• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to the use of cellulosic fibers with improved meterability for reinforcing composite materials, in particular those with polymeric matrix materials, which are known as thermosets or elastomers, as well as moldings produced therefrom.
    公开号:AT511909A1
    申请号:T11852011
    申请日:2011-08-16
    公开日:2013-03-15
    发明作者:
    申请人:Chemiefaser Lenzing Ag；
    IPC主号:
    专利说明:

    Lenzing AG, PL0519 ·· * * »· * • ·
    Use of cellulosic fibers having improved dosing properties for reinforcing composite materials and thereby produced
    moldings
    The present invention relates to the use of cellulose fibers with improved metering ability for reinforcing composite materials, in particular those with polymeric matrix materials, which are known as thermosets or elastomers and shaped articles produced therefrom.
    State of the art
    The use of carbon fibers, aramid fibers and glass fibers in composites has long been state of the art
    Due to the increasing demand for sustainable raw materials, it is natural to produce composites based on natural fibers such as cotton, hemp or flax.
    The problems of these natural fibers, such as odor, outgassing and fogging, yellowing during processing, which are sometimes recognizable even after processing in the finished component, are currently not solved. In addition, climatic conditions during the growth phase affect the uniformity of the fibers, especially in terms of diameter and weak points. These lead in the component to different, not influenceable property distributions, which must be compensated in the component design as a precaution by a forced increase in the use of materials.
    Another aspect to consider is the so-called L / D ratio, which describes the ratio of diameter to fiber length. The higher this ratio, the better the mechanical reinforcement effect in the component. On the contrary, however, the fact that with longer fibers the meterability and dispersibility decreases. This is due to the fact that with increasing length of the fibers these interlock more easily and thus
    REFUNDABLE 1
    Lenzing AG, PL0519 • ·
    Diameter be considered. In addition to its direct influence on the L / D ratio, it has been proven that with a reduction in diameter, the number of fibers per unit of reinforcement increases and so does the surface area available for fiber / matrix adhesion.
    task
    The task now was to develop high quality composite materials, which do not have the disadvantages of natural fibers described above. In addition, the fibers should be readily metered and easily and uniformly dispersible in the thermoset or elastomer matrix. Furthermore, the so produced, high-quality composite parts should be able to be produced inexpensively.
    Description of the invention
    The solution to the above-described problem consists in the use of fibers with a number-weighted average diameter of 5 pm to 20 pm and a number-weighted mean length of 200 to δΟΟμιη for producing such composite materials.
    To determine the influence of the L / D ratio cellulosic synthetic fibers with different diameters, but the same weighted length were prepared and measured. As the L / D ratio decreases, so does the measured strength. As already described above, the L / D ratio for the improvement effect of the mechanical properties of a decisive size, surprisingly for cellulosic synthetic fibers, a ratio of greater than 30, preferably greater than 40, has emerged as very advantageous. Fibers having a diameter outside the above-specified range of the invention were difficult to meter or disperse because of the length necessary to achieve the L / D ratio.
    REPLACED 2
    Lenzing AG, PL0519 w »···« »« ···· • «t · * · · · · · · ·« · · · · «· ♦ ·» «« V * ·· «· 4 · · 4 ········································································································································································ With increasing length of the fibers, these tend to entangle and form tangles and agglomerates. In the case of the fiber according to the invention, this tendency is considerably lower, while maintaining the L / D ratio, due to the small length which is possible due to the small diameter.
    The fiber of the invention is further characterized by being a cellulosic synthetic fiber, i. H. is made of a cellulosic raw material, preferably pulp, but also, for example, cotton linters or other cellulosic materials, by physical transformation or by a chemical derivatization as the starting material. Fibers of this type are marketed under the name Modal, Viscose, Tencel or Lyocell, among others. The cellulosic raw material and thus the starting material for these fibers has the advantage of high chemical purity, which causes the fibers less discolored under the influence of temperature than, for example, natural fibers. By targeted reduction of the fiber length while maintaining the L / D ratio and the specified diameter range fibers according to the invention can be produced.
