ENERGY ABSORPTION MEMBER AND PROTECTION EQUIPMENT

专利摘要:
energy-absorbing member an energy-absorbing member containing a porous polymeric material is provided. the polymeric material is formed from a thermoplastic composition containing a continuous phase that includes a matrix polymer and within which a nano-inclusion and micro-inclusion additive are dispersed in the form of discrete domains. a porous network is defined in the material that includes a plurality of nanopores with an average cross-sectional dimension of about 800 nanometers or less.
公开号:BR112015030878B1
申请号:R112015030878-3
申请日:2014-06-06
公开日:2020-12-15
发明作者:Vasily A. Topolkaraev；Ryan J. Mceneany；Neil T. Scholl；Mark M. Mleziva；Peter S. Lortscher
申请人:Kimberly-Clark Worldwide, Inc.；
IPC主号:

专利说明:

Related Orders
[001] The present application claims priority to US provisional applications serial number 61 / 833,996, filed on June 12, 2013, and 61 / 907,548, filed on November 22, 2013, which are incorporated in their entirety in this document by reference. Fundamentals of the Invention
[002] In most clothing and impact protective clothing, such as bulletproof vests (ballistic), helmets, elbow or shin guards, etc. impact energy is transferred through a rigid material and subsequently to the body, causing bruises or impact trauma. Body armor, for example, usually contains several layers of Kevlar® and Spectra® fabric contained within a fabric cover, which is collectively referred to as a "ballistic package". As a bullet enters a layer of Kevlar®, it becomes entangled in the fibers and its forward movement is stopped, but this does not cushion or absorb the transfer of energy from the impact. To reduce impact trauma, trauma packs are often used in conjunction with ballistic packs. These trauma packs are also typically constructed from Kevlar® or Spectra® fabrics, but are not made of layers that are thinner than the layers in the ballistic packs. However, trauma packs can add substantial weight and decrease the flexibility of the garment. As a result of these problems, foam fillers have also been developed as shock absorbers. However, despite being able to compress and flatten under pressure, foam materials are generally unable to act as good energy absorbers due to the fact that they do not flow and do not mold into specific shapes.
[003] As such, there is currently a need for an improved material for use as an energy-absorbing member in a variety of articles, such as in protective clothing. Summary of the Invention
[004] In accordance with an embodiment of the present invention, an energy-absorbing member comprising a polymeric material is disclosed. The polymeric material is formed from a thermoplastic composition containing a continuous phase that includes a matrix polymer. A micro-inclusion additive and nano-inclusion additive are also dispersed within the continuous phase in the form of discrete domains, in which a porous network is defined in the material that includes a plurality of nanopores having an average cross-sectional dimension of about 800 nanometers or less.
[005] Other properties and aspects of the present invention will be discussed in more detail below. Brief Description of the Figures
[006] A complete and clarifying description of the present invention, including its best mode, directed to people skilled in the art, is established more particularly in the rest of the specification, which makes reference to the attached figures in which: Fig. 1 is a front view of a modality of the protective clothing that the energy-absorbing member of the present invention can employ; Fig. 2 is a perspective view of another embodiment of protective clothing that can employ the energy-absorbing member of the present invention; Fig. 3 is a cross-sectional view of an embodiment of an energy-absorbing member that can be employed in the present invention; Fig. 4 is a cross-sectional view of another embodiment of an energy-absorbing member that can be employed in the present invention; and Fig. 5 is a cross-sectional view of yet another embodiment of an energy-absorbing member that can be employed in the present invention; Figures 6-7 are SEM microphotographs of the unstretched film of Example 3 (the film was cut parallel to the direction of the machine); Figures 8-9 are SEM microphotographs of the stretched film of Example 3 (the film was cut parallel to the direction of the machine direction); Figures 10-11 are SEM microphotographs of the unstretched film of Example 4, where the film was cut perpendicular to the machine direction in Fig. 10 and parallel to the machine direction in Fig. 11; and Figures 12-13 are SEM microphotographs of the stretched film of Example 4 (the film was cut parallel to the machine direction orientation).
[007] The repeated use of reference characters in this specification and in the figures aims to represent characteristics or elements that are the same or analogous to the invention. Detailed Description of Representative Modalities
[008] Detailed references will be made to various modalities of the invention, with one or more examples described below. Each example is provided by way of explanation of the invention, without limitation of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one modality, can be used in another modality to produce yet another modality. Thus, it is intended that the present invention covers such modifications and variations that are within the scope of the appended claims and their equivalents.
[009] In general, the present invention is directed to an energy-absorbing member that contains a porous polymeric material (e.g., film, fibrous material, molded article, etc.). The polymeric material is formed from a thermoplastic composition containing a continuous phase that includes a matrix polymer, micro-inclusion additive, and nano-inclusion additive. Additives can be selected so that they have an elastic modulus different from the matrix polymer. In this way, the micro-inclusion and nano-inclusion additives can be dispersed within the continuous phase as discrete microscale and nanoscale phase domains, respectively. The present inventors have found that the microscale and nanoscale phase domains are able to interact in a unique way when subjected to a deformation and elongation force (for example, stretching) to create a pore network. That is, it is believed that the stretching force can initiate the intensive localized shear zones and / or stress intensity zones (for example, normal stresses) close to the discrete microscale phase domains, as a result of stress concentrations that arise from the incompatibility of materials. These zones of shear intensity and / or stress cause an initial detachment in the polymer matrix adjacent to the microscale domains. In particular, however, the shear intensity and / or stress zones located can also be created close to the discrete nanoscale phase domains that overlap the microscale zones. Such overlapping shear and / or stress zones further cause the detachment to occur in the polymer matrix, thereby creating a substantial number of nanopores adjacent to the nanoscale and / or microscale domains.
[0010] Through the techniques noted above, a porous mesh can be deformed in the polymeric material so that the average percentage volume occupied by the pores within a given unitary volume of the material is relatively high, such as about 15% to about 80% per cm3, in some modalities, from about 20% to about 70%, and in some modalities, from about 30% to about 60% per cubic centimeter of the material. A substantial portion of the pores is also of a "nanoscale" ("nanopores") size, such as those with an average cross-sectional dimension of about 800 nanometers or less, in some embodiments, from about 5 to about 250 nanometers, and in some modalities, from about 10 to about 100 nanometers. The term "transverse dimension" generally refers to a characteristic dimension (for example, width or diameter) of a pore, which is substantially orthogonal to its main axis (for example, length) and also normally orthogonal to the direction of the stress applied during stretching. Such nanopores can, for example, constitute about 15% by volume or more, in some embodiments about 20% by volume or more, in some embodiments about 30% by volume to about 100% by volume, and in some embodiments from about 40% by volume to about 90% by volume of total pore in the polymeric material.
[0011] Due to their location close to the discrete phase domains (for example, microscale and / or nanoscale), the nanopores of the polymeric material can help to dissipate energy under load and increase the impact resistance in low-speed high-impact impacts. Without claiming to be limited by theory, for example, it is believed that when subjected to a relatively low to medium impact force, a pressure wave can be created that propagates relatively slowly through the polymeric material. As the wave continues, the polymeric material can be reversible compressed or deformed and can thus cushion a part of the body during impact, absorbing a part of the impact energy through internal deformation of the pore structure. During a high-speed impact, the force in the impact zone can be much greater and the resulting pressure wave can proceed much faster. The pressure wave can reach the outer limit of the material much more quickly or from the moment of impact. The result is a wave of internal pressure that occurs at a much higher pressure, leading to a much faster internal balance at greater pressure. In addition, individual pores are compressed faster than they can relieve pressure by emptying themselves into adjacent cells. Thus, at high impact speeds, the polymeric material can be compressed in a non-destructive way only as much as the porous structure can resist with the concomitant increase in the pressure of the compressed air within the pore volume. After the pressure limit is reached, further compression of the polymeric material requires destructive deformation of the porous structure similar to conventional rigid closed cell foams, except that the pores of the present invention can still recover their original shape. The sum of the effects of the above pressure is to make the polymeric material very rigid during a high speed impact, but still capable of recovering a substantial proportion of its original shape.
[0012] The resulting polymeric material can, for example, exhibit a high degree of impact resistance. The material may, for example, have a Charpy notched impact resistance of about 10 kilojoules per square meter (“kJ / m2”) or more, in some embodiments, around 20 kJ / m2 or more, in some embodiments, about 35 kJ / m2 or more, and in some embodiments, from about 45 kJ / m2 to about 100 kJ / m2, measured at 23 ° C according to ASTM D6110-10. In addition, the polymeric material is capable of absorbing a substantial amount of energy when subjected to a high speed charge. For example, the total energy absorbed by the polymeric material can be about 2 Joules or more, in some embodiments, about 3 Joules or more, and in some embodiments, from about 4 to about 20 Joules. Likewise, the peak load deflection of the polymeric material can also be about 10 millimeters or more, in some embodiments, about 12.5 millimeters or more, and in some embodiments, from about 15 to about 50 millimeters , and the peak load of about 250 Newtons or more, in some embodiments, about 350 Newtons or more, and in some embodiments, from about 400 to about 1000 Newtons. The total energy absorbed, peak load deflection, and peak load can be determined by a high speed drill test conducted according to ASTM D3763-10 at a speed of 12.5 meters per second and a temperature of 23 ° Ç.
[0013] The polymeric material can also have a variety of additional functions. For example, due to its unique porous structure, the polymeric material can generally be permeable to water vapors. The permeability of water vapor material can be characterized by its relatively high water vapor transmission rate (“WVTR”), which is the rate at which water vapor penetrates through the material, as measured in units of grams per square meter for 24 hours (g / m2 / 24 h). For example, the polyolefin material may exhibit a TTVA of about 300 g / m2-24 hours or more, in some embodiments around 500 g / m2-24 hours or more, in some embodiments around 1,000 g / m2-24 hours or more, and in other modes, from about 3,000 to about 15,000 g / m2-24 hours, as determined in accordance with ASTM E96 / 96M-12, Procedure B or INDA Test Procedure IST-70.4 (01). In addition to allowing the passage of vapors, the relatively high pore volume of the material also significantly decreases the density of the material, which may allow the use of lighter, more flexible materials, which still obtain good energy-absorbing properties. For example, the composition may have a relatively low density, such as about 1.2 grams per cubic centimeter (“g / cm3”) or less, in some embodiments, about 1.0 g / cm3 or less, in some embodiments, from about 0.2 g / cm3 to about 0.8 g / cm3, and in some embodiments, from about 0.1 g / cm3 to about 0.5 g / cm3. The polymeric material can also generally be impermeable to fluids (e.g., liquid water), thereby allowing the material to insulate a surface from water penetration. In this regard, the polymeric material may have a relatively high hydrostatic charge of about 50 cm ("cm") or more, in some embodiments about 100 cm or more, in some embodiments about 150 cm or more, and in some embodiments, from about 200 cm to about 1000 cm, as determined in accordance with ATTCC 127-2008.
[0014] In addition, the polymeric material can act as a thermal barrier that exhibits, for example, a relatively low thermal conductivity, such as about 0.40 watts per meter-kelvin ("W / m-K") or less , in some modalities, about 0.20 W / mK or less, in some modalities, about 0.15 W / mK or less, in some modalities, from about 0.01 to about 0.12 W / mK , and in some embodiments, from about 0.02 to about 0.10 W / mK. Notably, the material is able to achieve such low thermal conductivity values at relatively low thicknesses, which can allow the material to have a greater degree of flexibility and conformability, as well as reducing the space it occupies in an article. For this reason, the polymeric material may also have relatively low "thermal admittance", which is equal to the thermal conductivity of the material divided by its thickness and provided in units of watts per square meter-kelvin ("W / m2K"). For example, the material may have a thermal admittance of about 1000 W / m2K or less, in some embodiments from about 10 to about 800 W / m2K, in some embodiments from about 20 to about 500 W / m2K, and in some modalities from about 40 to about 200 W / m2K. The actual thickness of the polymeric material may depend on its particular shape, however, it typically ranges from about 5 micrometers to about 100 millimeters, in some modalities from about 10 micrometers to about 50 millimeters, in some modalities from about 200 micrometers at about 25 millimeters, and in some embodiments, from about 50 micrometers to about 5 millimeters.
[0015] Several modalities of the present invention will now be described in more detail. I. Thermoplastic Composition A. Matrix polymer
[0016] As indicated above, the thermoplastic composition contains a continuous phase within which the micro-inclusion and nano-inclusion additives are dispersed. The continuous phase contains one or more matrix polymers, which typically constitute about 60% by weight to about 99% by weight, in some embodiments from about 75% by weight to about 98% by weight, and in some embodiments, from about 80% by weight to about 95% by weight of the thermoplastic composition. The nature of the matrix polymer (s) used to form the continuous phase is not critical and any suitable polymer can be employed in general, such as polyesters, polyolefins, styrenic polymers, polyamides, etc. In certain embodiments, for example, polyesters can be used in the composition to form the polymer matrix. Any of a variety of polyesters can generally be used, such as aliphatic polyesters, such as polycaprolactone, polyesteramides, polylactic acid (PLA) and its copolymers, polyglycolic acid, polyalkylene carbonates (eg polyethylene carbonate), copolymers of poly-3-hydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxybutyrate-co-4-hydroxybutyrate, poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), poly-3 -hydroxybutyrate-co-3-hydroxyhexanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxidecanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate, and aliphatic polymers based succinate (for example, polybutylene succinate, polybutylene adipate succinate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (for example, polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene isophthalate adipate, polybutylene isophthalate adipate, etc.); aromatic polyesters (for example, polyethylene terephthalate, polybutylene terephthalate, etc.); and so on.
[0017] In certain cases, the thermoplastic composition may contain at least one polyester which is rigid in nature and thus have a relatively high glass transition temperature. For example, the glass transition temperature ("Tg") can be about 0 ° C or more, in some embodiments, from about 5 ° C to about 100 ° C, in some embodiments, about 30 ° C at about 80 ° C, and in some embodiments, from about 50 ° C to about 75 ° C. The polyester can also have a melting temperature of about 140 ° C to about 300 ° C, in some embodiments, from about 150 ° C to about 250 ° C, and in some embodiments, about 160 ° C at about 220 ° C. The melting temperature can be determined using differential scanning calorimetry (“DSC”) according to ASTM D-3417. The glass transition temperature can be determined by dynamic mechanical analysis in accordance with ASTM E1640-09.
[0018] A particularly suitable rigid polyester is polylactic acid, which can generally be derived from monomeric units of any lactic acid isomer, such as levogyrous lactic acid (“L-lactic acid”), dextrogyrous lactic acid (“D- lactic ”), meso-lactic acid or combinations thereof. Monomeric units can also be formed by anhydrides of any isomer of lactic acid, including L-lactide, D-lactide, meso-lactide or combinations thereof. Cyclic dimers of these lactic acids and / or lactides can also be used. Any known polymerization method, such as polycondensation or ring opening polymerization, can be used to polymerize lactic acid. A small amount of a chain extension agent (for example, a diisocyanate compound, an epoxy compound or acid anhydride) can also be employed. The polylactic acid can be a homopolymer or a copolymer, such as one that contains monomeric units derived from L-lactic acid and monomeric units derived from D-lactic acid. Although not required, the content ratio of one of the monomeric units derived from L-lactic acid and the monomeric unit derived from D-lactic acid is preferably about 85 mol% or more, in some embodiments, about 90 mol% or more and, in other embodiments, about 95 mol% or more. Various polylactic acids, each with a different ratio between the monomeric unit derived from L-lactic acid and the monomeric unit derived from D-lactic acid, can be mixed in any random percentage. Of course, polylactic acid can be mixed with other types of polymers (for example, polyolefins, polyesters, etc.).
[0019] In a specific modality, polylactic acid has the following general structure:

