EP0322650A1 - Process for bleaching and sterilising cork articles, and cork articles bleached by said process - Google Patents
Process for bleaching and sterilising cork articles, and cork articles bleached by said process Download PDFInfo
- Publication number
- EP0322650A1 EP0322650A1 EP88120920A EP88120920A EP0322650A1 EP 0322650 A1 EP0322650 A1 EP 0322650A1 EP 88120920 A EP88120920 A EP 88120920A EP 88120920 A EP88120920 A EP 88120920A EP 0322650 A1 EP0322650 A1 EP 0322650A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen peroxide
- articles
- cork
- solution
- peroxide solution
- 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.)
- Granted
Links
- 239000007799 cork Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 49
- 238000004061 bleaching Methods 0.000 title claims description 13
- 230000001954 sterilising effect Effects 0.000 title description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000001035 drying Methods 0.000 claims abstract description 26
- 230000005855 radiation Effects 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003381 stabilizer Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 235000014101 wine Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical class [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019987 cider Nutrition 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
- B67B—APPLYING CLOSURE MEMBERS TO BOTTLES JARS, OR SIMILAR CONTAINERS; OPENING CLOSED CONTAINERS
- B67B1/00—Closing bottles, jars or similar containers by applying stoppers
- B67B1/03—Pretreatment of stoppers, e.g. cleaning, steaming, heating, impregnating or coating; Applying resilient rings to stoppers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/20—Compounds of alkali metals or ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/003—Treating of wood not provided for in groups B27K1/00, B27K3/00 by using electromagnetic radiation or mechanical waves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/02—Staining or dyeing wood; Bleaching wood
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/04—Combined bleaching or impregnating and drying of wood
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K7/00—Chemical or physical treatment of cork
Definitions
- An interesting technique for bringing cork articles into contact with the hydrogen peroxide solution consists in placing the articles in a basket with an openwork or porous wall, hanging the basket above the hydrogen peroxide solution containing a surfactant with high foaming power, then blowing air into the hydrogen peroxide solution so as to cause the formation of an upward flow of foam which reaches the items in the basket.
- the concentration of surfactant, the temperature of the solution and the flow rate of the blown air are adjusted so that, in stationary operating conditions, the flow of foam overflows the basket containing the cork articles, then breaks and falls back into the solution.
- This technique has the advantage of consuming less energy than the techniques already described for immersing or watering the articles to be treated. It also makes it unnecessary to use anti-foaming agents which are often necessary with other techniques.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Detergent Compositions (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
- Packages (AREA)
- Gloves (AREA)
Abstract
On blanchit des articles en liège par traitement au moyen d'une solution aqueuse alcaline de peroxyde d'hydrogène et séchage des articles, imprégnés de peroxyde d'hydrogène, en présence d'un rayonnement ultraviolet.Cork articles are bleached by treatment with an alkaline aqueous solution of hydrogen peroxide and drying of the articles, impregnated with hydrogen peroxide, in the presence of ultraviolet radiation.
Description
La présente invention concerne un procédé de blanchiment et de stérilisation d'articles en liège au moyen d'une solution aqueuse de peroxyde d'hydrogène.The present invention relates to a process for bleaching and sterilizing cork articles using an aqueous solution of hydrogen peroxide.
Il est connu depuis de nombreuses années de blanchir et de stériliser les articles en liège au moyen de solutions aqueuses alcalines d'hypochlorite. De tels procédés présentent parfois l'inconvénient de fournir des articles en liège qui renferment encore, même après lavage, de petites quantités de chlore sous forme de composés organiques. Ces composés peuvent être la cause d'odeurs désagréables et dénaturer le goût des matières alimentaires qui sont mises en contact avec les articles ainsi blanchis. Pour remédier à ces inconvénients, on a proposé de blanchir les articles en liège avec du peroxyde d'hydrogène, dans le but d'éliminer la formation des composés organiques chlorés. La demande de brevet français FR-A1-2569369 fournit un procédé de blanchiment d'articles en liège en quatre étapes consistant, dans une première étape, à traiter les articles par une solution aqueuse contenant du peroxyde d'hydrogène, un stabilisant de celui-ci et une substance alcaline, dans une deuxième étape, à laver les articles à l'eau, dans une troisième étape, à traiter les articles par une solution aqueuse d'une substance acide et, dans une quatrième étape, à sécher les articles. Ce procédé apporte toutefois le désavantage de nécessiter un traitement complexe en de multiples étapes mettant en oeuvre des solutions acide et basique et de ne pas permettre de blanchir les articles en liège à un niveau de blancheur suffisamment élevé requis par la plupart des utilisations de ces articles.It has been known for many years to bleach and sterilize cork articles with aqueous alkaline hypochlorite solutions. Such methods sometimes have the disadvantage of providing cork articles which still contain, even after washing, small amounts of chlorine in the form of organic compounds. These compounds can be the cause of unpleasant odors and distort the taste of food materials which are brought into contact with the articles thus bleached. To overcome these drawbacks, it has been proposed to whiten cork articles with hydrogen peroxide, in order to eliminate the formation of chlorinated organic compounds. French patent application FR-A1-2569369 provides a process for bleaching cork articles in four stages consisting, in a first stage, in treating the articles with an aqueous solution containing hydrogen peroxide, a stabilizer thereof. ci and an alkaline substance, in a second step, washing the articles with water, in a third step, treating the articles with an aqueous solution of an acidic substance and, in a fourth step, drying the articles. However, this method has the disadvantage of requiring complex treatment in multiple stages using acidic and basic solutions and of not allowing the cork articles to be bleached at a sufficiently high level of whiteness required by most uses of these articles. .
