EP1285025A1 - Oxygen absorbent films and structures comprising same - Google Patents
Oxygen absorbent films and structures comprising sameInfo
- Publication number
- EP1285025A1 EP1285025A1 EP01936522A EP01936522A EP1285025A1 EP 1285025 A1 EP1285025 A1 EP 1285025A1 EP 01936522 A EP01936522 A EP 01936522A EP 01936522 A EP01936522 A EP 01936522A EP 1285025 A1 EP1285025 A1 EP 1285025A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- grafted
- film
- copolymer
- oxygen
- quinones
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
Definitions
- the present invention relates to an oxygen-absorbing film and more particularly to a polyolefinic film comprising quinones and grafted carboxylic acids and also relates to a packaging comprising such a film.
- packaging which is made up of a multilayer structure to preserve it during transport, distribution until consumption.
- This structure comprises a film of a polymer forming an oxygen barrier such as EVOH (copolymer of ethylene and vinyl alcohol or copolymer of ethylene and saponified vinyl acetate) or polyamides.
- EVOH copolymer of ethylene and vinyl alcohol or copolymer of ethylene and saponified vinyl acetate
- Structures comprising a barrier film and an oxygen-absorbing film have been developed so that the barrier film is on the outside and the oxygen-absorbing film on the inside of the package.
- the internal surface of the packaging defines the surface of the packaging in contact with the food it contains and the external surface of the packaging defines the surface of the packaging in direct contact with the ambient air.
- these structures also include other films, for example, made of polyethylene or polypropylene, which provide the mechanical strength of the structure and protection against water.
- the polyolefin film of the present invention comprising quinones and grafted carboxylic acids is an oxygen-absorbing film useful in the technique described above.
- the invention also relates to a structure comprising one or more oxygen-absorbing films and one or more barrier films.
- Patent applications WO 94 12590, WO 96 34070 and WO 99 10251 describe the technique described above in the field of the invention and more particularly the oxygen-absorbing film as well as its operation.
- This technique consists in introducing into a polymer film molecules of anthraquinone (AQ).
- AQ anthraquinone
- the operating principle of this system is broken down into 3 stages: Activation: The quinone molecules are reduced to hydroquinone molecules under UV irradiation, the necessary protons being supplied by proton donors contained in the polymer. This activation is done after the packaging is manufactured, so there is no need to manufacture this film under an inert atmosphere.
- Destruction of H 2 0 2 This is carried out by a reducing agent contained in the polymer.
- the amount of this reducing agent can be adjusted so as not to destroy all of the H 2 O 2 so as to leave a sufficient amount to obtain a bactericidal effect.
- the constituents of the oxygen-absorbing film are the following polymers: - mixtures of polymer with oxygen-absorbing molecules. These are not grafted polyolefins, that is to say that there is no chemical link between the absorbent molecule and the polymer. - copolymers of styrene, 2-hydroxyethyl methacrylate and vinylanthraquinone. EVOHs grafted with an anthraquinone functionalized with an acid chloride. - ethylene-acrylic acid copolymers which have reacted with bromoethyl anthraquinone to give ethylene / anthra quinone acrylate copolymers.
- quinones and carboxylic acids can be grafted onto polymers carrying epoxide groups and that they can be very easily transformed into a film, this film being able to be used as an oxygen absorber in the structures mentioned more high.
- the present invention relates to a film comprising copolymers of ethylene and of an unsaturated epoxide and comprising quinones and carboxylic acids grafted on these copolymers.
- the advantage of these films is that they can be manufactured easily and that the quinones which are grafted onto the copolymers are easy to manufacture.
- Another advantage is that these films can be activated by simple passage under UV, the proton donor being included in the polymer.
- a carboxylic acid R1 COOH is grafted which causes the appearance of a hydroxyl function (proton donor) at the time of grafting and which optionally provides other hydroxyl functions present on its radical R1. This improves the activation of quinone functions.
- a polymer comprising grafted quinones can be mixed with a polymer comprising hydroxyl functions, the mixture then being transformed into a film. It is also possible to mix a polymer comprising quinones and grafted carboxylic acids described above with a polymer comprising grafted quinones and / or with a polymer comprising proton donors, for example hydroxyl functions.
