WO2002100958A1 - Composition aqueuse de revetement contenant des agents d'absorption de radiations uv - Google Patents
Composition aqueuse de revetement contenant des agents d'absorption de radiations uv Download PDFInfo
- Publication number
- WO2002100958A1 WO2002100958A1 PCT/FR2002/001820 FR0201820W WO02100958A1 WO 2002100958 A1 WO2002100958 A1 WO 2002100958A1 FR 0201820 W FR0201820 W FR 0201820W WO 02100958 A1 WO02100958 A1 WO 02100958A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- agents
- organic
- composition according
- encapsulated
- Prior art date
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Definitions
- the main object of the present invention is an anti-UV coating composition and the use of anti-UV agents, in an encapsulated form, in the field of coatings.
- anti-UV agents exhibit chemical incompatibility with other components of the coating. This is particularly the case for benzotriazoles which can be the cause of a flocculation problem when they are brought into contact with the various ingredients for formulating a coating, such as, for example, filler, pigment and / or additive. In this case, to partially prevent this reactivity of anti-UV agents, they are generally introduced at the end of the formulation. However, the addition of anti-UV agents at the end of the formulation can in certain cases be in turn the cause of a problem. homogenization. Anti-UV agents are not always dispersed equitably within the coating composition.
- the object of the present invention is precisely to propose a new mode of formulation for these anti-UV agents within the coating compositions which makes it possible to remedy the aforementioned drawbacks.
- its main object is an aqueous coating composition containing organic agents for absorbing UV radiation, characterized in that said agents are present at least partially in said composition in a form encapsulated in particles of at least an organic (co) polymer A.
- the inventors have thus demonstrated that the presence of anti-UV agents in a form encapsulated in polymer particles was particularly advantageous in terms of anti-UV efficacy.
- This specific mode of formulation makes it possible on the one hand to protect the anti-UV agents from any parasitic reaction with respect to the other components of the coating and on the other hand to obtain better homogenization of the anti-UV agent in the coating composition. What is more, the protective effect of the coating is also significantly extended over time. This results in better anti-UV efficacy at the level of the final coating.
- Anti-UV agents can be present in the coating composition, either completely in an encapsulated form, or only partially in this encapsulated form.
- anti-UV absorbent agents which can be used in the context of the present invention can be any conventional organic anti-UV agent, subject of course to their solubility in the solvent and the (co) polymer A retained.
- anti-UV agents there may be mentioned in particular: oxybenzones, dioxybenzones, sulisobenzones, menthyl anthranilate, para-aminobenzoic acid, amyl para-dimethylaminobenzoic acid, octyl para-dimethylaminobenzoate , ethyl 4-bis (hydroxypropyl) para-aminobenzoate, polyethylene glycol para-aminobenzoate (PEG-25), ethyl 4-bis (hydroxypropyl) aminobenzoate, diethanolamine para-methoxycinnamate, para- 2-ethoxyethyl methoxycinnamate, ethylhexyl para-methoxycinnamate, octyl para-methoxycinnamate, isoamyl para-methoxycinnamate, 2-cyano-3,3-diphenyl acrylate, 2 salicylate -ethoxybenzone, 2-cyan
- Tinuvin 1130® (CIBA), G-4375®, G-4374® (RHODIA-l'OREAL), phenol derivatives such as vaniline or ortho-vaniline, salicylic derivatives (salicylic aldehyde) and benzophenones (C -81®, EFKA-
- the polymer particles in which the anti-UV agents are encapsulated are composed of an organic polymer obtained by emulsion polymerization of at least one anionic monomer (1) ethylenically unsaturated polymerizable by the radical route.
- this organic polymer is a latex.
- the latex used in the context of the composition according to the invention is preferably prepared from polymerizable monomers (1) chosen from styrene, polyolefins such as butadiene, acrylonitrile and methacrylonitrile, acrylic esters and / or vinyl acetate-versatate.
- acrylic esters denotes the esters of acrylic acid and of methacrylic acid with the C ⁇ -C- ⁇ 2 alkanols, preferably C- ⁇ -C 8 , such as methyl acrylate, acrylate ethyl, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate , isobutyl methacrylate.
- the styrene may be replaced in whole or in part by amethylstyrene or vinyltoluene.
- the monomer from which the polymer is derived is copolymerized with a nonionic ethylenically unsaturated monomer (2) polymerizable by the radical route.