L'invention remédie à ces inconvénients des procédés connus en fournissant un procédé nouveau de blanchiment et de stérilisation d'articles en liège à l'aide d'une solution aqueuse de peroxyde d'hydrogène qui permet d'obtenir des blancheurs élevées et qui ne nécessite pas d'étapes intermédiaires de traitement des articles entre l'étape de blanchiment et l'étape de séchage.The invention overcomes these disadvantages of known methods by providing a new method of bleaching and sterilization of cork articles using an aqueous solution of hydrogen peroxide which makes it possible to obtain high whiteness and which does not require intermediate stages of treatment of the articles between the bleaching stage and the drying step.
A cet effet, l'invention concerne un procédé pour blanchir et stériliser des articles en liège au moyen d'une solution aqueuse alcaline de peroxyde d'hydrogène selon lequel, après traitement des articles par la solution de peroxyde d'hydrogène, on sèche les articles, imprégnés de peroxyde d'hydrogène, en présence d'un rayonnement ultraviolet.To this end, the invention relates to a process for bleaching and sterilizing cork articles by means of an aqueous alkaline solution of hydrogen peroxide, according to which, after treatment of the articles with the hydrogen peroxide solution, the articles, impregnated with hydrogen peroxide, in the presence of ultraviolet radiation.
Les articles en liège auxquels s'applique le procédé selon l'invention sont d'une manière indifférente, des objets décoratifs ou utilitaires constitués, au moins pour la majeure partie de leur structure, du produit naturel qu'est le liège fourni par l'écorce des chênes-lièges.The cork articles to which the process according to the invention applies are indifferently decorative or utilitarian objects made up, at least for the major part of their structure, of the natural product that is the cork supplied by the bark of cork oaks.
Par solution aqueuse alcaline de peroxyde d'hydrogène, on entend désigner une solution aqueuse qui contient au moins une substance alcaline et du peroxyde d'hydrogène. En général, des solutions qui contiennent de 10 à 300 g H₂O₂ par litre conviennent bien pour la mise en oeuvre du procédé selon l'invention. De manière avantageuse, on utilise des solutions qui contiennent de 30 à 150 g H₂O₂ par litre.By alkaline aqueous solution of hydrogen peroxide is meant an aqueous solution which contains at least one alkaline substance and hydrogen peroxide. In general, solutions which contain from 10 to 300 g of H₂O₂ per liter are very suitable for carrying out the process according to the invention. Advantageously, solutions are used which contain from 30 to 150 g H₂O₂ per liter.
La substance alcaline mise en oeuvre dans la solution aqueuse est un composé chimique inorganique susceptible de fixer le pH de la solution dans la zone alcaline supérieure à 8,5 lorsqu'on le dissout dans l'eau. On peut mettre en oeuvre un de ces composés seul; on peut aussi incorporer à la solution plusieurs de ces composés en mélange. Les mélanges tampons de substances alcalines peuvent, par exemple, être utilisés.The alkaline substance used in the aqueous solution is an inorganic chemical compound capable of fixing the pH of the solution in the alkaline zone greater than 8.5 when it is dissolved in water. One of these compounds can be used alone; it is also possible to incorporate several of these compounds as a mixture into the solution. Buffer mixtures of alkaline substances can, for example, be used.
On choisira avantageusement la dose de substance alcaline à incorporer à la solution de peroxyde d'hydrogène de manière que le pH de la solution s'établisse dans la plage comprise entre 9,0 et 10,5.The dose of alkaline substance to be incorporated into the hydrogen peroxide solution is advantageously chosen so that the pH of the solution is established in the range between 9.0 and 10.5.
