Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • 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]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane

Definitions

• the field of the invention is that of non-stick and water-repellent coatings for flexible supports, for example paper or polymer film.
• the non-stick coatings considered are more particularly those based on silicone elastomer crosslinked in situ, that is to say after coating on solid supports, for example in paper or in polymer film, of non-crosslinked liquid silicone formulations.
• non-stick silicone coatings referred to in this presentation are those comprising one or more polyorganosiloxane (POS) crosslinkable by polyaddition (POS Si-H / POS Si-Ninyle), by polycondensation, by cationic or radical polymerization , under thermal and / or actinic activation and / or using an electron beam.
• POS polyorganosiloxane
• the liquid silicone coating formulations contain, in addition to the silicone polymers, a polycondensation or polyaddition catalyst or a cationic or radical initiator, as well as at least one system.
• adhesion modulator for example based on silicone resin comprising siloxy units Q: (SiO 4/2 ) and / or T: (RSiO 3/2 ).
• the silicone phase can be diluted in a solvent.
• the liquid silicone formulation is an aqueous dispersion / emulsion.
• the primary function of such a silicone coating is the anti-adhesion of its external face, the fact remains that the coating must be fixed, by its internal face, on the flexible solid support, with very strong adhesion.
• the anti-adhesion of the external face of the silicone coating is expressed through the release force, which must be low and controlled, for the element intended to be placed on the support coated with the non-stick silicone film.
• this element can be the adhesive side of a label or a ribbon of the same name.
• the adhesion of the silicone coating on its support must be very high.
• This adhesion property can be assessed, for example, using the "rub off” trade test, which consists of rubbing the surface of the coating with a finger and measuring the number of successive passes which lead to degradation of the coating.
• the solid supports coated with a non-stick silicone film can be for example:
• this element being able to be made of paper or polymer film of polyvinyl chloride (PNC), PolyEster, PolyPropylene type, or
• non-adhesive side of this element being generally printed or printable so as to be able to serve as a label capable of being detached from its support and glued by simple pressure on an article to be identified.
• deposition rate of non-stick silicone is between 0.1 and
• Glassine-type papers with a grammage equal to 60-65 g / m 2 are papers made from a highly refined bisulfite pulp which leads to significant entanglement of the fibers and which contributes to "closing" the paper.
• the two phases of glassine paper are coated with a layer based on polyvinyl alcohol and carboxymethyl cellulose. The paper is then calendered to give it a certain transparency.
• a DOW CORNING / DOW CORNLNG-TORAY patent dating from 1971 discloses the use of a mixture of acetoxysilane and 3-GLYcydoxypropyltriMethOxysilane (GLYMO) to improve the adhesion on supports by paper of elastomeric silicone coatings crosslinking by condensation.
• GLYMO 3-GLYcydoxypropyltriMethOxysilane
• European patent EP-B-0 272 809 relates to an adhesion promoter intended to be incorporated in POS compositions crosslinkable by radical route under actinic activation (UN) or by exposure to an electron beam.
• This adhesion promoter is based on a mixture of alkoxylated silane such as for example: vinyltrimethoxysilane / ⁇ - ⁇ - (aminoethyl) - ⁇ -aminopropyl-trimethoxysilane. It is in fact a co-hydrolisal of these 2 alkoxysilanes which condense to form copolymers.
• Such an adhesion promoter is added to a silicone composition based on POS crosslinkable by the radical route under a UN or under an electron beam (polydimethylsiloxane / ⁇ -mercaptopropylmethylsiloxane copolymer with trimethylsiloxy ends), in a proportion of 0.1 to 30 parts in promoter weight per 100 parts by weight of POS.
• French patent application FR-A-2 469 435 discloses adhesion promoters based on alkoxysilane (methyltrimethoxysilane / ⁇ - (aminoethyl) -aminopropyl-trimethoxysilane) in admixture with a dibutyltin diacetate catalyst.
