Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B7/00—Insulated conductors or cables characterised by their form
  • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
  • H01B7/29—Protection against damage caused by extremes of temperature or by flame
  • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0853—Ethylene vinyl acetate copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/02—Copolymers with acrylonitrile
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/02—Inorganic materials
  • C09K21/04—Inorganic materials containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/14—Macromolecular materials
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
  • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
  • F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34928—Salts
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L13/00—Compositions of rubbers containing carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
  • C08L15/005—Hydrogenated nitrile rubber

Definitions

• This invention relates to a fire-resistant rubber composition.
• This invention also relates to a fire-resistant hose comprising the fire-resistant rubber composition.
• Rubber hose is in wide use for material transfer and fluid power applications.
• Fire resistance standards for hose used in transportation vehicles have become increasingly stringent. The most stringent standards apply to hose used on railway passenger trains, in particular trains that travel substantially through tunnels. Examples of such standards include British Standard BS 6853:1999 [class Ia], Norme Frangais or French Standard NF F 16-101 [category A1], and German Standard DIN 5510-2.
• hose must comply with the various conventional design requirements, such as listed in relevant railway standards including UIC 830-1 and the like. Hose performance includes such factors as burst pressure, cold flexibility, oil resistance, hot air resistance, ozone resistance, and structural integrity of various adhered layers. It is generally recognized in the art that the more fire retarding additives one mixes into the rubber in an attempt to meet fire standards, the worse the physical properties become.
• US Patent No. 5,34-0,867 discloses a flame-retardant rubber composition based on red phosphorous and a nitrile-group containing elastomer, but the LOI is only about 27.5%.
• US Patent No. 4,533,687 discloses a fire-retarding synergistic blend of ATH and red phosphorous in combination with organopolysiloxane for improving the fire-resistance of olefin-type elastomers, but the highest LOI repo rted is only 30%. What is needed for a hose to comply with NF F 16-101 is an LOI greater than 34%.
• the invention is directed to a rubber composition with improved fire resistance and to a hose comprising the rubber composition.
• the rubber composition comprises: 100 parts by weight of elastomer comprising 50-1 00 parts of at least one olefin-type elastomer; at least one fire-retardant boron source; at least one phosphorous source; at least 75 parts of at least one fire-retardant metal-hydrate; and at least one selected from the group consisting of a fire-retardant nitrogen compound and a nitrile-contai ning elastomer.
• the rubber composition comprises: 100 parts by weight of an elastomer base comprising a blend of a halogen-free olefin-type elastomer and from about 10 to less than 50 parts of a halogen-free nitrile-containing elastomer; 10-20 parts of a boron source; 2-34 parts of a phosphorous source; 75-195 parts of a metal hydrate; and up to 16 parts of a fire- retarding nitrogen compound.
• the rubber composition comprises: 100 parts by weight of an elastomer base comprising a blend of EVM and less than 50 parts HNBR; 10 to 20 parts of zinc borate; 2 to 8 parts of red phosphorous; 75 to 195 parts of aluminum trihydrate; 14 to 26 parts of trioctylphosphate; and up to 16 parts of melamine phosphate.
• the rubber composition may optionally comprise conventional rubber chemicals such as antioxidants, processing aids, antiozonants, curatives, coagents, and fillers. The properties of the composition may thus be adjusted to meet specific physical characteristics such as modulus, tensile strength, abrasion resistance , low temperature flexibility, and the like.
• the rubber composition should also not comprise toxic smoke-generating fire-retardant ingredients, such as halogen-containing fire retardants, antimony compounds, more than 20 parts carbon black, or the like.
• the hose articles of the invention encompass various types of reinforced hose generally of a flexible nature including, by way of illustration, railroad air-brake hose, sand-brake hose and coolant hose, automotive radiator and heater hose, hydraulic hose, protective sleeve for cable, and the like.
• the invention is not limited to any specific type of hose.
• the hose may comprise a cover utilizing the fire- resistant composition, a tube utilizing the composition, or both.
• the tube and cover may comprise distinct embodiments of the composition.
• the invention is a fluid handling system comprising a fire-retardant hose as described above, a pump, and a connector.
• FIG. 1 is a perspective view, with parts in section, of a hose constructed in accordance with the present invention.
• FIG. 2 is a schematic representation of a fluid-handling system comprising a hose constructed in accordance with the present invention. DETAILED DESCRIPTION OF THE INVENTION