    The cellulosic synthetic fibers according to the invention are preferably so-called high-strength cellulosic synthetic fibers. For the purposes of the present invention, "high strength" is to be understood to mean cellulosic synthetic fibers which, in the case of a single fiber titer T (in dtex), have a strength (Bc) in the conditioned state of Bc (cN) > 1.3VT + 2T.
    Especially positive has been the use of Lyoceli fibers because of their high tensile strength at acceptable elongation. This fiber type has a tensile strength in the conditioned state of at least 35 cN / tex at an elastic modulus of around 10GPa (determined according to Lenzing Standard TIPQA 03/06 on dry individual fibers by means of a Vibrodyn measuring device with 50 mg preload). Likewise, other cellulosic synthetic fibers, such as modal fibers, can be used. However, these then often show less reinforcing effect in the finished component due to their mechanically lower strength values.
    | REPLACED I 3
    Lenzing AG, PL0519 " '' '*' ··· ♦ · · # * * * * «« «* * * * *« * «# ** *« * • «« * * * * * * * * * «« · · · · · · · ·
    The fibers of the invention may be made of pure gellulosene when prepared by milling standard fibers. In addition, however, modified fibers are possible if they were prepared by grinding of correspondingly modified starting fibers. For example, these modified fibers may be chemically derivatized or spun, i. H. incorporated incorporated additives. Likewise, starting fibers with non-round cross sections can be assumed.
    Suitable fiber types are, for example, those with trilobal cross sections, as described, inter alia, in WO 2006/060835 or ribbon fibers with a rectangular cross section. All of these variants are possible only through the previous deformation process from the spinning solution. In particular, the incorporation of additives is not feasible in this form with natural fibers or pulp; there is only a superficial application possible. Therefore, it is possible by the present invention to provide fibers which, for example, integrate even better into the plastic matrix or bring along other functionalities. A purely superficial application of additives is of course also possible with fibers according to the invention.
    However, the present invention by no means precludes that the composite material produced according to the invention also contains other fiber materials, in particular pulp and / or natural fibers, in addition to the cellulosic synthetic fibers. This may even be expressly desired for various applications. It is just an advantage of the use according to the invention of cellulosic synthetic fibers that they can mix with such other fiber materials without problems and can be processed together. Surprisingly, in addition to the reinforcing effect with regard to mechanical values such as modulus of elasticity, strength and elongation in brittle, thermoset materials, a significant improvement in the elastic behavior, for example their impact strength, could also be established. In contrast to glass fiber reinforced composite materials, this leads to a less brittle fracture behavior and thus to a reduced hazard potential. Also in elastomeric polymeric matrix materials
    SUBSEQUENT 4 • * * · • · a «I 1
    Lenzing AG, PL0519 an improvement of the mechanical properties could be observed when using the inventive Easern. Among other things, while reducing elongation, the strength of the composite was increased.
    The fibers according to the invention can be used in all composite materials, in particular in polymeric matrices. Preferably, they are used at processing temperatures that do not damage the fibers. Often, however, processing at higher temperatures does not adversely affect the properties of the composite.
    The invention is therefore also the use of such cellulosic synthetic fibers in composites, especially in those with polymeric matrix materials non-thermoplastic nature. These matrix materials of non-thermoplastic nature are preferably selected from the substance classes of thermosets or elastomers. The polymeric matrix preferably consists either of petroleum-based substances, of substances based on renewable raw materials or of a mixture of these substances.
    Examples of thermosets are urea resins, phenolic resins, melamine resins,
    Epoxy resins or polyester resins.
    Examples of elastomers are natural rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, butadiene rubber,
    Silicone rubber and ethylene-propylene-diene rubber.