• Such an adhesion promoter is associated with POS compositions carrying OH and / or OR groups crosslinkable by polycondensation. This adhesion promoter does not appear to be particularly effective.
• the French invention patent FR-B-2 719 598 discloses silicone elastomeric coating compositions of EVF type that can be cold cured, comprising at least one POS Si-Ni, at least one POS and Si-H, a platinum catalyst, an adhesion promoter, optionally a mineral filler, optionally a crosslinking inhibitor and optionally a POS resin.
• the adhesion promoter includes:
• NTMS vinyltrimethoxysilane
• GLYMO 3-GLYcydoxypropyltriMethOxysilane
• the silicone phase has an overall dynamic viscosity at 25 ° C. greater than 3000 mPa.s.
• the Si-Ni oils used have a viscosity of 100,000 mPa.s and 10,000 mPa.s respectively, while the viscosity of POS Si-H oil is of the order of 300 mPa. s.
• these silicone compositions crosslinkable at room temperature by polyaddition are intended to be applied to supports which are preferably fibrous and more preferably still to textile supports made of synthetic fibers of the polyester or polyamide type.
• a common use of these crosslinkable silicone compositions is the coating of air bags intended for the protection of an occupant of a vehicle ("air bag").
• the silicone composition according to FR-B-2 719 598 cannot really be considered as completely liquid.
• adhesion promoter which it comprises necessarily comprises 3 constituents: alkoxylated and alkenylated silane (vinyltrimethoxysilane) / alkoxylated and epoxidized silane (GLYMO) / metal chelate (butyl titanate).
• silicone compositions comprising long silicone oils of high viscosity
• the POSs used are short POSs of low viscosity
• European patent application EP-A-0 771 901 is another illustration of the use of a polyorganosiloxane composition for coating a textile support, in this case coated with a silicone elastomer material.
• This textile support coated with a silicone multilayer is in this case constituted by a conveyor belt, usable in particular for food contact.
• the silicone composition used is a viscous composition loaded with silica and comprising an ⁇ , ⁇ -divinylated polydimethylsiloxane oil, with a maximum viscosity equal to 1000 mPa.s, a charge of aluminum hydroxide, a Karstedt platinum catalyst, a PolyDiMethylSiloxane ⁇ , ⁇ -hydrogen oil with a viscosity of 40 mPa.s, another PDMS oil with ⁇ SiH units with a viscosity of 30 mPa.s, as well as a crosslinking inhibitor of the ethynylcyclohexanol type.
• this is a viscous coating composition for textile support, said coating being carried out without scrolling of the support or with scrolling at very low speed.
• the overall dynamic viscosity of this composition is much greater than 1000 mPa.s.
• the silicone coating composition according to EP-A-0 771 901 does not solve the problem of producing, at very high running speed, a crosslinked elastomeric coating which is non-stick and water-repellent, on a solid support, with very strong adhesion.
• One of the essential objectives of the present invention is to provide a liquid silicone formulation which can be used as a coating base for producing - at very high speed - a non-stick, water-repellent cross-linking elastomer coating on a solid support, said formulation allowing a excellent adhesion of the coating to the support, while having all the anti-adhesion and / or hydrophobicity characteristics as well as all the desired mechanical qualities.
• Another essential objective of the present invention is to provide a non-crosslinked liquid silicone formulation having rheological characteristics such that they can be easily applied to the surface of a support film circulating at very high speed, said formulation once coated then being able to crosslink to form a hardened coating firmly attached to the support by one of its faces and the other face of which has non-stick and / or water-repellent properties, as well as optimal mechanical qualities.
• Another essential objective of the invention is to provide a liquid silicone formulation which can be used as a coating base for the production at very high speed of crosslinked non-stick elastomeric coatings on a solid support of very closed paper type (glassine) or of polyester or polypropylene film, said coating being perfectly bonded to the support.
