Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/60—Polyamides or polyester-amides
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
  • C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
  • C08G18/345—Polycarboxylic acids having at least three carboxylic acid groups having three carboxylic acid groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
  • C08G18/8074—Lactams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/14—Polyamide-imides
• • 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
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to aqueous solutions of polyimide structure and, if appropriate, polyamide structure-containing resins having blocked isocyanate groups (also referred to below as “polyimides or polyamideimides” or “resins”) which are easy to form high-quality, very flexible coatings with the for polyamide-imides, excellent thermal properties and chemical resistance, a process for their preparation and their use.
• polyimides or polyamideimides also referred to below as "polyimides or polyamideimides” or “resins”
• JP 2005 120134 describes water-soluble polyamideimides which are obtained by reacting aromatic polyisocyanates and tribasic acid anhydrides.
• high molecular weight polymers having number average molecular weights between 5,000 and 50,000 g / mol are brought into the aqueous phase.
• the adjustment of the high molecular weight is done by specific choice of the equivalence ratio of isocyanate groups to acid and anhydride groups. It is pointed out that while molecular weights below 5000 g / mol simplify the handling and thus the dispersion of the resin, the properties of the products are reduced. Resins and their solutions that are easy to process but at the same time also lead to coatings with a high level of properties are desirable.
• the polyamide-imides thus formed can also be reacted with blocked or unblocked polyisocyanates.
• the examples do not list such reactions, either with unblocked isocyanates or with blocked isocyanates.
• a statement on the workability of the polyamide-imides or their solutions can not be found in the US patent.
• No. 4,429,073 describes water-soluble polyetherimides which are obtainable, for example, from the reaction of bis (ether anhydrides) with polyamines. After cleavage of the imide with water in the presence of an amine, cross-linking can be achieved by adding a trifunctional isocyanate component, which is favored by blocking on the isocyanate. In the embodiments, an alcohol or phenol are used as blocking agents.
• crosslinked coatings do not have sufficient flexibility and adhesion for all requirements.
• polyamide-imides and polyimides are well-known.
• high molecular weight polyamideimides are synthesized from polycarboxylic acid hydrides, lactams and polyisocyanates, these being added to one another with ring opening of the lactam.
• the resulting polymers are characterized by a special temperature resistance (DE 1770202), but are highly viscous and must therefore be processed at high temperatures. About other qualities of these films, the Scripture is no statement.
• the further reaction of the polymers with selected lactams leads, as described in DE 3332033, to thermoplastics with good mechanical properties.
• the two Japanese documents JP 58-002097 and JP59-137454 report lactam and blocked polyamideimide resins from the reaction of aromatic diisocyanates with tricarboxylic anhydrides and the blocking agent in the presence of basic solvents.
• the lactam-blocked polyamide-imide resins can also be reacted with bases, other blocked isocyanates, and polyester resins, aiming at faster curing of the films obtained therefrom and improvement in flexibility and heat shock of the resulting coatings.
• the invention relates to a process for preparing aqueous solutions of NCO groups of blocked resins having number average molecular weights (M n ) of from 1,000 to 7,000 g / mol, which have polyimide structures and optionally also polyamide structures, characterized in that first off
• a polymer is prepared, to which optionally further amounts
• the resulting resin is finally dissolved in water; wherein the water may be added to the resin or the resin is added to the water.
• a solution is to be understood as meaning a homogeneous solution or a colloidal solution up to a finely divided dispersion.
• water-soluble also includes water-dispersible in this document.
• M n number-average molecular weights
• the amount of isocyanate groups of component a) is preferably from the amounts of the isocyanate-reactive groups of components b), bl), b2), d), dl) and d2) in a molar ratio of 0.95 to 1 to 1, 15 to 1, the amount of isocyanate groups of component a) to the amount of isocyanate-reactive groups of component c) in a molar ratio of 1 to 0.05 to 1 to 0.35, and the amount of basic groups of component e) to Amount of acid and / or acid anhydride groups of components b), bl), b2), d), dl) and d2) used in a molar ratio of 1 to 1 to 2 to 1.