Des substances alcalines qui ont donné de bons résultats sont l'hydroxyde, le carbonate et les phosphates de métaux alcalins utilisés séparément ou en mélange. Les meilleurs résultats ont été obtenus avec l'hydroxyde de sodium utilisé à raison de 2 à 20 g/l de solution de peroxyde d'hydrogène ou avec le carbonate de sodium à raison de 5 à 50 g/l de solution.Alkaline substances that have worked well are the hydroxide, carbonate and phosphates of alkali metals used separately or as a mixture. The best results have been obtained with sodium hydroxide used at a rate of 2 to 20 g / l of hydrogen peroxide solution or with sodium carbonate at a rate of 5 to 50 g / l of solution.
Selon l'invention, la solution aqueuse de peroxyde d'hydrogène peut aussi contenir un ou plusieurs additifs habituellement utilisés dans les solutions de blanchiment, tels que, par exemple, des stabilisants du peroxyde d'hydrogène, des agents tensio-actifs, des agents d'azurage optique, des régulateurs de viscosité ou de pH, des agents anti-corrosion, des agents protecteurs du liège.According to the invention, the aqueous solution of hydrogen peroxide may also contain one or more additives usually used in bleaching solutions, such as, for example, stabilizers of hydrogen peroxide, surfactants, agents optical brightening, viscosity or pH regulators, anti-corrosion agents, cork protecting agents.
Dans le procédé selon l'invention, il est avantageux de mettre en oeuvre un stabilisant dans la solution de peroxyde d'hydrogène.In the process according to the invention, it is advantageous to use a stabilizer in the hydrogen peroxide solution.
A titre de stabilisant, on peut incorporer à la solution de peroxyde d'hydrogène toute espèce de stabilisant connu pour prévenir la décomposition prématurée du peroxyde d'hydrogène en oxygène et en eau. Des exemples de tels stabilisants sont le silicate de sodium, les polyphosphates de métaux alcalins, les stabilisants organiques appartenant à la classe des polyphosphonates ou à celle des acides aminopolycarboxyliques et leurs sels. Le silicate de sodium, utilisé à raison de 2 à 50 g/l de solution, a donné de bons résultats et est préféré en raison de sa grande disponibilité et de son prix peu élevé.As a stabilizer, any kind of stabilizer known to prevent premature decomposition of hydrogen peroxide into oxygen and water can be incorporated into the hydrogen peroxide solution. Examples of such stabilizers are sodium silicate, polyphosphates of alkali metals, organic stabilizers belonging to the class of polyphosphonates or to that of aminopolycarboxylic acids and their salts. Sodium silicate, used in an amount of 2 to 50 g / l of solution, has given good results and is preferred because of its high availability and its low price.
L'emploi d'un agent tensio-actif dans la solution de peroxyde d'hydrogène utilisée conformément à l'invention se révèle souvent utile pour améliorer l'imprégnation des articles en liège avec la solution de peroxyde d'hydrogène. A cette fin, il est souhaitable d'utiliser un agent tensio-actif qui soit inerte vis-à-vis du peroxyde d'hydrogène présent dans la solution aqueuse alcaline. Des agents tensio-actifs conformes à ce souhait appartiennent généralement aux classes des tensio-actifs anioniques, ou non ioniques tels que, par exemple, les alcools polyalkoxylés à chaîne carbonée linéaire.The use of a surfactant in the hydrogen peroxide solution used in accordance with the invention often proves useful to improve the impregnation of cork articles with the hydrogen peroxide solution. To this end, it is desirable to use a surfactant which is inert with respect to the hydrogen peroxide present in the alkaline aqueous solution. Surfactants according to this wish generally belong to the classes of surfactants anionic, or nonionic such as, for example, polyalkoxylated alcohols with a linear carbon chain.
Le procédé de blanchiment selon l'invention comprend deux étapes successives : une première étape consistant à traiter les articles en liège par la solution aqueuse de peroxyde d'hydrogène et une deuxième étape consistant à sécher les articles traités à la première étape.The bleaching process according to the invention comprises two successive stages: a first stage consisting in treating the cork articles with the aqueous solution of hydrogen peroxide and a second stage consisting in drying the articles treated in the first stage.
Dans le procédé selon l'invention, l'étape de séchage est effectuée par tout moyen ou appareil de séchage connu tel que le séchage à l'air chaud en étuve ventilée, le séchage par exposition au rayonnement infrarouge ou le séchage sous vide partiel.In the method according to the invention, the drying step is carried out by any known drying means or apparatus such as drying with hot air in a ventilated oven, drying by exposure to infrared radiation or drying under partial vacuum.