    For example, according to the invention, the cellulosic synthetic fibers for the production of thermoset composite materials are already mixed into the not yet cured mixture of the starting materials-usually consisting of resin and hardener component and, if appropriate, other additives, and then shaping and crosslinking are initiated. The individual steps are known in principle to the person skilled in the art,
    For example, already known methods such as Resin Transfer Molding (RTM), Shield Molding Compound (SMC), Bulk Molding Compound (BMC) are used. I REPLACED 5
    Lenzing AG, PL0519
    Such a thermoset material produced according to the invention can be used, inter alia, for the production of boards, prepregs for further processing, molded parts for transportation, the automotive industry and aviation industry such as door panels or dashboards, housings for the electrical and electronics industry, cladding or components for the furniture and construction industries or for the sports industry, for example, energy-absorbing layers in ski, helmets, tennis rackets or golf clubs or as reinforcement for, for example, surfboards, skateboards or boats. By improving the impact strength of the material according to the invention can also be used as a protection or decorative coating for workpieces such as protective covers for boats or skateboards. For the production of elastomeric composite materials, the cellulosic synthetic fibers according to the invention are mixed with the other starting materials in a manner known to those skilled in the art. The mixture is then brought to the desired shape and crosslinked, these two steps can take place simultaneously or sequentially. For example, the components and the cellulosic fibers are mixed in an internal mixer and then rolled into a so-called "coat" or a plate. This intermediate product can then be further processed in processes such as the injection molding process. The elastomeric composite of the present invention may be used, inter alia, to modify the properties of tires, sheets, tubes, straps, shoe soles, gaskets, fasteners, bellows, floor coverings or damping elements. In one experiment, the elastomer composites of the invention were subjected to a tensile test, with a significant increase in the force / elongation curve in the range between 30% and 70% elongation. The curve thus obtained exhibited a plateau-like horizontal course to rupture after an almost linear increase, whereas
    6 ____NESSED
    Lenzing AG, PL0519 »* * * * * * * * * * * * * * · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ,
    The present invention therefore also relates to the shaped bodies according to the invention produced in this way according to the patent claims.
    For both thermosets and elastomers as the matrix material, the use of interfacial modifier often brings about an improvement in the property profile by changing the fiber / matrix properties of the composite. For example, it is recommended to use what are known as adhesion promoters, in particular in the case of hydrophobic matrix materials, in order to improve the fiber / matrix adhesion to cellulose. Depending on the nature of the adhesion promoter, it can either be applied to the fibers prior to introduction into the matrix material or added to the matrix material. In many cases, however, due to the readily accessible 15 OH groups of the cellulosic synthetic fiber on the use of
    Adhesives are waived. An opposite modification of the property profile of the composite material is also possible by, for example, reducing the fiber / matrix adhesion to the cellulose by means of silicone finishing agents. Additives that act in this way may be termed 20 "hold-ins".
    | RETURNED 7
    权利要求:
    Claims (13)
    [1]
    ib-Huw ii bw.'sy of-Lma rHitN / wtbtN'WitJx + ^ j rtifc; rtn cjy ^ ö ΗΠ: + -4 J 1 DJD b.Ie! 'ID

    Lenzing AG, PL0519 Claims 1, molded articles of fiber-reinforced composite material, comprising a polymeric, non-thermoplastic matrix material and cellulosic synthetic fibers, characterized in that these cellulosic synthetic fibers have a mean diameter between 5 and 20 pm and a number-weighted mean length between 200 and 800 pm.
    [2]
    A molded article according to claim 1, wherein the polymeric, non-thermoplastic matrix material is a thermoset or elastomer.
    [3]
    3. Shaped body according to claim 1, wherein the polymeric, non-thermoplastic matrix material, a thermoset and the molded body, a plate, a prepreg for further processing, a molding for transportation, automotive and aerospace industry such as a door trim or a dashboard, a housing for the electric 15 and electronics industry, a panel or a component for the furniture and construction industry, a part for the sports industry, for example for energy-absorbing layers in ski, helmets, tennis rackets orGotfschlögern, a reinforcement element for surfboards, skateboards or boats, a protective or decorative coating for 20 workpieces or protective covers for boats or skateboards is.
