• 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:
    LIGHT ITEMS, COMPOSITIONS OF COMPOSITES, AND PROCESSES FOR THE PRODUCTION OF THE SAME. The present invention provides a composite material comprising hollow glass microspheres and a microcellular thermoplastic resin, articles molded from such materials, and methods for producing such materials.
    公开号:BR112014022720B1
    申请号:R112014022720-9
    申请日:2013-03-07
    公开日:2020-10-27
    发明作者:Ibrahim Sedat Gunes；Baris Yalcin；Stephen E. Amos；Onur Sinan Yordem；Charles T. Stone
    申请人:3M Innovative Properties Company；
    IPC主号:
    专利说明:

    Technology field
    [001] The present description is related to light articles, in particular formatted thermoplastic articles, and processes for their production. summary
    [002] In a first aspect, the present description provides a composite material comprising hollow glassy microspheres and a microcellular thermoplastic resin.
    [003] In a second aspect, the present description provides a molded article comprising hollow glassy microspheres and a microcellular thermoplastic resin.
    [004] In another aspect, the present description provides a method, the method comprising feeding to a microcellular foam injection molding machine of a first pre-composite material comprising a mixture of thermoplastic and hollow glass microspheres. The method further comprises injecting a supercritical fluid into the mixture and blending the mixture and the supercritical fluid at high pressure to form a blend. The method further comprises injection of the blend into a molding tool.
    [005] In particular methods of the method, the mixture may additionally comprise particulate charges selected from the group consisting of talc, wolastonite, fiberglass, calcium carbonate, carbon black, molded colored pigments, carbon fibers, carbon nanotubes , ceramic microspheres, hollow ceramic microspheres, glass microspheres, ceramic fibers and nanoparticles.
    [006] The selected particulate charges can be in their pure form or the particles can be treated on the surface chemically or physically.
    [007] In particularly even further modalities, the method may further comprise feeding the mixture in the injection molding machine a supercritical fluid selected from the group consisting of CO2 and N2 and blending the mixture and the supercritical fluid within the molding machine by injecting microcellular foam to form a uniform blend.
    [008] In another aspect, the present description provides a method which comprises feeding to a microcellular foam injection molding machine of a first material comprising a pre-composite mix batch of a thermoplastic and hollow glass microspheres . The method further comprises injecting a supercritical fluid into the mixture and blending the mixture and the supercritical fluid at high pressure to form a blend and injecting the blend into a molding tool.
    [009] In particular methods of the method, the mixture may additionally comprise particulate charges selected from the group consisting of talc, wolastonite, glass fiber, calcium carbonate, carbon black, molded colored pigments, carbon fibers, carbon nanotubes , ceramic microspheres, hollow ceramic microspheres, glass microspheres, ceramic fibers and nanoparticles.
    [010] In particularly even further modes, the method may further comprise feeding the mixture in the injection molding machine a supercritical fluid selected from the group consisting of CO2 and N2 and blending the mixture and the supercritical fluid within the molding machine by injecting microcellular foam to form a uniform blend.
    [011] In another aspect, the present description provides a method which comprises feeding to a microcellular foam injection molding machine from a dry blend comprising a thermoplastic, hollow microspheres, mineral oil and a second material comprising CO2 or N2 in its supercritical state. This method further comprises mixing the dry blend and the second material inside the microcellular injection molding machine to form a molten blend and injection of the blend into a molding tool. Brief description of the drawings
    [012] Figure 1a is a scanning electron microscopy (SEM) of a polypropylene material that has been foamed using the MuCell process.
    [013] Figure 1b is a scanning electron microscopy (SEM) of a polypropylene material containing im30k of hollow vitreous microspheres that has been foamed using the MuCell process.
    [014] Figures may not be drawn to scale. Similar reference numbers can be used in all figures to denote similar parts. Detailed Description
    [015] In the field of plastics, there is still a need to reduce the density and thus the weight of formatted articles. Such a reduction, however, must provide a good balance between aesthetic, dimensional and mechanical properties, and such plastics must be relatively inexpensive and efficient to produce. With the recent increase in raw material prices, and transportation regulations in the form of vehicular greenhouse gas emissions, the search has been intensified to reduce the amount of polymers, specifically petroleum-based polymers, and to produce light and attractive materials.
