EP1528974A1 - Sound-insulating material and method for the production thereof - Google Patents
Sound-insulating material and method for the production thereofInfo
- Publication number
- EP1528974A1 EP1528974A1 EP03793726A EP03793726A EP1528974A1 EP 1528974 A1 EP1528974 A1 EP 1528974A1 EP 03793726 A EP03793726 A EP 03793726A EP 03793726 A EP03793726 A EP 03793726A EP 1528974 A1 EP1528974 A1 EP 1528974A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rubber
- sound
- particles
- insulating material
- pur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
- B29B17/0042—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
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- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/027—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles the foaming continuing or beginning when the mould is opened
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
- C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- G—PHYSICS
- G10—MUSICAL INSTRUMENTS; ACOUSTICS
- G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
- G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/16—Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/162—Selection of materials
- G10K11/165—Particles in a matrix
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- 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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
- B29C44/206—Using expandable particles or beads as starting material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0001—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular acoustical properties
- B29K2995/0002—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular acoustical properties insulating
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- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/30—Polymeric waste or recycled polymer
-
- 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
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the invention relates to a sound-insulating material, in particular for motor vehicles, which is made from thermoplastic rubber and PUR plastic, and to a method for producing such a material.
- Heavy-duty molded parts or heavy-layer mats are used in motor vehicle technology, in particular for soundproofing the passenger compartment against engine noise and driving noise. Heavy-duty molded parts and heavy-duty mats are also used to remove noise (structure-borne noise insulation) from vibrating body parts.
- the heavy layer material usually contains ethylene-propylene-diene rubber (EPDM). Heavy spar (BaS0 4 ) has proven itself as a heavy filler.
- Conventional heavy layer material which is used for sound insulation in motor vehicles, in particular for the deadening of body parts, has a relatively high weight. This is disadvantageous in the effort to reduce the fuel consumption of motor vehicles by reducing the vehicle weight.
- the object of the present invention is to provide a sound-insulating material of the type mentioned at the outset To create especially for the automotive industry, which has a relatively low weight with good sound-absorbing effect. Furthermore, an inexpensive method for producing such a material is to be specified.
- the solution to this problem according to the invention is that the rubber and the PUR plastic are mixed with one another, the rubber forming a matrix in which a multiplicity of gas-filled, elastic hollow bodies are embedded.
- thermoplastic rubber particles and PUR plastic particles are extruded with the addition of a blowing agent to form a foam-like mixed material, the blowing agent being added in the form of micro-hollow bodies containing blowing agent, which have a shell made of mixed polymer and expand under the influence of heat.
- the invention creates a foamed heavy layer material, specifically a heavy layer material with a rubber matrix which contains expanded, elastic hollow bodies.
- the material according to the invention is distinguished both by good sound insulation and sound damping properties and by a relatively low weight.
- the rubber particles used are recycling material which is obtained by crushing old and / or waste material comprising EPDM rubber.
- Recycled material for the PUR plastic particles can preferably also be used by crushing old and / or waste material containing PUR foam into pellets or flakes or the like. This conserves raw material resources and reduces raw material costs in the production of heavy layer material.
- Fig. 1 is a schematic longitudinal sectional view of an extrusion device
- Fig. 2 is a cross-sectional view of a portion of a heavy layer mat made of material according to the invention.
- the sound-insulating material according to the invention can have various shapes. It can be used, for example, in the form of a mat, a molded part or a coating produced by injection molding, in particular injection molding.
- An extrusion device 2 is used to produce the material according to the invention, which is generally designated 1 in FIG. 2.
- the extrusion device essentially has the structure shown in FIG. 1.
- the extrusion device 2 has a feed or filling zone 3 with a filling funnel 4, a transition and compression zone 5 Ejection zone 6 and a nozzle 7 as an extrusion tool.
- the nozzle 7 can in particular be designed as a gap nozzle.
- the nozzle 7 and the various zones 3, 5, 6 are provided with independently controllable heating devices 8, 9, 10, 11.
- the extrusion device 2 is supplied with thermoplastic rubber particles, polyurethane plastic particles and a blowing agent via the filling funnel 4.
- the thermoplastic rubber particles are recycling material in the form of pellets, which is obtained by crushing EPDM rubber-containing material.
- the EPDM rubber particles fed to the extrusion device 2 preferably have an average grain size in the range from 2 to 8 mm.
- the EPDM rubber particles contain heavy spar (BaS0 4 ) or another heavy filler.
- the PUR plastic particles are preferably also recycling material. It is obtained by crushing PUR foam material and is in the form of pellets or flakes, which preferably have an average grain size in the range of 1 to 6 mm.