• useful polyisocyanates a) are aromatic polyisocyanates, aliphatic or cycloaliphatic polyisocyanates.
• Preferred polyisocyanates are those having a uniform or average molecular weight of from 140 to 500 g / mol, with an average average NCO functionality of not more than 2.6.
• Such polyisocyanates are, for example, 1,4-phenylenediisocyanate, 2,4- and 2,6-diisocyanatotoluene (TDI) and any desired mixtures of these isomers, 4,4'-, 2,4'- and 2,2'-diisocyanates.
• TDI 2,4- and 2,6-diisocyanatotoluene
• natodiphenylmethane or any mixtures of these isomers or mixtures of these isomers with their higher homologs, as obtained in a conventional manner by phosgenation of aniline / formaldehyde condensates, 1,5-naphthylene diisocyanate 1,4-butane diisocyanate, 2nd - methyl pentane-l, 5-diisocyanate, 1,5-hexane diisocyanate, 1,6-hexane diisocyanate (HDI), 1,3- and 1, 4-cyclohexane diisocyanate and any mixtures of these isomers, 2,4- and 2,6-di - Isocyanato-1-methylcyclohexane and any mixtures of these isomers, 3,5,5-trimethyl-3-isocyanatomethylcylohexanisocyanat and dicyclohexylmethane-2,4'- and -4,4'-di
• Diisocyanates which are very particularly preferably used are 4,4'-, 2,4'- and 2,2'-diisocyanatodiphenylmethane or any desired mixtures of these isomers.
• Suitable components b) include cyclic tricarboxylic monoanhydrides such as trimellitic anhydride, hemimellitic anhydride and benzophenone-3,4,3'-tricarboxylic anhydride, and tetracarboxylic dianhydrides such as pyromellitic anhydride and benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride or mixtures of these compounds , Preference is given to tricarboxylic monoanhydrides such as trimellitic anhydride, hemimellitic anhydride and benzophenone-3,4,3'-tricarboxylic anhydride. Particularly preferred component b) is trimellitic anhydride.
• the tri- or tetracarboxylic acids b1) formed from components b) by hydrolysis can also be used at least proportionally.
• aliphatic, alicyclic or aromatic dicarboxylic acids or their anhydrides b2) can be used to change the properties of the coatings according to the requirements. In this way, e.g. an elastification of the coating take place.
• component b2) there are succinic, glutaric, adipic, pimelic, cork, azelaic, sebacic, nonandicarboxylic, decanedicarboxylic, terephthalic, isophthalic, o-phthalic, tetrahydrophthalic and hexahydrophthalic acids and acid anhydrides, such as o-phthalic or succinic anhydride in question.
• Suitable blocking agents c) for the NCO groups of component a) are 3,5-dimethylpyrazole, butanone oxime and lactams with secondary amide nitrogen atoms, such as, for example, ⁇ -caprolactam, ⁇ -valerolactam and butyrolactam.
• Preferred component c) are 3,5-dimethylpyrazole and ⁇ -caprolactam.
• Particularly preferred component c) is ⁇ -caprolactam.
• Also suitable as blocking agents c) are mixtures of said blocking agents c). Particularly suitable are mixtures of 3,5-dimethylpyrazole and ⁇ -caprolactam in a molar ratio of 0.1 to 0.9 to 0.9 to 0.1.
• suitable components d), d1) and d2) are the same compounds which have already been mentioned as component b), bl) and b2).
• Suitable components e) include, for example, amines substituted with alkyl groups which do not carry any further functional groups. These include propylamine, butylamine, dibutylamine, tri- methylamine, triethylamine, tributylamine, dimethylisopropylamine, ethyldiisopropylamine, dimethylcyclohexylamine, N-methylmorpholine and N-ethylmorpholine.
• other organic amines e) which have further reactive groups are also suitable, for example ethanolamine, diethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine and triethanolamine.
• amines which are trialkyl-substituted for example trimethylamine, triethylamine, tributylamine, dimethylisopropylamine, ethyldiisopropylamine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, N-methyldiethanolamine and triethanolamine.