• the hose 11 comprises an elastomeric inner tube 12, a reinforcement member 14 telescoped over and preferably adhered to the inner tube 12, and an elastomeric outer cover 16 telescoped over and preferably adhered to the reinforcement member 14.
• the reinforceme nt member 14 is formed of a suitable reinforcement material which may include organic or inorganic fibers or brass-plated steel wires. Useful organic fiber reinforcement materials include nylon, polyester, aramid, cotton and rayon.
• the reinforcement construction may be of any suitable type such as braid, spiral, knit or wrapped, but in the embodiment shown, is of a braid construction.
• the reinforcement member 14 may comprise one or more layers of fiber reinforcement and one or more fiber reinforcement materials.
• the inner tube 12 may consist of multiple elastomeric or plastic layers which may or may not be of the same composition.
• the elastomeric outer cover 16 is made of suitable materials designed to withstand the exterior environment encountered.
• the inner tube 12 and the outer cover 16 may be made of the same material.
• the hose 11 may be formed by any conventional methods i including molding and extrusion. At least one elastomeric layer of either the inner tube 12 or outer cover 16 may be made more fire resistant according to the present invention, thus improving the fire resistance of the hose.
• the hose comprises at least one layer of rubber of the inventive composition. In another embodiment of the invention, substantially all of the rubber in the hose is of the inventive composition.
• the inventive composition may be adjusted using known rubber compounding techniques to achieve different properties for various layers.
• the inner tube layer 12 has a lower loading of fillers for higher dynamic performance, while the outer cover layer 16 has a higher filler loading to give higher abrasion resistance and toughness.
• the rubber composition of the present invention comprises a halogen-free elastomeric blend mixed with several fire-retardant ingredients and various optional ingredients.
• each individual component is known in the art, the combination is new.
• the effects of each component are generally known for some polymer systems in the art, the effects of combining these ingredients and/or using them in different polymer systems are unpredictable. It is generally unknown whether the effects of individual ingredients will be additive, synergistic or antagonistic when combined. What is generally known is that increased amounts of any particular fire retardant ingredient or combination, while increasing the fire resistance of the compound, will degrade the physical properties and/or the processing characteristics of the resulting composition. Thus, the improvements sought are very difficult to achieve.
• the halogen-free elastomer is selected from the group of olefin-based polymers, and acrylate polymers, and includes olefin-based copolymers such as ethylene-acrylic copolymers and ethylene-vinylacetate (EVM) copolymers.
• Olefin- based polymers include ethylene-alpha-olefins such as ethylene-propylene, ethylene-butene, and ethylene-octene and ethylene-alpha-olefin-diene terpolymers. These elastomers are generally quite flammable, but generate low smoke. They require significant compounding effort to achieve the physical properties required for hose.
• the EVM may have a vinylacetate content in the range from 35% to 75%.
• One embodiment of the invention comprises EVM having a vinylacetate content of about 50%.
• a second halogen-free elastomer is a nitrile-containing elastomer and is preferably selected from the group consisting of nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene (HNBR), and nitrile-butadiene terpolymers in which a third monomer, such as styrene, one of various acrylates or the like, is typically included to adjust glass transition temperature, for example to improve low or high temperature properties.
• the nitrile-containing co- and terpolymers may be hydrogenated or carboxylated or both.
• One embodiment of the invention comprises HNBR because of its high strength and heat resistance and compatibility with EVM.
• the HNBR may have a nitrile content in the range from 17% to 50% and a residual unsaturation level in the range from 0% to 15%.
• One embodiment of the invention comprises HNBR having a nitrile content of about 34% and unsaturation of about 4%.
• the nitrile-containing elastomer is also believed to function as a fire-retardant source of nitrogen or promote cnar formation.
• the metal hydrate is preferably one or more selected from the group aluminum trihydrate (ATH), magnesium hydroxide, calcium hydroxide, magnesium carbonate and the like.
• Metal hydrate is selected as a filler because of its cost effectiveness and the large amount of water released at high temperatures, which dilutes the oxygen supply in the atmosphere surrounding the hose.
• the metal hydrate may optionally be surface treated with stearic acid , silane, or the like for improved dispersion or reinforcement.
• One embodiment of the invention comprises ATH sold under the trademark of Apyral 6OD by ⁇ NIabaltec with a particle size of 4.5 ⁇ m and a surface area of 6.5 m 2 /g.
• the amount of metal hydrate may be in the range of from 75 parts to 195 parts based on 1 00 parts of elastomer. Below 75 parts, there will not be sufficient fire-retarding effect. Above 195 parts, the processability and physical properties of the compound will degrade. In particular, excessively high levels of metal hydrate lead to excessively high- viscosity compounds that cannot be mixed and/or extruded properly.