• Another essential objective of the present invention is to propose a process for producing at high speed a crosslinked elastomeric coating which is non-stick and water-repellent on a solid support, a process in which:
• (meth) acrylate said patterns to be saturated being intended to allow polymerization of the graft functionalized POS; "and an outer layer based on a non-stick silicone elastomer perfectly attached to the pre-coating based on functionalized grafted and polymerized POS is coated.
• Another essential objective of the invention is to provide a solid support, for example in closed paper of the glassine type or in a polymer film of the polypropylene or polyester type, on which would be securely attached to a non-stick and / or water-repellent crosslinked silicone elastomer coating.
• These objectives, among others, are achieved by the present invention which firstly relates to a liquid silicone formulation, usable as a coating base for the production - at very high speed - of crosslinked elastomeric coatings which are non-stick and water-repellent on a support.
• this formulation comprising in particular: at least one silicone composition based on at least one polyorganosiloxane (I) crosslinkable by polyaddition, by polycondensation, by cationic or radical route, under thermal and / or actinic activation and / or obtained with using an electron beam,> - at least one catalyst / initiator (II), - optionally, at least one adhesion modulator system (III), characterized:
• M being chosen from the group formed by: Ti, Zr, Ge, Li, Mn, Fe, Al,
• the POS (I) of higher viscosity has (have) a dynamic viscosity ⁇ at 25 ° C less than 1000 mPa.s, preferably less than 900 mPa.s, and more preferably still less than 800mPa.s,
• the invention makes it possible to access high levels of adhesion of the non-stick silicone elastomer coating crosslinked on various supports.
• a crosslinked elastomeric silicone coating which is non-stick and / or water-repellent on supports known to be difficult, such as, for example, polyethylene terephthalate PET films, PE polyethylene films or polypropylene PP films. , as well as tightly closed papers such as glassines.
• the formulation according to the invention has the singularity that it is liquid, that is to say that it has sufficiently low viscosity characteristics, so that its application on solid supports circulating at very high speed, is easily achievable. In practice, this corresponds to an overall dynamic viscosity at 25 ° C less than or equal to 1000 mPa.s.
• This rheological characteristic of the liquid silicone formulation is partly due to the fact that the POS (s) (s) more viscous, has (have) a dynamic viscosity ⁇ at 25 ° C less than 1000 mPa.s, preferably less than 900 mPa.s, and more preferably still less than 800mPa.s.
• Such a low viscosity liquid character makes it possible to achieve very thin coating thicknesses on the order of a micrometer.
• the term “very high speed” of travel of the support to be coated corresponds, in accordance with the invention, to a speed, for example, greater than or equal to: 40 m / min, preferably 60 m / min, and more preferably still at 70 m / min, and better still at 500 m min.
• a Corona treatment is particularly recommended for polymeric supports.
• the Corona treatment consists in degrading the surface of the support by an electric discharge and creating reactive functions which will promote attachment.
• the epoxidized alkoxysilane (IN.l.) of the promoter (IN) is chosen:
• R 1 is a linear or branched al yl radical in C ⁇ -C
• R 2 is a linear or branched alkyl radical y is equal to 0, 1, 2 or 3
• ⁇ E and D which are identical or different radicals chosen from linear or branched C ⁇ -C 4 alkyls, ⁇ z which is equal to 0 or 1,
• ⁇ R 3 , R 4 , R 5 which are identical or different radicals representing hydrogen or a linear or branched C1-C4 alkyl, ⁇ R 3 and R 4 or R 5 can alternately constitute together with the two carbons carrying epoxy, an alkyl ring having from 5 to 7 members, - either from epoxidized alkoxysilanes (IN.lb) constituted by epoxyfunctional polydiorganosiloxanes comprising at least one unit of formula:
• X is the radical as defined above for the formula (IN.1 a)
• G ' has the same meaning as that of G' given above and r has a value between 0 and 3.
• IN.l compounds are therefore preferably epoxidized alkoxysilanes comprising only one silicon atom.