- ethylenically unsaturated monomers (2) which can be polymerized with the monomers (1) above, and the amount of which can range up to 40% by weight of the total of the monomers, can in particular be chosen from:
- ethylenic monomers comprising a sulfonic acid group and its alkali or ammonium salts, for example vinyisulfonic acid, vinylbenzene sulfonic acid, ⁇ -acrylamido methylpropane-sulfonic acid, 2-sulfoethylenemethacrylate,
- (e) ethylenically unsaturated monomers comprising a secondary, tertiary or quaternary amino group or a heterocyclic group containing nitrogen, for example vinylpyridines, vinylimidazole, aminoalkyl (meth) acrylates and (meth) acrylamides) aminoalkyl such as dimethylaminoethylacrylate or methacrylate, ditertiobutylaminoethyl acrylate or -methacrylate, dimethyl amino methyl acrylamide or -methacrylamide, as well as zwietterionic monomers such as sulfopropyl (dimethyl) aminopropyl acrylate, (f) esters meth) acrylics with alkanediols preferably containing 2-8 carbon atoms such as glycol mono (meth) acrylate, hydroxypropyl mono (meth) acrylate, 1-4 butanediol mono (meth) acrylate as well as monomers
- latex contains by weight: 25-90%, and preferably 45-75%, of styrene and / or acrylonitrile,
- acrylate homopolymers or styrene acrylate copolymers will be preferred.
- the polymerization of the latex is carried out in a manner known per se as an aqueous emulsion of the polymerizable monomers in the presence of at least one radical initiator and preferably of a transfer agent, for example of the mercaptan type with a concentration of monomers in the reaction medium. generally between 20 and 60% by weight.
- the polymerization can be carried out continuously, batchwise or semi-continuously with the introduction of a portion of the monomers continuously and be of the "seeded” or “incremental” type according to any known variant for obtaining particles of homogeneous and heterogeneous structure .
- the anti-UV agents are preferably encapsulated in the latexes by transfer in post-polymerization.
- This technique exploits the swelling capacity of latexes in the presence of solvent. By dissolving the solid or liquid material in this solvent, it is thus transferred and encapsulated in the latex.
- it is generally sufficient to mix the latex with an emulsion of the dissolved active material. Under the effect of strong agitation, collisions will allow the latex particles to swell. This operation can be carried out between 20 and 100 ° C and ⁇ 2 ° C. However, generally the best compromise between reaction speed and evaporation is in the range 45-60 ° C.
- the particles are thus obtained by removing water / drying an aqueous dispersion comprising the anti-UV agents and the organic (co) polymer A.
- This aqueous dispersion of the system can be prepared by introducing the anti-UV agent either during the synthesis of said
- the introduction of anti-UV agents into the latex is carried out after completion of the aqueous emulsion polymerization of the monomer composition.
- the level of dry extract of the aqueous dispersion comprising the mixture of anti-UV agents and of organic compound is of the order of 20 to 70%, preferably of the order of 30 to 60% by weight.
- the method comprises:
- the expected product is obtained in the form of a powder.
- the first step namely the encapsulation step in the presence of a swelling "transfer" solvent of the polymer.
- esters such as ethyl acetate, methyl propionate, the mixture of glutarate / adipate / methyl succinate (solvent "RPDE”) .... ketones such as methyl ethyl ketone, cyclohexanone ...
- alcohols such as propanol, pentanol, cyclohexanol .... aliphatic and cyclic hydrocarbons such as heptane, decane, cyclohexane, decaline ...
- chlorinated aliphatic derivatives such as dichloromethane .... aromatic derivatives such as toluene, ethylbenzene ...
- chlorinated aromatic derivatives such as trichlorobenzene .... dialkylethers.
- the transfer agent is of course chosen so as to allow the solubilization of the anti-UV agent retained, and thus to ensure its vectorization in the latex particle.
- the anti-UV agent in a solid form, one generally proceeds to its pre-solubilization in the transfer solvent considered, for example, the solvent RHODIASOLV RPDE already used in paint as a coalescing agent.
- the resulting solution is then added with stirring to the latex saturated with the solvent in question.
- This saturation has two functions. It allows first of all to produce a self-emulsion without requiring the addition of surfactant. Then it avoids precipitation or premature release of the molecule to be transferred by avoiding the solubilization of part of the transfer solvent. In fact, this loss of solvent risks causing, under certain circumstances, an excessive increase in the concentration in the emulsion droplets and would induce supersaturation accompanied by precipitation of the anti-UV.