[0020] In a specific example of a suitable polylactic acid polymer that can be used in the present invention is commercially available from Biomer, Inc. of Krailling, Germany) under the name BIOMER ™ L9000. Other suitable polylactic acid polymers are commercially available from Natureworks LLC of Minnetonka, Minnesota (NATUREWORKS®) or Mitsui Chemical (LACEA ™). Still other suitable polylactic acids can be described in U.S. Patent Nos. 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254; and 6,326,458.
[0021] Polylactic acid normally has a number of average molecular weight ("Mn") ranging from about 40,000 to about 180,000 grams per mol, in some embodiments, from about 50,000 to about 160,000 grams per mol and, in some embodiments, from about 80,000 to about 120,000 grams per mol. Likewise, the polymer usually also has an average weight molecular weight ("Mw") that ranges from about 80,000 to about 250,000 grams per mol, in some embodiments, from about 100,000 to about 200,000 grams per mol and, in some embodiments, from about 110,000 to about 160,000 grams per mol. The ratio between the average weight molecular weight and the number of the average molecular weight (“Mw / Mn”), that is, the "polydispersity index", is also relatively low. For example, the polydispersity index usually ranges from about 1.0 to about 3.0, in some embodiments, from about 1.1 to about 2.0, and, in embodiments, from about 1.2 about 1.8. The average molecular weight and average weight numbers can be determined by methods known to those skilled in the art.
[0022] Polylactic acid may also have an apparent viscosity of about 50 to about 600 Pascal-seconds (Pa ^ s), in some embodiments, from about 100 to about 500 Pa ^ s, and in some embodiments, of about 200 to about 400 Pa ^ s, as determined at a temperature of 190 ° C and a shear rate of 1000 sec-1. The melt flow rate of polylactic acid (on a dry basis) can also vary from about 0.1 to about 40 grams for 10 minutes, in some embodiments, from about 0.5 to about 20 grams for 10 minutes , and, in some embodiments, from about 5 to about 15 grams for 10 minutes, determined at a load of 2160 grams and at 190 ° C.
[0023] Some types of pure polyester (for example, polylactic acid) can absorb water from the environment, such that it has a moisture content of about 500 to 600 parts per million (“ppm”), or even higher, based on dry weight of the initial polylactic acid. The moisture content can be determined in several ways, as is known in the art, such as according to ASTM D 7191-05, as described below. Since the presence of water during melt processing can hydrolytically degrade the polyester and reduce its molecular weight, it is sometimes desired to dry the polyester before mixing it. In most modalities, for example, it is desired that the polyester has a moisture content of about 300 parts per million ("ppm") or less, in some modalities, of about 200 ppm or less, in some modalities, of about 1 to about 100 ppm, before mixing with micro-inclusion and nano-inclusion additives. Drying of the polyester can occur, for example, at a temperature of about 50 ° C to about 100 ° C and, in some embodiments, from about 70 ° C to about 80 ° C. B. Microinclusion additive
[0024] As used in this document, the term "microinclusion additive" generally refers to any amorphous, crystalline or semi-crystalline material capable of being dispersed within the polymer matrix in the form of discrete domains of microscale size. For example, before drawing, the domains may have an average cross-sectional dimension of about 0.05 μm to about 30 μm, in some modalities, from about 0.1 μm to about 25 μm, in some modalities, from about 0.5 μm to about 20 μm, and in some embodiments, from about 1 μm to about 10 μm. The term "transverse dimension" generally refers to a characteristic dimension (for example, width or diameter) of a domain, which is substantially orthogonal to its main axis (for example, length) and also substantially orthogonal to the direction of the stress applied during stretching. Although normally formed from the micro-inclusion additive, it should be understood that the micro-scale domains can also be formed from a combination of the micro-inclusion and nano-inclusion additives and / or other components of the composition.
[0025] The microinclusion additive is generally polymeric in nature and has a relatively high molecular weight to help improve the melt strength and stability of the thermoplastic composition. Typically, the microinclusion polymer can generally be immiscible with the matrix polymer. In this way, the additive can be better spread as the discrete phase domains within a continuous phase of the matrix polymer. The discrete domains are able to absorb energy due to an external force, which increases the stiffness and the general resistance of the resulting material. Domains can have a variety of different shapes, such as elliptical, spherical, cylindrical, plate-like, tubular, etc. In one embodiment, for example, the domains are substantially elliptical in shape. The physical dimension of an individual domain is typically small enough to minimize the propagation of cracks through the polymeric material when applying external stress, but large enough to initiate microscopic plastic deformation and allow for shear and / or intensity zones of stress in and around particle inclusions.
[0026] Although the polymers can be immiscible, the microinclusion additive can, however, be selected because it has a solubility parameter that is relatively similar to that of the matrix polymer. This can improve the interfacial compatibility and physical interaction of the discrete and continuous phase boundaries and thus reduce the likelihood of the compound breaking. In that respect, the ratio between the solubility parameter for the matrix polymer and that of the additive is usually about 0.5 to about 1.5 and, in some embodiments, from about 0.8 to about 1, two. For example, the polymeric microinclusion additive may have a solubility parameter of about 15 to about 30 MJoules1 / 2 / m3 / 2 and, in some embodiments, from about 18 to about 22 MJoules1 / 2 / m3 / 2 , while polylactic acid may have a solubility parameter of about 20.5 MJoules1 / 2 / m3 / 2. The term “solubility parameter”, as used in this document, refers to the “Hildebrand Solubility Parameter”, which is the square root of the density of cohesive energy and is calculated according to the following equation:
where: Δ Hv = heat of vaporization R = ideal gas constant T = temperature Vm = molecular volume
[0027] Hildebrand's solubility parameters for various polymers are also available from Wyeych's Solubility Handbook of Plastics (2004), which is incorporated into this document by reference.
[0028] The microinclusion additive can also have a certain melt flow rate (or viscosity) to ensure that the discrete domains and the resulting pores can be maintained properly. For example, if the melt flow rate of the additive is too high, it tends to flow and disperse uncontrollably in the continuous phase. This results in lamellar or plate-like domains or co-continuous phase structures that are difficult to maintain and are also likely to crack prematurely. On the other hand, if the melt flow rate of the additive is too low, it will tend to agglutinate and form very large elliptical domains, which are difficult to disperse during mixing. This may cause an irregular distribution of the additive throughout the continuous phase. In this regard, the present inventors have found that the ratio between the melt flow rate of the microinclusion additive and the melt flow rate of the matrix polymer is usually about 0.2 to about 8, in some embodiments, from about 0.5 to about 6 and, in some embodiments, from about 1 to about 5. The microinclusion additive can, for example, have a melt flow rate of about 0.1 to about 250 grams for 10 minutes, in some modalities, from about 0.5 to about 200 grams for 10 minutes and, in some modalities, from about 5 to about 150 grams for 10 minutes, determined in a load of 2160 grams and the 190 ° C.
[0029] In addition to the properties noted above, the mechanical characteristics of the microinclusion additive can also be selected to achieve the desired porous network. For example, when a mixture of the matrix polymer and the micro-inclusion additive is applied with an external force, stress concentrations (for example, including normal or shear stress) and shear and / or plastic production zones can be applied. be initiated around and in the discrete phase domains as a result of the stress concentrations that arise from a difference in the elastic modulus of the additive and the matrix polymer. Higher concentrations of stress promote a more intense localized plastic flow in the domains, allowing them to become significantly stretched when stresses are applied. These elongated domains allow the composition to exhibit a more flexible and softer behavior than the matrix polymer, such as when it is a rigid polyester resin. To improve stress concentrations, the microinclusion additive can be selected to have a relatively low Young's modulus of elasticity compared to the matrix polymer. For example, the ratio of the modulus of elasticity of the matrix polymer to that of the additive is usually about 1 to about 250, in some embodiments, from about 2 to about 100 and, in some embodiments, about 2 to about 50. The modulus of elasticity of the micro-inclusion additive can, for example, vary from about 2 to about 1000 megapascals (MPa), in some embodiments, from about 5 to about 500 MPa and, in some modalities, from about 10 to about 200 MPa. On the other hand, the modulus of elasticity of polylactic acid, for example, is usually from about 800 MPa to about 3000 MPa.
[0030] Although a wide variety of micro-inclusion additives that have the properties identified above can be employed, particularly suitable examples of such additives may also include synthetic polymers, such as polyolefins (for example, polyethylene, polypropylene, polybutylene, etc.); styrenic copolymers (for example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-butadiene-styrene, etc.); polytetrafluoroethylenes; polyesters (for example, recycled polyester, polyethylene terephthalate, etc.); polyvinyl acetates (for example, poly (ethylene vinyl acetate), polyvinyl acetate and chloride, etc.); polyvinyl alcohols (for example, polyvinyl alcohol, poly (ethylene vinyl alcohol), etc.); polyvinyl butyrals; acrylic resins (for example, polyacrylate, polymethylacrylate, polymethylmethacrylate, etc.); polyamides (for example, nylon); polyvinyl chlorides; polyvinylidene chlorides; polystyrenes; polyurethanes; etc. Suitable polyolefins may, for example, include ethylene polymers (for example, low density polyethylene (“LDPE”), high density polyethylene (“HDPE”), linear low density polyethylene (“LLDPE”), etc.), propylene homopolymers (for example, syndiotactic, atactic, isotactic, etc.), propylene copolymers, and so on.
[0031] In a given embodiment, the polymer is a propylene polymer, such as homopolypropylene, or a propylene copolymer. The propylene polymer can, for example, be formed by a substantially isotactic polypropylene homopolymer or by a copolymer containing an amount equal to or less than about 10% of the other monomer, i.e., at least about 90% by weight of propylene. Such homopolymers can have a melting point of about 160 ° C to about 170 ° C.
[0032] In yet another embodiment, the polyolefin can be a copolymer of ethylene or propylene with another α-olefin, such as α-olefin C3-C20 or α-olefin C3-C12. Specific examples of suitable α-olefins include 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1- pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. The particularly desired comonomers of α-olefin are 1-butene, 1-hexene and 1-octene. The ethylene or propylene content of such copolymers can vary from about 60 mol% to about 99 mol%, in some embodiments, from about 80 mol% to about 98.5 mol%, and in some embodiments, from about 87 mol% to about 97.5 mol%. The α-olefin content can vary from about 1 mol% to about 40 mol%, in some embodiments, from about 1.5 mol% to about 15 mol%, and in some embodiments, from about 2.5 mol% to about 13 mol%.
[0033] Examples of olefin copolymers for use in the present invention include ethylene-based copolymers available under the name EXACT ™, from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are available under the designation ENGAGE ™, AFFINITY ™, DOWLEX ™ (LLDPE) and ATTANE ™ (ULDPE) from Dow Chemical Company of Midland, Michigan. Other suitable ethylene polymers are described in U.S. Patent Nos. 4,937,299 to Ewen et al .; 5,218,071 to Tsutsui et al .; 5,272,236 to Lai, et al .; and 5,278,272 to Lai, et al. Suitable propylene copolymers are also commercially available under the VISTAMAXX ™ designations of ExxonMobil Chemical Co. of Houston, Texas; FINA ™ (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMER ™ available from Mitsui Petrochemical Industries; and VERSIFY ™, available from Dow Chemical Co. of Midland, Michigan. Suitable polypropylene homopolymers can include Exxon Mobil 3155 polypropylene, Exxon Mobil Achieve ™ resins, and Total M3661 PP resin. Other examples of suitable propylene polymers are described in U.S. Patent Nos. 6,500,563 to Datta et al .; 5,539,056 to Yang et al .; and 5,596,052 to Resconi et al.
[0034] A wide variety of known techniques can be employed, in general, to form the olefin copolymers. For example, olefin polymers can be formed using a free radical or a coordinating catalyst (for example, Ziegler-Natta). Preferably, the olefin polymer is formed by a single site coordination catalyst, such as a metallocene catalyst. Such a catalyst system produces ethylene copolymers, in which the comonomer is randomly distributed within a molecular chain and uniformly distributed among the different molecular weight fractions. Metallocene-catalyzed polyolefins are described, for example, in U.S. Patent 5,571,619 to McAlpin et al .; 5,322,728 for Davis et al .; 5,472,775 to Obijeski et al .; 5,272,236 to Lai et al .; and 6,090,325 for Wheat, et al. Examples of metallocene catalysts include bis (n-butylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) scandium chloride, bis (indenyl) zirconium dichloride, methyl (dichloro) dichloride bis (methylcyclopentadienyl) zirconium, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafnocene dichloride, isopropyl dichloride (cyclopentadienyl, -1-flourenyl) zirconium, molybdocene dichloride, nickelocene, dichlorocene, nickelocene, dichlorocene zirconocene chloride, zirconocene dichloride, and so on. Polymers produced using metallocene catalysts typically have a narrow molecular weight range. For example, metallocene-catalyzed polymers may have polydispersity numbers (Mw / Mn) below 4, controlled short chain branch distribution and controlled isotacticity.
[0035] Regardless of the materials used, the relative percentage of the microinclusion additive in the thermoplastic composition is selected to achieve the desired properties without significantly affecting the basic properties of the composition. For example, the microinclusion additive is normally employed in an amount of about 1% by weight to about 30% by weight, in some embodiments, from about 2% by weight to about 25% by weight and, in some embodiments , from about 5% by weight to about 20% by weight of the thermoplastic composition, based on the weight of the continuous phase (polymer (s) of the matrix). The concentration of the microinclusion additive in the entire thermoplastic composition can be from about 0.1% by weight to about 30% by weight, in some embodiments, from about 0.5% by weight to about 25% by weight and , in some embodiments, from about 1% by weight to about 20% by weight. C. Nanoinclusion additive
[0036] As used herein, the term "nanoinclusion additive" generally refers to any amorphous, crystalline or semicrystalline material that is capable of being dispersed within the polymer matrix in the form of discrete domains of a nanoscale size. For example, prior to stretching, the domains may have an average cross-sectional dimension of about 1 to about 1000 nanometers, in some modalities, from about 5 to about 800 nanometers and, in some modalities, from about 10 to about 500 nanometers, and in some modalities, from about 20 to about 200 nanometers. It should also be understood that nanoscale domains can also be formed from a combination of micro-inclusion and nano-inclusion additives and / or other components of the composition. For example, the nanoinclusion additive is normally employed in an amount of about 0.05% by weight to about 20% by weight, in some embodiments, from about 0.1% by weight to about 10% by weight and in some embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase (polymer (s) of the matrix). The concentration of the nano-inclusion additive in the entire thermoplastic composition can be from about 0.01% by weight to about 15% by weight, in some embodiments, from about 0.05% by weight to about 10% by weight and, in some embodiments, from about 0.3% by weight to about 6% by weight of the thermoplastic composition.