- thermoplastic rubber particles and the polyurethane plastic particles can be obtained, for example, by comminuting sound-insulating composite components contained in end-of-life vehicles, which are usually designed as multi-layer acoustic spring-mass systems and have a polyurethane foam layer as acoustic spring and a heavy layer layer made of EPDM rubber have as an acoustic mass.
- Micro-hollow bodies containing blowing agents are added as blowing agents, which have a gas-tight, highly elastic shell made of mixed polymer and expand under the action of heat.
- the hollow micro-bodies are essentially spherical and have an average grain size in the range from 8 to 20 ⁇ m and a density in the range from 1000 to 1300 kg / m 3 in the unexpanded state.
- the blowing agent is a liquid or gaseous hydrocarbon, for example isobutane.
- the hollow micro-bodies expand under the influence of heat, their respective volume then being able to reach a multiple, for example more than 40 times their original volume.
- the expansion of the hollow micro-bodies begins at a certain temperature. Typical expansion temperatures are in the range of, for example, 80 to 200 ° C.
- the expanded hollow micro-bodies can be easily compressed and are so elastic that they can withstand multiple load or pressure changes without bursting their sheath.
- the heating devices 8, 9, 10, 11 of the extrusion device 2 are controlled such that a temperature of 40 to 50 ° C. in the area of the feed zone 3 and a temperature of 110 to 130 ° C. in the area of the transition and compression zone 5 during the extrusion , a temperature of 120 to 150 ° C in the area of the discharge zone 6 and a temperature of 120 to 150 ° C in the area of the nozzle 7.
- thermoplastic rubber particles, PUR plastic particles and hollow micro-bodies can be fed to the extrusion device 2 together as a mixture.
- thermoplastic rubber particles, the PUR plastic particles and the propellant-containing hollow micro-bodies are fed to the extrusion device 2 in succession in separate batches.
- the mixture fed to the extrusion device 2 or the extruded material preferably has the following composition:
- thermoplastic rubber particles 70 to 99% by weight of thermoplastic rubber particles, 1 to 20% by weight of PUR plastic particles and 0.5 to 10% by weight of hollow micro-bodies containing blowing agent.
- FIG. 2 A cross section of a section of the extruded material 1 is shown schematically in FIG. 2.
- the oplastic EPDM rubber 12 and the PUR plastic 13 are mixed with one another in a substantially homogeneous manner, the rubber 12 forming a matrix in which a multiplicity of expanded, elastic hollow micro-bodies 14 are embedded.
- the material 1 according to the invention thus represents a foamed one
- Heavy layer material that predominantly has closed cells.
- the density of the material 1 is in the range from 0.2 to 1.5 kg / cm 3 .
- the density of the material 1 is preferably below 1.0 kg / cm 3 , and particularly preferably below 0.5 kg / c 3 .
- Conventional, non-foamed heavy layer material has a density of typically approximately 1.8 kg / cm 3 .
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Multimedia (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Soundproofing, Sound Blocking, And Sound Damping (AREA)
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
Abstract
The invention relates to a sound-insulating material, or a coating, which is made of rubber and PUR plastic, and a method for producing such a material. In order to reduce the weight of the sound-insulating material while providing said material with essentially the same or even an improved sound-deadening effect, the rubber (12) and the PUR plastic (13) are mixed together, the rubber forming a matrix in which a plurality of gas-filled, elastic hollow bodies (14) are embedded. Thermoplastic rubber particles and PUR plastic particles are extruded by adding a blowing agent so as to obtain a foam-type mixed material. The blowing agent is added in the form of microhollow bodies containing a blowing agent.
Description
SCHALLISOLIERENDES MATERIAL UND VERFAHREN ZU DESSEN HERSTELLUNG SOUND INSULATING MATERIAL AND METHOD FOR THE PRODUCTION THEREOF
Die Erfindung betrifft ein schallisolierendes Material, insbesondere für Kraftfahrzeuge, das aus thermoplastischem Kautschuk und PUR-Kunststoff hergestellt ist, sowie ein Verfahren zur Herstellung eines solchen Materials .The invention relates to a sound-insulating material, in particular for motor vehicles, which is made from thermoplastic rubber and PUR plastic, and to a method for producing such a material.
In der Kraftfahrzeugtechnik werden Schwerschichtformteile bzw. Schwerschichtmatten insbesondere zur Schalldämmung des Fahrgastraumes gegen Motorgeräusche sowie Fahrgeräusche eingesetzt. Ferner werden Schwerschichtformteile und Schwerschichtmatten zur Entdröhnung (Körperschalldämmung) von schwingenden Karosserieteilen verwendet . Das Schwerschichtmaterial enthält neben Schwerfüllstoffen üblicherweise Ethylen-Propylen-Dien-Kautschuk (EPDM) . Als Schwerfüllstoff hat sich unter anderem Schwerspat (BaS04) bewährt .Heavy-duty molded parts or heavy-layer mats are used in motor vehicle technology, in particular for soundproofing the passenger compartment against engine noise and driving noise. Heavy-duty molded parts and heavy-duty mats are also used to remove noise (structure-borne noise insulation) from vibrating body parts. In addition to heavy fillers, the heavy layer material usually contains ethylene-propylene-diene rubber (EPDM). Heavy spar (BaS0 4 ) has proven itself as a heavy filler.