- the material to be encapsulated is liquid, it is not necessary to perform its pre-solubilization in such a solvent.
- the latex water must be saturated with solvent to allow emulsification.
- the anti-UV agent having a melting point below the boiling point of water (case of vanilin which melts at 85 ° C.), can be transferred as a simple liquid.
- the choice of transfer agent is made so that it is identical to the co-solvent used for the formulation of the aqueous coating composition, for which the anti-UV / (co ) organic polymer A.
- esters of ethyl acetate, butyl acetate type aliphatic hydrocarbons, aromatic hydrocarbons,
- glycol ethers or esters glycol ethers or esters
- esters of ester type (Rhodiasolv RPDE®).
- the protocol used is as follows:
- a solution of the anti-UV agent to be transferred for example Tinuvin-1130®, is prepared in a transfer solvent, for example RPDE (20% by mass of Tinuvin1130® in RPDE) at 50 ° C. with stirring.
- a transfer solvent for example RPDE (20% by mass of Tinuvin1130® in RPDE) at 50 ° C. with stirring.
- the mass of the (co) polymer A considered is introduced into a beaker. Latex water is supersaturated using of the solvent retained, preferably generally identical to the transfer solvent.
- a surfactant is added to facilitate the emulsion.
- the anti-foaming agent is added, if necessary at this stage.
- the presence of an anti-foaming agent in fact relates to the characteristics of the latex, namely whether it is foamy or not. The whole mixture is brought to 50 ° C.
- the solution of the anti-UV agent is then added slowly, generally over 15 minutes, with vigorous stirring while avoiding the formation of bubbles.
- the mixture is then kept stirring at 50 to 55 ° C for 1 hour and then allowed to cool.
- the diameter of the polymer particles containing the anti-UV agents can be of the order of 30 nm to 2 ⁇ m, and preferably is between 50 and 200 nanometers.
- the amount of anti-UV agents which can be incorporated into said particles of organic (co) polymer A can range from 2 to 70, preferably from 20 to 60 parts by weight of anti-UV agents per 100 parts by weight of (co) organic polymer A.
- the degree of encapsulation can be adjusted between approximately 1 and 10%, and preferably approximately 3% by weight per relative to the weight of organic (co) polymer A.
- the degree of encapsulation can be adjusted between approximately 1 and 10%, and preferably approximately 3% by weight per relative to the weight of organic (co) polymer A.
- UV is implemented in an encapsulated form
- this rate of encapsulation is greater.
- this degree of encapsulation can be 20 to 30% by weight relative to the weight of organic (co) polymer A.
- the particles of organic (co) polymer have at their surface at least one emulsifying agent. , at a rate at least 0.1%, more generally of the order of 0.1 to 15% of the weight of dry polymer.
- This emulsifier level is a function of the size of said particles.
- emulsifying agents mention may be made of: - anionic emulsifiers such as: salts of fatty acids; alkylsulfates (sodium lauryl sulfate), alkylsulfonates, alkylarylsulfonates (sodium dodecylbenzene sulfonates, sodium di-butylnaphthalene sulfonate), alkylsulfosuccinates or succinamates (disioctylsulfosuccinamate disodium, n-octadecylsulfosuccinamodic disodium alphosphatins); sodium dodecyldiphenylether disulfonate; sulfonates of alkylphenolpolyglycolic ethers; ester salts of alkylsulfopolycarboxylic acids; the condensation
- ethoxylated or ethoxy-propoxylated sorbitan esters fatty ethoxylated or ethoxy-propoxylated amines di (phenyl-1 ethyl) ethoxylated or ethoxy-propoxylated tri (1-phenyl-ethyl) phenols ethoxylated or ethoxy-propoxylated alkyl phenols ethoxy-propoxylated.
- alkyl betaines alkyldimethyl betaines, alkyl amidopropyl betaines, alkylamidopropyl dimethyl betaines, alkyltrimethyl sulfobetaines, imidazoline derivatives such as alkylampho alkylamphodiacetates, alkylampho-propionates, alkyl-amphodipropionates, alkylsultaines or alkylamidopropyl-hydroxysultaines, condensation products of fatty acids and protein hydrolysates, amphoteric derivatives of alkylpolyamines such as Amphionic XL® sold by Rhône-Poulenc, Ampholac 7T / X® and Ampholac 7C / X® sold by Berol Nobel, proteins or protein hydrolysates .