    [016] Use of controlled gas in its supercritical state during molding by extrusion or injection of polymers showed the creation of a foamed part and, therefore, light, with a smaller amount of polymeric resins. The microcellular foaming process presents inherent process optimization challenges (multiple mold iterations) to produce malleable and aesthetically pleasing parts when significant weight reduction (for example, over 12% weight reduction) is to be achieved.
    [017] Applicants have found, and provide in the present description, that they can surprisingly use microcellular foaming processes in combination with hollow glass microspheres to achieve weight reduction with good mechanical and dimensional properties. As can be seen in the examples, not all foaming techniques provide desired results when applied to thermoplastic resins filled with hollow glass microspheres. Surprisingly, applicants have found that a specific combination of microcellular foaming processes in combination with hollow glass microspheres does in fact provide enhanced weight reduction with retention of mechanical and dimensional properties. Applicants have further discovered that microcellular thermoplastic resins comprising hollow glassy microspheres and molded articles made from them can provide improved weight reduction with retention of mechanical and dimensional properties.
    [018] As used here, and unless the context otherwise indicates, the following terms may have the meanings indicated.
    [019] The term “microcellular” typically refers to pore sizes of 0.1 to 100 micrometers.
    [020] The term "hollow microsphere" refers to a hollow round particle that has a maximum dimension less than one millimeter.
    [021] The term "supercritical fluid" refers to any substance at a temperature and pressure above its critical point, where different liquid and gas phases do not exist. Supercritical fluids can have the gaseous property of being able to penetrate solids, and the liquid property of being able to dissolve materials. Useful fluids may include, for example, CO2, N2, water and argon.
    [022] The term "polymer" refers to a macromolecule that has at least 10 sequential monomer units (or a substance composed of such macromolecules).
    [023] The term “thermoplastic” refers to melt processable polymers.
    [024] The term "thermoplastic polyolefin (TPO)" refers to three-phase polymer / rubber / filler blends, where some TPO formulations may omit rubber and / or filler.
    [025] The term “injection dimension” refers to the distance between the position of the thread assembly (portion of the complete barrel) and the zero position of the thread of an injection molding thread. The injection dimension is the measurement of the polymer available for injection for each part.
    [026] The present description is directed, in one aspect, to methods and materials that can solve the previously mentioned problems through the incorporation of hollow vitreous microspheres in the supercritical gas defoaming and in the formatting process.
    [027] In another aspect, the description is forwarded to processes and compositions for the production of light and aesthetically and dimensionally stable articles. The processes may include delivery as separate materials from a first material that includes a mixture of thermoplastic (for example, thermoplastic polyolefin) and hollow glassy microspheres with or without other particulate fillers (for example, talc, fiberglass, CaCO3 and etc.) and a second material that is essentially CO2 or N2 in its supercritical fluid state; applying a shear force and high pressure to the first and second materials, while the materials are at an elevated temperature to blend the materials to form a molten blend; injection of a third material and pressurization of the melted blend; discharge of the melted blend at the point where the supercritical fluid expands to its gaseous form in the presence of hollow glassy microspheres.
    [028] In some modalities, articles formed using the mentioned methods and compositions present pore sizes created by the expansion of the supercritical fluid in the range of 0.1 to 200 micrometers, preferably between 0.1 and 100 microns and more preferably between 0.1 and 30 microns.
    [029] The formatting of the blended blend containing the supercritical fluid can be performed using any one or a combination of various techniques for producing formatted articles. In general, the process is performed on molding machines that have been modified to allow the measurement, application and mixing of the supercritical fluid in the polymer.
    [030] In order to impart a microcellular structure to the molded parts, the microcellular foaming process is based on the homogeneous cell nucleation that occurs when a single phase polymer solution and a supercritical fluid pass through an injection port and to the interior of a mold cavity. The addition of supercritical fluid to the molten polymer pressurizes the solution, and the pressure drop as the solution enters the mold allows the supercritical fluid to create cell nuclei. The cells then expand until the material fills the mold, the expansion capabilities of the supercritical fluid are expanded, or the flow front freezes.