• alkenylated alkoxysilanes (IN.2)
• the ones corresponding to the following general formula (IN.2) are preferably chosen to enter into the constitution of the adhesion promoter according to the invention:
• R 6 , R 7 , R 8 are hydrogenated or hydrocarbon radicals identical or different from each other and representing hydrogen, a linear branched C alkyl . -C 4 or a phenyl optionally substituted by at least one C ⁇ -C 3 alkyl,
• - A is a linear or branched C1-C4 alkylene, or a divalent group of formula -CO-O-alkylene - * -, where the alkylene residue is as defined above and the valence - is linked to Si via G , - G is a valence link,
• R and R are identical or different radicals and represent a linear or branched C1-C4 alkyl
• the compound (IN.3) can consist of, or include, a metal chelate.
• the metal M chosen may comprise one or more ligands such as those derived, in particular from a ⁇ -diketone, such as for example acetylacetone.
• the compound (IN.3) may also consist of or comprise a metal alkoxide having the formula M (OJ) n defined above where the alkoxy radicals are for example the n-propoxy and n-butoxy radicals. Note that, in this formula, one or more alkoxy OJ radicals can be replaced by one or more ligands constituting a chelate, such as for example an acetylacetone ligand.
• the preferred compounds (IN.3) are those in which the metal M is chosen from the following list: Ti, Zr, Ge, Li, Mn, Fe, Al, Mg.
• titanium is more particularly preferred, and more especially still titanium tetrabutanolate or butyl titanate: ti (OBu) 4 .
• compounds (IN.3) which are very suitable are those in the structure of which the metal M is chosen from the list: Ti, Zr, Ge, Li, Mn, Fe, Al, Mg and is associated: as regards from a chelate to ligands of acetylacetonate type, being an alkoxide to n-propoxy or n-butoxy radicals.
• the composition chosen is as follows:
• the weight ratio (IN.l) or (IN-2) / (IN.3) which is used according to the invention is between 5 and 0.5, and preferably is of the order of 1. Still quantitatively, it can be specified that the adhesion promoter (IN) is present at a rate of 0.1 to 10% by weight, relative to all of the constituents.
• liquid silicone formulations according to the invention it is advantageous to use at least one adhesion modulating system (111), to allow the control of the anti-adhesion properties of the crosslinked silicone coating.
• adhesion modulator system in silicone formulations for paper or adhesive non-sticking having a polymer support, mention may be made of European patent application EP-A-0 601 938, the content of which is fully included. in this talk.
• the adhesion modulator system (III) can be based on:
• radicals R mentioned above represent linear or branched alkyl radicals in C ⁇ -C 6 , cycloalkenyls in C 5 ⁇ C ⁇ 2 and / or phenyl.
• part of the radicals R are functional groups which are: a in the case of the formulations which crosslink by polyaddition:
• alkenyl groups which are identical or different from one another in C -C ⁇ 2 , alkenyl (C 3 -C) or oxyalkylene (C 2 -C 4 ); (2i) hydrogen atoms linked directly to Si; (3i) and / or hydroxyl groups linked directly to Si; these aforementioned resins comprising at least 0.1 mol%, preferably from 0.5 to
• ⁇ E and D which are identical or different radicals chosen from linear or branched C 1 -C 4 alkyls, ⁇ z which is equal to 0 or 1,
• ⁇ R, R, R which are identical or different radicals representing hydrogen or a linear or branched C ⁇ -C alkyl, ⁇ R 3 and R 4 or R 5 can alternately constitute together with the two carbons carrying the epoxy , an alkyl ring having from 5 to 7 members.
• resins MQ, MDQ, MDT, MDTQ where the functions (i) to (4i) can be carried by the units M, D and / or T.
