997-05-13 | Enamelon, Inc. | Plural chambered squeezable dispensing tube |
-
2001
- 2001-06-08 FR FR0107526A patent/FR2825689B1/en not_active Expired - Fee Related
-
2002
- 2002-06-06 US US10/478,688 patent/US20040206774A1/en not_active Abandoned
- 2002-06-06 WO PCT/FR2002/001923 patent/WO2002100733A1/en not_active Application Discontinuation
- 2002-06-06 CZ CZ20033297A patent/CZ20033297A3/en unknown
- 2002-06-06 PL PL02364375A patent/PL364375A1/en unknown
- 2002-06-06 EP EP02745489A patent/EP1392573A1/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB869742A (en) * | 1958-03-17 | 1961-06-07 | Domestos Ltd | Squeeze container |
| US4907393A (en) * | 1987-10-16 | 1990-03-13 | Omori Machinery Co., Ltd. | Packaging method and apparatus |
| WO1996011861A1 (en) * | 1994-10-12 | 1996-04-25 | Chevron Chemical Company | Oxygen scavenging article for use in packages |
| US6089404A (en) * | 1998-05-16 | 2000-07-18 | Wella Aktiengesellschaft | Tube with a metallic casing and a label and method of making same |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2825689A1 (en) | 2002-12-13 |
| US20040206774A1 (en) | 2004-10-21 |
| FR2825689B1 (en) | 2003-08-01 |
| CZ20033297A3 (en) | 2005-08-17 |
| PL364375A1 (en) | 2004-12-13 |
| EP1392573A1 (en) | 2004-03-03 |
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