- the present invention also relates to a structure comprising at least one oxygen barrier film and at least the preceding oxygen-absorbing film.
- the present invention also relates to a package comprising the above structure and in which, starting from the inside of the package and going outward, there is first the oxygen-absorbing film and then the barrier film to the 'oxygen.
- the invention relates to an oxygen-absorbing film comprising a copolymer of ethylene and an unsaturated epoxide, said copolymer being grafted with at least one quinone and with at least one carboxylic acid R1-COOH or its derivatives in which R1 denotes any group other than a quinone.
- R1 denotes an alkyl, cycloalkyl or aromatic radical. According to one embodiment of the film, the radical R1 carries at least one hydroxyl function.
- R1-COOH is DMPA.
- the copolymer of ethylene and an unsaturated epoxide is a copolymer comprising as comonomers ethylene, an alkyl (meth) acrylate, an unsaturated epoxide, said copolymer containing from 0 to 40 % by weight of alkyl (meth) acrylate and up to 10% by weight of unsaturated epoxide.
- the grafted quinones are chosen from the group comprising benzoquinone, anthraquinone and naphthoquinone, said quinones comprising a chemical function, called grafting, capable of reacting with the epoxide group of the unsaturated epoxide .
- the chemical function, called grafting, of the quinones is a carboxylic acid function.
- this comprises either (i) the copolymer comprising at least one grafted quinone and at least one carboxylic acid R1-COOH, or its derivatives, grafted and (ii) a " copolymer comprising at least one R1-COOH carboxylic acid, or its derivatives, grafted and no grafted quinones, or (i) the copolymer comprising at least one grafted quinone and at least one R1-COOH carboxylic acid, or its derivatives, grafted and ( iii) a copolymer comprising at least one grafted quinone and no carboxylic acids R1-COOH, or its grafted derivatives.
- the copolymer (ii) comprising at least one carboxylic acid R1-COOH or its grafted derivatives and no grafted quinones is EVOH or a copolymer of formula (1): OH
- the invention also relates to a structure comprising at least one oxygen barrier film and at least one oxygen absorbing film as described above.
- the oxygen barrier film is made of EVOH, polyamide, polyketone or PVDF.
- the latter successively comprises: a polyolefin film, an EVOH film, a polyolefin film and an oxygen-absorbing film as described above.
- the invention also relates to a package comprising the structure as described above, in which, starting from the inside of the package and going towards the outside, there is first of all the oxygen-absorbing film described previously, then the oxygen barrier film.
- the copolymers of ethylene and an unsaturated epoxide may be polyethylenes grafted with an unsaturated epoxide or copolymers of ethylene and an unsaturated epoxide which are obtained for example by radical polymerization.
- unsaturated epoxides to be grafted or copolymerized there may be mentioned: aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, glycidyl (meth) acrylate, and alicyclic glycidyl esters and ethers such as 2-cyclohexene- 1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbomene-2-methyl-2-glycidyl carboxylate and endo cis-bicyclo (2,2, 1) - 5-heptene-2,3-diglycidyl dicarboxylate.
- aliphatic glycidyl esters and ethers such as allyl glycidyl ether,
- polyethylene means homo- or co-polymers.
- comonomers we can cite:
- alpha-olefins advantageously those having from 3 to 30 carbon atoms, as examples of alpha olefins, mention may be made of propylene, 1-butene, 1-pentene, 3-methyl-1-butene , 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene , 1-octadecene, 1 - eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene, and 1 -triacontene; these alpha-olefins can be used alone or as a mixture of two or more than two,
- esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, the alkyls possibly having up to 24 carbon atoms, examples of alkyl acrylate or methacrylate are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate,
- - dienes such as, for example, 1,4-hexadiene.
- the polyethylene can comprise several of the preceding comonomers.
- the polyethylene which can be a mixture of several polymers, comprises at least 50% and preferably 75% (in moles) of ethylene, its density can be between 0.86 and 0.98 g / cm 3 .
- the MFI viscosity index at 190 ° C, 2.16 kg
- LDPE low density polyethylene
- HDPE high density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very low density polyethylene
- metallocene catalysis that is to say the polymers obtained by copolymerization of ethylene and of alphaolefin such as propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of an atom of zirconium or titanium and two cyclic alkyl molecules linked to the metal.