• the resins which are well suited are : crosslinking formulations by polyaddition: MD Vi Q MM Vi Q MM Vi D Vi Q MM Vi DD vi Q
• crosslinking formulations under radiation MD H Q MM H Q
• the silicone composition is preferably a mixture formed from:
• - T is an alkenyl group
• - Z is a monovalent hydrocarbon group, free from any unfavorable action on the activity of the catalyst and chosen from alkyl groups having from 1 to 8 carbon atoms included, optionally substituted by at least one halogen atom, and also pa ⁇ ni aryl groups,
• - a is 1 or 2
• b is 0, 1 or 2
• a + b is between 1 and 3
• the polyorganosiloxane (1.2) comprises siloxyl units of formula:
• - L is a monovalent hydrocarbon group, free from any adverse action on the activity of the catalyst and chosen from alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and also among the aryl groups,
• - d is 1 or 2
• e is 0, 1 or 2
• d + e has a value between 1 and 3, - possibly, at least part of the other units being units of average formula:
• the proportions of (1.1) and of (1.2) are such that the molar ratio of the hydrogen atoms bonded to silicon in (1.2) to the alkenyl radicals bonded to silicon in (1.1) is between 0.4 and 10.
• Crosslinking inhibitors (N) which can be used are for example alpha acetylenic alcohols or maleates-fumarates.
• the formulation may comprise one or more conventional additives in the field of silicone non-stick coatings for solid support, for example made of paper. They may, for example, be anti-misting additives: silica particles, e.g.
• the formulation according to the invention may be an organic solution, it is preferable that it is in the form of an aqueous emulsion / dispersion.
• the conventional additives of such emulsions / dispersions can be used.
• emulsifying agents which can be used, alone or as a mixture, mention may be made of conventional anionic agents such as fatty acid salts, alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, sulfosuccinates, alkyl phosphates of alkali metals, the salts of abietic acid, hydrogenated or not, nonionic agents such as polyethoxylated fatty alcohols, polyethoxylated and optionally sulfated alkyl phenols, polyethoxylated fatty acids. These can be used at a rate of 0.1 to 3% use relative to the total mass of the formulation.
• the present invention relates to the use of the formulation as defined above as a coating base for the production - at very high speed - of crosslinked elastomeric coatings which are non-stick and water-repellent on a solid support. , preferably chosen:
• the present invention also relates to the solid support at least partially coated with the aid of the formulation as defined above.
• the silicone formulation according to the invention can be applied directly to the support to be coated or alternatively, according to a variant, after treatment of the latter using a pre-layer making it possible to reduce the penetration of the anti-adhesion agent or agents into the support and / or of reducing the sensitivity of the support to water, said pre-layer being obtained by coating by means of an aqueous emulsion based on a functionalized polyorganosiloxane grafted with unsaturated units, for example of the acrylic type.
• the present invention also relates to a process for producing - at very high speed - crosslinked elastomeric coatings non-stick and water-repellent on a solid support, characterized in that it essentially consists:
• the symbols R are similar or different and represent a linear or branched C 10 alkyl group, a linear or branched C 20 alkenyl group, a C 6 -C 1 aryl or aralkyl group, optionally substituted by atoms halogen;
• the symbols X are similar or different and represent an epoxyfunctional hydrocarbon group, containing from 2 to 20 carbon atoms and linked to a silicon atom by a Si-C or Si-OC bond;
• the symbols Y are similar or different and represent an ethylenically unsaturated hydrocarbon residue which may contain one or more heteroelement (s) O or N, this residue being linked to a silicon atom of the motif of formula (A) by an Si-C bond and being capable of reacting radically with said ethylenically unsaturated monomer (s);
• - a, b and c are equal to 0, 1, 2 or 3;
• the graft functionalized polyorganosiloxane comprising the pre-layer can be combined with a polymeric material of acrylic type.
• a polymeric material of acrylic type For more details, refer to PCT WO-01/04 418.
• liquid silicone formulation according to the invention makes it possible to produce a non-stick silicone coating on a solid support comprising the precoat referred to in the process defined above as well as in PCT application WO-01/04418.