• component e) tertiary amine and OH group-bearing compounds such as N, N-dimethylethanolamine, N-methyldiethanolamine and triethanolamine.
• solvents which dissolve the solvents allow dispersibility of the resin.
• Suitable solvents are those which have no isocyanate-reactive groups and are capable of dissolving the resins at temperatures below 15O 0 C. Dioethyl sulfoxide, dimethylacetamide, dipropylene glycol dimethyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, N-cyclohexylpyrrolidone, N-octylpyrrolidone, N-methylbutyrolactam, N-methylvalerolactam and N-methylcaprolactam are suitable for this group of solvents.
• Preferred solvents are N-methylpyrrolidone, N-ethylpyrrolidone, N-methylbutyrolactam, N-methylvalerolactam and N-methylcaprolactam.
• Particularly preferred solvents are N-methylpyrrolidone and N-ethylpyrrolidone.
• Mixtures of the solvents mentioned are also suitable, in particular those mixtures of N-ethylpyrrolidone with N-methylpyrrolidone, dimethyl sulfoxide, dimethylacetamide or dipropylene glycol dimethyl ether.
• the amount of solvent is such that a rapid escape of the resulting from the reaction of isocyanate with carboxylic acid groups carbon dioxide is possible. In this way, foaming of the mixture in the reaction vessel is prevented.
• the amount of solvent should be chosen so that the viscosity of the resins is so low that they then dissolve in water, or can be dispersed. Thus, the viscosity necessary for successful dispersion is u.a. also dependent on the effectiveness of the dispersing apparatus.
• the amount of solvent, based on the sum of the raw materials used, is preferably a), b), b1), b2), d), d1), d2) and c) 20 to 100% by weight, preferably 30 to 90% by weight and especially preferably from 40 to 80% by weight.
• the preparation of the solutions according to the invention takes place in several steps.
• First, the components a) to c) are reacted in any order at temperatures of 20 to 80 0 C with each other, with the proviso that when adding the component c) at least the equimolar amount of NCO groups is opposite and thus the complete incorporation of the component is ensured.
• the temperature control or else the rate at which the components are added is selected so that the evolution of CO 2 takes place in a controlled manner and there is no escape of the reaction mixture from the reaction vessel.
• the amount of foam that may be produced may only be dimensioned so that sufficient mixing is ensured.
• the reaction temperature is raised in the further course of the reaction to about 110 0 C to 150 0 C, so that over time as uniform as possible reaction takes place.
• the reaction mixture is kept at the final temperature until the deposited amount of CO 2 is 90 to 120%, preferably 95 to 110% and most preferably 98 to 110% of theory.
• the blocking agent c) and the components b), bl) and b2) are completely or only partially presented and diluted with a part or else the entire amount of solvent.
• the components can be mixed at temperatures of 10 0 C to 150 0 C, but preferably the mixing takes place at 20 to 8O 0 C.
• Optionally retained amounts of solvent can be added at any point. Furthermore, the procedure is as described above.
• component a) It is likewise preferred to initially charge component a) and to meter in components b), bl), b2) and c), either singly or in mixture, preferably in a mixture, at the abovementioned temperatures, completely or in stages.
• component e) After the desired CO is cleaved 2 amount in one of the selected embodiments, and optionally component d), dl) and / or d2) of the polymer solution is added is component e) at temperatures of 10 to 100 0 C, preferably 30 to 80 0 C, more preferably 40 to 80 0 C added and for 0.5 to max. Stirred for 20 h. Subsequently, water is added to the resin solution under shear. The amount of water is such that the solids content of the aqueous resins 10 to 40 wt .-%, preferably 15 to 35 wt .-% and particularly preferably 20 to 30 wt .-% is.
• the temperature of the water is 20 to 100 0 C, preferably 40 to 80 0 C and particularly preferably 50 to 80 0 C.
• the mixture is stirred with sufficient energy input until a homogeneous solution or a finely divided dispersion is obtained. Subsequently, the aqueous form of delivery of the resin is cooled.