    [031] The thermoplastic materials according to the present description contain at least hollow glassy microspheres as a component in the formulation. More particularly, the thermoplastic material can be selected from polyolefin, a polyamide based on engineering thermoplastic, or high temperature engineering polymers like PBT, polyketones like, but not limited to PEEK and PEK, polysulfones like, but not limited to PSS, PEI, PAI, fluoropolymers like, but not limited to PVDF. Thermoplastic materials according to the present description can, where desirable, comprise a combination of thermoplastic resins.
    [032] The thermoplastic resins used in the first material may contain particulate charges in addition to hollow glassy microspheres. Thermoplastic polyolefins, for example, can refer to three-stage thermoplastic polymer-rubber-blend blends commonly used by resin manufacturers and processing companies. The thermoplastic polymer phase can be based on PP (polypropylene), PP copolymer or, on occasion, PE (polyethylene). The thermoplastic polymer is typically chosen as the matrix phase due to its low cost, ease of processing and a wide range of properties that can be adapted by the chemistry of the resin and / or additives.
    [033] Common rubbers in these formulations include butadiene, EPR (ethylene propylene rubber), EPDM (EP-diene rubber), EO (ethylene-octene), EB (ethylene-butadiene), SEBS (styrene-ethylene-butadiene-styrene ). Rubbers in a three-component formulation can, in some embodiments, optimize the impact properties of the thermoplastic phase (eg, polypropylene) that are typically low, specifically at low temperatures.
    [034] The fillers in such formulations include, but are not limited to, talc, glass fiber, carbon fiber, wolastonite, carbon black, molded colored pigments, carbon fibers, carbon nanotubes, ceramic microspheres, microspheres of hollow ceramics, glass microspheres, ceramic fibers and nanoparticles and MOS whisker fibers (magnesium oxysulfate available from Milliken). Also contemplated here is the possible inclusion in the compositions and articles described herein of suitable additives of a type such as a clarifier or nucleator, lubricants, glidants, stabilizers, acid neutralizers, antistatic, UV stabilizers, thermal stabilizers, and any combination of the same.
    [035] Desirably, as used in the process of the present invention, the first material is a pre-composite polymer masterbatch, which refers to a “concentrate” containing only hollow glass microspheres and thermoplastic resin, while other particulate charges (for example, talc , glass fiber, calcium carbonate, carbon fiber, wolastonite, and MOS whisker fibers (magnesium oxysulfate), if used, are incorporated into a second material, preferably the same thermoplastic as the first material. The description also contemplates processes, compositions and articles related to materials that are substantially free of charge in addition to hollow glassy microspheres.
    [036] Additional materials can be added during the process as shown in the present invention. These materials can essentially include CO2 or N2 in its supercritical fluid state. The creation of the single-phase solution, in which the supercritical fluid is fully dissolved and uniformly dispersed in the molten polymer, in some modalities, takes place inside the injection cylinder under carefully controlled process conditions.
    [037] The supercritical fluid can be measured in mass flow into the polymer for a fixed amount of time. During this dosing period, suitable temperature, pressure and shear conditions are established within the cylinder. The back pressure, screw speed and cylinder temperature control, as well as the geometry of the mixing screw and the supercritical fluid injector, all play a role in establishing the process conditions that create the single-phase solution.
    [038] An apparatus for producing such microcellular thermoplastic resins can be, for example, an Mucell®-enabled Engel injection molding machine, as further described in the example section.
    [039] The microcellular molding process described here uses either nitrogen or carbon dioxide as the foaming agent. Each has its advantages depending on the application objectives. Differences in the effectiveness of the two defoaming agents stem from their behavior in the polymeric melt.