• the present invention finally relates to a solid support at least partially coated using the formulation as defined above or obtained by the process in which a layer of a primer primer is produced, said solid support being characterized in that it is intended for adhesive labels.
• CORONA treatment can be defined as follows: Shennan Treater GX10 device set to a power of 1KW for a width of 400mm.
• Poly 2 Ninyleum oil at the middle and end of the chain, poly (dimethyl) (methylvinyl) siloxane ⁇ , ⁇ bis vinyldimethylsiloxy, viscosity 500 cps, Ni content 0.08 lmoles / 100g
• Poly 3 oil SiH homopolymer, poly (dimethyl) siloxane ⁇ , ⁇ bis hydrogen dimethylsiloxy, viscosity 20 cps, 1.55 moles of SiH / lOOg.
• Poly 4 copolymer SiH oil, poly (dimethyl) (methyl hydrogen) siloxane ⁇ , ⁇ bis hydrogen dimethylsiloxy, viscosity 25 cps, 1.33 moles of SiH / lOOg.
• Formulations A to H are control formulations.
• Formulations I to P are in accordance with the invention. Some of these formulations are evaluated using the following tests: - Smear test (fingerprint): evaluation of the level of crosslinking of the coating by qualifying the oily nature of the surface A, B, C, D.
• - Migration / Dewetting on an adhesive having been in contact with the silicone coating, a thin line of Shearman ink with a surface tension of 31 mJ / m 2 is deposited and the time taken by this ink to dewetting and forming droplets is monitored. This time is expressed in seconds.
• - Migration Scotch test Peel strength: the test used meets the Finat standards n ° 3 and 10 of edition n ° 5 of 1999.
• Table 2 below gives the coating conditions, the types of formulations tested and the results of the tests.
• the formulations not in accordance with the invention have very poor resistance to the rub off test. All the formulations according to the invention, added with promoter (IV) are good. On the other hand, they have no impact on the other performance of the coating: non-stick (peeling), polymerization.
• Example 2 Evaluation of the additives on a PET support
• the support tested is a PET stretch film ref 6001 from the company Toray. This film is not Corona treated.
• the list of formulations evaluated is grouped in Tables 6 and 7. It is recalled that a result of 10 in the rub off test is excellent while a result of 0 is bad. The rub off is measured just after coating / crosslinking and after a certain time of aging.
• Coating / crosslinking conditions Laboratory coatings EUCLLD Weight of coated silicone: 0.6 - 0.7g / m 2 Crosslinking in an oven: 150 ° C / 10s
• Coating / crosslinking conditions Laboratory coatings EUCLLD Weight of coated silicone: 0.7 - 0.9g / m 2 Crosslinking in an oven: 150 ° C and 30 s
• the polymers used are those of Example 1 except:
• Poly 5 Ninylée oil at the end of the chain, viscosity 1000 cps and a vinyl content of 0.0107 moles / 100g.
• Example 3 Effect of Different Mixtures of IN Promoter According to the Invention with Respect to Attachment to a PET Support CORONA Treated
• a Corona treatment does not compensate for the absence of the IV adhesion promoter characteristic of the formulation according to the invention.
• the Corona treatment must be combined with the silicone formulation of the invention to obtain good performance in the rub off test.
• the IN promoter which gives the best performance consists of a 50/50 Titanate (IN.3) / GLYMO (IN.li) mixture and it must be added at a rate of 5% in the silicone formulation. There is no impact of the additives, except with 4% titanate, on the non-stick performance of the coatings.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Paints Or Removers (AREA)
• Paper (AREA)
• Laminated Bodies (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesive Tapes (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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  • 2001-10-26 FR FR0113915A patent/FR2831547B1/fr not_active Expired - Fee Related
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  • 2002-10-24 US US10/493,577 patent/US20050053793A1/en not_active Abandoned
  • 2002-10-24 BR BR0213759-3A patent/BR0213759A/pt not_active IP Right Cessation
  • 2002-10-24 JP JP2003538286A patent/JP2005506437A/ja active Pending
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