- metallocene catalysts are usually composed of two metal-linked cyclopentadienic rings. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoinane (MAO).
- Hafnium can also be used as the metal to which cyclopentadiene is attached.
- Other metallocenes can include transition metals of groups IV A, V A, and VI A. Metals of the lanthamide series can also be used.
- - EPR elastomers ethylene - propylene - rubber
- - ethylene- (meth) acrylate copolymers which may contain up to 60% by weight of alkyl (meth) acrylate and preferably 2 to 40% by weight.
- copolymers of ethylene and the unsaturated epoxide these are the copolymers of ethylene, the unsaturated epoxide and optionally another monomer which can be chosen from the comonomers which have been mentioned. above for ethylene copolymers intended to be grafted.
- the copolymers of ethylene and of an unsaturated epoxide are advantageously ethylene / alkyl (meth) acrylate / unsaturated epoxide copolymers obtained by copolymerization of the monomers and not by grafting of the unsaturated epoxide onto the polyethylene. They contain from 0 to 40% by weight of alkyl (meth) acrylate, preferably 5 to 35% and up to 10% by weight of unsaturated epoxide, preferably 0.1 to 8%.
- the unsaturated epoxide to be copolymerized is advantageously glycidyl (meth) acrylate.
- the alkyl (meth) acrylate is chosen from methyl (meth) acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate.
- the amount of alkyl (meth) acrylate is advantageously from 20 to 35%.
- the MFI is advantageously between 5 and 100 (in g / 10 min at 190 ° C. under 2.16 kg), the melting temperature is between 60 and 110 ° C.
- quinones which will be grafted onto the preceding copolymers, mention may be made, for example, of benzoquinone, anthraquinone, and naphthoquinone.
- Quinone carries a function capable of reacting with the epoxide group of the copolymer.
- carboxylic acids such as carboxylic acids, salts of carboxylic acids, anhydrides of dicarboxylic acids, alcohols and amines.
- carboxylic acids are solids at room temperature. They are put in " powder, then they are added in the preceding copolymers in the molten state by carrying out an intimate mixing.
- the device in which this intimate mixing is made can be any device used for mixing thermoplastics such as an extruder single or double screw, a kneader or a KO kneader BUSS®.
- the functionalized quinones are added to these mixing devices using hoppers or any device for introducing powders.
- the granulometry of these powders can be very variable. the finer the more homogeneous the incorporation of these powders into the molten polymer, advantageously it is at most 200 ⁇ m and preferably between 10 and 150 ⁇ m.
- the copolymer in the molten state containing the grafted quinones can be sent to a device to film it or cooled and recovered in the form of granules to be filmed later like most thermoplastics.
- the thickness of the film can be between 10 and 300 ⁇ m and preferably between 15 and 150 ⁇ m.
- the proportion of functionalized quinone to be used is one quinone per epoxide function.
- AQ carboxylated anthraquinone
- grafting on the copolymer of ethylene and of an unsaturated epoxide can be represented by the following equation:
- R1 denotes an alkyl, cycloalkyl or aromatic radical which can carry one or more hydroxyl functions.
- the conditions are similar to those of the grafting of quinones and even easier when R1-COOH is liquid.
- R1-COOH is the product of following formula called DMPA (abbreviation of Di Methylol Propionic Acid): H0 2 CC (CH 2 OH) 2-CH3.
- DMPA abbreviation of Di Methylol Propionic Acid
- the quinone functions can then be activated, but it is recommended to do so only when the packaging is closed or ready to be closed. This activation can be done by exposure to UN. or any wavelength appropriate to the quinones used, by heat, gamma rays, a corona discharge or even an electron beam.
- the film may also contain a destroyer of PH2O2 formed such as for example a triphenylphosphine, a triphenylphosphite, triethylphosphite, triisopropylphosphite, tris (nonylphenyl) phosphite, tris (mono and bis-nonylphenyl) phosphite, butylhydroxytoluene, butylhydroxyanisole, tris (2,4-di-ter-butylphenyl) phosphite, dilaurylthiodipropionate, 2,2'-methylene-bis- (6-t-butyl-p- cresol), tetrakis (2,4 -d-ter-butylphenyl) 4,4'-biphenylenediphosphonite, poly (4-vinylpyridine) or mixtures thereof.