[0037] The nanoinclusion additive can be polymeric in nature and have a relatively high molecular weight to help improve the melt strength and stability of the thermoplastic composition. To increase its ability to become dispersed in nanoscale domains, the nano-inclusion additive can also be selected from materials that are generally compatible with the matrix polymer and the micro-inclusion additive. This can be particularly useful when the matrix polymer or micro-inclusion additive has a polar fraction, such as a polyester. An example of such a nano-inclusion additive is a functionalized polyolefin. The polar compound can, for example, be provided by one or more functional groups, and the non-polar component can be provided by an olefin. The nano-inclusion additive olefin compound can generally be formed of any branched or linear α-olefin monomer, oligomer, or polymer (including copolymers) derived from an olefin monomer, as described above.
[0038] The functional group of the nanoinclusion additive can be any group, segment and / or molecular block that provides a polar component for the molecule and is not compatible with the matrix polymer. Examples of segment and / or molecular blocks not compatible with polyolefin may include acrylates, styrenics, polyesters, polyamides, etc. The functional group may be ionic in nature and comprise charged metal ions. Particularly suitable functional groups are maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, a reaction product of maleic anhydride and diamine, methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, etc. Maleic anhydride modified polyolefins are particularly suitable for use in the present invention. Such modified polyolefins are usually formed by grafting maleic anhydride into a material of the polymeric backbone. These maleatated polyolefins are available from EI du Pont de Nemours and Company under the name Fusabond®, such as the P series (chemically modified polypropylene), E series (chemically modified polyethylene), C series (chemically modified ethylene vinyl acetate), series A (chemically modified ethylene acrylate copolymers or terpolymers), or series N (chemically modified ethylene-propylene diene monomer ("EPDM") or ethylene-octene). Alternatively, maleatated polyolefins are also available from Chemtura Corp. under the name of Polybond® and Eastman Chemical Company under the name of Eastman G series.
[0039] In certain embodiments, the nano-inclusion additive can also be reactive. An example of such a reactive nano-inclusion additive is a polyepoxide that contains, on average, at least two axirane rings per molecule. Without the intention of limiting themselves by theory, it is believed that these polyepoxide molecules can induce a reaction of the matrix polymer (for example, polyester) under certain conditions, thereby improving their melt resistance without significantly reducing the temperature of glass transition. The reaction may involve chain extension, side chain branching, grafting, copolymer formation, etc. Chain extension, for example, can occur through a variety of different reaction pathways. For example, the modifier can allow a nucleophilic reaction for ring opening through a carboxyl terminal group of a polyester (esterification) or through a hydroxyl group (etherification). Side reactions of oxazoline can occur to form esteramide fractions. Through these reactions, the molecular weight of the matrix polymer can be increased to counteract degradation frequently during the melting process. Although it is desirable to induce a reaction with the matrix polymer as described above, the present inventors have found that too much reaction can cause crosslinking between the main structures of the polymer. If this crosslinking has been allowed to proceed to a significant extent, the resulting polymer mixture may become brittle and difficult to process in a material with the desired properties of strength and elongation.
[0040] In this regard, the present inventors have found that polyepoxides with relatively low epoxy functionality are particularly effective, which can be quantified by "epoxy equivalent weight". The epoxy equivalent weight reflects the amount of resin that contains a molecule of an epoxy group, and can be calculated by dividing the average molecular weight in number of the modifier by the number of epoxy groups in the molecule. The polyepoxide of the present invention normally has an average molecular weight in number of about 7,500 to about 250,000 grams per mol, in some embodiments, from about 15,000 to about 150,000 grams per mol and, in some embodiments, from about 20,000 to about 100,000 grams per mole, with a polydispersity index ranging from 2.5 to 7. Polyepoxide may contain less than 50, in some embodiments, from 5 to 45 and, in some embodiments, from 15 to 40 epoxy groups. In turn, the epoxy equivalent weight may be less than about 15,000 grams per mole, in some embodiments, from about 200 to about 10,000 grams per mole and, in some embodiments, from about 500 to about 7,000 grams per mol.
[0041] The polyepoxide can be a linear or branched homopolymer or copolymer (e.g., random, graft, block, etc.) containing terminal epoxy groups, skeletal oxirane units, and / or pendant epoxy groups. The monomers used to form these polyepoxides can vary. In a specific embodiment, for example, the polyepoxide contains at least one epoxy-functional monomeric (meth) acrylic component. As used herein, the term “(meth) acrylic” includes acrylic and methacrylic monomers, as well as their salts or esters, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meth) acrylic monomers can include, but are not limited to, those containing 1,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate and glycidyl itoconate.
[0042] Polyepoxide normally has a relatively high molecular weight, as indicated above, so that it can not only result in chain extension, but also to achieve the desired morphology of the mixture. The melt flow rate resulting from the polymer is thus typically within a range of about 10 to about 200 grams for 10 minutes, in some embodiments, from about 40 to about 150 grams for 10 minutes, and in some modalities, from about 60 to about 120 grams for 10 minutes, determined in a load of 2160 grams and at a temperature of 190 ° C.
[0043] If desired, additional monomers can also be used in the polyepoxide to help achieve the desired molecular weight. Such monomers may vary and include, for example, ester monomers, (meth) acrylic monomers, olefin monomers, amide monomers, etc. In a specific embodiment, for example, the polyepoxide includes at least one linear or branched α-olefin monomer, such as those having 2 to 20 carbon atoms and preferably 2 to 8 carbon atoms. Specific examples include ethylene, propylene, 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1- nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. The particularly desired α-olefin comonomers are ethylene and propylene.
[0044] Another suitable monomer may include a (meth) acrylic monomer that is not epoxy-functional. Examples of such (meth) acrylic monomers can include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-acrylate -butyl, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, acrylate methylcyclohexyl, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, methacrylate, methacrylate, methacrylate of n-amyl, n-hexyl methacrylate, i-amyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, methacrylate methacrylate , cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, isobornyl methacrylate, etc., good as comb inactions.
[0045] In a particularly desirable embodiment of the present invention, polyepoxide is a terpolymer formed by an epoxy-functional monomeric (meth) acrylic component, an α-olefin monomeric component, and a non-epoxy-functional monomeric (meth) acrylic component . For example, the polyepoxide can be poly (ethylene-co-methylacrylate-co-glycidyl methacrylate), which has the following structure:
where x, y and z are 1 or greater.
[0046] The epoxy-functional monomer can be transformed into a polymer using a variety of known techniques. For example, a monomer containing polar functional groups can be grafted into the main structure of a polymer to form a graft copolymer. Such grafting techniques are well known in the art and described, for example, in U.S. Patent No. 5,179,164. In other embodiments, a monomer containing epoxy-functional groups can be copolymerized with a monomer to form a random block or copolymer using known free radical polymerization techniques, such as high pressure reactions, reaction systems with Ziegler-Natta catalyst, systems reaction with single site catalyst (eg metallocene), etc.
[0047] The relative part of the monomeric component (s) can be selected to achieve a balance between epoxy reactivity and melt flow rate. More specifically, a high epoxy monomer content can result in good reactivity with the matrix polymer, but a very high content can reduce the melt flow rate in such a way that the polyepoxide adversely affects the melt resistance of the mixture. polymer. Thus, in most modalities, the epoxy-functional acrylic (meth) monomer (s) constitutes (in) about 1% by weight to about 25% by weight, in some modalities, from about 2% by weight to about 20% by weight and, in some embodiments, from about 4% by weight to about 15% by weight of the copolymer. The α-olefin monomer (s) can also comprise from about 55% by weight to about 95% by weight, in some embodiments, from about 60% by weight to about 90% by weight. by weight and, in some embodiments, from about 65% by weight to about 85% by weight of the copolymer. When used, other monomeric components (for example, non-epoxy-functional (meth) acrylic monomers) may constitute from about 5% by weight to about 35% by weight, in some embodiments, from about 8% by weight to about from 30% by weight and, in some embodiments, from about 10% by weight to about 25% by weight of the copolymer. A specific example of a suitable polyepoxide that can be used in the present invention is commercially available from Arkema under the name LOTADER® AX8950 or AX8900. LOTADER® AX8950, for example, has a melt flow rate of 70 to 100 g / 10 min and has a 7% by weight to 11% by weight glycidyl methacrylate monomer content, an acrylate monomer content methyl content of 13% by weight to 17% by weight, and an ethylene monomer content of 72% by weight to 80% by weight. Another suitable polyepoxide is commercially available from DuPont under the name ELVALOY® PTW, which is an ethylene terpolymer, butyl acrylate, and glycidyl methacrylate and has a melt flow rate of 12 g / 10 min.
[0048] In addition to controlling the type and relative content of the monomers used to form the polyepoxide, the overall weight percentage can also be controlled to achieve the desired benefits. For example, if the level of modification is very low, the desired increase in melt strength and mechanical properties may not be achieved. The present inventors have also found, however, that if the level of modification is too high, processing may be restricted due to strong molecular interactions (eg, crosslinking) and physical network formation by epoxy-functional groups. Thus, polyepoxide is normally employed in an amount of about 0.05% by weight to about 10% by weight, in some embodiments, from about 0.1% by weight to about 8% by weight, in some embodiments from about 0.5% by weight to about 5% by weight and, in some embodiments, from about 1% by weight to about 3% by weight, based on the weight of the matrix polymer employed in the composition. Polyepoxide may also constitute about 0.05% by weight to about 10% by weight, in some embodiments, from about 0.05% by weight to about 8% by weight, in some embodiments, from about 0 , 1% by weight to about 5% by weight and, in some embodiments, from about 0.5% by weight to about 3% by weight, based on the total weight of the composition.
[0049] Other reactive nano-inclusion additives can also be employed in the present invention, such as functionalized oxazoline polymers, functionalized cyanide polymers, etc. When used, such reactive nano-inclusion additives can be used within the concentrations noted above for the polyepoxide. In a specific embodiment, a polyolefin grafted with oxazoline can be used, that is, a polyolefin grafted with a monomer containing an oxazoline ring. Oxazoline may include a 2-oxazoline, such as 2-vinyl-2-oxazoline (for example, 2-isopropenyl-2-oxazoline), 2-fatty-alkyl-2-oxazoline (for example, obtainable by oleic acid ethanolamine , linoleic acid, palmitoleic acid, gadoleic acid, erucic acid and / or arachidonic acid) and combinations thereof. In another embodiment, oxazoline can be selected from ricinoloxazoline maleinate, undecyl-2-oxazoline, soy-2-oxazoline, castor-2-oxazoline and combinations thereof, for example. In yet another modality, oxazoline is selected from 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline and combinations thereof.
[0050] Nanocharges can also be used, such as carbon black, carbon nanotubes, carbon nanofibers, nano-clay, metallic nanoparticles, nanosilica, nanoalumina, etc. Nano-clays are particularly suitable. The term "nano-clay" generally refers to nanoparticles of a clay material (a naturally occurring mineral, an organically modified mineral, or a synthetic nanomaterial), which normally have a platelet structure. Examples of nanoclay include, for example, montmorillonite (2: 1 layered smectite clay structure), bentonite (aluminum phyllosilicate formed primarily by montmorillonite), kaolinite (1: 1 aluminosilicate with a flattened structure and an empirical Al2Si2O5 formula (OH) 4), haloisite (1: 1 aluminosilicate with a tubular structure and empirical formula of Al2Si2O5 (OH) 4), etc. An example of a suitable nanoclay is Cloisite®, which is a montmorillonite nanoclay and is commercially available from Southern Clay Products, Inc. Other examples of synthetic nanoclay include, but are not limited to, mixed metal hydroxide nanoclay, double hydroxide nanoclay layered (eg, sepiocyte), laponite, hectorite, saponite, indonite, etc.
[0051] If desired, the nanoclay may contain a surface treatment to help improve compatibility with the matrix polymer (eg, polyester). The surface treatment can be organic or inorganic. In one embodiment, an organic surface treatment is employed that is obtained by the reaction of an organic cation with the clay. Suitable organic cations may include, for example, organoquaternary ammonium compounds that are capable of exchanging cations with clay, such as dimethyl bis [hydrogenated tallow] ammonium chloride (2M2HT), benzyl methyl bis chloride [hydrogenated tallow] ammonium (MB2HT ), methyl tris chloride [hydrogenated tallow alkyl] (M3HT), etc. Examples of commercially available organic nanoclay may include, for example, Dellite® 43B (Laviosa Chimica from Livorno, Italy), which is a montmorillonite clay modified with dimethyl tallow benzyl hydrogenated ammonium salt. Other examples include Cloisite® 25A and Cloisite® 30B (Southern Clay Products) and Nanofil 919 (Süd Chemie). If desired, the nanocharge can be mixed with a carrier resin to form a masterbatch that increases the compatibility of the additive with the other polymers in the composition. Particularly suitable carrier resins include, for example, polyesters (for example, polylactic acid, polyethylene terephthalate, etc.); polyolefins (for example, ethylene polymers, propylene polymers, etc.); and so on, as described in more detail above.
[0052] In certain embodiments of the present invention, several nano-inclusion additives can be used in combination. For example, a first nanoinclusion additive (e.g., polyepoxide) can be dispersed as domains with an average cross-sectional dimension of about 50 to about 500 nanometers, in some embodiments, from about 60 to about 400 nanometers, and in some modalities, from about 80 to about 300 nanometers. A second nanoinclusion additive (for example, nanocharge) can also be dispersed as domains that are smaller than the first nanoinclusive additive, such as those with an average cross-sectional dimension of about 1 to about 50 nanometers, in some embodiments, from about 2 to about 45 nanometers, and in some modalities, from about 5 to about 40 nanometers. When used, the first and / or second nanoinclusion additives normally comprise from about 0.05% by weight to about 20% by weight, in some embodiments, from about 0.1% by weight to about 10% by weight. weight, and in some embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase (polymer (s) of the matrix). The concentration of the first and / or second nano-inclusion additives in the entire thermoplastic composition can range from about 0.01% by weight to about 15% by weight, in some embodiments, from about 0.05% by weight to about 10% % by weight, and in some embodiments, from about 0.1% by weight to about 8% by weight of the thermoplastic composition. D. Other Components
[0053] A wide variety of ingredients can be used in the composition for several different reasons. For example, in a specific modality, an interphasic modifier can also be used in the thermoplastic composition to help reduce the degree of friction and connectivity between the microinclusion additive and the matrix polymer and thus increase the degree and uniformity of the take-off . In this way, the pores can be distributed more evenly throughout the composition. The modifier can be in liquid or semi-solid form at room temperature (for example, 25 ° C) so that it has a relatively low viscosity, allowing it to be incorporated more easily into the thermoplastic composition and migrate more easily to the polymer surfaces. In this respect, the kinematic viscosity of the interphasic modifier is normally about 0.7 to about 200 centistokes ("cs"), in some modalities, from about 1 to about 100 cs and, in some modalities, from about 1.5 to about 80 cs, determined at 40 ° C. In addition, the interphasic modifier is also normally hydrophobic so that it has an affinity for the microinclusion additive, resulting, for example, in a change in the interfacial tension between the matrix polymer and the additive. By reducing the physical forces at the interfaces between the matrix polymer and the microinclusion additive, it is believed that the hydrophobic, low-viscosity nature of the modifier can help facilitate take-off. As used in this document, the term "hydrophobic" usually refers to a material that has a water and air contact angle of about 40 ° or more and, in some cases, about 60 ° or more. In contrast, the term "hydrophilic" usually refers to a material that has a contact angle of water and air less than about 40 °. A suitable test for measuring the contact angle is ASTM D5725-99 (2008).