• the boron source is preferably selected from the group consisting of boric acid, sodium borate, and zinc borate.
• One embodiment of the invention comprises zinc borate sold under the trademark Firebrake ZB by Luzenac.
• Zinc borate is believed to react synergistically with ATH to produce a fire-resistant, smoke- suppressing char.
• the amount of boron source may be in the range from about 10 parts to about 20 parts based on 100 parts of elastomer, which is the optimum range for the synergistic effect with ATH.
• a nitrogen compound is preferably selected from the group consisting of melamine, melamine cyanurate, ammonium phosphates and melamine phosphates. It is chosen for its ability to act as a heat sink, inert gas-phase diluent, poor fuel, and because it produces a porous, insulating char. The foaming/char- f ⁇ rming effect is known as intumescence.
• the choice of nitrogen compound is generally based on compatibility with the elastomer blend. A suitably chosen nitrogen compound can improve the rubber physical properties while permitting a reduction in the amount of metal hydrate, thus improving processability and performance without sacrificing fire-resistance.
• a preferred amount of nitrogen compound is the range from about 4 parts to about 16 parts based on 100 parts of elastomer. Below 4 parts, the fire retarding effect will not be sufficient, and much more of the metal hydrate will be required resulting in poor physical properties and high viscosity.
• One embodiment of the invention comprises melamine phosphate (sold for example under the trademark Melagarp MP by Italmatch, or Melapur MP by Ciba Specialties) as the nitrogen compound.
• the phosphorous source is preferably from the group ammonium polyphosphate, red phosphorous, and phosphate esters.
• One embodiment of the invention comprises red phosphorous because of its well known fire-retarding, char-forming synergy with ATH. Red phosphorous is also believed to improve the fire resistance of nitrile-containing elastomers.
• the red phosphorous may be predispersed or bound in polymeric resin for ease in handling. For example, red phosphorous bound in ethylene-vinylacetate (EVA) may be used.
• EVA ethylene-vinylacetate
• the amount of red phosphorous (sold under the trademark Masteret 40470 by- Italmatch) should be in the range from about 2 to about 8 parts per 100 parts elastomer for optimum fire retarding synergy with the ATH.
• Another embodiment of the invention comprises a combination of red phosphorous and phosphorous-containing plasticizer such as trioctylphosphate as the phosphorous.
• the amount of phosphorous source may thus be increased to as much as 34 parts per 100 parts of elastomer.
• the phosphorous-containing plasticizer is beliaved to serve the dual role of promoting char forming and providing a way to adjust the modulus or flexibility of the composition.
• the plasticizer may preferably be a phosphate ester such as trioctylphosphate (TOF), triphenylphosphate, tricresylphosphate and the like.
• One embodiment of the invention comprises TOF (exemplified by Disflamoll TOF, sold under that trademark by Lanxess), which is particularly useful for improving the cold flexibility of the rubber.
• the amount of plasticizer is not critical but is chosen to give the desired physical properties. Typically the amount of plasticizer will be in range from about 10 to about 26 parts, but is not limited to that range.
• silica is believed to be helpful for char-forming.
• silica is primarily used as the reinforcing filler, giving control over the modulus and increasing the tensile strength of the rubber composition.
• Silica is inert to fire, so it does not contribute to smoke as carbon black does.
• Suitable silica sources include clays, talcs, fumed or precipitated silicas or silicates (for example various grades sold under the trademark Vulkasil by Bayer or Ultrasil by Degussa), and siliceous earth (for example that sold under the trademark Sillitin N82 by Hoffmann Minerals), and these may optionally be silane treated.
• the amount of silica is not critical, but may be chosen to give the desired physical properties.
• a small amount of carbon black less than about 20 parts per hundred parts elastomer, may be used to provide coloring.
• the large amounts of carbon black typically used in rubber compounding should be avoided because of carbon black's contribution to smoke. In one embodiment of the invention, less than about 10 parts of carbon black may be used. In another embodiment of the invention, no more than about 5 parts of carbon black may be used.
• conventional plasticizers should be avoided because they would impart increased flammability and smoke.
• Curatives are required in the composition to produce required physical properties.
• Peroxide curatives or vulcanization by ionizing radiation are preferred because both HNBR and EVM can be cured with free radicals. Free radical curing does not introduce any toxic fumes or heavy metals as some types of conventional sulfur-based accelerators would. Nevertheless, sulfur cure systems can be used if carefully chosen to avoid these problems.
• Further optional components may be used as known to those skilled in the art. These include but are not limited to antioxidants, antiozonants, process aids, coagents, reinforcing fibers, inert fillers, coupling agents, vulcanizing agents, adhesion promoters, pigments, plasticizers, and the like. As mentioned above, ingredients containing heavy metals, halogens, or otherwise likely to contribute to toxic fumes or smoke should be avoided or kept to a minimum.