Herkömmliches Schwerschichtmaterial, das zur Schalldämmung in Kraftfahrzeugen, insbesondere zur Entdröhnung von Karosserieteilen eingesetzt wird, besitzt ein relativ hohes Gewicht. Dies ist hinsichtlich der Bestrebung, den Kraftstoffverbrauch von Kraftf hrzeugen durch Verringerung des Fahrzeuggewichts zu reduzieren von Nachteil .Conventional heavy layer material, which is used for sound insulation in motor vehicles, in particular for the deadening of body parts, has a relatively high weight. This is disadvantageous in the effort to reduce the fuel consumption of motor vehicles by reducing the vehicle weight.
Aufgabe der vorliegenden Erfindung ist es, ein schallisolierendes Material der eingangs genannten Art
insbesondere für den Automobilbau zu schaffen, das bei guter schalldämmender Wirkung ein relativ geringes Gewicht aufweist. Des Weiteren soll ein kostengünstiges Verfahren zur Herstellung eines solchen Materials angegeben werden.The object of the present invention is to provide a sound-insulating material of the type mentioned at the outset To create especially for the automotive industry, which has a relatively low weight with good sound-absorbing effect. Furthermore, an inexpensive method for producing such a material is to be specified.
Hinsichtlich des Materials besteht die Lösung dieser Aufgabe erfindungsgemäß darin, dass der Kautschuk und der PUR-Kunststoff miteinander gemischt sind, wobei der Kautschuk eine Matrix bildet, in der eine Vielzahl gasgefüllter, elastischer Hohlkörper eingebettet ist.With regard to the material, the solution to this problem according to the invention is that the rubber and the PUR plastic are mixed with one another, the rubber forming a matrix in which a multiplicity of gas-filled, elastic hollow bodies are embedded.
Das erfindungsgemäße Verfahren ist dementsprechend im wesentlichen dadurch gekennzeichnet, dass thermoplastische Kautschuk-Teilchen und PUR-Kunststoff-Teilchen unter Zugabe eines Treibmittels zu einem schaumstoffartigen Mischmaterial extrudiert werden, wobei das Treibmittel in Form von Treibmittel enthaltenden Mikrohohlkörpern zugegeben wird, die eine Hülle aus Mischpolymer aufweisen und unter Wärmeeinwirkung expandieren.Accordingly, the process according to the invention is essentially characterized in that thermoplastic rubber particles and PUR plastic particles are extruded with the addition of a blowing agent to form a foam-like mixed material, the blowing agent being added in the form of micro-hollow bodies containing blowing agent, which have a shell made of mixed polymer and expand under the influence of heat.
Durch die Erfindung wird ein aufgeschäumtes Schwerschichtmaterial geschaffen, und zwar ein Schwerschicht- material mit einer Kautschuk-Matrix, die expandierte, elastische Hohlkörper enthält. Das erfindungsgemäße Material zeichnet sich sowohl durch gute Schalldämm- sowie Schalldämpfungseigenschaften als auch durch ein relativ geringes Gewicht aus.The invention creates a foamed heavy layer material, specifically a heavy layer material with a rubber matrix which contains expanded, elastic hollow bodies. The material according to the invention is distinguished both by good sound insulation and sound damping properties and by a relatively low weight.
Eine vorteilhafte Ausgestaltung der Erfindung besteht darin, dass als Kautschuk-Teilchen Recycling-Material verwendet wird, das durch Zerkleinern von EPDM-Kautschuk aufweisendem Alt- und/oder Abfallmaterial gewonnen wird.
Vorzugsweise kann auch Recycling-Material für die PUR- Kunststoff-Teilchen verwendet werden, indem PUR- Schaumstoff aufweisendes Alt- und/oder Abfallmaterial zu Pellets bzw. Flocken oder dergleichen zerkleinert wird. Hierdurch werden Rohstoffressourcen geschont und die Rohstoffkosten bei der Herstellung von Schwerschicht- material gesenkt .An advantageous embodiment of the invention is that the rubber particles used are recycling material which is obtained by crushing old and / or waste material comprising EPDM rubber. Recycled material for the PUR plastic particles can preferably also be used by crushing old and / or waste material containing PUR foam into pellets or flakes or the like. This conserves raw material resources and reduces raw material costs in the production of heavy layer material.
Weitere bevorzugte und vorteilhafte Ausgestaltungen der Erfindung sind in den Unteransprüchen angegeben.Further preferred and advantageous embodiments of the invention are specified in the subclaims.