- said emulsifier is anionic or noni
- composition of the coating comprises, as main component, a latex derived from an organic (co) polymer B.
- This (co) polymer is chosen from the (co) polymers proposed for the (co ) polymers A intended to form the encapsulation particles.
- the (co) polymer B can therefore be of identical or different composition to that of the (co) polymer A used for the encapsulation.
- this aqueous coating composition can of course combine other conventional additives, in particular mineral fillers and / or mineral and / or organic pigments.
- composition can also contain anti-foaming agents, biocides, surfactants, rheological agents, coalescing agents, dispersing agents and / or thickening agents and antioxidant agents.
- the various constituents are mixed in a manner known per se.
- the coating composition according to the invention can be used in different applications, such as water-based paints (primer, plaster, semi-thick coating (RSE), stain, varnish, floor paint and roof paint).
- water-based paints primary, plaster, semi-thick coating (RSE), stain, varnish, floor paint and roof paint.
- the invention also relates to any coating, in particular those described above, comprising anti-UV agents encapsulated in accordance with the above.
- the coating composition can be applied according to usual techniques. By way of examples, it can be applied to surfaces by any suitable means such as a brush, roller and / or sprayer.
- the surfaces on which the coating composition according to the invention is applicable are of various types, for example, wood, metal (such as aluminum), cement, brick and concrete.
- the present invention also relates to the use of anti-UV absorption agents in an encapsulated form to prepare an aqueous anti-UV coating composition.
- anti-UV agents are formulated in particles of organic (co) polymers A as defined above.
- Figure 1 Measurement of the transmittance on a stain based on Rodopas D 2027® in the presence and absence of encapsulated or non-encapsulated anti-UV agents.
- Figure 2 Measurement of the transmittance on a stain based on Rodopas DS 913® in the presence and absence of encapsulated or non-encapsulated anti-UV agents.
- Figure 3 Evolution of the db * variation on a wooden plate of a stain based on Rhodopas D 2027 * in the presence and absence of anti-UV agents, encapsulated or not.
- Figure 4 Evolution of the db * variation on a wooden plate of a stain based on Rhodopas DS 913® in the presence and absence of anti-UV agents, encapsulated or not.
- Rhodopas D 2027® and DS 913® are (co) polymers of styrene acrylate or any acrylate.
- the formulation in which the encapsulated anti-UV particles are incorporated is a glossy stain based on Rhodopas DS 913® or D 2027®.
- Table I gives a detailed account of the nature of the components and their quantity by weight in the coating formulations tested.
- the wood and glass plates are exposed to UV radiation and to a humid atmosphere according to a test representative of natural aging. Each cycle lasts 8 hours and is made up of 2 periods: UV-A illumination for 4 hours at 60 ° C for exposure to 100% humidity without runoff at 60 ° C.
- the stains applied to the glass slides are exposed to Q-UVA aging and, at regular intervals, a transmittance measurement is carried out using a UV-visible spectrometer.
- a solution of the anti-UV agent to be transferred for example Tinuvin-1130®, is prepared in a transfer solvent, for example RPDE (20% by mass of Tinuvin 1130® from RPDE) at 50 ° C. with stirring. .
- a transfer solvent for example RPDE (20% by mass of Tinuvin 1130® from RPDE) at 50 ° C. with stirring. .
- the mass of (co) polymer A retained is introduced into a beaker.
- the water in the latex is supersaturated using the solvent retained, preferably generally identical to the transfer solvent. If necessary, a surfactant is added to facilitate the emulsion.
- the anti-foaming agent Generally, that which is present in the latex is sufficient and the anti-foaming agent. The whole mixture is brought to 50 ° C.
- a coating composition of stain + anti-UV type (conventional test).
- the formulation selected is a bright colorless aqueous stain based on latex D 2027® or DS 913®.
- the final level of anti-UV is 2% relative to the stain or 7.4% relative to the dry polymer.
- the stains are prepared from free and encapsulated molecules. In the case of "free" molecules, a single stain is prepared and the UV inhibitors are added at the end of the preparation in the form of a solution in the RPDE. The level thereof is adjusted so as to be present in the same proportions as for the encapsulated molecules. For these, the preparation is individual, the encapsulating latex being supplemented with conventional latex to obtain the desired quantity of binder.
- Coatings performance test a) monitoring of the transmittance of the stain film in the UV and the visible.