    [040] Carbon dioxide, which becomes a supercritical fluid at 31.1 ° C and 7.2 MPa (72.2 bar), is 4 to 5 times more soluble in polymers than nitrogen, which becomes a supercritical fluid at -147 ° C and 3.4 MPa (34 bar). For example, the saturation point in an uncharged polymer is about 1.5 to 2 percent nitrogen, by weight, depending on temperature and pressure conditions, while the carbon dioxide saturation point is closer to 8 percent by weight.
    [041] Without sticking to the theory, the plasticizing nature of carbon dioxide should help preserve the integrity of the hollow microsphere in this high pressure injection molding process.
    [042] As will be understood, the classification of materials as "first", "second" and "third" in this description is for convenience. Except where specified, the use of these terms should not be used to exclude other materials and should not be used to infer or suggest any specific sequence of processing steps.
    [043] Other ingredients can be used in addition to the first, second, and third materials discussed here, including, but not limited to, one or more fillers, reinforcements, photostabilizers, dyes, flame retardants, thermal stabilizers, nucleators, or the like . It is contemplated that two of the first and second materials can be supplied together as a kit, as in one or more suitable containers. Such kits, as well as their individual component materials, are therefore within the scope of this description.
    [044] The articles according to the present description can be used in numerous applications that require light polymeric materials. For example, such items can be used in transport vehicles (for example, as bumpers, grilles, side linings, stirrups, fenders, rear doors, in wire and cable applications, instrument panels, consoles, internal trim , door panels, heater housings, battery holders, headlight housings, front ends, ventilation wheels, reservoirs, and soft sandpaper). Articles can be conformed. Articles can also be part of a set.
    [045] It is possible, for example, that a shaped article produced in accordance with the teachings of the present invention is laminated to another structure, such as by welding, adhesive bonding, a closure or any combination thereof. It is also possible that the articles may be part of an overlapped or co-injection molded assembly.
    [046] Articles can also be treated in a secondary operation to optimize their properties. By way of example, but not limited to, they may be coated, or otherwise, surface treated. For example, in one embodiment, the surfaces of a structure can optionally undergo a preliminary treatment before being attached to another structure. This optional treatment may include cleaning and degreasing, plasma coating, corona discharge treatment and coating with another surface treatment, coating with a bonding agent, or any combination thereof.
    [047] Without adhering to the theory, it is believed that this surprising result is due to the efficient gas cell nucleation effect in the presence of hollow vitreous microspheres. In the presence of hollow microspheres, significant density reductions of 12%, 25% or possibly even greater, depending on the density of the resin, can be achieved due to the synergistic effect of the hollow glass microspheres and the improved supercritical gas expansion process, the result of which it cannot be achieved using only the hollow microspheres or the supercritical gas expansion process (compare Table 6, line 2, 3 with 3 to 8).
    [048] Figure 1a is a scanning electron microscopy (SEM) image of a microcellular polypropylene without the addition of hollow glass microspheres. Figure 1b is a similar microcellular polypropylene, but with the addition of hollow glass microspheres. As can be seen from the image in Figure 1b, the hollow glassy microspheres are, on average, larger than the empty spaces present in the microcellular polypropylene.
    [049] The description of the present invention can also be understood as including the following specific modalities:
    [050] Mode 1. A composite material comprising hollow glass microspheres and a microcellular thermoplastic resin.
    [051] Mode 2. The composite material of mode 1, wherein a thermoplastic resin identical in chemical composition to the microcellular thermoplastic resin according to claim 1, such identical thermoplastic resin not being microcellular, the identical thermoplastic resin has a density P and the composite material has a density that is less than 0.88P.
    [052] Mode 3. The composite material of mode 1 or 2, additionally comprising glass fibers.
    [053] Modality 4. The composite material of any of the previous modalities, in which the microcellular thermoplastic resin is selected from polypropylene, polyethylene, polyamide, and a combination of them.
    [054] Mode 5. The composite material of mode 4, in which polypropylene is a high hardness polypropylene.
    [055] Modality 6. The composite material of any of the previous modalities, additionally comprising talc.
    [056] Mode 7. A molded article comprising hollow vitreous microspheres and a microcellular thermoplastic resin.