La durée et la température du séchage ne sont en général pas critiques. Elles dépendent de la technique de séchage choisie, de la porosité de surface des articles en liège et de la puissance de l'irradiation UV. Elles peuvent se déterminer aisément par une expérimentation de laboratoire à la portée de l'homme du métier. Des durées de séchage comprises entre 2 et 10 heures et des températures situées dans la plage de 15 à 95°c conviennent généralement bien lorsque le séchage est effectué à pression atmosphérique.The drying time and temperature are generally not critical. They depend on the drying technique chosen, the surface porosity of the cork articles and the power of UV irradiation. They can be easily determined by laboratory experimentation within the reach of the skilled person. Drying times between 2 and 10 hours and temperatures in the range of 15 to 95 ° C are generally suitable when drying is carried out at atmospheric pressure.
Selon l'invention, le séchage est exécuté sur des articles en liège imprégnés de peroxyde d'hydrogène et en présence d'un rayonnement ultraviolet.According to the invention, the drying is carried out on cork articles impregnated with hydrogen peroxide and in the presence of ultraviolet radiation.
A cet effet, conformément à l'invention, il est recommandé de ne pas soumettre les articles en liège à un lavage intensif entre l'étape de traitement avec la solution de peroxyde d'hydrogène et l'étape de séchage. La procédure qui est généralement préférée consiste à soumettre les articles en liège à un simple égouttage entre ces deux étapes, en évitant expressément de les laver, même partiellement.To this end, in accordance with the invention, it is recommended not to subject the cork articles to intensive washing between the treatment step with the hydrogen peroxide solution and the drying step. The procedure which is generally preferred consists in subjecting the cork articles to a simple draining between these two stages, by expressly avoiding washing them, even partially.
Il est généralement avantageux que les articles en liège contiennent encore plus de 0,05 g H₂O₂/100 g de liège et, de préférence, plus de 0,10 g H₂O₂/100 g de liège lorsque débute l'exposition au rayonnement UV dans l'étape de séchage. Il n'y a en principe pas de limite supérieure à la quantité de peroxyde d'hydrogène imprégnant les bouchons. En pratique, des quantités comprises entre 0,1 et 1 g/100 g conviennent dans la majorité des cas.It is generally advantageous for the cork articles to still contain more than 0.05 g H₂O₂ / 100 g of cork and, preferably, more than 0.10 g H₂O₂ / 100 g of cork when exposure to UV radiation begins. 'drying step. In principle there is no upper limit on the amount of peroxide of hydrogen permeating the plugs. In practice, amounts between 0.1 and 1 g / 100 g are suitable in the majority of cases.
Par rayonnement ultraviolet, on entend désigner un rayonnement électro-magnétique dont la longueur d'onde est comprise dans la plage commençant à 200 nm et se terminant à 350 nm et dont la puissance est au minimum de 5 watts. Ce rayonnement est obtenue au moyen de lampes électriques à vapeur métallique bien connues dans l'industrie, notamment dans les techniques de désinfection.By ultraviolet radiation is meant an electromagnetic radiation whose wavelength is in the range starting at 200 nm and ending at 350 nm and whose power is at least 5 watts. This radiation is obtained by means of metallic vapor electric lamps well known in the industry, in particular in disinfection techniques.
Dans le procédé selon l'invention, les articles en liège peuvent être soumis à l'action du rayonnement ultraviolet pendant toute la durée du séchage.In the process according to the invention, the cork articles can be subjected to the action of ultraviolet radiation during the entire drying time.
Dans une variante du procédé selon l'invention, on soumet les articles en liège au rayonnement ultraviolet pendant une fraction seulement de l'étape de séchage, de préférence pendant la première partie du séchage. Par exemple, après une irradiation de 2 à 6 heures en présence d'ultraviolet, on poursuit le séchage en l'absence de rayonnement UV.In a variant of the process according to the invention, the cork articles are subjected to ultraviolet radiation during only a fraction of the drying step, preferably during the first part of drying. For example, after an irradiation of 2 to 6 hours in the presence of an ultraviolet, the drying is continued in the absence of UV radiation.