Suitable low-viscosity hydrophobic interphasic modifiers may include, for example, silicones, silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, alkylene glycols (eg ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.), alkane diols (eg 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6 hexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1 , 3-cyclobutanediol, etc.), amine oxides (eg octyldimethylamine oxide), fatty acid esters, fatty acid amides (eg oleamide, erucamide, stearamide, ethyl bis (stearamide), etc.), mineral and vegetable oils, and so on. A particularly suitable liquid or semi-solid is polyether polyol, such as that commercially available under the name Pluriol® WI from BASF Corp. Another suitable modifier is a partially renewable ester, such as the one commercially available under the name Hallstar HALLGREEN® IM.
[0055] When used, the interphasic modifier may comprise from about 0.1% by weight to about 20% by weight, in some embodiments, from about 0.5% by weight to about 15% by weight, and in some embodiments, from about 1% by weight to about 10% by weight of the thermoplastic composition, based on the weight of the continuous phase (matrix polymer (s)). The concentration of the interphasic modifiers in the entire thermoplastic composition can be from about 0.05% by weight to about 20% by weight, in some embodiments from about 0.1% by weight to about 15% by weight and, in some embodiments, from about 0.5% by weight to about 10% by weight.
[0056] When used in the quantities noted above, the interphasic modifier will have a feature that allows it to easily migrate to the interfacial surface of the polymers and facilitate detachment without damaging the general melting properties of the thermoplastic composition. For example, the interphasic modifier does not normally have a plasticizing effect on the polymer by reducing its glass transition temperature. On the contrary, the present inventors have found that the glass transition temperature of the thermoplastic composition can be substantially the same as that of the polymer of the initial matrix. In that respect, the ratio of the glass temperature of the composition to that of the matrix polymer is normally about 0.7 to about 1.3. in some modalities, from about 0.8 to about 1.2, and in some modalities, from about 0.9 to about 1.1. The thermoplastic composition can, for example, have a glass transition temperature of about 35 ° C to about 80 ° C, in some embodiments, from about 40 ° C to about 80 ° C, and in some embodiments, from about 50 ° C to about 65 ° C. The melt flow rate of the thermoplastic composition can also be similar to that of the matrix polymer. For example, the melt flow rate of the composition (on a dry basis) can be about 0.1 to about 70 grams per 10 minutes, in some embodiments, from about 0.5 to about 50 ranges per 10 minutes and, in some embodiments, from about 5 to about 25 grams for 10 minutes, determined on a load of 2160 grams and at a temperature of 190 ° C.
[0057] Compatibilizers can also be used to improve interfacial adhesion and reduce the interfacial tension between the domain and the matrix, thus allowing the formation of smaller domains during mixing. Examples of suitable compatibilizers may include, for example, epoxy functionalized copolymers or maleic anhydride chemical fractions. An example of a maleic anhydride compatibilizer is maleic anhydride grafted with polypropylene, which is commercially available from Arkema under the names Orevac ™ 18750 and Orevac ™ CA 100. When used, compatibilizers can make up about 0.05% by weight to about 10% by weight, in some embodiments, from about 0.1% by weight to about 8% by weight, and in some embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase matrix.
[0058] Other suitable materials that can also be used in the thermoplastic composition, such as catalysts, antioxidants, stabilizers, surfactants, waxes, solid solvents, fillers, nucleating agents (eg calcium carbonate, etc.), particulate compounds, and other materials added to increase the processability and mechanical properties of the thermoplastic composition. However, a beneficial aspect of the present invention is that good properties can be provided without the need for several conventional additives, such as blowing agents (for example, chlorofluorocarbons, hydrochlorofluorocarbons, hydrocarbons, carbon dioxide, supercritical carbon dioxide, nitrogen, etc.) and plasticizers (for example, solid or semi-solid polyethylene glycol). In fact, the thermoplastic composition can generally be free of blowing agents and / or plasticizers. For example, blowing agents and / or plasticizers can be present in an amount of no more than about 1% by weight, in some embodiments, not more than about 0.5% by weight, and in some embodiments, about from 0.001% by weight to about 0.2% by weight of the thermoplastic composition. In addition, due to the stress-bleaching properties, as described in more detail below, the resulting composition can achieve an opaque color (e.g., white) without the need for conventional pigments, such as titanium dioxide. In certain embodiments, for example, pigments may be present in an amount of no more than about 1% by weight, in some embodiments, no more than about 0.5% by weight and, in some embodiments, about 0.001 % by weight to about 0.2% by weight of the thermoplastic composition. II. Polymeric Materials
[0059] As indicated above, the polymeric material of the present invention is, in most cases, formed by extracting a thermoplastic composition containing the matrix polymer, micro-inclusion additives, nano-inclusion additive, as well as other optional components. To form the initial thermoplastic composition, the components are typically mixed using any one of a variety of known techniques. In one embodiment, for example, components can be supplied separately or in combination. For example, the components can first be dry blended to form an essentially homogeneous dry mix, and can be supplied simultaneously or in sequence to a melt processing device that dispersively mixes the materials. Discontinuous and / or continuous fusion processing techniques can be employed. For example, a mixer / kneader, Banbury mixer, Farrel continuous mixer, single screw extruder, double screw extruder, laminators, etc. can be used to mix and process materials by melting. Particularly suitable fusion processing devices may be a co-rotating twin screw extruder (eg, ZSK-30 extruder available from Werner & Pfleiderer Corporation of Ramsey, New Jersey or a USALAB 16 Thermo Prism ™ extruder, available from Thermo Electron Corp., Stone, England). These extruders can include supply and ventilation ports and provide a high intensity distributive and dispersive mix. For example, components can be introduced into the same feed ports as the twin screw extruder and mixed by melting to form a substantially homogeneous molten mixture. If desired, other additives can also be injected into the polymer melt and / or introduced separately into the extruder at a different point along its length.
[0060] Regardless of the processing technique in question, the resulting melt-melt composition typically contains micro-scale domains of the micro-inclusion additive and nanoscale domains of the nano-inclusion additive, as described above. The degree of shear / pressure and heat can be controlled to ensure sufficient dispersion, but not so high as to negatively reduce the size of the domains, so that they are unable to achieve the desired properties. For example, mixing normally occurs at a temperature of about 180 ° C to about 300 ° C, in some embodiments, from about 185 ° C to about 250 ° C, and in some embodiments, from about 190 ° C at about 240 ° C. Likewise, the apparent shear rate during melt processing ranges from about 10 seconds-1 to about 3000 seconds-1, in some embodiments, from about 50 seconds-1 to about 2000 seconds-1, and in some modalities, from about 100 seconds-1 to about 1200 seconds-1. The apparent shear rate can be equal to 4Q / πR3, where Q is the volumetric flow rate (“m3 / s”) of the polymer melt and R is the radius (“m”) of the capillary (for example, extruder) through which the molten polymer flows. Obviously, other variables, such as the residence time during melt processing, which is inversely proportional to the production rate, can also be controlled to achieve the desired degree of homogeneity.
[0061] To achieve the desired shear conditions (for example, rate, dwell time, shear rate, melt processing temperature, etc.), the speed of the extruder thread (s) can be selected with a certain interval. Generally, an increase in the temperature of the product is observed with the increase in the screw speed due to the additional input of mechanical energy in the system. For example, the thread speed can vary from about 50 to about 600 revolutions per minute (“rpm”), in some modalities, from about 70 to about 500 rpm, and in some modalities, from about 100 to about 300 rpm. This can result in a temperature high enough to disperse the microinclusion additive without adversely impacting the size of the resulting domains. The melt shear rate and, in turn, the degree to which the additives are dispersed, can also be increased during the use of one or more distributive and / or dispersive mixing elements within the extruder mixing section. Distributive mixers suitable for single screw extruders may include, for example, Saxon, Dulmage, Cavity Transfer, etc. Likewise, suitable dispersive mixers may include Blister ring, Leroy / Maddock, CRD mixers, etc. As is well known in the art, mixing can be further improved by using pins in the barrel that create a bending and reorientation of the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers, and Vortex Intermeshing Pin (VIP) mixers ).
[0062] Once mixed, the porous mesh structure is introduced by extracting the composition in a longitudinal direction (for example, machine direction), transverse direction (for example, machine direction), etc., as well as combinations of themselves. To perform the desired extraction, the thermoplastic composition can be formatted in a precursor format, extracted, and then converted into the desired material (for example, film, fiber, etc.). In one embodiment, the precursor form may be a film with a thickness from about 1 to about 5000 micrometers, in some embodiments from about 2 to about 4000 micrometers, in some embodiments from about 5 to about 2500 micrometers, and in some embodiments, from about 10 to about 500 micrometers. As an alternative to forming a precursor form, the thermoplastic composition can also be extracted in situ as it is being shaped into the desired shape for the polymeric material. In one embodiment, for example, the thermoplastic composition can be extracted while it is being formed into a film or fiber.
[0063] In any case, several extraction techniques can be employed, such as suction (for example, fiber extraction units), elastic frame extraction, biaxial extraction, multiaxial extraction, profile extraction, vacuum extraction, etc. In one embodiment, for example, the composition is pushed with a machine sense advisor ("MDO"), such as those commercially available from Marshall and Willams, Co. of Providence, Rhode Island. MDO units typically have a plurality of extraction cylinders (for example, 5 to 8) that progressively push and taper the film towards the machine. The composition can be extracted by means of discrete extraction operations, whether individual or multiple. It should be noted that some of the cylinders in an MDO device may not be operating at progressively higher speeds. To extract the composition in the manner described above, it is generally preferable that the MDO cylinders are not heated. However, if desired, one or more cylinders can be slightly heated to facilitate the extraction process, as long as the temperature of the composition remains below the ranges determined above.
[0064] The degree of extraction depends, in part, on the nature of the material being extracted (for example, fiber or film). Generally, the composition is extracted (for example, in the machine direction) at an extraction rate from about 1.1 to about 3.5, in some embodiments from about 1.2 to about 3 , 0, and in some embodiments, from about 1.3 to about 2.5. The pull rate can be determined by dividing the length of the stretched material by its length before stretching. The tensile rate can also vary to help achieve the desired properties, such as within the range of about 5% to about 1500% per minute of deformation, in some embodiments, from about 20% to about 1000% per minute. minute of deformation, and in some modalities, from about 25% to about 850% per minute of deformation. Generally, the composition is maintained at a temperature below the glass temperature of the matrix polymer and / or micro-inclusion additive during extraction. Among other things, this helps to ensure that the polymer chains are not altered to such an extent that the porous network becomes unstable. For example, the composition can be extracted at a temperature of at least about 10 ° C, in some embodiments at least about 20 ° C, and in some embodiments, at least about 30 ° C below the glass transition temperature. matrix polymer. For example, the composition can be extracted at a temperature of from about 0 ° C to about 50 ° C, in some embodiments from 15 ° C to about 40 ° C, and in some embodiments, at from about 20 ° C to about 30 ° C. Although the composition is usually extracted without the application of external heat (for example, heated cylinders), this heat can be optionally employed in order to improve processability, reduce extraction force, increase extraction rates and improve fiber uniformity.
[0065] Stretching as described above can result in the formation of pores that have a "nanoscale" ("nanopores") dimension, such as an average cross-sectional dimension of about 800 nanometers or less, in some embodiments, of about 5 to about 250 nanometers, and in some embodiments, from about 10 to about 100 nanometers. Micropores can also be formed around and in the microscale domains during stretching to have an average cross-sectional dimension of about 0.5 to about 30 micrometers, in some embodiments, from about 1 to about 20 micrometers, and in some modalities, from about 2 micrometers to about 15 micrometers. Micropores and / or nanopores can have any regular or irregular shape, such as spherical, elongated, etc. In certain cases, the axial dimension of the micropores and / or nanopores can be greater than the transverse dimension so that the aspect ratio (the ratio between the axial dimension and the transverse dimension) is from about 1 to about 30, in some modalities, from about 1.1 to about 15, and in some modalities, from about 1.2 to about 5. The "axial dimension" is the dimension in the direction of the main axis (for example, length), which it is usually in the direction of the stretch.
[0066] The present inventors have also discovered that pores (for example, micropores, nanopores, or both) can be distributed in a substantially homogeneous manner throughout the material. For example, pores can be distributed in columns that are oriented in a direction generally perpendicular to the direction in which the tension is applied. These columns can generally be parallel to each other over the entire width of the material. Without intending to be limited by theory, it is believed that the presence of this homogeneously distributed porous network can result in high thermal resistance, as well as good mechanical properties (for example, energy dissipation under load and impact resistance). There is a stark contrast to conventional techniques for creating pores that involve the use of blowing agents, which tends to result in an uncontrolled pore distribution and poor mechanical properties. Notably, the formation of the porous network by the process described above does not necessarily result in a substantial change in the transverse size (for example, width) of the material. In other words, the material is not substantially narrowed, which allows the material to retain a greater degree of strength properties.
[0067] In addition to forming a porous network, stretching can also significantly increase the axial dimension of the microscale domains so that they have a generally linear, elongated shape. For example, elongated microscale domains can have an axial dimension of about 10% or more, in some embodiments from about 20% to about 500% and, in some embodiments, from about 50% to about 250% greater than the axial dimension of the domains before stretching. The average axial dimension after stretching can, for example, vary from about 0.5 to about 250 micrometers, in some modalities from about 1 to about 100 micrometers, in some modalities from about 2 to about 50 micrometers , and in some modalities from about 5 to about 25 micrometers. The microscale domains can also be relatively thin and thus have a small cross-sectional dimension. For example, the transverse dimension may be from about 0.05 to about 50 micrometers, in some embodiments, from about 0.2 to about 10 micrometers, and in some embodiments, from about 0.5 to about 5 micrometers. This can result in an aspect ratio for the microscale domains (the ratio of the axial dimension to the cross-sectional dimension) from from 2 to about 150, in some embodiments from about 3 to about 100, and in some modalities, from about 4 to about 50.
