US20040206774A1 - Use of oxygen absorbing substances for making flexible tubes - Google Patents
Use of oxygen absorbing substances for making flexible tubes Download PDFInfo
- Publication number
- US20040206774A1 US20040206774A1 US10/478,688 US47868804A US2004206774A1 US 20040206774 A1 US20040206774 A1 US 20040206774A1 US 47868804 A US47868804 A US 47868804A US 2004206774 A1 US2004206774 A1 US 2004206774A1
- Authority
- US
- United States
- Prior art keywords
- tube according
- oxygen
- destroyed
- microcapsules
- tube
- 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.)
- Abandoned
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000001301 oxygen Substances 0.000 title claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 30
- 239000000126 substance Substances 0.000 title claims description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- 239000006096 absorbing agent Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000003094 microcapsule Substances 0.000 claims description 14
- 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
- 150000001875 compounds 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
- 238000007906 compression Methods 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 229920001817 Agar Polymers 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 102000008186 Collagen Human genes 0.000 claims description 3
- 108010035532 Collagen Proteins 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- 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 3
- 239000001828 Gelatine Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008272 agar Substances 0.000 claims description 3
- 229940072056 alginate Drugs 0.000 claims description 3
- 235000010443 alginic acid Nutrition 0.000 claims description 3
- 229920000615 alginic acid Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229940105329 carboxymethylcellulose Drugs 0.000 claims description 3
- 229920001436 collagen Polymers 0.000 claims description 3
- 230000005670 electromagnetic radiation Effects 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 229960004667 ethyl cellulose Drugs 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- -1 polyethylene-imine Chemical compound 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- UKVYVZLTGQVOPX-IHWYPQMZSA-N (z)-3-aminobut-2-enoic acid Chemical compound C\C(N)=C\C(O)=O UKVYVZLTGQVOPX-IHWYPQMZSA-N 0.000 claims description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 2
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 235000006708 antioxidants Nutrition 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- 229960003067 cystine Drugs 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229930182817 methionine Natural products 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
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000002775 capsule Substances 0.000 claims 8
- 238000012986 modification Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 6
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000003570 air Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002966 varnish Substances 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
- 239000002537 cosmetic Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 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
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005354 coacervation Methods 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 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
- 239000000118 hair dye Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 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
- 239000007921 spray Substances 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
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 metallic receptacles such as aluminium alloy tubes designed for storage and distribution of liquid to pasty products. These tubes form an excellent barrier to gas diffusion and are particularly suitable for containing products sensitive to oxidation.
- Aluminium alloy tubes are obtained by impact extrusion of a slug. They comprise a cylindrical or truncated skirt with one open end and one end connected to a dispensing head.
- the said dispensing head or collar comprises a distribution neck generally delimiting an orifice that has not yet been opened and a shoulder connecting the neck to the skirt.
- the inner surface of the tube is covered by a varnish and an annular seal near the open end composed of a “latex based” resin, typically an adhesive resin based on synthetic rubber or an acrylic type resin, the said resins being in suspension in an aqueous solution.
- the tubes are packaged upside down with the orifice sealed and/or closed off by a cap and then sent to the packager.
- the packager fills them by delivering the product to be packaged through the open end.
- the portion of the skirt close to the open end fitted with the annular seal is flattened along a diameter such that the parts of the wall facing each other can come into contact over their entire surface and be adjacent to each other.
- This flattened end is then folded over itself several times (usually 2 or 3 folds are made) and then compressed. Consequently, due to the adhesive seal trapped in the folds thus formed, the tube containing the product is finally sealed so as to make the said tube leak tight.
- the seal is self-adhesive or thermo-adhesive depending on the material used.
- the purpose of the invention is a metal tube comprising a cylindrical or truncated skirt having one open end and another end connected to a dispensing head, the inner surface of the said cylindrical skirt being covered with an adhesive annular seal close to the said open end, characterised in that the said adhesive seal comprises an oxygen absorbing agent that is released when the tube is finally sealed.
- the tube is metallic because its wall has an excellent barrier property to oxygen diffusion, significantly better than is possible with a wall made of a polymer material.
- this tube will be an aluminium alloy, for practical shaping reasons.
- the Applicant has found that it is advantageous to release an oxygen absorbing agent previously contained in the seal close to the said pocket, to absorb oxygen contained in the residual air pocket remaining in contact with the product after the tube is sealed.