Dans la première étape précitée du procédé selon l'invention, la mise en contact de la solution aqueuse de peroxyde d'hydrogène avec les articles en liège peut se faire indifféremment selon différentes techniques déjà connues par elles-mêmes. Une technique de mise en contact ayant donné de bons résultats est la technique d'immersion des articles en liège dans un bain de blanchiment constitué de la solution de peroxyde d'hydrogène pendant un temps déterminé au cours duquel on peut avantageusement agiter les articles dans la solution. Un mode de réalisation conforme à cette technique consiste, par exemple, à placer les articles dans un panier à paroi ajourée ou poreuse, à immerger le panier dans la solution de peroxyde d'hydrogène et à lui imprimer un mouvement de rotation alternatif à vitesse lente durant la période de la première étape de traitement.In the aforementioned first step of the process according to the invention, the contacting of the aqueous hydrogen peroxide solution with the cork articles can be done indifferently according to various techniques already known by themselves. A contacting technique which has given good results is the technique of immersing the cork articles in a bleaching bath consisting of the hydrogen peroxide solution for a determined time during which the articles can advantageously be stirred in the solution. An embodiment in accordance with this technique consists, for example, of placing the articles in a basket with an openwork or porous wall, immersing the basket in the hydrogen peroxide solution and imparting to it an alternating rotation movement at slow speed during the period of the first stage of treatment.
Une autre technique de mise en contact des articles en liège avec la solution de peroxyde d'hydrogène consiste à déposer les articles sur une surface poreuse et à projeter sur ceux-ci la solution de peroxyde d'hydrogène par arrosage à l'aide d'un jet de solution qui balaye la totalité de la surface des articles à traiter. La solution de peroxyde d'hydrogène est recueillie sous la surface poreuse supportant les articles en liège et est recyclée vers le dispositif d'arrosage.Another technique for bringing cork articles into contact with the hydrogen peroxide solution consists in depositing the articles on a porous surface and spraying them thereon. solution of hydrogen peroxide by sprinkling with a jet of solution which scans the entire surface of the articles to be treated. The hydrogen peroxide solution is collected under the porous surface supporting the cork articles and is recycled to the sprinkler.
Une technique intéressante de mise en contact des articles en liège avec la solution de peroxyde d'hydrogène consiste à disposer les articles dans un panier à paroi ajourée ou poreuse, à suspendre le panier au-dessus de la solution de peroxyde d'hydrogène contenant un agent tensio-actif à fort pouvoir moussant, puis à insuffler de l'air dans la solution de peroxyde d'hydrogène de façon à provoquer la formation d'un flux ascendant de mousse qui atteint les articles dans le panier. On règle la concentration en tensio-actif, la température de la solution et le débit de l'air insufflé de telle façon qu'en régime stationnaire de fonctionnement, le flux de mousse déborde le panier contenant les articles en liège, puis se casse et retombe dans la solution. Cette technique présente l'avantage de consommer moins d'énergie que les techniques déjà décrites d'immersion ou d'arrosage des articles à traiter. Elle rend de plus inutile l'emploi d'agents anti-mousse souvent nécessaires avec les autres techniques.An interesting technique for bringing cork articles into contact with the hydrogen peroxide solution consists in placing the articles in a basket with an openwork or porous wall, hanging the basket above the hydrogen peroxide solution containing a surfactant with high foaming power, then blowing air into the hydrogen peroxide solution so as to cause the formation of an upward flow of foam which reaches the items in the basket. The concentration of surfactant, the temperature of the solution and the flow rate of the blown air are adjusted so that, in stationary operating conditions, the flow of foam overflows the basket containing the cork articles, then breaks and falls back into the solution. This technique has the advantage of consuming less energy than the techniques already described for immersing or watering the articles to be treated. It also makes it unnecessary to use anti-foaming agents which are often necessary with other techniques.
L'invention s'applique à tous les articles en liège. En particulier, elle s'applique avantageusement aux carreaux, panneaux et plaques en liège ainsi qu'aux bouchons en liège utilisés dans l'industrie du flaconnage. Elle trouve une application particulièrement intéressante pour blanchir les bouchons en liège utilisés dans l'industrie alimentaire, tout spécialement pour obturer les boutielles contenant des liquides tels que le vin, le cidre et les spiritueux.The invention applies to all cork articles. In particular, it advantageously applies to cork tiles, panels and plates as well as to cork stoppers used in the bottle industry. It finds a particularly interesting application for bleaching the cork stoppers used in the food industry, especially for sealing the bottles containing liquids such as wine, cider and spirits.
Lorsqu'il est appliqué au blanchiment des bouchons, le procédé selon l'invention présente l'avantage de la simplicité par rapport aux procédés classiques à l'hypochlorite qui nécessitent une étape de lavage. Il permet aussi l'obtention d'un blanchiment plus poussé que les procédés connus utilisant du peroxyde d'hydrogène et améliore notamment la netteté du timbrage des bouchons destinés à l'usage alimentaire. D'une manière générale, la mise en oeuvre du procédé selon l'invention permet l'élimination de tous les agents chimiques utilisés dans les procédés connus dans l'étape du lavage des bouchons, tels que les acides citrique et tartrique, les sulfites et l'acide chlorhydrique.When applied to the bleaching of stoppers, the method according to the invention has the advantage of simplicity compared to conventional hypochlorite methods which require a washing step. It also makes it possible to obtain more extensive bleaching than known processes using hydrogen peroxide and in particular improves the clarity of the stamping of caps intended for food use. In general, the implementation of the method according to the invention allows the elimination of all the chemical agents used in the known methods in the step of washing the plugs, such as citric and tartaric acids, sulfites and hydrochloric acid.