    [4]
    The molded article according to claim 1, wherein the polymeric non-thermoplastic matrix material is an elastomer and the molded article is a tire, a plate, a hose, a belt, a shoe sole, a gasket, a connector, a bellows, a floor covering or a cushioning member.
    [5]
    5. Use of cellulosic synthetic fibers having a mean diameter of between 5 and 20 pm and a number-weighted average length of between 200 and 600 pm, for the production of fiber-reinforced composite materials with polymeric matrix materials, characterized in that said Lenzing AG, PL0519 \ itJ-HUla-üWII MOniLHb rH I fcN I WtbtH 'WiBi CbiC rtU eJS ^ B Hn: -H4JJ I b-iHb-H bJb b.lj'lb • · * · ** * «# tt
    [6]
    6. matrix materials are non-thermoplastic materials, preferably thermosets or elastomers. Use according to claim 3, wherein the cellulosic synthetic fibers are high strength cellulosic synthetic fibers. Use according to claim 3, wherein the cellulosic synthetic fibers belong to the fiber genus Lyocell. 8. Use according to claim 3, wherein the composite material in addition to the cellulosic synthetic fibers and other fiber materials, in particular pulp and / or natural fibers. Use according to claim 3, wherein the polymeric matrix can consist of either petroleum-based substances, of substances based on renewable raw materials or of a mixture of these substances. The use according to claim 3, wherein an interface modifier is used to alter the fiber / matrix properties of the composite. 11. Use according to claim 8, wherein as an interface modifier either an adhesion promoter or a pressure reducer is used. 12. 20 Use ceulosic synthetic fibers according to claim 3 with thermosets as matrix materials for the production of plates, prepregs for further processing, moldings for transportation, the automotive industry and aviation industry Türverieungen or dashboards, housings for the electrical and electronics industry. Coverings or components for the furniture and construction industry, parts for the sports industry, for example for energy-absorbing layers in ski, helmets, tennis rackets or golf clubs, reinforcing elements for surfboards, skateboards or boats, protective coatings for workpieces or protective covers for boats or skateboards , 9 16/08/201 1 22:02 Nr .: R126 P.013 / 015 Ib-HUli-dBII CI.-BkJ Won: LHb n-tltmWtSti'f'WiBi + ^ JrbfB rtJi bb ^ b Hn! + < * J I b * ss b.LH'IS Lenzing AG, PL0519 i i; : V :: v *. *. m * * · * ·. ^! · * ♦♦ * i it
    13. Use of cellulosic synthetic fibers according to claim 3 with elastomers as matrix materials for the production of tires, plates, hoses, belts, shoe soles, gaskets, fasteners, bellows, floor coverings or 5 damping elements, 10 16/08/2011 22:02 Nr .: R126 P 014/015 Lenzing AG, PL0519 • * * * tt ♦ * < 1. A molded article of fiber-reinforced composite material comprising a polymeric, non-thermoplastic matrix material and cellulosic synthetic fibers, characterized in that these cellulosic synthetic fibers have a mean diameter between 5 and 20 pm and a number-weighted mean length between 200 and 800 pm. A molded article according to claim 1, wherein the polymeric, non-thermoplastic matrix material is a thermoset or elastomer. A molded article according to claim 1, wherein the polymeric non-thermoplastic matrix material is a thermoset and the molded article is a plate, a prepreg for further processing, a molding for transportation, automotive and aerospace industries such as a door trim or instrument panel, a housing for the electrical and Electronics industry, a panel or a component for the furniture and construction industry, a part for the sports industry, for example, energy-absorbing layers in ski, helmets, tennis rackets or golf clubs, a reinforcement for surfboards, skateboards or boats, a protective or decorative coating for workpieces or protective covers for boats or skateboards. The molded article according to claim 1, wherein the polymeric non-thermoplastic matrix material is an elastomer and the molded article is a tire, a plate, a hose, a belt, a shoe sole, a gasket, a connector, a bellows, a floor covering or a cushioning member. 5. Use of cellulosic synthetic fibers having a mean diameter of between 5 and 20 pm and a number-weighted mean length of between 200 and 800 pm, for the production of fiber-reinforced composite materials with polymeric matrix materials, characterized in that they are Lenzing AG, PL0519 «B 4 · «* ♦ B * ·« * «· · * ·« IB 4 I * B 4 B '* «B« 4 * * «· I» SB ··· 4 t of "B" matrix materials are non-thermoplastic materials, plastic materials, or plasticized elastomers. Use according to claim 3, wherein the cellulosic synthetic fibers are high strength cellulosic synthetic fibers.