- the oxygen absorbing agent may be incorporated directly into the “latex based” resin from which the seal is made, in the form of a chemical that remains passive until it is brought into contact with the product to be packaged.
- the oxygen absorbing agent may be incorporated directly into the “latex based” resin from which the seal is made, in the form of a chemical that remains passive until it is brought into contact with the product to be packaged.
- products like those described in U.S. Pat. No. 4,536,409 & U.S. Pat. No. 4,702,966 can be incorporated, which become reducing after reaction with water contained in the product with which they come into contact due to their sensitivity to humidity.
- the oxygen absorbing agent can also be simply included in an envelope, or preferably in a large number of microcapsules incorporated in the said “latex based” resin used to make the seal, this envelope or these microcapsules being destroyed after the tube is filled and/or finally sealed.
- the oxygen absorbing agent is packaged inside the microcapsules and is easy to mix in a liquid resin such as the resin used to make the seal.
- a liquid resin such as the resin used to make the seal.
- the microcapsules are simply incorporated and mixed in this aqueous suspension, then the said “latex based” resin is deposited on the internal wall of the tube when it is still in the liquid form. In general, this wall is already covered with a layer of varnish, usually a phenol epoxy type varnish.
- the “latex based” resin may possibly be dried at ambient temperature (self-adhesive seal) or at a high temperature (thermal adhesive seal). The microballs remain trapped in the hardened seal after drying.
- microcapsules may be destroyed mechanically, taking advantage of the operations necessary for the final seal (compression and then folding of the edges of the open end, compression of the final seal, etc).
- the envelope of these microcapsules can also be destroyed (or made permeable to oxygen) for example using a different type of mechanical action (for example ultrasound) or by adding external energy (addition of heat, electromagnetic radiation such as microwaves, ultraviolet or infrared radiation) or by a chemical method (addition of a solvent, water, lipids, pH of the packaged product, etc.).
- the substance released during final sealing absorbs residual oxygen in the air pocket trapped in the receptacle after filling with the product to be packaged and after closing the said receptacle.
- this substance is provided in a sufficiently large quantity so that it can also absorb any oxygen that diffuses through the interface between the flattened, glued or folded parts of the seal while the product is being used.
- This substance is chosen as a function of usage conditions of the product packaged in the tube. It may be any oxidisable compound compatible with use of the product to be distributed such as iron powder, a metallic salt such as a ferrous salt or a cobalt salt, an oxidisable compound chosen from the group containing reduced forms of quinone, or an oxidisable composition comprising an active oxygen absorbing compound chosen from among the group containing organic anti-oxidants, phosphites, phosphines and organic phosphates, hydroquinone, substituted hydroquinone, sulphates, sulphites, phosphites and metal nitrites, thiodipropinoic acid and its esters and salts, thio-bis (ethylene glycol beta-aminocrotonate), cysteine, cystine, methionine, primary, secondary and tertiary amines and derivatives of them.
- the diameter of the microcapsules varies between 1 and 50 ⁇ m.
- the envelopes are made by drying, spray cooling, prilling), are coated with molten polymers, gelified polymers, hydrosoluble polymers in a fluidised bed, by phase separation (simple or complex coacervation), by solvent elimination, polymerisation, cross linking, polycondensation, etc.
- microcapsule envelopes may be hydro or liposoluble with various natures of polymers such as agar, alginate, wax, collagen, polylactate, polyglycolate, gelatine, chitosane, ethyl-cellulose, carboxymethyl-cellulose, polysaccharide, polyvinyl alcohol, polyethylene-imine, vinyl acetate and mixes thereof.
- polymers such as agar, alginate, wax, collagen, polylactate, polyglycolate, gelatine, chitosane, ethyl-cellulose, carboxymethyl-cellulose, polysaccharide, polyvinyl alcohol, polyethylene-imine, vinyl acetate and mixes thereof.
Abstract
A metal tube for storing and distributing liquids, the tubes typically being manufactured of an aluminum alloy, comprising a cylindrical or truncated skirt having one end and another end linked to a dispensing head, the inner surface of the cylindrical skirt being covered, proximate to the open end, with an adhesive annular seal; and wherein the adhesive seal comprises an oxygen absorbing agent that is released when the tube is finally sealed; and wherein the oxygen absorbing agent is directly incorporated in the resin used for producing the seal to ensure that the oxygen absorbing agent is released only when the tube is finally sealed.