L'invention concerne aussi les articles en liège traités selon le procédé décrit plus haut. En particulier, il concerne les bouchons en liège, notamment ceux utilisés pour obturer les bouteilles et flacons de vins et de spiritueux.The invention also relates to cork articles treated according to the method described above. In particular, it relates to cork stoppers, in particular those used for sealing bottles and flasks of wines and spirits.
L'invention va maintenant être décrite de manière non limitative au moyen des exemples concrets qui suivent.The invention will now be described in a nonlimiting manner by means of the concrete examples which follow.
Dans un bécher en verre de 1000 ml, on a préparé une solution aqueuse de peroxyde d'hydrogène par dissolution dans de l'eau à 70°C d'une quantité suffisante de solution commerciale de peroxyde d'hydrogène à 35 g/100 g de solution pour réaliser une concentration en H₂O₂ égale à 100 g/l. On y a ensuite dissous un volume réglé de NaOH N pour obtenir après homogénéisation une concentration de 10 g NaOH/l. Le pH de la solution aqueuse alcaline de peroxyde d'hydrogène ainsi obtenue a été de 9,7.In an 1000 ml glass beaker, an aqueous solution of hydrogen peroxide was prepared by dissolving in water at 70 ° C a sufficient quantity of commercial hydrogen peroxide solution at 35 g / 100 g. of solution to achieve a H₂O₂ concentration equal to 100 g / l. A controlled volume of NaOH N was then dissolved therein to obtain, after homogenization, a concentration of 10 g NaOH / l. The pH of the aqueous alkaline hydrogen peroxide solution thus obtained was 9.7.
Dans l'essai 1, on a mis en oeuvre une solution de peroxyde d'hydrogène ne contenant aucun stabilisant. Dans le cas des essais 2 et 3, on a incorporé à la solution de peroxyde d'hydrogène, à titre de stabilisant, du silicate de sodium 38°Bé en quantités respectives de 7 g/l (essai N° 2) et 70 g/l (essai N° 3).In test 1, a hydrogen peroxide solution containing no stabilizer was used. In the case of tests 2 and 3, 38 ° Bé sodium silicate was incorporated into the hydrogen peroxide solution, as stabilizer, in respective amounts of 7 g / l (test No. 2) and 70 g / l (test No. 3).
On a enfermé des bouchons en liège non blanchi dans un panier en métal inoxydable muni de nombreuses ouvertures, puis on a immergé le panier dans le bécher contenant la solution aqueuse de peroxyde d'hydrogène et on l'y a maintenu pendant 1 heure en agitant la solution en continu à l'aide d'un agitateur magnétique réglé à 100 tours/minute.Unbleached cork stoppers were enclosed in a stainless steel basket with numerous openings, then the basket was immersed in the beaker containing the aqueous hydrogen peroxide solution and kept there for 1 hour with stirring. the solution continuously using a magnetic stirrer set at 100 revolutions / minute.
Après traitement avec la solution aqueuse de peroxyde d'hydrogène, on a retiré les bouchons en liège du panier métallique, on les a égouttés et disposés, sans les laver, dans une étuve ventilée dont le courant d'air chaud a été réglé à 50°C et qui contenait un générateur de rayonnement UV sous la forme de 3 tubes lumineux de marque PHILIPS et de type TUV-6W. Le séchage a ensuite été poursuivi dans cette étuve en présence du rayonnement UV pendant 180 minutes.After treatment with the aqueous peroxide solution of hydrogen, the cork stoppers were removed from the metal basket, they were drained and placed, without washing them, in a ventilated oven whose hot air flow was adjusted to 50 ° C and which contained a generator. UV radiation in the form of 3 light tubes of the PHILIPS brand and of the TUV-6W type. The drying was then continued in this oven in the presence of UV radiation for 180 minutes.