Nachfolgend wird die Erfindung anhand eines Ausführungs- beispiels unter Bezugnahme auf die anliegende Zeichnung näher erläutert. Es zeigen:The invention is explained in more detail below on the basis of an exemplary embodiment with reference to the accompanying drawing. Show it:
Fig. 1 eine schematische Längsschnittdarstellung einer Extrudiervorrichtung undFig. 1 is a schematic longitudinal sectional view of an extrusion device and
Fig. 2 eine Querschnittansicht auf einen Abschnitt einer aus erfindungsgemäßem Material hergestellten Schwerschichtmatte .Fig. 2 is a cross-sectional view of a portion of a heavy layer mat made of material according to the invention.
Das erfindungsgemäße schallisolierende Material kann verschiedene Formen aufweisen. Es kann beispielsweise in Form einer Matte, eines Formteils oder einer durch Spritzgießen, insbesondere Hinterspritzen hergestellten Beschichtung zum Einsatz kommen.The sound-insulating material according to the invention can have various shapes. It can be used, for example, in the form of a mat, a molded part or a coating produced by injection molding, in particular injection molding.
Zur Herstellung des erfindungsgemäßen Materials, das in Fig. 2 allgemein mit 1 bezeichnet ist, wird eine Extrudiervorrichtung 2 verwendet . Die Extrudiervorrichtung hat im wesentlichen den in Fig. 1 gezeigten Aufbau. Wie an sich bekannt, weist die Extrudiervorrichtung 2 eine Einzugs- oder Einfüllzone 3 mit Fülltrichter 4, eine Übergangs- und Kompressionszone 5, eine
Ausstoßzone 6 und eine Düse 7 als Extrusionswerkzeug auf. Die Düse 7 kann insbesondere als Spaltdüse ausgebildet sein. Die Düse 7 und die verschiedenen Zonen 3, 5, 6 sind mit unabhängig voneinander steuerbaren Beheizungseinrichtungen 8, 9, 10, 11 versehen.An extrusion device 2 is used to produce the material according to the invention, which is generally designated 1 in FIG. 2. The extrusion device essentially has the structure shown in FIG. 1. As is known per se, the extrusion device 2 has a feed or filling zone 3 with a filling funnel 4, a transition and compression zone 5 Ejection zone 6 and a nozzle 7 as an extrusion tool. The nozzle 7 can in particular be designed as a gap nozzle. The nozzle 7 and the various zones 3, 5, 6 are provided with independently controllable heating devices 8, 9, 10, 11.
Über den Fülltrichter 4 werden der Extrudiervorrichtung 2 thermoplastische Kautschuk-Teilchen, Polyurethan- Kunststoff-Teilchen und ein Treibmittel zugeführt.The extrusion device 2 is supplied with thermoplastic rubber particles, polyurethane plastic particles and a blowing agent via the filling funnel 4.
Bei den thermoplastischen Kautschuk-Teilchen handelt es um Recycling-Material in Form von Pellets, das durch Zerkleinern von EPDM-Kautschuk aufweisendem Material gewonnen wird. Die der Extrudiervorrichtung 2 zugeführten EPDM-Kautschuk-Teilchen haben vorzugsweise eine mittlere Korngröße im Bereich von 2 bis 8 mm. Die EPDM-Kautschuk- Teilchen enthalten Schwerspat (BaS04) oder einen anderen Schwerfüllstoff .The thermoplastic rubber particles are recycling material in the form of pellets, which is obtained by crushing EPDM rubber-containing material. The EPDM rubber particles fed to the extrusion device 2 preferably have an average grain size in the range from 2 to 8 mm. The EPDM rubber particles contain heavy spar (BaS0 4 ) or another heavy filler.
Bei den PUR-Kunststoff-Teilchen handelt es sich vorzugsweise ebenfalls um Recycling-Material. Es wird durch Zerkleinern von PUR-Schaumstoff aufweisendem Material gewonnen und liegt in Form von Pellets bzw. Flocken vor, die vorzugsweise eine mittlere Korngröße im Bereich von 1 bis 6 mm.The PUR plastic particles are preferably also recycling material. It is obtained by crushing PUR foam material and is in the form of pellets or flakes, which preferably have an average grain size in the range of 1 to 6 mm.
Die thermoplastischen Kautschuk-Teilchen und die Polyurethan-Kunststoff-Teilchen können beispielsweise durch Zerkleinern von in Altautos enthaltenen schallisolierenden Verbundbauteilen gewonnen werden, die üblicherweise als akustisches Feder-Masse-System mehrlagig ausgebildet sind und eine Polyurethanschaumschicht als akustische Feder und eine Schwerschichtlage aus EPDM-Kautschuk als akustische Masse aufweisen.