- a destroyer of PH2O2 formed such as for example a trip
- the copolymer comprising the grafted quinones is mixed with a polymer comprising hydroxyl functions.
- a polymer comprising hydroxyl functions can be, for example, EVOH or a polymer of the following formula (1) in which R1-COOH has the same meaning as above:
- This polymer (1) can be obtained by reaction of the copolymer (2) shown below with the reagent R1-COOH.
- the copolymer (2) is a copolymer of ethylene and of an unsaturated epoxide.
- copolymer (2) By way of example of copolymer (2), mention may be made of polyolefins, polystyrene, PMMA, polyamides, fluorinated polymers, polycarbonate, saturated polyesters such as PET or PBT, thermoplastic polyurethanes (TPU) and polyketones, all these polymers being grafted with an unsaturated epoxide such as for example glycidyl (meth) acrylate.
- the copolymer (2) is chosen from copolymers of ethylene and of an unsaturated epoxide. These copolymers have been described above.
- the barrier film is advantageously made of EVOH, polyamide, polyketone or PVDF.
- this structure also comprises one or more polyolefin films to reinforce the structure and for protection against water.
- the barrier film is made of EVOH
- the structure advantageously comprises a polyolefin film such as polyethylene or polypropylene on each side of the barrier film.
- EVOH is sensitive to humidity and loses its oxygen barrier property in the presence of moisture.
- the structure of the invention therefore successively comprises: a polyolefin film, an EVOH film, a film of polyolefin and the film containing the quinones and carboxylic acids grafted as oxygen absorbers of thicknesses advantageously (in the same order in ⁇ m):
- the structure further comprises a polyolefin film, the oxygen-absorbing film thus being sandwiched between two polyolefin films. Since the polyolefins are very permeable to oxygen, this polyolefin film therefore does not hinder the reaction of oxygen with the reduced quinones. It would not be departing from the scope of the invention to have a binder such as a coextrusion binder between the preceding layers.
- the present invention also relates to a package comprising the above structure. It can be formed by the structure that is closed by any means on itself to make sachets or bags.
- the structures of the invention may be only part of the packaging, for example, it is the film which closes a tray.
- this tray is made of a barrier material but does not contain an oxygen-absorbing film, the oxygen absorber included in the closing film of the tray being sufficient.
- the grafting of 2-carboxyanthraquinone is carried out in the molten state in a LEISTRITZ® rotary twin screw extruder.
- the thermal profile of the extruder is set at 200 ° C.
- the LOTADER AX8840® is introduced into the feed hopper in the first zone of the extruder using a weight metering device.
- 2-carboxyanthraquinone is introduced in powder form using another doser.
- the proportions used are: 88% of LOTADER AX 8840® / 12% of 2-carboxyanthraquinone.
- the reactive extrusion of the mixture of the 2 components is carried out at a flow rate of 6 kg / h, at a screw rotation speed equal to 50 revolutions / min.
- the grafted product is extruded in the form of a rod which is cooled in a water tank, then granulated after passing through a granulator.
- the product obtained has a melt index (MFI) measured at 190 ° C under 2.16 kg equal to 2 • g / 10min.
- MFI melt index
- the DMPA is then grafted onto the graft copolymer obtained previously according to a similar procedure.
- the product was then extruded in the form of a 100 ⁇ m film using a SCAMIA® brand cast film extruder.
- the film is perfectly transparent and has a slight “copper” color.
- Example 2 Co-grafting of 2-carboxyanthraquinone and DMPA on the LOTADER AX8840®.
- the grafting is carried out in the molten state in a kneader, an internal BRABENDER® laboratory mixer.
- the temperature of the mixer body was set at 220 ° C.
- LOTADER AX 8840®, 2-carboxyanthraquinone and DMPA are introduced into the mixer chamber and the reagents are mixed for 4 min.
- the proportions used are: 91% of LOTADER AX 8840® / 6% of 2-carboxyanthraquinone / 3% of DMPA.
- the speed of rotation of the blades is fixed at 50 rpm.
- the product was characterized by NMR and infrared. The product is then shaped in a press to give a film of 200 ⁇ m.
- Example 3- Activation of the final product of example 1 or 2 by photoreduction under UV.