    [057] Mode 8. A method comprising: feeding to a microcellular foam injection molding machine of a first pre-composite material comprising a mixture of thermoplastic and hollow glass microspheres; injecting a supercritical fluid into the mixture and blending the mixture and the supercritical fluid at high pressure to form a blend; and injection of the blend into a molding tool.
    [058] Mode 9. The method of mode 8, in which the mixture additionally comprises particulate charges selected from the group consisting of talc, wolastonite, fiberglass, calcium carbonate, carbon black, molded colored pigments.
    [059] Mode 10. The method of mode 8 or 9, additionally comprising: feeding to the mixture in the injection molding machine a supercritical fluid selected from the group consisting of CO2 and N2; and blending the mixture and supercritical fluid inside the microcellular foam injection molding machine to form a uniform blend.
    [060] Mode 11. A method comprising: dry mixing a first material comprising a pre-composite mixing masterbatch of a thermoplastic and hollow glass microspheres with a second thermoplastic material to produce a first blend; feeding the blend to a microcellular foam injection molding machine; injection of a supercritical fluid into the blend at high pressure to form a second blend; and injection of the second blend into a molding tool.
    [061] Mode 12. The method of mode 11, in which the mixture additionally comprises particulate charges selected from the group consisting of talc, wolastonite, fiberglass, carbon black carbonate, molded colored pigments.
    [062] Mode 13. The method of mode 11 or 12, additionally comprising: feeding to the mixture in the injection molding machine a supercritical fluid selected from the group consisting of CO2 and N2; and blending the mixture and supercritical fluid inside the microcellular foam injection molding machine to form a uniform blend.
    [063] Mode 14. A method comprising: feeding to a microcellular foam injection molding machine from a dry blend that comprises a thermoplastic, hollow microspheres and a supercritical fluid selected from the group consisting of CO2 and N2; mixing the dry blend and the second material inside the microcellular injection molding machine to form a molten blend; and injection of the blend into a molding tool.
    [064] Mode 15. The method of mode 14, additionally comprising the addition of a surface bonding agent to the dry blend prior to injecting the blend into the molding tool.
    [065] Mode 16. The method of mode 14, in which the dry blend additionally comprises a mineral oil. Material Examples Table 1

    Example preparation
    [066] The examples were made on a 24 MM co-rotating twin-screw extruder with a 28: 1 L / D that had seven cylinder temperature zones and a matrix zone (PRISM TSE-24 MC, available with to Thermo Electron Corporation). The examples contained the materials identified in Table 2. Table 2

    * The quantities in Table 2 are given as a percentage by weight
    [067] In Example 1, the extruder was equipped with a side filler, a water bath and a pelletizing system. The IM30K was introduced using the side filler downstream in zone 4 of the 7 heating zones available on the extruder. Zone 1 was the region fed with PP resin and was cooled with water. The temperatures in zones 2 to 7 have been adjusted to 190 ° C, 220 ° C, 220 ° C, 220 ° C, 220 ° C and 220 ° C, respectively. The matrix temperature was adjusted to 220 ° C. The thread rotation speed was set to 300 rpm. Both the main feeder and the side filler feeder were volumetric feeders and were calibrated to produce 20%, by weight, of IM30K in PP. The extrudate was cooled in a water bath and pelleted. The speed of the twin screw extruder was about 2.7 kg / h (about 6 lbs / h). When PP-MAPP was used, it was dry mixed with the PP resin before starting to feed into the extruder.
    [068] In Example 2, the extruder was equipped with a resin feeder, a side filler, an upper feeder, a water bath and a pelletizing system. The polymeric resin was fed slowly into zone 1 through a volumetric pellet feeder and passed through a set of kneading blocks to ensure complete melting before the glass bubbles were introduced into zone 4. GBs were fed slowly into a side feeder through a supply feeder. Glass fibers were introduced in zone 6. Transport elements with a high depth channel (DO / Di: 1.75) were used in the GB 4 feed zone as well as in subsequent zones. Further downstream in zone 7, a short set of distributive elements was used. The temperature profile and the thread speed were the same for all materials. Zone 1 was cooled to water and temperatures in zones 2 to 7 were adjusted to 195 ° C, 220 ° C, 220 ° C, 220 ° C, 220 ° C, 220 ° C and 220 ° C, respectively. The thread speed was 300 rpm.