Als Treibmittel werden Treibmittel enthaltende Mikrohohlkorper zugegeben, die eine gasdichte, hochelastische Hülle aus Mischpolymer aufweisen und unter Wärmeeinwirkung expandieren. Die Mikrohohlkorper sind im wesentlichen kugelförmig und weisen im nicht-expandierten Zustand eine mittlere Korngröße im Bereich 8 bis 20 μm und eine Dichte im Bereich von 1000 bis 1300 kg/m3 auf.The thermoplastic rubber particles and the polyurethane plastic particles can be obtained, for example, by comminuting sound-insulating composite components contained in end-of-life vehicles, which are usually designed as multi-layer acoustic spring-mass systems and have a polyurethane foam layer as acoustic spring and a heavy layer layer made of EPDM rubber have as an acoustic mass. Micro-hollow bodies containing blowing agents are added as blowing agents, which have a gas-tight, highly elastic shell made of mixed polymer and expand under the action of heat. The hollow micro-bodies are essentially spherical and have an average grain size in the range from 8 to 20 μm and a density in the range from 1000 to 1300 kg / m 3 in the unexpanded state.
Bei dem Treibmittel handelt es sich um einen flüssigen oder gasförmigen Kohlenwasserstoff, beispielsweise um Isobutan. Unter Wärmeeinwirkung expandieren die Mikrohohlkorper, wobei ihr jeweiliges Volumen dann ein Vielfaches, beispielsweise mehr als das 40-fache ihres ursprünglichen Volumens erreichen kann. Die Expansion der Mikrohohlkorper setzt ab einer bestimmten Temperatur ein. Typische Expansionstemperaturen liegen im Bereich von beispielsweise 80 bis 200°C. Die expandierten Mikrohohlkorper können leicht zusammengedrückt werden und sind so elastisch, dass sie mehreren Last- bzw. Druckwechsel ohne ein Zerplatzen ihrer Hülle widerstehen.The blowing agent is a liquid or gaseous hydrocarbon, for example isobutane. The hollow micro-bodies expand under the influence of heat, their respective volume then being able to reach a multiple, for example more than 40 times their original volume. The expansion of the hollow micro-bodies begins at a certain temperature. Typical expansion temperatures are in the range of, for example, 80 to 200 ° C. The expanded hollow micro-bodies can be easily compressed and are so elastic that they can withstand multiple load or pressure changes without bursting their sheath.
Die Beheizungseinrichtungen 8, 9, 10, 11 der Extrudiervorrichtung 2 werden so gesteuert, dass während der Extrusion im Bereich der Einzugszone 3 eine Temperatur von 40 bis 50°C, im Bereich der Übergangs- und Kompressionszone 5 eine Temperatur von 110 bis 130°C, im Bereich der Ausstoßzone 6 eine Temperatur von 120 bis 150°C und im Bereich der Düse 7 eine Temperatur von 120 bis 150°C herrschen.The heating devices 8, 9, 10, 11 of the extrusion device 2 are controlled such that a temperature of 40 to 50 ° C. in the area of the feed zone 3 and a temperature of 110 to 130 ° C. in the area of the transition and compression zone 5 during the extrusion , a temperature of 120 to 150 ° C in the area of the discharge zone 6 and a temperature of 120 to 150 ° C in the area of the nozzle 7.
Die thermoplastischen Kautschuk-Teilchen, PUR-Kunststoff- Teilchen und Mikrohohlkorper können der Extrudiervorrichtung 2 zusammen als Mischung zugeführt werden. Zur
Vermeidung von Entmischungen bzw. zur Erzeugung einer möglichst homogenen Extrusionsmasse ist es aber gegebenenfalls vorteilhaft, wenn die thermoplastischen Kautschuk-Teilchen, die PUR-Kunststoff-Teilchen und die Treibmittel enthaltenden Mikrohohlkorper der Extrudiervorrichtung 2 in getrennten Chargen nacheinander zugeführt werden.The thermoplastic rubber particles, PUR plastic particles and hollow micro-bodies can be fed to the extrusion device 2 together as a mixture. to Avoiding segregation or to produce an extrusion composition that is as homogeneous as possible, however, it may be advantageous if the thermoplastic rubber particles, the PUR plastic particles and the propellant-containing hollow micro-bodies are fed to the extrusion device 2 in succession in separate batches.
Die der Extrudiervorrichtung 2 zugeführte Mischung bzw. das extrudierte Material weist vorzugsweise folgende Zusammensetzung auf:The mixture fed to the extrusion device 2 or the extruded material preferably has the following composition:
70 bis 99 Gew.-% thermoplastische Kautschuk-Teilchen, 1 bis 20 Gew.-% PUR-Kunststoff-Teilchen und 0,5 bis 10 Gew.-% Treibmittel enthaltende Mikrohohlkorper .70 to 99% by weight of thermoplastic rubber particles, 1 to 20% by weight of PUR plastic particles and 0.5 to 10% by weight of hollow micro-bodies containing blowing agent.