Description
- The invention relates to metallic receptacles such as aluminium alloy tubes designed for storage and distribution of liquid to pasty products. These tubes form an excellent barrier to gas diffusion and are particularly suitable for containing products sensitive to oxidation.
- Aluminium alloy tubes are obtained by impact extrusion of a slug. They comprise a cylindrical or truncated skirt with one open end and one end connected to a dispensing head. The said dispensing head or collar comprises a distribution neck generally delimiting an orifice that has not yet been opened and a shoulder connecting the neck to the skirt. The inner surface of the tube is covered by a varnish and an annular seal near the open end composed of a “latex based” resin, typically an adhesive resin based on synthetic rubber or an acrylic type resin, the said resins being in suspension in an aqueous solution.
- Once made, the tubes are packaged upside down with the orifice sealed and/or closed off by a cap and then sent to the packager. The packager fills them by delivering the product to be packaged through the open end. When filling is complete, the portion of the skirt close to the open end fitted with the annular seal is flattened along a diameter such that the parts of the wall facing each other can come into contact over their entire surface and be adjacent to each other. This flattened end is then folded over itself several times (usually 2 or 3 folds are made) and then compressed. Consequently, due to the adhesive seal trapped in the folds thus formed, the tube containing the product is finally sealed so as to make the said tube leak tight. The seal is self-adhesive or thermo-adhesive depending on the material used.
- Until recently, this type of practice was fully satisfactory because the essential requirement was leak tightness to liquids to prevent a product contained in the tube from leaking. At the moment, aluminium alloy tubes are less frequently used for packaging products for daily consumption (such as toothpaste), but they are still particularly in demand for packaging products sensitive to degradation by ambient air, and particularly easily oxidisable products. Thus, cosmetics for which the invention is applicable include hair dyes and anti-aging creams, containing products such as retinol or vitamin C.
- Formulations offered by cosmetics manufacturers are changing: they are becoming more and more efficient but they are also becoming more and more sensitive to oxidation. Under the conditions described above, the seal is perfectly satisfactory for leak tightness requirements for liquids, but not for more severe gas tightness requirements, particularly for oxygen. Therefore, it is found that the final sealing of the tube described above is no longer sufficient to preserve the packaged product, since the product is immediately oxidised by oxygen in the air trapped when the tube is being sealed or gradually oxidised by air that diffuses through the adhesive seal.
- Therefore, the Applicant attempted to solve the problems that arise due to the appearance of these new products particularly sensitive to oxidation.
- The purpose of the invention is a metal tube comprising a cylindrical or truncated skirt having one open end and another end connected to a dispensing head, the inner surface of the said cylindrical skirt being covered with an adhesive annular seal close to the said open end, characterised in that the said adhesive seal comprises an oxygen absorbing agent that is released when the tube is finally sealed.
- The tube is metallic because its wall has an excellent barrier property to oxygen diffusion, significantly better than is possible with a wall made of a polymer material. Preferably, this tube will be an aluminium alloy, for practical shaping reasons. The Applicant has found that it is advantageous to release an oxygen absorbing agent previously contained in the seal close to the said pocket, to absorb oxygen contained in the residual air pocket remaining in contact with the product after the tube is sealed.
- In order to be released only at the time of the final seal, the oxygen absorbing agent may be incorporated directly into the “latex based” resin from which the seal is made, in the form of a chemical that remains passive until it is brought into contact with the product to be packaged. For example, products like those described in U.S. Pat. No. 4,536,409 & U.S. Pat. No. 4,702,966 can be incorporated, which become reducing after reaction with water contained in the product with which they come into contact due to their sensitivity to humidity.
- The oxygen absorbing agent can also be simply included in an envelope, or preferably in a large number of microcapsules incorporated in the said “latex based” resin used to make the seal, this envelope or these microcapsules being destroyed after the tube is filled and/or finally sealed.
- The oxygen absorbing agent is packaged inside the microcapsules and is easy to mix in a liquid resin such as the resin used to make the seal. The microcapsules are simply incorporated and mixed in this aqueous suspension, then the said “latex based” resin is deposited on the internal wall of the tube when it is still in the liquid form. In general, this wall is already covered with a layer of varnish, usually a phenol epoxy type varnish. The “latex based” resin may possibly be dried at ambient temperature (self-adhesive seal) or at a high temperature (thermal adhesive seal). The microballs remain trapped in the hardened seal after drying.
