Classifications

• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/06—Elements
• • 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
• • 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
  • B29B17/0036—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting of large particles, e.g. beads, granules, pellets, flakes, slices
• • 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
  • B29B9/00—Making granules
  • B29B9/02—Making granules by dividing preformed material
  • B29B9/04—Making granules by dividing preformed material in the form of plates or sheets
• • 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
  • B29B9/00—Making granules
  • B29B9/12—Making granules characterised by structure or composition
  • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
• • 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
  • C08J3/12—Powdering or granulating
• • 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
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
• • 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
  • B29K2307/00—Use of elements other than metals as reinforcement
  • B29K2307/04—Carbon
• • 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
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Definitions

• the present invention relates to a process for the production of pellets of fiber composites suitable for further processing in a plastic manufacturing process, wherein the pellets contain carbon fibers and at least one thermoplastic matrix material.
• Carbon fibers are used as fiber reinforcement of thermoplastic or thermoset bonded fiber composites (FVW). In order to achieve maximum reinforcing effects, this has hitherto been done mainly in the form of endless carbon fiber materials such as filament yarn, multifilament yarn or so-called rowings.
• carbon fibers are not offered on the market as chopped fibers with finite fiber lengths, for example in the range from 20 mm to 80 mm, as they are known from the field of classical textile processing, also because they are more problematic to process.
• Carbon fiber fabrics have been used increasingly for several years as a high-performance fibrous reinforcement. The main applications are, for example, in aircraft construction, shipbuilding, vehicle construction and wind turbines.
• CONFIRMATION COPY to supply the carbon fiber components contained therein to new applications in which they can at least partially replace expensive primary carbon fibers.
• the starting materials must be metered in an always constant mass ratio of fibers and thermoplastic polymer. Good metering and mixing can only be achieved if the two mixing partners are the same or at least very similar in terms of their geometric dimensions, particle surface and bulk volumes. Short fibers and ground dusts, however, have very large differences in these parameters compared to the plastic granules used, which usually have a diameter of about 3 mm to 5 mm, a smooth surface and thus a good flowability.
• the individual fibers In short fiber bundles, the individual fibers entangle among themselves in a random position, form fiber bridges and lumps of material that clog the opening of the hopper on extruders and injection molding machines and allow only an uncontrollable sporadic indentation into the machine.
• the resulting interruptions of a continuous flow of material for the machine feed can lead to significant deviations of the desired mixing ratio of reinforcing fiber and plastic matrix in the final product, which means that mechanical component properties can not be ensured.
• raw materials for extrusion or injection molding containing carbon primary fibers have heretofore been produced from endless fiber strands.
• the endless fibers are bundled together and before cutting in lengths of 3 mm to 12 mm with a strongly adhesive binder layer, also referred to as sizing or sizing. net, glued to a thick continuous fiber bundle. It is also possible to bundle continuous fibers and then to encase or impregnate them with a polymer melt, to solidify them and to cut them to the desired length. Only endless primary carbon fibers can be used as starting material in these processes.
• the final fibers resulting from waste treatment processes or the material recycling of old CFRP components can not be added directly to the starting materials for extrusion or injection molding as fibers. Only when it is possible to bring these into a well-dosed and free-flowing form, the way is cleared, the in their own resources still produce high-quality carbon fibers from waste or old parts of meaningful economic recycling.
• the production of primary carbon fibers usually takes place either from suitable organic precursor fibers such as polyacrylonitrile (PAN) or viscose fibers by controlled pyrolysis or from pitch, in which case melt spinning first produces a pitch fiber which is then oxidized and carbonized ,
• PAN polyacrylonitrile
• pitch oxidized and carbonized
• a corresponding method is known, for example, from EP 1 696 057 A1.
• the primary fibers made of pitch are processed into staple fiber mats in which the fibers have an orientation in a preferred direction.
• the known method includes inter alia a combing process for parallelization of the fibers.
• the fibers bound in a matrix material are separated from the matrix material and the resulting free fibers are immediately wetted with a binder.
• the separation of the fibers from the semifinished product takes place in an oven, ie by pyrolysis. End product are in this process fiber bundles of wetted fibers, to their further processing in the document no information.