    [7]
    7. Use according to claim 3, wherein the cellulosic synthetic fibers belong to the fiber genus Lyocell.
    [8]
    8. Use according to claim 3, wherein the composite material in addition to the cellulosic synthetic fibers and other fiber materials, in particular pulp and / or natural fibers.
    [9]
    9. Use according to claim 3, wherein the polymeric matrix may consist of either petroleum-based substances, of substances based on renewable raw materials or of a mixture of these substances.
    [10]
    10. Use according to claim 3, wherein an interface modifier is used to change the fiber / matrix properties of the composite.
    [11]
    11. Use according to claim 8, wherein as an interface modifier either an adhesion promoter or a pressure reducer is used.
    [12]
    12. Use of cellulosic synthetic fibers according to claim 3 with 20 thermosets as matrix materials for the production of plates, prepregs for further processing, moldings for transport, automotive and aerospace industry such as door panels or dashboards, housings for the electrical and electronics industry, panels or components for the furniture - and construction industry, parts 25 for the sports industry, for example, energy absorbing layers in ski, helmets, tennis rackets or golf clubs, reinforcing elements for surfboards, skateboards or boats, protective or decorative coatings for workpieces or protective covers for boats or skateboards. 9 _____ FOLLOW-UP Lenzing AG, PL0519 * · · ·· «·········· «T * * ·· t · ·« * * i
    [13]
    13. Use of acetal-based plastic fibers according to An & prtjth'3 * with elastomers as matrix materials for the production of tires, plates, hoses, belts, shoe soles, gaskets, fasteners, bellows, floor coverings or damping elements. 10 ___________ | SUBSEQUENT
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    引用文献:
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    DE1478022A1|1964-07-09|1970-07-23|Dunlop Rubber Co|Spielbaelle|
    DE4408855A1|1994-03-16|1995-09-21|Rawema Industrieanlagen Gmbh|Solid or foamed plastic using biomass as filler|
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    DE4332587C2|1993-09-24|1998-01-15|Color Plastic Chemie Albert Sc|Fiber-containing plastic, process for its production, use of the plastic for the production of a masterbatch or a polymer compound|
    DE10251518B4|2002-11-04|2009-10-01|Deutsches Zentrum für Luft- und Raumfahrt e.V.|Continuous manufacturing process for the production of fiber composite materials from renewable raw materials|
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    法律状态:
    2021-04-15| MM01| Lapse because of not paying annual fees|Effective date: 20200816 |
    优先权:
    申请号 | 申请日 | 专利标题
    AT11852011A|AT511909B1|2011-08-16|2011-08-16|USE OF CELLULOSE FIBERS WITH IMPROVED DOSAGE CAPACITY FOR REINFORCING COMPOSITE MATERIALS AND MOLDED BODIES MADE THEREFROM|AT11852011A| AT511909B1|2011-08-16|2011-08-16|USE OF CELLULOSE FIBERS WITH IMPROVED DOSAGE CAPACITY FOR REINFORCING COMPOSITE MATERIALS AND MOLDED BODIES MADE THEREFROM|
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