- These microcapsules may be destroyed mechanically, taking advantage of the operations necessary for the final seal (compression and then folding of the edges of the open end, compression of the final seal, etc). The envelope of these microcapsules can also be destroyed (or made permeable to oxygen) for example using a different type of mechanical action (for example ultrasound) or by adding external energy (addition of heat, electromagnetic radiation such as microwaves, ultraviolet or infrared radiation) or by a chemical method (addition of a solvent, water, lipids, pH of the packaged product, etc.).
- The substance released during final sealing absorbs residual oxygen in the air pocket trapped in the receptacle after filling with the product to be packaged and after closing the said receptacle. Preferably, this substance is provided in a sufficiently large quantity so that it can also absorb any oxygen that diffuses through the interface between the flattened, glued or folded parts of the seal while the product is being used.
- This substance is chosen as a function of usage conditions of the product packaged in the tube. It may be any oxidisable compound compatible with use of the product to be distributed such as iron powder, a metallic salt such as a ferrous salt or a cobalt salt, an oxidisable compound chosen from the group containing reduced forms of quinone, or an oxidisable composition comprising an active oxygen absorbing compound chosen from among the group containing organic anti-oxidants, phosphites, phosphines and organic phosphates, hydroquinone, substituted hydroquinone, sulphates, sulphites, phosphites and metal nitrites, thiodipropinoic acid and its esters and salts, thio-bis (ethylene glycol beta-aminocrotonate), cysteine, cystine, methionine, primary, secondary and tertiary amines and derivatives of them.
- The diameter of the microcapsules varies between 1 and 50 μm. Depending on the nature of the oxygen absorbing agent, the envelopes are made by drying, spray cooling, prilling), are coated with molten polymers, gelified polymers, hydrosoluble polymers in a fluidised bed, by phase separation (simple or complex coacervation), by solvent elimination, polymerisation, cross linking, polycondensation, etc.
- Depending on their composition, microcapsule envelopes may be hydro or liposoluble with various natures of polymers such as agar, alginate, wax, collagen, polylactate, polyglycolate, gelatine, chitosane, ethyl-cellulose, carboxymethyl-cellulose, polysaccharide, polyvinyl alcohol, polyethylene-imine, vinyl acetate and mixes thereof.
Claims (16)
1. Metallic tube comprising a cylindrical or truncated skirt with one open end and one end connected to a dispensing head, the inner surface of the said cylindrical skirt being covered by an annular adhesive seal near the said open end, characterised in that the said adhesive seal comprises an oxygen absorbing agent that is released when the tube is finally sealed.
2. Tube according to claim 1 , in which the oxygen absorbing agent is incorporated directly into the resin used to make the adhesive seal, in the form of a chemical that remains passive until it is brought into contact with the product to be packaged.
3. Tube according to claim 1 , in which the oxygen absorbing agent is included in at least one envelope incorporated in the resin used to make the said adhesive seal.
4. Tube according to claim 3 , in which the oxygen absorbing agent is included in microcapsules with diameter varying between 1 and 50 μm, and incorporated in the resin used to make the said adhesive seal.
5. Tube according to claim 3 , in which the envelope is selected from capsules capable of being destroyed mechanically during final sealing, by compression and then folding of the edges of the open end of the skirt.
6. Tube according to claim 3 , in which the envelope is selected from capsules capable of being destroyed using ultrasound.
7. Tube according to claim 3 , in which the envelope is selected from capsules capable of being destroyed or made permeable to oxygen by adding external energy, such as heat, electromagnetic radiation such as microwaves, ultraviolet or infrared radiation.
8. Tube according to claim 3 , in which the envelope is selected from capsules capable of being destroyed or made permeable to oxygen by a chemical method, such as addition of a solvent, water, lipids, modification due to the pH of the packaged product.
9. Tube according to claim 1 , in which the said substance absorbing the oxygen is provided in a sufficiently large quantity so that it can also absorb any oxygen that diffuses through the interface between the flattened, glued or folded parts of the seal while the product is being used.
10. Tube according to claim 1 , in which the said substance absorbing the oxygen belongs to the group containing iron powder, metallic salts such as a ferrous salt or a cobalt salt, oxidisable compounds chosen from the group containing reduced forms of quinone, or oxidisable compositions comprising an active oxygen absorbing compound chosen from among the group containing organic anti-oxidants, phosphites, phosphines and organic phosphates, hydroquinone, substituted hydroquinone, sulphates, sulphites, phosphites and metal nitrites, thiodipropinoic acid and its esters and salts, thio-bis (ethylene glycol beta-aminocrotonate), cysteine, cystine, methionine, primary, secondary and tertiary amines and derivatives thereof.