    [069] In Example 3, the extruder was equipped with a resin feeder, a side filler, an upper feeder, a water bath and a pelletizing system. The polymeric resin (PP-TRC, as received or the dry blend of PP-TRC and PP-Less Talc) was slowly fed into zone 1 through a volumetric pellet feeder and passed through a set of kneading blocks to ensure its complete melting before the glass bubbles were introduced into zone 4. GBs were fed slowly into a side feeder through a supply feeder. Transport elements with a high depth channel (DO / Di: 1.75) were used in the GB 4 feeding zone as well as in subsequent zones. The temperature profile and the thread speed were the same for all materials. Zone 1 was cooled to water and temperatures in zones 2 to 7 were adjusted to 240 ° C, 240 ° C, 240 ° C, 230 ° C, 230 ° C, 230 ° C and 230 ° C, respectively. The thread speed was 250 rpm.
    [070] In Example 4, the extruder was equipped with a resin feeder, a side filler, an upper feeder, a water bath and a pelletizing system. The Z-101 was fed slowly into zone 1 through a volumetric pellet feeder and passed through a set of kneading blocks to ensure its complete melting before the glass bubbles and glass fibers were introduced simultaneously into a side feeder in zone 4 through two individual volumetric feeders. Transport elements with a high depth channel (DO / Di: 1.75) were used in zone 4 as well as in subsequent zones. The temperature profile and the thread speed were the same for all materials. Zone 1 was cooled to water and temperatures in zones 2 to 7 were adjusted to 270 ° C, 275 ° C, 280 ° C, 280 ° C, 280 ° C, 280 ° C and 280 ° C, respectively. The thread speed was 250 rpm.
    [071] In Example 5, the extruder was equipped with a resin feeder, a side filler, an upper feeder, a water bath and a pelletizing system. PP was fed slowly into zone 1 through a volumetric pellet feeder and passed through a set of kneading blocks to ensure complete melting before the glass bubbles were introduced into a side feeder in zone 4 through a volumetric feeder. The talc was also fed through a volumetric feeder in zone 1. Transport elements with a high depth channel (DO / Di: 1.75) were used in zone 4 as well as in subsequent zones. The temperature profile and the thread speed were the same for all materials. Zone 1 was the region fed with PP resin and was cooled with water. The temperatures in zones 2 to 7 have been adjusted to 190 ° C, 220 ° C, 220 ° C, 220 ° C, 220 ° C and 220 ° C, respectively. The matrix temperature was adjusted to 220 ° C. The thread rotation speed was set to 300 rpm. Microcellular injection molding
    [072] The test samples were molded on an Mucell®-enabled Engel injection molding machine to the specifications shown in Table 3, using a mold to obtain ASTM I type tensile test samples (as described in ASTM D638-10: Standard Test Method for Tensile Properties of Plastics). Table 3

    [073] The injection molding parameters shown in Table 4 were kept constant for all samples in a specific example, except the injection dimension, which varied depending on the composition as detailed below. The injection dimension was used to adjust the defoaming in the mold cavity. The injection dimension was reduced to a point where an entire sample could not be molded. The SCF% is defined as the percentage of the total weight of the part. It is calculated using the following formula. % SCF = SCF Dosing Time x 12.6 x SCF Flow / Injection weight in grams Table 4

    Testing methods Density
    [074] The density of the injection molded parts was measured from the known weight of the injection molded parts divided by the volume of the test samples. The volume of the test samples was determined from the known molded weight of the unfilled polypropylene homopolymer “Profax” 6523, available from LyondellBasell, and its known density (0.9 g / cc) as measured by the Micromeritics AccuPyc gas pycnometer 1330 in a 10 cc container using helium gas as the displacement medium.
    [075] The mechanical properties of injection molded composites were measured using the standard ASTM test methods mentioned in Table 5 and a modified version of the ASTM D790. Table 5
    * FM and FS were measured using a modified version of the ASTM D-790 three-point flexion test, the modification being that the test samples used were ASTM type 1 test samples typically used on the ASTM D-638.
    [076] Table 6 shows the effect of hollow vitreous microspheres and glass fibers on the density and mechanical properties achieved in microcellular polymers. Table 6


    * N / A indicates that the mechanical properties reported are for materials in their native form, not prepared by the microcellular process. CO2 corresponds to carbon dioxide N2 corresponds to diatomic nitrogen
    权利要求:
    Claims (10)
    [0001]
    1. Composite material CHARACTERIZED by the fact that it comprises hollow vitreous microspheres and a microcellular thermoplastic resin.
    [0002]
    2. Composite material according to claim 1, CHARACTERIZED by the fact that an identical thermoplastic resin in chemical composition to the microcellular thermoplastic resin, as defined in claim 1, whose identical thermoplastic resin is not microcellular, the identical thermoplastic resin has a density P and the composite material has a density that is less than 0.88P.
    [0003]
    3. Composite material according to claim 1 or 2, CHARACTERIZED by the fact that it also comprises glass fibers.
    [0004]
    Composite material according to any one of claims 1 to 3, CHARACTERIZED by the fact that the microcellular thermoplastic resin is selected from polypropylene, polyethylene, polyamide, and a combination of these.
    [0005]
    5. Composite material according to any one of claims 1 to 4, CHARACTERIZED by the fact that it further comprises a particulate charge selected from the group consisting of talc, wolastonite, fiberglass, calcium carbonate, carbon black, colored pigments molded.
    [0006]
    6. Molded article CHARACTERIZED by the fact that it comprises hollow glassy microspheres and a microcellular thermoplastic resin.
    [0007]
    7. Method CHARACTERIZED by the fact that it comprises: feeding a microcellular foam injection molding machine with a first pre-composite material that comprises a mixture of a thermoplastic and hollow glass microspheres; injecting a supercritical fluid into the mixture and blending the mixture and supercritical fluid at high pressure to form a blend; and inject the blend into a molding tool.
    [0008]
    8. Method, according to claim 7, CHARACTERIZED by the fact that the mixture also comprises particulate charges selected from the group consisting of talc, wolastonite, fiberglass, calcium carbonate, carbon black, molded colored pigments.
    [0009]
    9. Method, according to claim 7 or 8, CHARACTERIZED by the fact that it further comprises: feeding the mixture in the injection molding machine with a supercritical fluid selected from the group consisting of CO2 and N2; and blending the mixture and supercritical fluid inside the microcellular foam injection molding machine to form a uniform blend.
    [0010]
    10. Method CHARACTERIZED by the fact that it comprises: dry blending of a first material comprising a pre-composite master batch of thermoplastic and hollow glass microspheres with a second thermoplastic material to produce a first blend; feeding the blend to a microcellular foam injection molding machine; inject a supercritical fluid into the blend at high pressure to form a second blend; and inject the second blend into a molding tool.
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    同族专利:
    公开号 | 公开日
    AU2013232474A1|2014-10-02|
    EP2825590B1|2017-04-19|
    EA201400921A1|2015-06-30|
    JP6436900B2|2018-12-12|
    KR20140144214A|2014-12-18|
    MX2014010980A|2014-10-06|
    EP2825590A1|2015-01-21|
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    US20150102528A1|2015-04-16|
    CA2867371A1|2013-09-19|
    EP2825590A4|2015-10-28|
    ES2629958T3|2017-08-16|
    AU2013232474B2|2015-06-18|
    JP2015510027A|2015-04-02|
    CN104334626A|2015-02-04|
    PL2825590T3|2017-09-29|
    AR090346A1|2014-11-05|
    WO2013138158A1|2013-09-19|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-10-27| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261611764P| true| 2012-03-16|2012-03-16|
    US61/611,764|2012-03-16|
    US201261671188P| true| 2012-07-13|2012-07-13|
    US61/671,188|2012-07-13|
    PCT/US2013/029636|WO2013138158A1|2012-03-16|2013-03-07|Light weight articles, composite compositions, and processes for making the same|
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