• not the water is supplied to the resin but the resin to the water - in otherwise unchanged conditions compared to the first embodiment.
• the resulting aqueous solutions of NCO groups of blocked polyamide-imide or polyimide resins according to the invention can be used as coating compositions or for the production of coating compositions.
• they are applied alone as a thermally curable 1K baking system.
• they can also be mixed in admixture with preferably OH-functional, but also with OH-free, aqueous binders and processed as an IK baking system.
• Suitable aqueous binders are the OH group-containing or OH-group-free primary or secondary polyacrylate dispersions, secondary polyester-polyacrylate dispersions, polyurethane dispersions customary in coating chemistry.
• compositions obtainable using the aqueous solutions according to the invention NCO groups of blocked Polyimidstruk- tur- and optionally also having polyamide structure-containing resins, and the coatings and coated substrates obtainable therefrom.
• the coating compositions of the invention may be applied to substrates such as e.g. Metal, plastic, glass or mineral substrates as well as on already coated substrates are applied.
• a preferred application is the use of the coating compositions according to the invention for the production of coatings on metal.
• a particularly preferred application is the use of the coating compositions according to the invention for coating metal casings, in particular in the area of can coating.
• the coating compositions according to the invention may also contain the auxiliaries and additives known per se from coating technology, such as, for example, Fillers and pigments included.
• the application of the coating agent can be carried out in a known manner, for example by brushing, pouring, knife coating, spraying, spraying, spinning, rolling or dipping.
• the baking of the coatings is carried out after prior drying - the evaporation of the coating at room temperature in a one-step or multi-step process.
• the baking takes place in a two-stage process in which first drying for 1 to 20 minutes, preferably 2 to 10 minutes at 50 to 130 0 C, preferably at 70 to 100 0 C, followed by drying in the second step 1 to 10 minutes, preferably 2 to 7 minutes at temperatures between 180 and 300 0 C, preferably 200-280 0 C takes place.
• the increase in temperature can also be carried out continuously in corresponding ovens to ensure optimum burn-in.
• the viscosity was measured with a cone-plate viscometer Physika MC 51 from Anton Paar.
• IR spectroscopy was performed on an FTIR spectroscope, MB-Series, Bomem.
• Solids content drying of the aqueous solution for 3 hours at 200 0 C in a convection oven.
• GPC The eluent used was N.N-dimethylacetamide at a flow rate of 0.6 ml / min.
• the stationary phase used was four columns, HEMA 3000, HEMA 300, HEMA 40, HEMA 40, from Polymer Standards Service, Mainz, Germany. Each column has a length of 300 mm and a diameter of 8 mm.
• the particle size of the filler is 10 ⁇ m.
• MEK wipe test pressure 1 kg: The test plate was fastened on the weighing pan of the balance by means of a film clamp and anti-slip foil. The balance was adjusted using the 100 g weight stone. A cotton swab soaked with MEK was agitated against the selected proof on the paint film until the paint film was destroyed. - -

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Polyurethanes Or Polyureas (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Paints Or Removers (AREA)

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• 2006
  • 2006-11-03 DE DE102006052240A patent/DE102006052240A1/de not_active Withdrawn
• 2007
  • 2007-10-24 WO PCT/EP2007/009211 patent/WO2008052688A2/de not_active Ceased
  • 2007-10-24 JP JP2009535593A patent/JP2010508427A/ja not_active Ceased
  • 2007-10-24 KR KR1020097011377A patent/KR20090086426A/ko not_active Ceased
  • 2007-10-24 BR BRPI0717885-9A2A patent/BRPI0717885A2/pt not_active IP Right Cessation
  • 2007-10-24 CN CNA2007800492659A patent/CN101578310A/zh active Pending
  • 2007-10-24 MX MX2009004560A patent/MX2009004560A/es unknown
  • 2007-10-24 EP EP07846503.6A patent/EP2087023B1/de not_active Not-in-force
  • 2007-10-24 CA CA002668174A patent/CA2668174A1/en not_active Abandoned
  • 2007-10-30 US US11/978,917 patent/US20080146764A1/en not_active Abandoned
• 2009
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