• thermoplastic fibers may be polypropylene, polyethylene, nylon or PET. These fibers are shredded to about 50 mm long strips before further processing.
• Waste material from heaven production is made by rolling needle-like
• Waste fiber materials are mixed and carded by means of a carding machine.
• the document contains no further explanation that
• a mat is first prepared, which is then formed into a body component of a vehicle.
• Fiber composite described in which one supplies a plastic granules an extruder, this melts and then supplies downstream cut glass fibers of uniform length. The mass is then from a slot nozzle
• Japanese Patent Abstract 2005089515 A describes a process for the production of pellets from fiber composites, in which carbon fibers and a thermoplastic matrix material comprising a phenolic resin and a rubber-containing styrene resin are processed into pellets in which the carbon fibers have an orientation in the longitudinal direction of the pellets ,
• the proportion of carbon fibers is 5 to 30 wt.%.
• This carbon fibers are used, which are produced by a conventional method primarily for pellet production and thus represent a relatively costly starting material.
• continuous fibers are assumed, and accordingly the length of the carbon fibers corresponds in each case to the length of the pellets.
• the object of the present invention is to provide a process for producing pellets of fiber composite materials of the type mentioned above, in which cost-effective available carbon fibers can be used as reinforcing fibers.
• carbon fiber-containing waste or old parts are isolated from carbon fibers, deposited flat together with the thermoplastic matrix material, pressed into a plate material under the action of heat, then cooled and comminuted to pellets, flakes or chips.
• the inventive method makes it possible to use finite carbon fibers, carbon fiber bundles or their mixture, for example, from textile production waste, bonded or cured production waste from recycled old CFRP components or the like as reinforcing fibers, whereby a more cost-effective starting material is available and contained in the aforementioned existing materials Carbon fibers are again fed to a meaningful use.
• the finite carbon fibers, carbon fiber bundles or mixtures thereof are brought into a free-flowing and readily meterable, compact form and can be used, for example, as starting materials for extrusion or injection molding.
• the carbon fibers are initially freed of interfering matrix substances.
• pyrolysis techniques can be used or the waste can be treated with supercritical solvents.
• the product of these separation processes results in finite carbon fibers.
• at least one layer of finite carbon fibers, carbon fiber bundles or a mixture thereof is first produced by laying them down flat in a pneumatic random weaving process, a carding process, a wet nonwoven process, a papermaking process or as a loose bed.
• a linear sliver is not produced as in the prior art, a linear sliver, but processed in a web forming carbon fibers directly to a thin and uniform mass of fiber surface and thus forms planar and mass uniform, carbon fiber-containing layers variably adjustable thicknesses and surface masses.
• the carbon fibers, carbon fiber bundles or mixtures thereof used according to the invention have an average fiber length of 3 mm to 150 mm, depending on the usable surface-forming method. Short fibers up to about 10 mm can be used with the Wet fleece process, longer fibers in the range of 20 to 150 mm can be processed with Wirrvliestechnik or a carding machine to a flat good.
• thermoplastic matrix material there are various preferred possibilities for mixing the carbon fibers with the thermoplastic matrix material.
• carbon fibers and thermoplastic fibers in the form of my fiber flake mixture or in each case can be supplied as separate layers and homogeneously mixed in the carding machine.
• short carbon fibers with thermoplastic particles for example short fibers, can be thoroughly intimately mixed with each other in the suspending liquid of the wet nonwoven system.
• thermoplastic layer consisting of at least one thermoplastic film, fibrous web layer or nonwoven layer, optionally in the form of a melt with at least one nonwoven web forming process, a mass-uniform, flat layer of finite carbon fibers, carbon fiber bundles or a mixture thereof by layering Bring the contact.
• thermoplastic component in the form of a powder or as particles having a diameter smaller than about 5 mm to at least one layer of finite carbon fibers, carbon fiber bundles or mixtures thereof or to incorporate them into such a layer.
• thermoplastic component in the form of finite fibers can be intimately and homogeneously mixed with the carbon fibers before or during a layer formation.