11. Tube according to claim 3 , in which the envelope is made of a material belonging to the group containing agar, alginate, wax, collagen, polylactate, polyglycolate, gelatine, chitosane, ethyl-cellulose, carboxymethyl-cellulose, polysaccharide, polyvinyl alcohol, polyethylene-imine, vinyl acetate and mixes thereof.
12. Tube according to claim 4 , in which the microcapsules are selected from capsules capable of being destroyed mechanically during final sealing, by compression and then folding of the edges of the open end of the skirt.
13. Tube according to claim 4 , in which the microcapsules are selected from capsules capable of being destroyed using ultrasound.
14. Tube according to claim 4 , in which the microcapsules are selected from capsules capable of being destroyed or made permeable to oxygen by adding external energy, such as heat, electromagnetic radiation such as microwaves, ultraviolet or infrared radiation.
15. Tube according to claim 4 , in which the microcapsules are selected from capsules capable of being destroyed or made permeable to oxygen by a chemical method, such as addition of a solvent, water, lipids, modification due to the pH of the packaged product.
16. Tube according to claim 4 , in which the microcapsules are made of a material belonging to the group containing agar, alginate, wax, collagen, polylactate, polyglycolate, gelatine, chitosane, ethyl-cellulose, carboxymethyl-cellulose, polysaccharide, polyvinyl alcohol, polyethylene-imine, vinyl acetate and mixes thereof.
Applications Claiming Priority (3)
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 |
FR0107526 | 2001-06-08 | ||
PCT/FR2002/001923 WO2002100733A1 (en) | 2001-06-08 | 2002-06-06 | Use of oxygen absorbing substances for making flexible tubes |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040206774A1 true US20040206774A1 (en) | 2004-10-21 |
Family
ID=8864105
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/478,688 Abandoned US20040206774A1 (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 (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863014A (en) * | 1986-08-11 | 1989-09-05 | Sashco, Inc. | Transparent building industry product with collapsible tube |
US4907393A (en) * | 1987-10-16 | 1990-03-13 | Omori Machinery Co., Ltd. | Packaging method and apparatus |
US5381914A (en) * | 1991-05-09 | 1995-01-17 | Toyo Seikan Kaisha, Ltd. | Container closure with liner |
US5628429A (en) * | 1995-11-22 | 1997-05-13 | Enamelon, Inc. | Plural chambered squeezable dispensing tube |
US5896994A (en) * | 1994-08-23 | 1999-04-27 | W. R. Grace & Co.-Conn. | Sealed article |
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 (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB869742A (en) * | 1958-03-17 | 1961-06-07 | Domestos Ltd | Squeeze container |
WO1996011861A1 (en) * | 1994-10-12 | 1996-04-25 | Chevron Chemical Company | Oxygen scavenging article for use in packages |
-
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 (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863014A (en) * | 1986-08-11 | 1989-09-05 | Sashco, Inc. | Transparent building industry product with collapsible tube |
US4863014B1 (en) * | 1986-08-11 | 1994-06-07 | Sashco Inc | Transparent building industry product with collapsible tube |
US4907393A (en) * | 1987-10-16 | 1990-03-13 | Omori Machinery Co., Ltd. | Packaging method and apparatus |
US5381914A (en) * | 1991-05-09 | 1995-01-17 | Toyo Seikan Kaisha, Ltd. | Container closure with liner |
US5896994A (en) * | 1994-08-23 | 1999-04-27 | W. R. Grace & Co.-Conn. | Sealed article |
US5628429A (en) * | 1995-11-22 | 1997-05-13 | Enamelon, Inc. | Plural chambered squeezable dispensing tube |
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 |
WO2002100733A1 (en) | 2002-12-19 |
FR2825689B1 (en) | 2003-08-01 |
CZ20033297A3 (en) | 2005-08-17 |
PL364375A1 (en) | 2004-12-13 |
EP1392573A1 (en) | 2004-03-03 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CEBAL SAS, FRANCE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:JUPIN, ALAIN;REEL/FRAME:014849/0492 Effective date: 20031210 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |