Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
  • B29C45/14688—Coating articles provided with a decoration
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/06—Coating with compositions not containing macromolecular substances
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
  • B29C45/14688—Coating articles provided with a decoration
  • B29C2045/14704—Coating articles provided with a decoration ink decorations
• • 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
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24058—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in respective layers or components in angular relation
  • Y10T428/24074—Strand or strand-portions
  • Y10T428/24091—Strand or strand-portions with additional layer[s]
  • Y10T428/24099—On each side of strands or strand-portions

Definitions

• the invention relates to a color varnish suitable for printing on the inside of insert molding parts, consisting essentially of one or more pigments, optionally customary auxiliaries, a binder which is dissolved in an organic solvent or a mixture of organic solvents.
• Screen printing inks and screen printing varnishes are widely used. It can e.g. B. Films made of transparent plastics can be printed on the back with screen printing inks. The printed foils are then reshaped and back-molded in an injection mold (insert molding). Various plastic parts such as B. differently printed or colored, interchangeable shells for mobile phones. This places high demands on the quality of the screen printing, since it has to be resistant to temperatures in the range of 260 ° C and pressures around 1000 bar during the back injection process and should not decrease in the course of the period of use of the parts in the printed image.
• Color lacquer suitable for printing on films made of transparent thermoplastic, in particular for printing on films which are used for insert molding parts, consisting essentially of
• a poly (meth) acrylate or a poly (meth) acrylimide compound which has a Vicater softening temperature VET (ISO 306 B) of at least 115 ° C. is used as the binder.
• the color varnish consists of
• a) one or more pigments preferably in an amount of 10 to 50% by weight
• a binder preferably in an amount of 10 to 50% by weight which is dissolved in
• an organic solvent or a mixture of organic solvents and d) optionally customary auxiliaries, preferably in an amount of up to 10% by weight, in particular of 0.1 to 10% by weight,
• the paint contains pigments, preferably in an amount of 10 to 50, particularly preferably 15 to 30% by weight, based on the liquid paint.
• Suitable pigments are e.g. B. carbon blacks, titanium dioxide, metal pigments, iron oxide red or iron oxide red types, cobalt pigments, for. B. cobalt blue types, cobalt green types, organic pigments.
• the paint contains a binder, in particular a polymeric binder, preferably in an amount of 10 to 50, in particular 15 to 35% by weight, based on the liquid paint.
• Poly (meth) acrylate or poly (meth) acrylimide compound which have a Vicater softening temperature VET (ISO 306 B) of at least 115 ° C., e.g. B. from 115 to 180 ° C, preferably at least 118 ° C, z. B. from 118 to 125 ° C, particularly preferably at least 125 ° C, in particular at least 130 ° C, z. B. from 140 to 180 ° C or from 145 to 160 ° C.
• VET Vicater softening temperature
• the binders mentioned are very temperature and weather resistant and therefore essential for the properties of the coating system.
• a poly (meth) acrylate compound that is a polymer can be used
• the monomers (m1) used in 50 to 90% by weight, based on the total monomers, are selected from the group of alkyl methacrylates with 1 to 6 carbon atoms in the ester radical, such as, for example, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, iso- Butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, isopentyl methacrylate, hexyl methacrylate, 2,2-dimethylbutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, and particularly preferably methyl methacrylate.
• alkyl methacrylates with 1 to 6 carbon atoms in the ester radical such as, for example, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate,
• the monomers (m 2) are selected from the group of vinyl aromatics, such as, for example, -halogenstyrene, p-methylstyrene, p-tert-butylstyrene, vinylnaphthalene, and preferably ⁇ -methylstyrene and particularly preferably styrene.
• vinyl aromatics such as, for example, -halogenstyrene, p-methylstyrene, p-tert-butylstyrene, vinylnaphthalene, and preferably ⁇ -methylstyrene and particularly preferably styrene.
• the monomeric maleic anhydride (m3) is used with a purity of at least 95%, preferably at least 99%.
• it is heated above its melting point of 52.85 ° C., preferably to temperatures between 55 and 80 ° C., particularly preferably between 60 and 80 ° C.
• the liquid maleic anhydride can be stored under an inert gas atmosphere at the above temperatures for several weeks.
• the alkyl acrylates (m4) can be present in proportions of up to 5% by weight to improve the theological properties of the terpolymers TP to be built in.
• alkyl acrylates with 1 to 6 carbon atoms in the ester radical are ethyl acrylate, isopropyl acrylate, propyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, and preferably butyl acrylate and particularly preferably methyl acrylate.
• the monomers (m1), (m2) and (m4) or their mixtures are liquid under the mixing conditions.
• Corresponding copolymers can be obtained in a manner known per se by radical polymerization.
• EP-A 264590 describes e.g. B. a process for the production of a molding composition from a monomer mixture of methyl methacrylate, vinyl aromatic, maleic anhydride and optionally from a lower alkyl acrylate, in which the polymerization is carried out up to a conversion of 50% in the presence or absence of a non-polymerizable organic solvent and in which the polymerization is continued from a conversion of at least 50% in the temperature range from 75 to 150 ° C. in the presence of an organic solvent to a conversion of at least 80% and then the low molecular weight volatile constituents are evaporated.
• JP-A 60-147 417 describes a process for producing a highly heat-resistant polymethacrylate molding composition in which a monomer mixture of methyl methacrylate, maleic anhydride and at least one vinylaromatic is introduced into a polymerization reactor which is suitable for solution or bulk polymerization at a temperature of 100 up to 180 ° C is fed and polymerized.
• DE-OS 44 40 219 describes a further manufacturing process.
• binders are those poly (meth) acrylate compounds which, for. B.
• EP-A 245 647 describes e.g. B. a process for the preparation of poly (meth) acrylate molding compositions by means of emulsion polymerization at polymerization temperatures of 0 to 100 ° C, for. B. from 20 to 90 ° C, in the presence of an initiator-controller ratio of at least 1: 2, preferably 1: 5 or above.
• the poly (meth) acrylate molding compositions obtained in this way have a proportion of tacticity in syndiotactic triads of over 60%, while the isotactic proportion is preferably less than 5%.
• the TD values of the molding compositions (2% depolymerization at a heating rate of 5 ° C./min) are preferably at least 290 ° C.
• the Vicater softening temperatures VET (ISO 306 B) are in the range from 115 to 122 ° C.
• Polymers prepared accordingly can consist of 90 to 100% by weight of methyl methacrylate units. In proportions of 0 to 10, preferably 0 to 5, in particular 0 to 2% by weight, free-radically polymerizable comonomers such as, for.
• methyl acrylate ethyl acrylate, methacrylonitrile, maleic acid, maleic anhydride, methacrylic ester or amides, styrene, p-methystyrene, vinyl ester or vinyl amides may be included.
• Poly (meth) acrylimide compounds which have been obtained from a partial or complete imidation of polymers of alkyl esters of methacrylic acid by reaction with an imidating agent can also be used as binders (see, for example, EP-A 441 148 or EP-A 666 161 ).
• Poly (meth) acrylimide compounds with a degree of imidation (glutarimide content) of 50 to 100, preferably 60 to 95, in particular 65 to 80% by weight are preferred.
• the poly (meth) acrylimide compounds usually contain other comonomers such as methacrylic acid and methacrylic anhydride at degrees of imidation below 100% as by-products of the imidation process. B. in amounts of 1 to 15 wt .-%.
• Suitable solvents are halogenated or preferably halogen-free aliphatic, cydoaliphatic, aromatic hydrocarbons, ketones, esters, ethers, alcohols or phenols, in which the binders mentioned dissolve well.
• Suitable solvents are e.g. B. toluene, xylene, tetrahydrofuran, ketones, such as acetone, methyl isobutyl ketone, isophorone, butanone, methyl ethyl ketone esters, such as methyl acetate, ethyl acetate, butyl acetate, butyl propionate, methoxypropyl acetate, alcohols such as methanol, ethanol or isopropanol, halogenated hydrocarbons such as chloroform, methylene chloride.
• ketones such as acetone, methyl isobutyl ketone, isophorone, butanone, methyl ethyl ketone esters, such as methyl acetate, ethyl acetate, butyl acetate, butyl propionate, methoxypropyl acetate
• alcohols such as methanol, ethanol or isopropanol
• B Mixtures of methyl ethyl ketone and alcohols, e.g. B. ethanol, isopropanol and / or butanol. Mixtures of xylene, methyl ethyl ketone, butyl acetate, ethoxylated alcohols, e.g. Example, ethoxy-butanol, and / or methoxybutyl acetate (Butoxyl®), where the mixture may contain smaller proportions of solvent naphtha (solution benzene or heavy benzene, mixtures of 50 to 70% cumene, 30 to 40 xylene and 2 to 7% naphthalene oil).
• solvent naphtha solution benzene or heavy benzene, mixtures of 50 to 70% cumene, 30 to 40 xylene and 2 to 7% naphthalene oil.
• the lacquer can optionally contain customary auxiliaries, preferably in an amount of up to 15% by weight, in particular from 0.1 to 10% by weight.
• auxiliaries used in paints are e.g. B. flow aids or UV protection agents or UV absorbers, optionally fillers, wetting agents, preservatives.
• UV protection agents such as are known as additives to plastics and are listed in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 15, pages 253 to 260, and / or advantageously by polymerizable UV Stabilizers reached.
• An example of polymerizable UV stabilizers is 3- (2-benzotriazolyl) -2-hydroxy-5-tert-octylbenzyl methacrylamide.
• UV absorbers can e.g. B. in amounts of 0.1 to 10 wt .-% based on the paint dry substance. Insert-molding / process
• the insert molding process uses foils made of transparent or translucent plastics that are printed on the back with screen printing inks.
• the printed foils are reshaped and reinforced on the back in an injection molding system by back injection with thermoplastic materials to give thicker insert molding parts.
• B. poly (meth) acrylates which consist of 80 to 99.9 wt .-% of methyl methacrylate and 0.1 to 20 wt .-% of other comonomers.
• Suitable comonomers are e.g. B. esters of methacrylic acid (e.g.
• esters of acrylic acid e.g. methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate
• acrylic acid e.g. methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate
• styrene and styrene derivatives such as ⁇ -methylstyrene or p- methylstyrene.
• Impact modifiers for polymethacrylate plastics are well known.
• As impact modifiers for the poly (meth) acrylates crosslinked single- or multi-layer emulsion polymers, which, for. B. consist of cross-linked polybutyl acetate, are used.
• Production and construction of impact-modified polymethacrylate molding compositions are known, for. B. in EP-A 0 113 924, EP-A 0 522 351, EP-A 0 465 049 and EP-A 0 683 028.
• the film thickness can e.g. B. 10 to 500, preferably 50 to 300 microns.
• the printed film is an intermediate product for the corresponding insert molding parts.
• the foils are screen-printed in a manner known per se (see, for example: E. Schulz: An instructive specialist seminar in Stuttgart: Printing on plastics, Packaging Review 11/1985, pp. 1262 - 1270 or W. Krause: " Screen printing on plastics, development tendencies ", Plastver für, No. 9, 1981, S. 1249 - 1251).
• the process for making insert molding parts includes the following process steps,
• the film is in a holding device, for. B. a hold-down, fixed and at a temperature that can be between room temperature, that is from about 20 ° C to below the Vicat softening temperature (VET according to ISO 306 method B), under pressure, for. B. by means of compressed air from z. B. 50 to 300 bar, formed.
• a corresponding method is e.g. B. known from EP-A 0 371 425.
• the printed foils are placed in such an injection molding tool that the printing is directed to the nozzle side and are z.
• Thermoplastic materials such as polycarbonate, mixtures of polycarbonate with acrylonitrile butadiene stryrene (ABS), ASA and preferably polymethyl methacrylate are suitable for back molding.
• B. Poly (meth) acrylates which consist of 80 to 99.9 wt .-% of methyl methacrylate and 0.1 to 20 wt .-% of other comonomers.
• Suitable comonomers are e.g. B. esters of methacrylic acid (e.g. ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate), esters of acrylic acid (e.g.
• methyl acrylate ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate) or styrene and styrene derivatives, such as ⁇ -methylstyrene or p- methylstyrene.
• Polymethyl methacrylates are particularly preferred, the copolymers of 98 to 95% by weight of methyl methacrylate and 2 to 5% by weight of methyl acrylate with an average molecular weight (weight average; measured by DSC or determined by means of gel chromatography) in the range from 100,000 to 200,000, preferably from 100,000 to 130,000 (Dalton). Z is particularly suitable.
• B. a molding composition which is a copolymer of 97 wt .-% methyl methacrylate and 3 wt .-% methyl acrylate and has an average molecular weight of about 110,000.
• Suitable tool temperatures are in the range from 40 to 80 ° C, preferably from 55 to 65 ° C.
• the melt temperature can be in the range from 220 to 300 ° C. are preferably from 240 to 260 ° C.
• the hot runner temperature of the tool can be in the range from 220 to 300 ° C., preferably from 240 to 260 ° C.
• the injection speed can be varied from low to high.
• the finished, cooled insert molding part can be removed from the mold.
• An insert molding part according to the invention consists of a film made of a thermoplastic, preferably a transparent thermoplastic, in particular a film made of a polymethyl methacrylate copolymer, which is printed on the back with the color lacquer according to the invention and on this side with a lacquer layer made of a thermoplastic material, which is preferably a polymethyl methacrylate copolymer, which was applied in a back injection process.
• the insert molding parts according to the invention can have numerous uses, e.g. B. as device covers covers z. B. for electronic devices, mobile phones (cell phones), backlit displays such. B. for instruments or z. B. as colored lights, e.g. B. flashing lights or taillights, e.g. B. in motor vehicles, rail vehicles or aircraft
• Advantageous effects of the invention e.g. B. as device covers covers z. B. for electronic devices, mobile phones (cell phones), backlit displays such. B. for instruments or z. B. as colored lights, e.g. B. flashing lights or taillights, e.g. B. in motor vehicles, rail vehicles or aircraft
• the color varnish according to the invention has the advantage that it is resistant to high pressures and temperatures during the injection molding process for the production of insert molding parts. Furthermore, the printed image shows no noticeable discoloration or yellowing even after the insert molding parts have been used for a long time.
• the insert molding parts according to the invention are notable for high transparency and weather resistance, in particular if the outer films and / or the back-coating lacquer is a polymethyl methacrylate copolymer.
• the insert molding parts obtainable according to the invention therefore meet high quality requirements such as, for. B. for backlit displays or lights in the automotive or aerospace industries.
• test specimens Commercial films made of impact-modified polymethyl methacrylate were printed on one side with various screen printing varnishes (varnishes 1 to 3) and then back-injected on the printed side with a polymethyl methacrylate plastic and thus reinforced to form insert molding parts (test specimens). The test specimens were then checked for washouts of the printing.
• the thickness of the foils used was 250 ⁇ m.
• the films were pre-dried with (MT) and without (OT)
• Lacquer 1 (according to the invention):
• the paint 1 consists of a solvent mixture
• the Vicater softening temperature of the VET binder according to ISO 306 B is in the range from 119 to 123 ° C
• Lacquer 2 (according to the invention):
• the composition corresponds to varnish 1 with the difference that a polymethacrylimide copolymer consisting of an approximately 70% imidized polymethyl methacrylate is contained as a binder.
• the copolymer also contains about 4 to 6% by weight of methacrylic acid and about 4 to 6% by weight of methacrylic anhydride as comonomers.
• the Vicater softening temperature of the VET binder according to ISO 306 B is in the range from 143 to 152 ° C
• composition corresponds to paint 1 with the difference that a commercially available polycarbonate is used as the binder.
• a hot runner tool with a needle valve gate was used.
• the cavity had a dimension of 100 x 100 mm with four different height levels of 1, 2, 3 and 4 mm (step plate).
• the printed foils were cut and placed in the tool so that the printing points in the direction of the injection nozzle.
• the back injection was carried out under the four different conditions A to D, where A is the highest requirement for the durability of the screen printing and D the lowest.
• Injection molding was carried out with a molding compound made of polymethyl methacrylate (copolymer of 97% by weight methyl methacrylate and 3% by weight methyl acrylate with an average molecular weight of approx. 110,000, measured by DSC or by means of gel chromatography).
• High injection speed 100% of the possible performance of the system.
• Low injection speed approx. 25% of the possible performance of the system.
• the insert molding parts were removed from the tool and the washout of the screen print was assessed visually with a grading system for washouts of the printed image.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Mechanical Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Injection Moulding Of Plastics Or The Like (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Coloring (AREA)
• Printing Methods (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)

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  • 2002-08-13 US US10/486,202 patent/US20040236019A1/en not_active Abandoned
  • 2002-08-13 EP EP02762443A patent/EP1425356A1/de not_active Withdrawn
  • 2002-08-13 JP JP2003523550A patent/JP4588996B2/ja not_active Expired - Fee Related
  • 2002-08-13 WO PCT/EP2002/009055 patent/WO2003018697A1/de active IP Right Grant
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  • 2002-08-13 CA CA002458265A patent/CA2458265A1/en not_active Abandoned
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