• the subject matter of the present invention is that at least one thermoplastic component is subsequently nents softened or melted by a hot process and the carbon fibers are preferably consolidated under surface pressure and cooling to a rigid layer or plate so that after another crushing process free-flowing and well dosed for injection molding and compounding pellets result.
• the adjustable fiber content in the resulting pallets with up to 95% can be set significantly above the limit of 35% mentioned in DE 44 19 579 A1 and so inexpensive carbon fiber concentrates in the form of pallets Compounding be provided.
• Temperature and pressure during thermal consolidation in combination with the percentage and the type of polymer of the melting or adhesive softening thermoplastic material determines the mechanical cohesion of all components in the pellet and thus the usability for the injection molding and the compounding.
• the present invention further provides a carbon fiber-containing pellet, which was prepared by a process of the aforementioned type and which preferably has a proportion of carbon fibers in the range of 5% to 95%, preferably in the range of 10% to 80% and in which preferably maximum edge removal of the pellet is 3 to 25 mm, preferably 5 to 10 mm. It is preferred in this case that the carbon fibers, carbon fiber bundles or mixtures thereof contained in the pellet do not have a uniform fiber length and portions thereof do not pass through the entire pellet body without interruption.
• a pellet according to the invention may, for example, in addition to carbon fibers, carbon fiber bundles or their mixture of carbon fiber-containing waste or used parts contain a proportion of carbon fibers, carbon fiber bundles or their mixture in the form of finite primary goods (virgin). Likewise, this pellet may also contain, in addition to carbon fibers, further reinforcing fiber components in finite form, in particular para-aramid, glass fibers, natural fibers, non-melting chemical fibers and / or fibers which melt higher than the matrix fibers.
• fiber length distribution for example drying techniques known per se, such as nonwoven carding, can be used as techniques for producing carbon fiber-containing fabrics of the invention, in particular by mass or volume , the formation of a loose bed via spreader when using short fibers to about 10 mm or by means of hopper at average fiber lengths> 10 mm, as well as wet techniques such as wet mat production or paper technology are used. Even powder spreading with extreme short fibers up to 5 mm is possible as a layer-forming process step.
• Carbon fiber starting materials for the process include:
• Residual carbon fibers and / or finite carbon fiber bundles obtained from waste containing resin, hard CFRP parts and / or old components, optionally additionally comminuted and / or defibered
• these can be incorporated directly into the process of layer formation or further comminuted to improve processability and / or, for example, with a size, adhesion-promoting substances or other additional agents which become effective in the later plastic, such as flame retardants, dyes, mold release agents or Tribology aids are equipped or mixed. It is also possible to add to the carbon fiber fabrics additionally functionally active extraneous fibrous materials, for example for impact modification or mechanical reinforcement such as para-aramid, glass fibers, natural fibers or non-melting chemical fibers or fibers which melt higher than the matrix fiber.
• Fibrous admixture components such as the later binding thermoplastic fibers can in an independent process step prior to film formation, for example via a textile fiber mixing line, or directly during film formation, for example in a carding, with the other fiber components intimately and homogeneously mixed. If one uses the possibilities of a system mixture, the individual fiber components are sorted, for example, deposited in different layers as batt or nonwoven webs one above the other. It is important here that the thermoplastic binder component penetrates all layers sufficiently after thermal consolidation in order to ensure a compact connection of all layers to one another.
• thermoplastic binder fibers can be achieved by a homogeneous mixture of all components with each other, for example, with an alternating structure of thin layers with thermoplastic and reinforcing component or, for example, by an intensive puncturing of thermoplastic binder fibers through the carbon fiber layer with a
• thermoplastic-bonding components a wide variety of known from the prior art thermoplastic Kunststoffmatrices come into consideration. This ranges from low-melting polyethylene to polypropylene, polyamides, up to the high-melting thermoplastics PEEK or PEI.
• the thermal solidification parameters such as temperature, residence time, pressure and possibly the use of an inert gas atmosphere must be adapted to the special features of these polymers.