[0068] As a result of the elongated and porous domain structure, the present inventors have found that the resulting polymeric material can expand evenly in terms of volume when extracted in the longitudinal direction, which is reflected in a reduced "Poisson's ratio", as determined according to the following equation:
where Etransversal is the transversal deformation of the material and Elongitudinal is the longitudinal deformation of the material. More specifically, the Poisson's ratio of the material can be approximately 0 or even negative. For example, the Poisson's ratio may be about 0.1 or less, in some embodiments from about 0.08 or less, and in some embodiments, from about -0.1 to 0.04. When the Poisson's ratio is zero, there is no contraction in the transverse direction when the material is expanded in the longitudinal direction. When the Poisson's ratio is negative, the transversal or lateral dimensions of the material also expand when the material is stretched in the longitudinal direction. Materials with a negative Poisson's ratio can thus exhibit an increase in width when stretched in the longitudinal direction, which can result in greater absorption of energy in the cross direction.
[0069] The polymeric material of the present invention can generally have a variety of different shapes, depending on the specific application, such as films, fibrous materials, molded articles, profiles, etc., as well as compounds and laminates thereof for use on a limb. energy absorption. In one embodiment, for example, the polymeric material is in the form of a fibrous material or a layer or components of a fibrous material, which may include individual staple fibers or filaments (continuous fibers), as well as yarns, fabrics, etc., formed from such fibers. Yarns can include, for example, several staple fibers that are twisted together ("spun yarn"), filaments grouped without twist ("zero-twist yarn"), filaments defined together with a degree of twist, single filament with or without torsion ("monofilament"), etc. The yarn may or may not be textured. Suitable fabrics may also include, for example, fabrics, knitted fabrics, non-woven fabrics (heat-sealed continuous filament fabric, blow-extruded fabric, carded and combed fabric, wet fabric, airway fabric, coform fabrics, hydraulically woven fabrics tangles etc) and others.
[0070] Fibers formed from the thermoplastic composition can generally have any desired configuration, including single-component and multi-component (for example, core-coating configuration, side-by-side configuration, segmented mixed configuration, island-in-sea configuration , and so on). In some embodiments, the fibers may contain one or more additional polymers as a component (eg, bicomponent) or constituent (eg, biconstituent) to further increase strength and other mechanical properties. For example, the thermoplastic composition can form a coating component of a bicomponent coating / core fiber, while an additional polymer can form the core component, or vice versa. The additional polymer can be a thermoplastic polymer, such as polyesters, for example, polylactic acid, polyethylene terephthalate, polybutylene terephthalate, and so on; polyolefins, for example, polyethylene, polypropylene, polybutylene, and so on; polytetrafluoroethylene; polyvinyl acetate; polyvinyl acetate chloride; polyvinyl butyral; acrylic resins, for example, polyacrylate, polymethylacrylate, polymethylmethacrylate, and so on; polyamides, for example, nylon; polyvinyl chloride; polyvinylidene chloride; polystyrene; polyvinyl alcohol; and polyurethanes.
[0071] When used, the fibers can, instead of suffering fractures, deform when pressure is applied. The fibers can thus continue to function as load-bearing members, even after the fiber has shown substantial elongation. In this respect, the fibers of the present invention are capable of exhibiting improved maximum elongation properties, for example, percentage of elongation of the fiber at its maximum loading. For example, the fibers of the present invention may exhibit a peak elongation of about 50% or more, in some embodiments, about 100% or more, in some embodiments, from about 200% to about 1500%, and in some embodiments some embodiments, from about 400% to about 800%, as determined according to ASTM D638-10 at 23 ° C. These stretches can be obtained for fibers that have a wide variety of average diameters, such as those ranging from about 0.1 to about 50 micrometers, in some modalities, from about 1 to about 40 micrometers, in some modalities , from about 2 to about 25 micrometers, and in some modalities, from about 5 to about 15 micrometers.
[0072] Although they have the ability to stretch under pressure, the fibers of the present invention can also remain relatively strong. For example, fibers may exhibit peak elastic stresses of about 25 to about 500 Megapascals ("MPa"), in some embodiments, from about 50 to about 300 MPa, and in some embodiments, from about 60 to about 200 MPa, as determined according to ASTM D638-10 at 23 ° C. Another parameter that is indicative of the relative strength of the fibers of the present invention is the "toughness", which indicates the tensile strength of a fiber expressed as the strength per unit of linear density. For example, the fibers of the present invention can have a toughness of about 0.75 to about 6.0 grams-strength ("gf") per denier, in some embodiments, from about 1.0 to about 4, 5 gf per denier, and in some embodiments, from about 1.5 to about 4.0 gf per denier. The denier of the fibers may vary, depending on the desired application. Normally fibers are formed to have a denier per filament (ie, the unit of linear density equal to the mass in grams per 9000 meters of fiber) less than about 6, in some embodiments, less than about 3 and, in some modalities, from about 0.5 to about 3.
[0073] If desired, the polymeric material of the present invention can be subjected to one or more additional steps, before and / or after extraction. Examples of such processes include, for example, grooved cylinder extraction, engraving, coating etc. In certain embodiments, the polymeric material can also be annealed to ensure that it retains the designed shape. Annealing normally occurs at temperatures above the glass transition temperature of the matrix polymer, such as temperatures from about 40 ° C to about 120 ° C; in some embodiments from about 50 ° C to about 100 ° C; and in other embodiments, from about 70 ° C to about 90 ° C. The fibers can also be surface treated using any of several known techniques to improve their properties. For example, high-energy beams (for example, plasma, x-rays, electron beam, etc.) can be used to remove or reduce any surface layers, change surface polarity, porosity, topography, weaken a surface layer , etc. If desired, such a surface treatment can be used before and / or extraction of the thermoplastic composition.
[0074] In certain embodiments of the present invention, the polymeric material can be incorporated into a fabric (for example, fabric, mesh, or non-woven fabric). The entire fabric can be formed from fibers of the polymeric material, or fabric can be a composite whose fibers are used in one component and / or laminate, where the fibers are used in one layer. In any case, the fabric can sometimes be a composite that employs additional material (s) in conjunction with the fibers of the polymeric material of the present invention. Any of a variety of materials can generally be used in combination with the polymeric material of the present invention as is known in the art. For example, textile fibers can be used in certain embodiments. Particularly suitable textile fibers generally include inelastic textile fibers, such as those formed from cotton, wool, Liberian fiber, silk, aromatic polyamides (eg Nomex® or Kevlar®), aliphatic polyamides (eg nylon), rayon, lyocell, etc.; elastic fibers, such as those formed of elastoesters (for example, REXE ™ by Teijin), lastol (for example, Dow XLA ™), spandex (for example, Lycra® by DuPont), etc .; as well as combinations of two or more types of textile fibers. "Spandex" is an elastic textile fiber formed by segmented polyurethane normally interspersed with relatively soft segments of polyethers, polyesters, polycarbonates, etc. Likewise, "elastoester" is an elastic textile fiber formed by a mixture of polyether / polyester and "lastol" is an elastic textile fiber formed by a crosslinked ethylene / α-olefin copolymer. Elastic textile fibers are particularly suitable for use in fabrics that have a similar feature to stretch.
[0075] In a specific embodiment, for example, the fabric is a weft or mesh composite that contains yarns formed from a combination of polymeric material fibers and textile fibers (for example, elastic fibers). A stretch-compost fabric may, for example, be formed of threads formed of elastic textile fibers and threads formed of fibers of the present invention, which may be relatively inelastic in nature. In a fabric, for example, the elastic threads can be oriented in the direction that the stretch exists, such as the filler thread in interlaced stretch fabrics. Alternatively, the fabric may be formed of yarns which are themselves a composite of fibers of the present invention and textile fibers (for example, elastic fibers). Stretch compound yarns can, for example, be formed by the single or double winding of elastic fibers with a yarn formed by the fibers of the present invention, coating (i.e. core rotation) of an elastic fiber with staple fibers formed from according to the present invention, mixing and entangling the elastic threads and threads formed by the fibers of the present invention (for example, with an air jet), twisting the elastic fibers and threads formed by the fibers of the present invention, etc. Compound fabrics can also be formed which employ a combination of textile yarns and yarns formed from a mixture of textile fibers and fibers of the present invention. III. Energy Absorption Member
[0076] The way in which the polymeric material of the present invention is formed from an energy absorbing member can vary. In certain embodiments, for example, the energy-absorbing member is formed entirely of the polymeric material of the present invention. In other embodiments, however, the energy-absorbing member may include the polymeric material as a layer or component and one or more additional layers or material components for a variety of purposes, such as for additional energy absorption, insulation, properties barrier, or as a cover. The additional material (s) may include other conventional types of materials, such as polymeric foams, films or sheets, nonwoven networks, fiberglass materials, cellulosic materials, strong fabrics, sheets , etc.
[0077] In a specific embodiment, for example, the energy absorbing member can be a laminated structure containing the polymeric material of the present invention and one or more additional layers. For example, the laminated structure may contain an outer structure layer facing away from the part to be protected (e.g., body part) and a polymeric material positioned adjacent to the structure layer and facing the part to be protected. The structure layer can be formed of a material with a high tensile strength, such as fibers formed from glass, graphite, para-aramid (eg Kevlar®), ultra-high molecular weight polyolefin (eg Spectra® ), etc., metal sheets, ceramic sheets, and so on. Although it has a high degree of strength, the materials of the structure layer can also be relatively hard and thus have a risk of breaking into pieces and risk of injury. In this respect, the polymeric material of the present invention, which is highly foldable and ductile, can be used in the laminated structure to absorb energy without breaking into pieces. Referring to Fig. 3, for example, a specific embodiment of a laminated energy-absorbing member 200 is shown which contains a polymeric material 220 positioned adjacent the outer structure layer 212. In the illustrated embodiment, the polymeric material 220 is relatively plan; however, it must be understood that any geometric shape or configuration can be employed. If desired, an inner structure layer 214, which can be formed by a material, as described above, can also be positioned adjacent to polymeric material 220 so that polymeric material 220 serves as a center layer sandwiched between two layers of structure .
[0078] Various other layers and / or material can also be incorporated into the laminated energy-absorbing member. For example, in certain embodiments, a shock-absorbing pad can be positioned between the polymeric material and the polymeric material to help improve energy absorption even further. The shock absorbent filler can be formed from conventional materials, such as a foamed material, or from the polymeric material of the present invention. In Fig. 4, for example, there is shown a modalities of a laminated energy-absorbing member 300 containing a polymeric material 220 positioned between structure layers 212 and 214. In the present embodiment, a first shock-absorbing pad 213 is also positioned between the structure layer 212 and the polymeric material 220, and a second shock absorbing pad 215 is also positioned between the structure layer 214 and the polymeric material 220. In still other embodiments, the strength reinforcing fibers can be incorporated into the layer containing the polymeric material (eg, center layer) to help further improve the limb's ability to absorb energy. In Fig. 5, for example, an energy-absorbing member 400 is shown that contains a center layer of polymeric material 220 positioned between structure layers 212 and 214. The center layer also contains a plurality of reinforcement fibers 230 strength (eg Kevlar® fibers). It is usually desired that the fibers be positioned in such a way that, even breaking or cracking, they do not penetrate or come into contact with the part to be protected. In this respect, the fibers 230 in the embodiment of Fig. 5 are above the polymeric material 220 so that they are not adjacent to the structure layer 220.
[0079] Regardless of its specific construction, the energy-absorbing member can be used on a variety of different types of articles. For example, the energy-absorbing member can be used in protective clothing, either forming the entire part of the clothing or simply a component of it (for example, padding). When used in protective clothing, the energy-absorbing member can be positioned adjacent to a part of the body (for example, chest, legs, arms, head, etc.) so that it can help reduce the risk of pressure trauma or sudden impacts. Various examples of protective clothing that may include the energy-absorbing member of the present invention may include, for example, body armor, bulletproof vests or jackets, robes or other clothing used for restlessness control, correction activities, clothing or equipment used in connection with martial arts, helmets, shin guards, elbow guards, gloves, ski boots, snowboard boots, clothing for use with motorcycles, skates (for example, hockey skates, figure skates, racing skates , inline skates, etc.), sports shoes, orthopedic molds or braces, and so on.
[0080] Referring to Fig. 1, for example, a type of protective clothing that can be formed according to the present invention is shown in the form of a shirt 10. Shirt 10 is designed to be used alone or under or over another piece of clothing, and generally includes a garment 14 that covers the front and back of a trunk, sleeves 16, and a plurality of fillers 18 positioned to protect soft tissues and vital organs. The energy-absorbing member of the present invention can be used to form the vest 14, fillers 18 and / or sleeves 16. In one embodiment, for example, the energy-absorbing member is used to form the fillers 18, as a structure lightweight fabric similar to knit is used to form garment 14 and sleeves 16. Yet another modality of protective clothing is shown in Fig. 2 as a bicycle or sports helmet 100. In this modality, the helmet is formed by an absorption member energy 112. Of course, it should be understood that different parts of helmet 100 can be protected in different ways. It is known, for example, that the temples of the skull are very susceptible to injury by impact, while the forehead is less due to its greater thickness. Thus, in certain embodiments, the energy-absorbing member can be employed in a region of the temple 122, but not necessarily in a frontal area 124.
[0081] The energy-absorbing members that include the polymeric material can be used on a wide variety of articles within any specific application. For example, when considering automotive applications, the polymeric material can be used in an energy-absorbing member as fibrous articles or as solid frames. For example, energy absorbing members can also improve the comfort and / or aesthetics of a vehicle (for example, coverings and / or fillers, seat coverings, bases for seat covers, carpets, seat belt coverings) trunk and liner floor coverings, etc.), and energy absorbing members that can also provide general temperature and / or noise insulation (for example, column upholstery, door trim fillers, linings hood, body parts, etc.).
[0082] Solid frames that include the polymeric material can be used in automotive energy absorption members. For example, the polymeric material can be integrated into passive safety components, such as deformation zones at the rear, front and / or side of a vehicle; inside the car's safety cell, as a component of the airbag or steering wheel (for example, a deformable steering column); as a load barrier; or as a component of a pedestrian safety system (for example, as a component of the bumper, hood, window frame, etc.).
[0083] Such a broad-based application of polymeric material is applicable to a wide variety of fields, and is not intended to be in any way limited to the automotive industry. For example, polymeric material can be used on energy-absorbing members throughout the transportation industry, including, without limitation, air and space applications (eg, airplanes, helicopters, space transport, military aerospace devices, etc.) , marine applications (boats, ships, recreational vehicles), trains, and so on.
[0084] The present invention can be better understood with reference to the following examples. Test Methods High Speed Drill Test:
[0085] A test can be performed to measure impact properties after being subjected to high speed drilling according to ASTM D3763-10 at a temperature of 23 ° C or -25 ° C (+ 2 ° C), and at a 50% relative humidity (+ 10%). An Instron Dynatup 9250HV high impact tester (with data acquisition system) can be employed to perform the test. The test speed can be 3.3 or 12.5 meters per second, the sample size can be 102 mm x 127 mm, and the Tup diameter can be 12.7 mm. The average deflection at peak load (mm), average peak load (N), average peak load energy (J), and average total energy (J) are determined. The total energy is determined from the load / deflection curve at the point where the load returns to zero. Charpy resistance to impact deformation:
[0086] Impact resistance can be determined in accordance with ASTM D6110-10, at a temperature of 23 ° C or 0 ° C (+2 ° C) and at a relative humidity of 50% (+ 10%). The sample can be about 3.1 mm wide, the extension can be 101.6 mm and the depth under deformation can be about 10.2 mm. The pendulum can have a capacity of 2.7 Joules. Impact resistance is calculated by dividing the impact energy in kilojoules by the area under deformation (square meters) with larger numbers that represent more resistant materials. Melt Flow Rate:
[0087] The melt flow rate (“MFR”) is the weight of a polymer (in grams) forced through an extrusion rheometer orifice (0.0825 inch in diameter) when subjected to a load of 2160 grams in 10 minutes, usually at 190 ° C, 210 ° C, or 230 ° C. Unless otherwise stated, the melt flow rate is measured according to the ASTM D1239 test method with a Tinius Olsen Extrusion Plastometer. Thermal Properties:
[0088] The glass transition temperature (Tg) can be determined by means of dynamic-mechanical analysis (DMA), according to ASTM E1640-09. A TA Instruments Q800 instrument can be used. Experimental runs can be performed in tension / tension geometry, in a temperature sweep mode in the range of -120 ° C to 150 ° C with a heating rate of 3 ° C / min. The frequency of the power amplitude can be kept constant (2 Hz) during the test. Three (3) independent samples can be tested to obtain an average glass transition temperature, which is defined by the peak value of the tangent curve δ, where the tangent δ is defined as the ratio between the loss module and the storage (tangent δ = E ”/ E ').
[0089] The melting temperature can be determined by means of differential scanning calorimetry (DSC). The differential scanning calorimeter can be a DSC Q100 differential scanning calorimeter, which can be prepared with a liquid nitrogen cooling accessory and with a UNIVERSAL ANALYSIS 2000 (version 4.6.6) analysis software program, both available from TA Instruments Inc. of New Castle, Delaware. To avoid direct handling of the samples, tweezers and other tools can be used. The samples can be placed on an aluminum plate and weighed to the nearest 0.01 milligram on an analytical balance. A lid can be placed over the material sample on the plate. Normally, resin pellets can be placed directly on the weighing pan.
[0090] The differential scanning calorimeter can be calibrated using an Indian metal standard and a reference base correction can be made, as described in the operating manual of the differential scanning calorimeter. The material sample can be placed in the test chamber of the differential scanning calorimeter for testing, and an empty plate can be used as a reference. All tests can be performed by purging with nitrogen of 55 cubic centimeters per minute (industrial grade) in the test chamber. For resin pellet samples, the heating and cooling program is a 2-cycle test that started with the chamber balance at -30 ° C, followed by a first heating period, at a heating rate of 10 ° C per minute to a temperature of 200 ° C, followed by equilibrating the sample at 200 ° C for 3 minutes, followed by a first cooling period at a cooling rate of 10 ° C per minute, at a temperature of -30 ° C, followed by equilibrating the sample at -30 ° C for 3 minutes, and then a second heating period, at a heating rate of 10 ° C per minute at a temperature of 200 ° C. For fiber samples, the heating and cooling program can be a 1-cycle test that starts with the chamber balance at -25 ° C, followed by a warm-up period at a heating rate of 10 ° C per minute at temperature of 200 ° C, followed by equilibrating the sample at 200 ° C for 3 minutes, and then a cooling period at a cooling rate of 10 ° C per minute to a temperature of -30 ° C. All tests are carried out with a nitrogen purge of 55 cubic centimeters per minute (industrial grade) in the test chamber.
[0091] Results can be evaluated using the UNIVERSAL ANALYSIS 2000 analysis software program, which identifies and quantifies the glass transition temperature (Tg) of the inflection, the endothermic and exothermic peaks, and the areas under the peaks in the DSC graphs . The glass transition temperature can be identified as the region of the graph line where a sharp change in slope has occurred, and the melting temperature can be determined using an automatic inflection calculation. Expansion Ratio, Density and Percent Pore Volume:
[0092] To determine the expansion ratio, density and percentage pore volume, the width (Wi) and thickness (Ti) of the sample were initially measured before stretching. The length (Li) before stretching could also be determined by measuring the distance between two marks on a sample surface. Consequently, the sample could be stretched to start emptying. The width (Wf), thickness (Tf) and length (Lf) of the sample could then be measured as close to 0.01 mm using a Digimatic Compass (Mitutoyo Corporation). The volume (Vi) before stretching could be calculated by Wi x Ti x Li = Vi. The volume (Vf) after stretching could be calculated by Wf x Tf x Lf = Vf. The expansion rate (Φ) can be calculated by Φ = Vf / Vi; the density (Pf) can be calculated by: Pf = Pi / Φ, where Pi is the density of the precursor material; and the percentage pore volume (% Vv) could be calculated by:% Vv = (1 - 1 / Φ) x 100. Moisture content:
[0093] The moisture content can be determined using an Arizona Instruments Computrac Vapor Pro moisture analyzer (Model No. 3100) substantially in accordance with ASTM D 7191-05, which is incorporated in its entirety in this document by reference for all purposes. . The test temperature (§X2.1.2) can be 130 ° C, the sample size (§X2.1.1) can be 2 to 4 grams, and the bottle purging time (§X2.1.4) can be 30 seconds. In addition, the final criteria (§X2.1.3) can be defined as a "prediction" mode, which means that the test ends when the internally programmed criteria (which mathematically calculate the moisture content parameter) are met. EXAMPLE 1
[0094] A thermoplastic composition was formed from 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of a micro-inclusion additive, 1.4% by weight of a nanoinclusion, and 3.8% by weight of an internal interfacial modifier was presented. The microinclusion additive was Vistamaxx ™ 2120 (ExxonMobil), which is a polypropylene-polyethylene copolymer / elastomer with a melt flow index of 29 g / 10 min (190 ° C, 2160 g) and a density of 0.866 g / cm3. The nanoinclusion additive was poly (ethylene-co-methyl acrylate-co-glycidyl methacrylate) (Lotader® AX8900, Arkema) with a melt flow rate of 5-6 g / 10 min (190 ° C / 2160 g) , a glycidyl methacrylate content of 7 to 11% by weight, methyl acrylate content of 13 to 17% by weight, and ethylene content of 72 to 80% by weight. The internal interfacial modifier was BASF PLURIOL® WI 285 Lubricant, which is a polyalkylene glycol functional fluid. The polymers were introduced into a co-rotating twin screw extruder (ZSK-30, diameter 30 mm, length 1328 mm) for compounds that were manufactured by Werner and Pfleiderer Corporation, of Ramsey, New Jersey. The extruder had 14 zones, numbered sequentially from 1-14, from the feed funnel to the mold. The first zone of barrel No. 1 received the resins by means of a gravimetric feeder at a total flow of 15 pounds per hour. PLURIOL® WI285 was added by means of an injection pump in barrel zone no. 2. The mold used to extrude the resin had 3 mold openings (6 mm in diameter) that were separated by 4 mm. After formation, the extruded resin was cooled on a conveyor belt cooled by ventilation and formed into pellets by a Conair pelletizer. The screw speed of the extruder was 200 revolutions per minute ("rpm"). The pellets were then fed en masse to a signal screw extruder heated to a temperature of 212 ° C where the molten mixture exited through a 4.5 inch slit and extracted at a film thickness ranging from 0.45 to 0 , 48 mm. The films were stretched towards the machine up to about 100% to initiate cavitation and vacuum formation (speed of 50 millimeters per minute) using an MTS 810 hydraulic tension frame.
[0095] Once formed, the material was subjected to a high speed drilling test according to ASTM D3763-10 and then tested for the average deflection of the material at peak load (mm), average peak load (N) , average energy at peak load (J), and average total energy. The tests were conducted at speeds of 3.3 m / s and 12.5 m / s, and at a temperature of 23 ° C and -25 ° C. A control sample that was made from a medium impact polypropylene copolymer (Pro-fax ™ SV954, Basell) was also tested. The results are shown in Tables 1-4. Table 1: Impact Properties (Speed of 3.3 m / s, Temperature of 23 ° C)
Table 2: Impact properties (speed of 12.5 m / s, temperature of 23 ° C)
Table 3: Impact Properties (Speed of 3.3 m / s, Temperature of -25 ° C)
Table 4: Impact properties (speed of 12.5 m / s, temperature of -25 ° C)
EXAMPLE 2
[0096] A thermoplastic composition consisting of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of Vistamaxx ™ 2120, 1.4% by weight of Lotader® AX8900, and 3.8% by weight of PLURIOL® WI 285. The polymers were introduced in a co-rotation twin screw extruder (ZSK-30, diameter 30 mm, length 1328 mm) for compounds that were manufactured by Werner and Pfleiderer Corporation, Ramsey, New Jersey. The extruder had 14 zones, numbered sequentially from 1-14, from the feed funnel to the mold. The first zone of barrel No. 1 received the resins by means of a gravimetric feeder at a total flow of 15 pounds per hour. PLURIOL® WI285 was added by means of an injection pump in barrel zone no. 2. The mold used to extrude the resin had 3 mold openings (6 mm in diameter) that were separated by 4 mm. After formation, the extruded resin was cooled on a conveyor belt cooled by ventilation and formed into pellets by a Conair pelletizer. The screw speed of the extruder was 200 revolutions per minute ("rpm"). The pellets were then introduced into an injection molder (Boy 22D) and injected into an ASTM test mold to create bars with a thickness of 3 mm, a width of 12.7 mm and a length of 127 mm. The bars were then elongated to 60% to initiate cavitation and void formation (speed of 50 millimeters per minute) using an MTS 810 hydraulic elastic frame. The bars were then adjusted back to ~ 127 mm in length to remove the non-empty part of the bar.
[0097] Once formed, the material was subjected to a Charpy notched impact resistance test in accordance with ASTM D6110-10 to determine the Charpy impact resistance (kJ / m2). The tests were conducted at a temperature of 23 ° C and 0 ° C. control samples were also tested that were made from an acrylonitrile-butadiene-styrene copolymer (Terluran® GP-22, BASF) (“Control Sample 1”) and a medium impact polypropylene copolymer (Pro-fax ™ SV954 , Basell) (“Control Sample 2”). The results are shown below in Table 5. Table 5: Impact Force
EXAMPLE 3
[0098] The possibility of forming films from a mixture of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of Vistamaxx ™ 2120 and 1.4% by weight of Lotader ® AX8900 Arkema) and 3.8% by weight of PLURIOL® WI 285. The polymers were introduced in a co-rotation twin screw extruder (ZSK-30, diameter 30 mm, length 1328 mm) for compounds that were manufactured by Werner and Pfleiderer Corporation, of Ramsey, New Jersey. The extruder had 14 zones, numbered sequentially from 1-14, from the feed funnel to the mold. The first zone of barrel No. 1 received the resins by means of a gravimetric feeder at a total flow of 15 pounds per hour. PLURIOL® WI285 was added by means of an injection pump in barrel zone no. 2. The mold used to extrude the resin had 3 mold openings (6 mm in diameter) that were separated by 4 mm. After formation, the extruded resin was cooled on a conveyor belt cooled by ventilation and formed into pellets by a Conair pelletizer. The screw speed of the extruder was 200 revolutions per minute ("rpm"). The pellets were then fed en masse to a signal screw extruder heated to a temperature of 212 ° C where the molten mixture exited through a 4.5 inch wide slit and extracted at a film thickness ranging from 36 μm to 54 μm. μm. The films were extracted in the machine direction up to about 100% in order to initiate cavitation and vacuum formation.
[0099] The morphology of the films was analyzed by scanning electron microscopy (SEM) before and after stretching. The results are shown in Figs. 6 to 9. As shown in Figs. 6-7, the microinclusion additive was initially dispersed by domains with axial size (in the machine direction) from about 2 to about 30 micrometers and a transverse dimension (in a transverse direction) from about 1 to about 3 micrometers, whereas the nanoinclusion additive was initially dispersed as spherical and spheroidal domains with axial size from about 100 to about 300 nanometers. Figs. 8 to 9 show the film after stretching. As indicated, pores were formed around inclusion additives. The micropores formed around the microinclusion additive were generally elongated in a slit-like shape, with a wide size distribution ranging from about 2 to about 20 micrometers in the axial direction. The nanopores associated with the nanoinclusion additive are generally between 50 and 500 nanometers in size. EXAMPLE 4
[00100] The compound pellets of Example 1 were dry blended with a third inclusion additive, which was a haloisite clay masterbatch (MNH MacroComp-731-36, Macrom) containing 22% by weight of a styrene copolymer-modified nano-clay and 78% by weight of polypropylene (Exxon Mobil 3155). The mixing ratio was 90% by weight of the pellets and 10% by weight of the clay masterbatch, which provided a total clay content of 2.2%. The dry mixture was then fed in bulk to a signal screw extruder heated to a temperature of 212 ° C, where the molten mixture came out through a 4.5 inch wide slit matrix and extracted to a film thickness in a range of 51 to 58 μm. The films were extracted in the machine direction up to about 100% in order to initiate cavitation and vacuum formation.
[00101] The morphology of the films was analyzed by electron scanning microscopy (SEM) before and after stretching. The results are shown in Figs. 10-13. As shown in Figs. 10-11, some of the nano-clay particles (visible as lighter regions) have become dispersed in the form of very small domains - that is, of axial dimension in a range of about 50 to about 300 nanometers. The masterbatch itself also formed domains of a microscale size (axial dimension from about 1 to about 5 micrometers). Also, the micro-inclusion additive (Vistamaxx ™) formed elongated domains, while the nano-inclusion additives (Lotader®, visible as ultrafine dark spots) and the nano-clay masterbatch formed spheroidal domains. The spheroidal film is shown in Figs. 12-13. As structured, the cavitated structure is more open and demonstrates a wide variety of pore sizes. In addition to highly elongated micropores, formed by the first inclusions (Vistamaxx ™), nano-clay masterbatch inclusions formed more open spheroidal micropores, with an axial dimension of about 10 microns or less and a cross-sectional dimension of about 2 microns. Spherical nanopores are also formed by the second inclusion additive (Lotader®) and the third inclusion additive (nano clay particles).
[00102] Although the invention has been described in detail in relation to its specific modalities, it will be contemplated that those skilled in the art, after obtaining an understanding of the above, will be able to easily conceive changes, variations and equivalents of these modalities. Accordingly, the scope of the present invention should be assessed as that of the appended claims and any equivalents thereto.

权利要求:
Claims (15)
[0001]
1. Energy-absorbing member (14, 16, 18, 112, 200, 300, 400) comprising a polymeric material (220), wherein the polymeric material is formed from a thermoplastic composition that contains a continuous phase that includes a matrix polymer, in which, in addition, a nano-inclusion additive and a micro-inclusion additive are dispersed within the continuous phase in the form of discrete domains, in which a porous network is defined in the material, characterized by the fact that the porous network includes a plurality of nanopores with an average cross-sectional dimension of about 800 nanometers or less; wherein the nano-inclusion additive and the micro-inclusion additive are polymeric; and wherein the concentration of the micro-inclusion additive in the entire thermoplastic composition is about 1% by weight to about 20% by weight and the concentration of the nano-inclusion additive in the entire thermoplastic composition is about 0.01% by weight at about 15% by weight.
[0002]
2. Energy-absorbing member according to claim 1, characterized by the fact that the polymeric material (220) has a Charpy impact notch strength of about 10 kJ / m2 or more, measured at 23 ° C, according to ASTM D6110-10; and / or where the total energy absorbed by the polymeric material is about 2 Joules or more, as determined by a high-speed drill test, performed according to ASTM D3763-10 at a speed of 12.5 meters per second and temperature of 23 ° C; and / or where the peak load deflection of the polymeric material is about 10 mm or more, as determined by a high-speed drill test conducted in accordance with ASTM D3763-10 at a speed of 12.5 meters per second and temperature of 23 ° C; and / or where the peak load of the polymeric material is about 250 N or more, as determined by a high-speed drilling test, performed according to ASTM D3763-10 at a speed of 12.5 meters per second and temperature of 23 ° C.
[0003]
3. Energy-absorbing member according to any of the preceding claims, characterized by the fact that the nanopores have a cross-sectional dimension of about 10 to about 100 nanometers and / or in which the total pore volume of the material polymeric is about 15% to about 80% per cubic centimeter; and / or where the nanopores make up about 20% of the volume or more of the total pore volume of the polymeric material; and / or where the microscale domains have an average axial dimension of about 0.5 micrometers to about 250 micrometers; and / or where the thermoplastic composition has a density of about 1.2 grams per cubic centimeter, or less.
[0004]
4. Energy-absorbing member according to any one of the preceding claims, characterized in that the continuous phase constitutes from about 60% by weight to about 99% by weight of the thermoplastic composition; and / or wherein the nano-inclusion additive constitutes from about 0.05% by weight to about 10% by weight of the entire thermoplastic composition.
[0005]
5. Energy-absorbing member according to any of the preceding claims, characterized by the fact that the matrix polymer includes a polyester or polyolefin; and / or wherein the matrix polymer includes a polyester having a glass transition temperature of about 0 ° C or more, such as polylactic acid.
[0006]
6. Energy-absorbing member according to any one of the preceding claims, characterized by the fact that the microinclusion additive is a polyolefin, such as a propylene homopolymer, propylene / α-olefin copolymer, ethylene / α copolymer -olefin, or a combination of these.
[0007]
7. Energy-absorbing member according to any of the preceding claims, characterized by the fact that the ratio between the matrix polymer solubility parameter and the microinclusion additive solubility parameter is about 0.5 to about 1.5, the ratio of the melt rate of the matrix polymer to the melt rate of the microinclusion additive is about 0.2 to about 8, and / or the ratio of the Young's modulus of the polymer matrix and Young's modulus of elasticity of the microinclusion additive is about 1 to about 250.
[0008]
8. Energy-absorbing member according to any one of the preceding claims, characterized by the fact that the nano-inclusion additive is a functionalized polyolefin, such as a polyepoxide.
[0009]
An energy-absorbing member according to any one of the preceding claims, characterized in that the thermoplastic composition further comprises an interphasic modifier, such as silicone, silicone-polyether copolymer, aliphatic polyester, aromatic polyester, alkylene glycol, alkane diol, amine oxide, fatty acid ester or a combination thereof, preferably in an amount of about 0.1% by weight to about 20% by weight of the composition, based on the weight of the continuous phase.
[0010]
An energy-absorbing member according to any one of the preceding claims, characterized by the fact that the polymeric material (220) is generally free of gaseous blowing agents.
[0011]
An energy-absorbing member according to any one of the preceding claims, characterized in that the porous network further includes micropores, preferably in the micropores having an aspect ratio of about 1 to about 30.
[0012]
Energy-absorbing member according to any one of the preceding claims, characterized in that the member is in the form of a fabric, preferably wherein the fabric is a knitted fabric or fabric which contains a plurality of threads , wherein at least a portion of the yarns includes the polymeric material.
[0013]
13. Energy-absorbing member, according to claims 1 to 12, characterized by the fact that the member is formed entirely of polymeric material; or where the polymeric material is a layer or component of the member, preferably where the energy absorbing member contains an outer coating layer (212, 214) positioned adjacent to the polymeric material, more preferably where the polymeric material is positioned between the outer covering layer and an inner shell layer.
[0014]
Energy-absorbing member according to claim 13, characterized in that the shell layer includes fibers for strengthening the strength, a metal sheet, a ceramic sheet or a combination thereof, preferably in which the member it has a layer that includes the polymeric material and a plurality of fibers for reinforcing the strength, more preferably where the strength reinforcing fibers are positioned above the polymeric material.
[0015]
15. Protective equipment (10, 100), characterized by the fact that it comprises the energy-absorbing member (14, 16, 18, 112, 200, 300, 400), as defined in any of the previous claims, in which the energy-absorbing member is configured to be positioned adjacent to a body part, preferably where the energy-absorbing member constitutes only one component of the equipment; or where the protective equipment is a bulletproof vest or jacket, armor, clothing or other clothing used for riot control, correction activities, clothing or equipment used in connection with martial arts, helmet, shin guard, protector elbow, gloves, ski boots, snowboard boots, motorcycle equipment, skateboard, sports shoes, orthopedic equipment and immobilizers or a combination of these.