Les bouchons blanchis et séchés ont ensuite fait l'objet d'une mesure de blancheur au moyen d'un réflectomètre de marque PHOTOVOLT. Les résultats des mesures de blancheur ont permis de calculer, pour chaque bouchon, par soustraction de la blancheur mesurée avant traitement, le gain de blancheur exprimé en degrés PHOTOVOLT. Les résultats obtenus ont été résumés au tableau I qui suit où l'on donne les gains de blancheurs extrêmes obtenus.The bleached and dried stoppers were then subjected to a whiteness measurement using a reflectometer of the PHOTOVOLT brand. The results of the whiteness measurements made it possible to calculate, for each stopper, by subtracting the whiteness measured before treatment, the whiteness gain expressed in degrees PHOTOVOLT. The results obtained have been summarized in Table I below which gives the extreme whiteness gains obtained.
A titre de comparaison, on a aussi porté au tableau I les résultats obtenus avec un procédé non conforme à l'invention, qui met en oeuvre une étape de lavage à l'eau entre la première étape de traitement au peroxyde d'hydrogène et l'étape de séchage. Toutes les autres conditions opératoires sont identiques à celles des exemples 1 à 3. L'essai 4R n'a pas fait usage de stabilisant à la première étape, les essais 5R et 6R ont mis en oeuvre, respectivement 7 et 70 g/l de silicate comme les essais 2 et 3.
On remarque l'efficacité supérieure du procédé selon l'invention.Note the higher efficiency of the process according to the invention.
Au tableau II, on a porté, dans le but de fournir les points de référence, les résultats obtenus avec les procédés non conformes à l'invention qui suivent :
Ces résultats montrent qu'aucun des procédés des exemples 4R à 11R, non conformes à l'invention, ne donne lieu à des degrés de blancheur aussi élevés que ceux obtenus aux exemples 1 à 3 conformes à l'invention.These results show that none of the methods of Examples 4R to 11R, not in accordance with the invention, give rise to degrees of whiteness as high as those obtained in Examples 1 to 3 in accordance with the invention.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88120920T ATE74818T1 (en) | 1987-12-30 | 1988-12-14 | PROCESS FOR BLEACHING AND STERILIZING CORK ITEMS AND BLEACHED CORK ITEMS USING THIS PROCESS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT8723281A IT1233447B (en) | 1987-12-30 | 1987-12-30 | WHITENING AND STERILIZATION PROCEDURE OF CORK ITEMS AND CORK ITEMS WHITENED THROUGH THAT PROCEDURE |
IT2328187 | 1987-12-30 |
Publications (2)
Publication Number | Publication Date |
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EP0322650A1 true EP0322650A1 (en) | 1989-07-05 |
EP0322650B1 EP0322650B1 (en) | 1992-04-15 |
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ID=11205617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88120920A Expired - Lifetime EP0322650B1 (en) | 1987-12-30 | 1988-12-14 | Process for bleaching and sterilising cork articles, and cork articles bleached by said process |
Country Status (8)
Country | Link |
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US (1) | US5098447A (en) |
EP (1) | EP0322650B1 (en) |
JP (1) | JPH01295801A (en) |
AT (1) | ATE74818T1 (en) |
AU (1) | AU603893B2 (en) |
DE (1) | DE3870190D1 (en) |
IT (1) | IT1233447B (en) |
PT (1) | PT89361B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0420999A1 (en) * | 1988-08-12 | 1991-04-10 | Henkel KGaA | Process for treating cork stoppers |
WO1992015744A1 (en) * | 1991-03-05 | 1992-09-17 | Lappage, James | Photobleaching process for natural fibres |
EP1426064A1 (en) * | 2001-08-20 | 2004-06-09 | Menicon Co., Ltd. | Disinfection method |
EP1584736A2 (en) * | 2004-03-24 | 2005-10-12 | National Institute of Advanced Industrial Science and Technology | Method for bleaching fibrous articles |
EP3308953A1 (en) * | 2016-10-14 | 2018-04-18 | Seoyon E-Hwa Co., Ltd. | Method of manufacturing natural cork film |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6008268A (en) | 1994-10-21 | 1999-12-28 | Kimberly-Clark Worldwide, Inc. | Photoreactor composition, method of generating a reactive species, and applications therefor |
US5699589A (en) * | 1996-05-03 | 1997-12-23 | Ripley; William G. | Laser cleaning and bleaching apparatus |