• the usable forms of the thermoplastic binder components ranging from small particles such as powders on short fibers, textile long fibers, nonwoven or fibrous layers, spunbonded nonwovens, foils up to
• thermoplastic binder After the combination of the finite carbon fibers with the thermoplastic binder in a laminar layer arrangement with a mass ratio of carbon fiber to thermoplastic that is as constant as possible, this stratification is heated so that the thermoplastic component softens or melts.
• thermoplastic component determines the achievable compactness of the plate product and the mechanical stability of the later pellets.
• the lower limit of the thermoplastic content is preferably about 5%, wherein for a detectable solidification effect carbon fibers and thermoplastic component should be as intimately as possible intimately mixed together. In sandwich processes, minimum binding contents of about 15 to 25% are advantageous in order to achieve a good cohesion in the later pellet.
• the resulting pellets are to be used in the compounding process, preference is given to working with a high carbon fiber and as low as possible binding polymer content in the interests of high economic efficiency. If the pellets are to be sprayed directly into components, the thermoplastic polymers are preferably used in proportions of> 50%, generally from 70 to 90%.
• the hardness of the pellets can be varied within a wide range via the proportion of the thermoplastic component. This ranges from a compact non-porous state over increasing porosities to a thermally consolidated low-density fiber web state.
• Carbon fiber fabrics can be used more fibrous materials in finite form. These can be supplied analogously to the carbon fiber components by fiber mixing processes before or during the layer formation or as separate system components during the material stratification.
• the thermally consolidated sheet is then crushed defined. This can be done, for example, by means of a stamping process, by means of a comb knife cutting technique or in combination with 2 knife cutting machines.
• the particle size depends on the conditions of the compounder or injection molder, is preferably not exceed 15 mm usually in its largest dimension. For example, easily processed pellets have maximum edge lengths of 5 to 10 mm. The pellets need not be regular or even in shape. Also of minor importance is the thickness of the pellets. For the purposes of good cohesion, very thick, high-mass pellets must have a higher minimum thermoplastic content than thin platelet-shaped pellets, which, due to their smaller mass during dosing and admixing, survive smaller inertial forces in mutual contact without destruction.
• the areas of use of such carbon pellets are preferably the
• thermoplastically bonded fiber composites Compounding and injection molding for the production of thermoplastically bonded fiber composites.
• Further fields of application with, in particular, low-melting binding components are, for example, the elastomer or rubber reinforcement or the use as low-strength pellets in duromer matrices which, for example, re-fibrillate by stirring processes in the thermoset, release the carbon fibers, so that they can then be readily distributed in the duromer matrix ,
• Embodiment 1 Processing of a fiber / fiber mixture into pellets for injection molding
• carbon fiber recycling fibers with a mean fiber length of 40 mm and a commercially available, textile PA6 staple fiber 3.3 dtex, 60 mm were used as starting material from 100% carbon fiber waste. Both materials were intimately mixed with one another in a mass ratio of 70% PA6 and 30% recycled carbon fibers (RCF) via a textile industry-typical mixed bed and subsequent mixing-opener technology as a so-called flake mixture.
• RCF recycled carbon fibers
• This fiber mixture was then submitted to a carding machine and the produced, flat mass uniform Krempelflor with a basis weight of 35 g / m 2 with a fiber blend of 70/30 PA6 / RCF on a Quertäfler to a Mehrfachflor harshung with a basis weight of 260 g / m 2 relined and then with a needle machine with 25 stitches / cm 2 so far solidified that the fleece for the subsequent processes on the one hand was safe to handle, on the other hand, the stitch intensity to obtain as long as possible Carbon fibers in the fleece were not too high.
• such needled webs of a basis weight of about 250-260 g / m 2 were in the form of pieces of 30 cm x 30 cm superimposed and pressed with a platen press at 240 ° C with 50 bar 100s and then cooled. Of the resulting plates were still
• the slabs were first cut longitudinally into strips on a knife cutting machine of the company Pierret with a cut of 6.3 mm and re-laying the strips in a cross section into chip-like pellets with edge lengths depending on the achieved cutting accuracy in a range of 4 to 10 mm ,
• the pellets are formed irregularly; ideally quadratic but usually irregular as a quadrilateral quadrangle or quadrilateral quadrangular to irregular triangles. These shapes result from the shredding technique of the plate product and are not of primary importance for use in injection molding. Rather, it is important that in the pellets no excessive proportions are present, which lead to the blocking of the feed hoppers at the following systems.