- a 0.6 g sample of the film prepared in example 1 or 2 was activated by passing under a UN bench. MI ⁇ ICURE type laboratory equipped with a mercury lamp. The irradiation time of the film was 12 s.
- Example 3 The activated film of Example 3 was then placed in a cell containing oxygen. The decrease in the quantity of gaseous oxygen was followed over time by gas chromatography: Volume of oxygen absorbed after 5 h: approximately 4 ml.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0006284 | 2000-05-17 | ||
FR0006284A FR2809113B1 (en) | 2000-05-17 | 2000-05-17 | OXYGEN ABSORBING FILMS AND STRUCTURES COMPRISING SUCH FILMS |
PCT/FR2001/001472 WO2001088023A1 (en) | 2000-05-17 | 2001-05-15 | Oxygen absorbent films and structures comprising same |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1285025A1 true EP1285025A1 (en) | 2003-02-26 |
Family
ID=8850312
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01936522A Withdrawn EP1285025A1 (en) | 2000-05-17 | 2001-05-15 | Oxygen absorbent films and structures comprising same |
Country Status (9)
Country | Link |
---|---|
US (1) | US20040077786A1 (en) |
EP (1) | EP1285025A1 (en) |
JP (1) | JP2003533572A (en) |
KR (1) | KR20030007645A (en) |
CN (1) | CN1443213A (en) |
AU (1) | AU2001262409A1 (en) |
CA (1) | CA2408873A1 (en) |
FR (1) | FR2809113B1 (en) |
WO (1) | WO2001088023A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006000055A1 (en) * | 2004-06-28 | 2006-01-05 | Commonwealth Scientific And Industrial Research Organisation | Oxygen scavenging composition and method for making same |
US8110261B2 (en) * | 2007-03-29 | 2012-02-07 | Multisorb Technologies, Inc. | Oxygen absorbing plastic structure |
US20170163781A1 (en) * | 2015-12-08 | 2017-06-08 | Ram Ramesh Seshan | User interface for contacts management and communication |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0584738A (en) * | 1991-09-30 | 1993-04-06 | Sekisui Chem Co Ltd | Production of colored intermediate film for safety glass and production of safety glass |
CN1096315A (en) * | 1992-11-24 | 1994-12-14 | 联邦科学及工业研究组织 | Deoxidizing compositions |
AUPO868497A0 (en) * | 1997-08-21 | 1997-09-11 | Commonwealth Scientific And Industrial Research Organisation | New uses for oxygen scavenging compositions |
JPH1152560A (en) * | 1997-08-06 | 1999-02-26 | Jsr Corp | Radiation sensitive resin composition |
FR2800084B1 (en) * | 1999-10-20 | 2002-01-04 | Atofina | POLYOLEFIN FILMS CONTAINING GRAFTED QUINONES AND STRUCTURES COMPRISING SUCH FILMS |
-
2000
- 2000-05-17 FR FR0006284A patent/FR2809113B1/en not_active Expired - Fee Related
-
2001
- 2001-05-15 CN CN01813020A patent/CN1443213A/en active Pending
- 2001-05-15 CA CA002408873A patent/CA2408873A1/en not_active Abandoned
- 2001-05-15 JP JP2001585238A patent/JP2003533572A/en not_active Withdrawn
- 2001-05-15 US US10/276,708 patent/US20040077786A1/en not_active Abandoned
- 2001-05-15 AU AU2001262409A patent/AU2001262409A1/en not_active Abandoned
- 2001-05-15 WO PCT/FR2001/001472 patent/WO2001088023A1/en not_active Application Discontinuation
- 2001-05-15 EP EP01936522A patent/EP1285025A1/en not_active Withdrawn
- 2001-05-15 KR KR1020027015553A patent/KR20030007645A/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO0188023A1 * |
Also Published As
Publication number | Publication date |
---|---|
KR20030007645A (en) | 2003-01-23 |
CN1443213A (en) | 2003-09-17 |
JP2003533572A (en) | 2003-11-11 |
US20040077786A1 (en) | 2004-04-22 |
AU2001262409A1 (en) | 2001-11-26 |
FR2809113B1 (en) | 2002-07-05 |
CA2408873A1 (en) | 2001-11-22 |
FR2809113A1 (en) | 2001-11-23 |
WO2001088023A1 (en) | 2001-11-22 |
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