US6152966A (en) * | 1998-05-13 | 2000-11-28 | Novo Nordisk A/S | Treatment of cork with a phenol oxidizing enzyme |
JP2000326312A (en) * | 1999-05-24 | 2000-11-28 | Aoi Kokuban Seisakusho:Kk | Cork board and treating method therefor |
US20040166345A1 (en) * | 2003-02-26 | 2004-08-26 | Wicht Charles A. | Processes and articles useful for preventing cork taint in beverages |
WO2005087951A2 (en) * | 2004-03-05 | 2005-09-22 | Gen-Probe Incorporated | Reagents, methods and kits for use in deactivating nucleic acids |
PT103117A (en) * | 2004-05-12 | 2005-11-30 | Ct Tecnologico Da Cortica | Treatment of cork for inhibition of substances causing organoleptic effect comprises spraying with inorganic salt solution |
EP2419249A1 (en) * | 2009-04-16 | 2012-02-22 | Colombin & Figlio S.P.A. | Process for the abatement of undesired volatile compounds from manufactured and semi-manufactured cork products |
CN114523537A (en) * | 2022-03-16 | 2022-05-24 | 东北林业大学 | Ultraviolet light catalyzed environment-friendly wood bleaching treatment method |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR907518A (en) * | 1939-02-06 | 1946-03-14 | Produits Peroxydes Soc D | Process for making used cork stoppers reusable |
GB1126233A (en) * | 1964-09-02 | 1968-09-05 | Gerhard Greiner | An improved process for articles made wholly or partly from cork |
FR1573944A (en) * | 1968-02-23 | 1969-07-11 | ||
FR2569369A1 (en) * | 1984-08-23 | 1986-02-28 | Montefluos Spa | Process for washing articles made of cork, and articles thus obtained |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IN153503B (en) * | 1979-01-11 | 1984-07-21 | Nat Res Dev | |
AU572470B2 (en) * | 1982-09-03 | 1988-05-12 | Cork & Seals Pty. Limited | Process for treatment of natural cork |
FR2574696B1 (en) * | 1984-12-19 | 1987-06-05 | Champagne M Sabate Sa Bouchons | SPECIAL TREATMENT PROCESS FOR CORK PRODUCTS |
-
1987
- 1987-12-30 IT IT8723281A patent/IT1233447B/en active
-
1988
- 1988-05-12 AU AU16085/88A patent/AU603893B2/en not_active Ceased
- 1988-12-14 EP EP88120920A patent/EP0322650B1/en not_active Expired - Lifetime
- 1988-12-14 DE DE8888120920T patent/DE3870190D1/en not_active Expired - Fee Related
- 1988-12-14 AT AT88120920T patent/ATE74818T1/en not_active IP Right Cessation
- 1988-12-27 JP JP63330756A patent/JPH01295801A/en active Pending
- 1988-12-29 PT PT89361A patent/PT89361B/en not_active IP Right Cessation
- 1988-12-30 US US07/292,169 patent/US5098447A/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR907518A (en) * | 1939-02-06 | 1946-03-14 | Produits Peroxydes Soc D | Process for making used cork stoppers reusable |
GB1126233A (en) * | 1964-09-02 | 1968-09-05 | Gerhard Greiner | An improved process for articles made wholly or partly from cork |
FR1573944A (en) * | 1968-02-23 | 1969-07-11 | ||
FR2569369A1 (en) * | 1984-08-23 | 1986-02-28 | Montefluos Spa | Process for washing articles made of cork, and articles thus obtained |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0420999A1 (en) * | 1988-08-12 | 1991-04-10 | Henkel KGaA | Process for treating cork stoppers |
WO1992015744A1 (en) * | 1991-03-05 | 1992-09-17 | Lappage, James | Photobleaching process for natural fibres |
EP1426064A1 (en) * | 2001-08-20 | 2004-06-09 | Menicon Co., Ltd. | Disinfection method |
EP1426064A4 (en) * | 2001-08-20 | 2004-12-15 | Menicon Co Ltd | Disinfection method |
EP1584736A2 (en) * | 2004-03-24 | 2005-10-12 | National Institute of Advanced Industrial Science and Technology | Method for bleaching fibrous articles |
EP1584736A3 (en) * | 2004-03-24 | 2006-01-11 | National Institute of Advanced Industrial Science and Technology | Method for bleaching fibrous articles |
EP3308953A1 (en) * | 2016-10-14 | 2018-04-18 | Seoyon E-Hwa Co., Ltd. | Method of manufacturing natural cork film |
US10427319B2 (en) | 2016-10-14 | 2019-10-01 | Seoyon E-Hwa Co., Ltd. | Method of manufacturing natural cork film |
Also Published As
Publication number | Publication date |
---|---|
IT1233447B (en) | 1992-04-01 |
ATE74818T1 (en) | 1992-05-15 |
EP0322650B1 (en) | 1992-04-15 |
US5098447A (en) | 1992-03-24 |
AU1608588A (en) | 1989-07-06 |
DE3870190D1 (en) | 1992-05-21 |
AU603893B2 (en) | 1990-11-29 |
PT89361B (en) | 1993-08-31 |
PT89361A (en) | 1989-12-29 |
JPH01295801A (en) | 1989-11-29 |
IT8723281A0 (en) | 1987-12-30 |
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