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同族专利:

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公开号 | 公开日

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RU2015155873A|2017-06-28|

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AU2014279704A1|2016-01-21|

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MX2015016823A|2016-04-18|

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JP2016530345A|2016-09-29|

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SG11201510051WA|2016-01-28|

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RU2630144C2|2017-09-05|

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KR102166745B1|2020-10-16|

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CN105283492A|2016-01-27|

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US20160108194A1|2016-04-21|

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MX356916B|2018-06-19|

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EP3008121B1|2018-04-25|

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EP3008121A4|2016-12-28|

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AU2014279704B2|2017-04-27|

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EP3008121A1|2016-04-20|

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CN105283492B|2018-11-16|

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KR20160018780A|2016-02-17|

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WO2014199277A1|2014-12-18|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US5027438A|1986-12-24|1991-07-02|Burlington Industries, Inc.|Operating room clothing with coated fabric|

---

CA2114663A1|1993-02-05|1994-08-06|Joshua B. Sweeney|Microporous polymer structures|

---

US5800758A|1997-09-16|1998-09-01|Kimberly-Clark Worldwide, Inc.|Process for making microporous films with improved properties|

---

US5968643A|1997-09-16|1999-10-19|Kimberly-Clark Worldwide, Inc.|Microporous film with improved properties|

---

US6824680B2|2001-05-07|2004-11-30|New Jersey Institute Of Technology|Preparation of microporous films from immiscible blends via melt processing and stretching|

---

US7943218B2|2006-08-14|2011-05-17|Frito-Lay North America, Inc.|Environmentally-friendly multi-layer flexible film having barrier properties|

---

AU2006347731B2|2006-08-31|2012-09-13|Kimberly-Clark Worldwide, Inc.|Highly breathable biodegradable films|

---

JP5309628B2|2007-03-23|2013-10-09|住友化学株式会社|Porous film|

---

AU2009262162B2|2008-06-27|2014-01-16|Lion Group, Inc.|Protective garment with thermal liner having varying moisture attraction|

---

US8759446B2|2008-06-30|2014-06-24|Fina Technology, Inc.|Compatibilized polypropylene and polylactic acid blends and methods of making and using same|

---

US8936740B2|2010-08-13|2015-01-20|Kimberly-Clark Worldwide, Inc.|Modified polylactic acid fibers|

---

JP2010280921A|2010-09-24|2010-12-16|Toray Ind Inc|White polylactic acid film|WO2014199275A1|2013-06-12|2014-12-18|Kimberly-Clark Worldwide, Inc.|Pore initiation technique|

---

WO2015187198A1|2014-06-06|2015-12-10|Kimberly-Clark Worldwide, Inc.|Hollow porous fibers|

---

US11155688B2|2013-06-12|2021-10-26|Kimberly-Clark Worldwide, Inc.|Polyolefin material having a low density|

---

WO2014199269A1|2013-06-12|2014-12-18|Kimberly-Clark Worldwide, Inc.|Porous polyolefin fibers|

---

US11084916B2|2013-06-12|2021-08-10|Kimberly-Clark Worldwide, Inc.|Polymeric material with a multimodal pore size distribution|

---

AU2014304179B2|2013-08-09|2017-08-17|Kimberly-Clark Worldwide, Inc.|Anisotropic polymeric material|

---

BR112016002594B1|2013-08-09|2021-08-17|Kimberly-Clark Worldwide, Inc.|METHOD TO SELECTIVELY CONTROL THE DEGREE OF POROSITY IN A POLYMERIC MATERIAL, AND, POLYMERIC MATERIAL|

---

AU2014304191B2|2013-08-09|2017-06-01|Kimberly-Clark Worldwide, Inc.|Microparticles having a multimodal pore distribution|

---

EP3152038B1|2014-06-06|2020-05-06|Kimberly-Clark Worldwide, Inc.|Thermoformed article formed from a porous polymeric sheet|

---

US9538813B1|2014-08-20|2017-01-10|Akervall Technologies, Inc.|Energy absorbing elements for footwear and method of use|

---

GB2549412B8|2014-11-26|2021-07-07|Kimberly Clark Co|Annealed porous polyolefin material|

---

WO2016122621A1|2015-01-30|2016-08-04|Kimberly-Clark Worldwide, Inc.|Film with reduced noise for use in an absorbent article|

---

AU2015380470A1|2015-01-30|2017-08-10|Kimberly-Clark Worldwide, Inc.|Absorbent article package with reduced noise|

---

JP6384507B2|2016-03-31|2018-09-05|トヨタ紡織株式会社|Energy absorber|

---

US10716351B2|2016-06-28|2020-07-21|Peter G. MEADE|Zero impact head gear|

---

US10539398B2|2017-08-16|2020-01-21|Nildson de Souza Rodrigues|Impact suppressor|

法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-15| 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 06/06/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361833996P| true| 2013-06-12|2013-06-12|

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US61/833,996|2013-06-12|

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US201361907548P| true| 2013-11-22|2013-11-22|

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US61/907,548|2013-11-22|

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PCT/IB2014/062029|WO2014199277A1|2013-06-12|2014-06-06|Energy absorbing member|

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