In Fig. 2 ist schematisch ein Querschnitt eines Abschnitts des extrudierten Materials 1 gezeigt. Der the oplastische EPDM-Kautschuk 12 und der PUR-Kunststoff 13 sind darin miteinander im wesentlichen homogenen gemischt, wobei der Kautschuk 12 eine Matrix bildet, in der eine Vielzahl expandierter, elastischer Mikrohohlkorper 14 eingebettet ist. Das erfindungsgemäße Material 1 stellt somit ein geschäumtesA cross section of a section of the extruded material 1 is shown schematically in FIG. 2. The oplastic EPDM rubber 12 and the PUR plastic 13 are mixed with one another in a substantially homogeneous manner, the rubber 12 forming a matrix in which a multiplicity of expanded, elastic hollow micro-bodies 14 are embedded. The material 1 according to the invention thus represents a foamed one
Schwerschichtmaterial dar, das überwiegend geschlossene Zellen aufweist. Das Raumgewicht des Materials 1 liegt im Bereich von 0,2 bis 1,5 kg/cm3. Bevorzugt liegt das Raumgewicht des Materials 1 unterhalb von 1,0 kg/cm3 , und besonders bevorzugt unterhalb von 0,5 kg/c 3. Herkömmliches, ungeschäumtes Schwerschichtmaterial weist dagegen ein Raumgewicht von üblicherweise ca. 1,8 kg/cm3 auf.
Heavy layer material that predominantly has closed cells. The density of the material 1 is in the range from 0.2 to 1.5 kg / cm 3 . The density of the material 1 is preferably below 1.0 kg / cm 3 , and particularly preferably below 0.5 kg / c 3 . Conventional, non-foamed heavy layer material, on the other hand, has a density of typically approximately 1.8 kg / cm 3 .
Claims
1. Schallisolierendes Material (1), insbesondere für Kraftfahrzeuge, hergestellt aus Kautschuk und PUR- , Kunststoff, d a d u r c h g e k e n n z e i c h n e t , dass der Kautschuk (12) und der PUR-Kunststoff (13) miteinander gemischt sind, wobei der Kautschuk (12) eine Matrix bildet, in der eine Vielzahl gasgefüllter, elastischer Hohlkörper (14) eingebettet ist.1. Sound-insulating material (1), in particular for motor vehicles, made of rubber and PUR, plastic, characterized in that the rubber (12) and the PUR plastic (13) are mixed together, the rubber (12) forming a matrix , in which a multiplicity of gas-filled, elastic hollow bodies (14) are embedded.
2. Schallisolierendes Material nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t , dass der Kautschuk (12) und/oder der PUR-Kunststoff (13) ein Recycling-Material ist.2. Sound-insulating material according to claim 1, so that the rubber (12) and / or the PUR plastic (13) is a recycling material.
3. Schallisolierendes Material nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t , dass es aus3. Sound-insulating material according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that it from
70 bis 99 Gew.-% Kautschuk (12), 1 bis 20 Gew.-% PUR-Kunststoff (13) und 0,5 bis 10 Gew.-% gasgefüllte, elastische Hohlkörper (14) zusammengesetzt ist.70 to 99% by weight of rubber (12), 1 to 20% by weight of PUR plastic (13) and 0.5 to 10% by weight of gas-filled, elastic hollow body (14) is composed.
4. Schallisolierendes Material nach mindestens einem der vorhergehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass der Kautschuk (12) ein EPDM-Kautschuk ist.4. Sound-insulating material according to at least one of the preceding claims, that the rubber (12) is an EPDM rubber.
5. Schallisolierendes Material nach mindestens einem der vorhergehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass die gasgefüllten, elastischen Hohlkörper (14) eine Hülle aus Mischpolymer aufweisen. 5. Sound-insulating material according to at least one of the preceding claims, characterized in that the gas-filled, elastic hollow body (14) have a shell made of mixed polymer.
6. Schallisolierendes Material nach mindestens einem der vorhergehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , dass es ein Raumgewicht von weniger als 1,5 kg/cm3 , vorzugsweise weniger als 1,0 kg/cm3 aufweist.6. Sound-insulating material according to at least one of the preceding claims, characterized in that it has a density of less than 1.5 kg / cm 3 , preferably less than 1.0 kg / cm 3 .