- T-1130® at 2% in a free form, that is to say prepared according to Example 2 or in a form encapsulated in Rhodopas D 2027® at the same rate.
- the transmittance is measured after exposing the stain to 250 UV cycles.
- the stain is a stain based on Rhodopas DS 913®. This stain is exposed to 350 UV cycles.
- the variation db * reflects the yellowing index of the coating.
- the variation db * is measured for three types of stain based on Rhodopas D 2027®, one without anti-UV agent, the second incorporating the anti-UV agent 1130® encapsulated in Rhodopas D 2027® and the third incorporating the anti-UV agent 1130® in free form.
- Rhodopas DS 913® with three types of anti-UV agents, T 1130®, G 4375® and C 81® which are encapsulated in Rhodopas DS 913 ® or introduced in free form.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02745471A EP1401968A1 (fr) | 2001-06-08 | 2002-05-30 | Composition aqueuse de revetement contenant des agents d'absorption de radiations uv |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR01/07548 | 2001-06-08 | ||
FR0107548A FR2825711A1 (fr) | 2001-06-08 | 2001-06-08 | Composition aqueuse de revetement contenant des agents d'absorption de radiations uv |
Publications (1)
Publication Number | Publication Date |
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WO2002100958A1 true WO2002100958A1 (fr) | 2002-12-19 |
Family
ID=8864122
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/001820 WO2002100958A1 (fr) | 2001-06-08 | 2002-05-30 | Composition aqueuse de revetement contenant des agents d'absorption de radiations uv |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1401968A1 (fr) |
FR (1) | FR2825711A1 (fr) |
WO (1) | WO2002100958A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8691248B2 (en) | 2008-03-11 | 2014-04-08 | Mary Kay Inc. | Stable three-phased emulsions |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2665170A1 (fr) * | 1990-07-30 | 1992-01-31 | Rhone Poulenc Chimie | Composes d'inclusion de cyclodextrines enfermant des anti-uv et leur utilisation dans les polymeres. |
JPH04224865A (ja) * | 1990-12-26 | 1992-08-14 | Moon Star Co | 水系ポリウレタンサスペンジョン組成物 |
US5541239A (en) * | 1995-01-24 | 1996-07-30 | Heywood, Jr.; Newell W. | Ultraviolet radiation protection for marine varnish |
WO2000002965A1 (fr) * | 1998-07-13 | 2000-01-20 | Fortunato Joseph Micale | Dispersion aqueuse de particules solides contenant comme principes actifs des composants absorbant le rayonnement ultraviolet, et procede pour obtenir cette dispersion |
-
2001
- 2001-06-08 FR FR0107548A patent/FR2825711A1/fr not_active Withdrawn
-
2002
- 2002-05-30 EP EP02745471A patent/EP1401968A1/fr not_active Withdrawn
- 2002-05-30 WO PCT/FR2002/001820 patent/WO2002100958A1/fr not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2665170A1 (fr) * | 1990-07-30 | 1992-01-31 | Rhone Poulenc Chimie | Composes d'inclusion de cyclodextrines enfermant des anti-uv et leur utilisation dans les polymeres. |
JPH04224865A (ja) * | 1990-12-26 | 1992-08-14 | Moon Star Co | 水系ポリウレタンサスペンジョン組成物 |
US5541239A (en) * | 1995-01-24 | 1996-07-30 | Heywood, Jr.; Newell W. | Ultraviolet radiation protection for marine varnish |
WO2000002965A1 (fr) * | 1998-07-13 | 2000-01-20 | Fortunato Joseph Micale | Dispersion aqueuse de particules solides contenant comme principes actifs des composants absorbant le rayonnement ultraviolet, et procede pour obtenir cette dispersion |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 199239, Derwent World Patents Index; Class A25, AN 1992-320225, XP002194515 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8691248B2 (en) | 2008-03-11 | 2014-04-08 | Mary Kay Inc. | Stable three-phased emulsions |
US9271903B2 (en) | 2008-03-11 | 2016-03-01 | Mary Kay Inc. | Stable three-phased emulsions |
US9918912B2 (en) | 2008-03-11 | 2018-03-20 | Mary Kay Inc. | Stable three-phased emulsions |
Also Published As
Publication number | Publication date |
---|---|
FR2825711A1 (fr) | 2002-12-13 |
EP1401968A1 (fr) | 2004-03-31 |
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