• nonwoven webs with a basis weight of 180 g / m 2 of 100% of a commercial textile PA6 fiber 3.3 dtex, 60 mm were prepared.
• the two nonwoven webs were needled only once with 12 stitches / cm 2 once from above.
• the second PA6 needle punched nonwoven fabric was rolled up at 180 g / m 2 as covering layer, so that a sandwich of 180 g / m 2 PA6 needled nonwoven fabric - 780 g / m 2 RCF pile layer - 180 g / m 2 PA6
• Needle felt was built. This sandwich was needle-punched with 25 stitches / cm 2 from top and bottom. As a result of the needling process, portions of the PA6 nonwoven covering layers were needled through the RCF layer, so that there was virtually a thorough mixing of PA6 with the RCF layer, which had a positive effect on the stability of the later achievable thermal consolidation level.
• the needle-punched nonwoven webs with PA6 outer layer and RCF in the core region were superimposed as 30 cm x 30 cm pieces and pressed with a platen press at 240 ° C. at 50 bar 100 s and then cooled. From the resulting plates, the still unconsolidated soft edges were cut off with a shearing shears.
• the slabs were first cut longitudinally into strips on a knife cutting machine of the company Pierret with a section of 9.8 mm and re-laying the strips in a cross section into chip-like pellets with edge lengths depending on the achieved cutting accuracy in a range of 7 to 14 mm ,
• the pellets are irregular, ideally quadratic, but mostly irregular, as a quadrilateral quadrangle or quadrilaterals, to irregular triangles.
• FIG. 1 shows a schematically simplified representation of the principle of a carding machine, which is suitable, for example, for producing a batt comprising, inter alia, carbon fibers according to the inventive method.
• the illustration shows at least one (in the drawing on the left) in the carding machine incoming fiber layer 10, which passes first via inlet rollers 1, 2 on a opposite the inlet rollers in the reverse rotation rotating licker 3.
• a transfer roller 4 is arranged which rotates counter to licker-in 3 and main drum 5.
• various workers 6 and 7 are arranged in different circumferential positions.
• the object of these devices is to fiberize the incoming fiber layer 10 in the carding machine to a single fiber and to form again to a thin and uniform uniform batt with a defined basis weight. In this case, preferably a fiber longitudinal orientation is desired.
• a batt 11 is discharged in the form of an endless surface, which for example has a basis weight to a maximum of about 80 g / m 2 , preferably at most about 60 g / m 2 , and a fiber longitudinal orientation of, for example, about 15 - 30 g / m 2

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• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Environmental & Geological Engineering (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
• Reinforced Plastic Materials (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Nonwoven Fabrics (AREA)

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• 2010
  • 2010-02-17 DE DE102010008349A patent/DE102010008349A1/de not_active Ceased
• 2011
  • 2011-02-03 JP JP2012553208A patent/JP5744066B2/ja not_active Expired - Fee Related
  • 2011-02-03 ES ES11704180.6T patent/ES2481403T3/es active Active
  • 2011-02-03 KR KR1020127024019A patent/KR101434076B1/ko not_active Expired - Fee Related
  • 2011-02-03 CA CA2789812A patent/CA2789812C/en active Active
  • 2011-02-03 CN CN201180010118.7A patent/CN102869481B/zh not_active Expired - Fee Related
  • 2011-02-03 MX MX2012009462A patent/MX2012009462A/es active IP Right Grant
  • 2011-02-03 WO PCT/EP2011/000485 patent/WO2011101093A2/de not_active Ceased
  • 2011-02-03 BR BR112012020688A patent/BR112012020688A2/pt not_active Application Discontinuation
  • 2011-02-03 PT PT11704180T patent/PT2536545E/pt unknown
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  • 2011-02-03 EP EP20110704180 patent/EP2536545B1/de active Active
• 2012
  • 2012-08-17 US US13/588,130 patent/US20130196154A1/en not_active Abandoned

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