7. Verfahren zur Herstellung eines schallisolierenden Materials (1) , insbesondere für Kraftfahrzeuge, d a d u r c h g e k e n n z e i c h n e t , dass thermoplastische Kautschuk-Teilchen und PUR-Kunststoff- Teilchen unter Zugabe eines Treibmittels zu einem Schaumstoffartigen Mischmaterial extrudiert werden, wobei das Treibmittel in Form von Treibmittel enthaltenden Mikrohohlkörpern (14) zugegeben wird, die eine Hülle aus Mischpolymer aufweisen und unter Wärmeeinwirkung expandieren.7. A method for producing a sound-insulating material (1), in particular for motor vehicles, characterized in that thermoplastic rubber particles and PUR plastic particles are extruded with the addition of a blowing agent to form a foam-like mixed material, the blowing agent being in the form of micro-hollow bodies containing blowing agent ( 14) is added, which have a shell made of copolymer and expand under the action of heat.
8. Verfahren nach Anspruch 7 , d a d u r c h g e k e n n z e i c h n e t , dass als thermoplastische Kautschuk-Teilchen Recycling-Material verwendet wird, das durch Zerkleinern von EPDM-Kau schuk aufweisendem Material gewonnen wird.8. The method of claim 7, d a d u r c h g e k e n n z e i c h n e t that recycling material is used as thermoplastic rubber particles, which is obtained by crushing EPDM rubber-containing material.
. Verfahren nach Anspruch 7 oder 8 , d a d u r c h g e k e n n z e i c h n e t , dass als PUR-Kunststoff-Teilchen Recycling-Material verwendet wird, das durch Zerkleinern von PUR-Schäumstoff aufweisendem Material gewonnen wird., A method according to claim 7 or 8, d a d u r c h g e k e n n z e i c h n e t that recycled material is used as the PUR plastic particles, which is obtained by crushing PUR foam material.
10. Verfahren nach einem der Ansprüche 7 bis 9, d a d u r c h g e k e n n z e i c h n e t , dass einer Extrudiervorrichtung (2) bezogen auf das herzustellende schallisolierende Material (1) 70 bis 99 Gew.-% thermoplastische Kautschuk- Teilchen, 1 bis 20 Gew.-% PUR-Kunststoff-Teilchen und 0,5 bis 10 Gew.-% Treibmittel enthaltende Mikrohohlkorper zugeführt werden.10. The method according to any one of claims 7 to 9, characterized in that an extrusion device (2) based on the soundproofing material to be produced (1) 70 to 99% by weight of thermoplastic rubber particles, 1 to 20% by weight of PUR plastic particles and 0.5 to 10% by weight of propellant hollow micro-bodies can be supplied.
11. Verfahren nach einem der Ansprüche 7 bis 10 d a d u r c h g e k e n n z e i c h n e t , dass die Treibmittel enthaltenden Mikrohohlkorper (14) kugelförmig ausgebildet sind.11. The method according to any one of claims 7 to 10, that the hollow micro-bodies (14) containing the propellant are spherical in shape.
12. Verfahren nach einem der Ansprüche 7 bis 11, d a d u r c h g e k e n n z e i c h n e t , dass die thermoplastischen Kautschuk-Teilchen, die PUR-Kunststoff- Teilchen und die Treibmittel enthaltenden Mikrohohlkorper der Extrudiervorrichtung in getrennten Chargen nacheinander zugeführt werden.12. The method according to any one of claims 7 to 11, so that the thermoplastic rubber particles, the PUR plastic particles and the hollow micro-particles containing the blowing agent are fed to the extrusion device in succession in separate batches.
13. Verfahren nach einem der Ansprüche 7 bis 12, d a d u r c h g e k e n n z e i c h n e t , dass die Extrudiervorrichtung (2) eine Einzugszone (3) , eine Übergangs- und Kompressionszone (5) und eine Ausstoßzone (6) mit daran anschließender Düse (7) aufweist und in der Weise beheizt wird, dass während der Extrusion folgende Temperaturen herrschen:13. The method according to any one of claims 7 to 12, characterized in that the extrusion device (2) has a feed zone (3), a transition and compression zone (5) and an ejection zone (6) with an adjoining nozzle (7) and in the Is heated in such a way that the following temperatures prevail during the extrusion:
40 bis 50°C im Bereich der Einzugszone,40 to 50 ° C in the area of the feed zone,
110 bis 130°C im Bereich der Übergangs- und110 to 130 ° C in the area of transition and
Kompressionszone,Compression zone,
120 bis 150°C im Bereich der Ausstoßzone, und120 to 150 ° C in the area of the discharge zone, and
120 bis 150°C im Bereich der Düse. 120 to 150 ° C in the area of the nozzle.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10237366 | 2002-08-13 | ||