• the hose or hose assembly of the present invention may also comprise a coupling, fitting or connector which is provided at either end of the hose to facilitate connection of the hose to other components of a complete fluid handling system.
• Other components of a fluid handling system include for example, one or more additional devices known in the art such as a pump, a valve, a vent, a manifold, a fitting, tubing, a gauge, a filter, a regulator, a fluid reservoir, an accumulator, and an operational device or active component.
• An active component may be for example an actuator, a brake, a motor, a cylinder, a robotic device, and the like.
• a pump may be for example a centrifugal pump, a diaphragm pump, a rotary pump, a blower, a compressor, a piston pump, a gear pump, a vane pump, or the like.
• Figure 2 represents a railroad air-brake system.
• the system comprises various lengths of the inventive hose 1 , various connecting fittings 2, 3 , 4, and 5, various valves 6, and 7, reservoirs 9, pipe or tubing 8, compressor 20, and brake cylinder 21.
• the compressor 20 may comprise a pump and a motor and supplies compressed air to the reservoirs 9.
• Fitting 5 may be an angle cock and fitting 4 may be a T.
• Example 1 is suitable for a rubber tube and has less filler and is more polymer rich than Example 2.
• Example * 2 is suitable for a cover compound.
• the resulting rubber compounds were formed into a 1 /4-inch hose for Example 3 and a 1-inch hose for Example 4 by sequential extrusion onto a mandrel.
• the tube compound was extruded first, followed by application of a polyester yarn braided reinforcement layer thereon, and finally the cover was extruded over the yam layer.
• the uncured hose was wrapped with nylon fabric, vulcanized, unwrapped and removed from the mandrel.
• Table 1 is suitable for a rubber tube and has less filler and is more polymer rich than Example 2.
• Example * 2 is suitable for a cover compound.
• the resulting rubber compounds were formed into a 1 /4-inch hose for Example 3 and a 1-inch hose for Example 4 by sequential extrusion onto a mandrel.
• the tube compound was extruded first, followed by application
• the two compositions of Examples 1 and 2 met the target for LOI as shown in Table 1.
• the physical properties of the two compositions were sufficient to ensure that the hose met the burst pressure target for railway brake hose as shown in Table 1.
• the flame resistance and smoke generation of the hose was sufficient to meet the Table 1
• LOI testing was carried out in accordance with the procedure of ASTM D-2863 (ISO 4589). Toxicity testing was carried out in a closed oven in non- flaming mode in accordance with the procedure of BS 6853:199,9 Annex B (NF X 70-100). Toxicity has no units of measure, being a weighted summation of dimensionless test results.
• Smoke testing was carried out by burning a piece or pieces of hose in accordance with the procedure of NF X 10-702. The smoke density result per NF X 10-702 and the toxicity result per NF X 70-100 were combined to obtain a Smoke Gas Index in accordance with the procedure of NF F 16-101.
• Rubber test specimens were tested for tensile strength using well-known rubber test methods. Burst strength of the hose was tested in accordance with the procedure of EN ISO 1402 (SAE J343). Smoke testing was also carried out by burning a 1 -meter bundle of hose, vertically in a closed chamber with an alcohol flame and measuring the optical density in accordance with the procedure of BS 6853:1999 Annex D. Thought the hose of Ex 3 and 4 did not pass this extremely stringent smoke test, it is believed that rubber and hose according to a different embodiment of this invention is capable of meeting this more stringent smoke standard.
• composition and hose of this invention are also believed to meet future fire resistance standards such as prEN 45545-2, which is expected to eventually replace current European local standards such as BS 6853 and NF F 16-101.
• the present invention provides a fire-resistant rubber composition and hose incorporating the same which combines the desired physical performance properties of hose with high LOI and low smoke and low toxic fume generation when subjected to fire.
• the composition may also be useful in wire and cable applications, power transmission belts, and molded rubber goods whenever extreme fire resistance is needed.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• General Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Inorganic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Rigid Pipes And Flexible Pipes (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (2)

Family

ID=36046419

Family Applications (1)

Country Status (6)

Cited By (7)

Families Citing this family (29)

Family Cites Families (31)

• 2005
  • 2005-10-26 WO PCT/US2005/038797 patent/WO2006047691A2/en not_active Ceased
  • 2005-10-26 AT AT05824748T patent/ATE406427T1/de not_active IP Right Cessation
  • 2005-10-26 ES ES05824748T patent/ES2309827T3/es not_active Expired - Lifetime
  • 2005-10-26 US US11/259,474 patent/US7754808B2/en active Active
  • 2005-10-26 DE DE602005009401T patent/DE602005009401D1/de not_active Expired - Lifetime
  • 2005-10-26 EP EP05824748A patent/EP1831329B1/en not_active Expired - Lifetime

Also Published As

Similar Documents

Legal Events