DE2002137366 DE10237366A1 (en) | 2002-08-13 | 2002-08-13 | Noise insulating material (1) especially for automobiles, prepared from rubber matrix containing gas-filled hollow bodies and PUR-plastic useful for noise damping in automobiles |
PCT/EP2003/008905 WO2004022298A1 (en) | 2002-08-13 | 2003-08-11 | Sound-insulating material and method for the production thereof |
Publications (1)
Publication Number | Publication Date |
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EP1528974A1 true EP1528974A1 (en) | 2005-05-11 |
Family
ID=30775292
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP03793726A Withdrawn EP1528974A1 (en) | 2002-08-13 | 2003-08-11 | Sound-insulating material and method for the production thereof |
Country Status (7)
Country | Link |
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US (1) | US20060052474A1 (en) |
EP (1) | EP1528974A1 (en) |
JP (1) | JP2006501323A (en) |
AU (1) | AU2003266273A1 (en) |
DE (1) | DE10237366A1 (en) |
MX (1) | MXPA05001547A (en) |
WO (1) | WO2004022298A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006039379A (en) * | 2004-07-29 | 2006-02-09 | Nishikawa Rubber Co Ltd | Sound insulating sheet |
JP5163297B2 (en) * | 2008-06-04 | 2013-03-13 | 横浜ゴム株式会社 | Sound insulation for road bridges |
US9637913B2 (en) * | 2009-04-10 | 2017-05-02 | Saint-Gobain Performance Plastics Corporation | Acoustic damping compositions having elastomeric particulate |
JP5525036B2 (en) * | 2009-04-10 | 2014-06-18 | サン−ゴバン パフォーマンス プラスティックス コーポレイション | Acoustic damping composition |
EP2501749B1 (en) | 2009-11-20 | 2013-09-18 | Basf Se | Resin foams containing microballoons |
DE102010035431A1 (en) | 2010-08-26 | 2012-03-01 | Entwicklungsgesellschaft für Akustik (EfA) mit beschränkter Haftung | Broadband sound absorber |
US8937106B2 (en) | 2010-12-07 | 2015-01-20 | Basf Se | Melamine resin foams with nanoporous fillers |
CN107189405B (en) * | 2017-06-23 | 2020-06-19 | 华南理工大学 | High-wear-resistance rubber-plastic blended foaming material and preparation method thereof |
EP4084995A4 (en) * | 2019-12-30 | 2023-07-26 | Pimsa Otomotiv Anonim Sirketi | A composite under vehicle protection |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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NL287627A (en) * | 1962-01-11 | |||
US4556603A (en) * | 1984-03-21 | 1985-12-03 | Phillips Petroleum Company | Method of making lightweight thermoplastic elastomer and product thereof |
US5658656A (en) * | 1992-01-10 | 1997-08-19 | Minnesota Mining And Manufacturing Company | Use of materials comprising microbubbles as acoustical barriers |
US5432204A (en) * | 1993-01-22 | 1995-07-11 | Woodbridge Foam Corporation | Foamed polymer and process for production thereof |
WO1996000754A1 (en) * | 1994-06-30 | 1996-01-11 | Minnesota Mining And Manufacturing Company | Polyurethane/urea elastomeric sealants |
DE19744364A1 (en) * | 1996-10-15 | 1998-04-16 | Henkel Kgaa | Binder composition used e.g. for coating, adhering and filling foam structure formation |
US6384145B1 (en) * | 1997-12-17 | 2002-05-07 | Cooper Technology Services Llc | Method for manufacture of elastomeric alloys using recycled rubbers |
DE19812442C1 (en) * | 1998-03-21 | 1999-10-28 | B & F Formulier Und Abfuell Gm | Double chamber cartridge to create a 2-component polyurethane foam |
JP3907332B2 (en) * | 1998-12-25 | 2007-04-18 | 横浜ゴム株式会社 | Manufacturing method of underwater sound absorbing wedge |
-
2002
- 2002-08-13 DE DE2002137366 patent/DE10237366A1/en not_active Withdrawn
-
2003
- 2003-08-11 EP EP03793726A patent/EP1528974A1/en not_active Withdrawn
- 2003-08-11 US US10/523,663 patent/US20060052474A1/en not_active Abandoned
- 2003-08-11 JP JP2004533363A patent/JP2006501323A/en active Pending
- 2003-08-11 WO PCT/EP2003/008905 patent/WO2004022298A1/en not_active Application Discontinuation
- 2003-08-11 AU AU2003266273A patent/AU2003266273A1/en not_active Abandoned
- 2003-08-11 MX MXPA05001547A patent/MXPA05001547A/en unknown
Non-Patent Citations (1)
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See references of WO2004022298A1 * |
Also Published As
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JP2006501323A (en) | 2006-01-12 |
AU2003266273A1 (en) | 2004-03-29 |
US20060052474A1 (en) | 2006-03-09 |
MXPA05001547A (en) | 2005-05-05 |
DE10237366A1 (en) | 2004-02-26 |
WO2004022298A1 (en) | 2004-03-18 |
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