multifunctional fabric

专利摘要:
MULTIFUNCTIONAL FABRIC A fabric that includes porous fibers is provided. Porous fibers are formed of a thermoplastic composition containing a continuous phase that includes a matrix polymer. A microinclusion additive and nanoinclusion additive may also be dispersed within the continuous phase in the form of discrete domains, wherein a porous network that includes a plurality of nanopores with an average transverse dimension of about 800 nanometers or less is defined in the composition.
公开号:BR112015029507B1
申请号:R112015029507-0
申请日:2014-06-06
公开日:2022-01-25
发明作者:Vasily A. Topolkaraev；Ryan J. Mceneany；Neil T. Scholl；Mark M. Mleziva
申请人:Kimberly-Clark Worldwide, Inc；
IPC主号:

专利说明:

Related Orders
[01] The present application claims priority to the U.S. provisional applications. US. 61/833,985, filed on June 12, 2013, and 61/907,552, filed on November 22, 2013, which have been incorporated in their entirety herein by reference thereto. Fundamentals of Invention
[02] Fabrics are generally used to provide protection from extreme temperatures, wind, rain, snow and other environmental conditions. Unfortunately, conventional fabrics are tough and bulky, and they can also retain moisture. To avoid at least some of these flaws, thin breathable fabrics have been developed to allow steam to be removed. Unfortunately, one of the common problems associated with many conventional types of breathable fabrics is that they are not generally multifunctional. For example, most breathable fabrics may have very limited water repellency or thermal insulation properties. Furthermore, such fabrics tend to be relatively inflexible and also to generate noise when in use. As such, there is currently a need for a fabric that contains a material capable of providing various benefits such as breathability, water repellency, thermal insulation, flexibility, etc. Summary of the Invention
[03] In accordance with an embodiment of the present invention, there is disclosed a fabric that includes a plurality of porous fibers formed by a thermoplastic composition containing a continuous phase that includes a matrix polymer. Microinclusion and nanoinclusion additives are dispersed within the continuous phase in the form of discrete domains, and a porous network is defined in the composition that includes a plurality of nanopores with an average transverse dimension of about 800 nanometers or less. In one embodiment, the fabric may be a yarn-containing fabric or knit, wherein at least a portion of the yarns include the porous fibers. If desired, the fabric may further contain textile fibers (e.g., generally inelastic textile fibers, elastic textile fibers, or a combination thereof). For example, the composite may include yarns formed from a combination of porous fibers and the textile fibers and/or may include yarns formed from porous fibers and yarns formed from textile fibers.
[04] Other properties and aspects of the present invention will be discussed in more detail below. Brief Description of Figures
[05] A complete and enlightening description of the present invention, including its best mode, addressed to persons skilled in the art, is set out more particularly in the remainder of the specification, which makes reference to the accompanying figures in which:
[06] Fig. 1 is a schematic illustration of a process that can be used in an embodiment of the present invention to form fibers;
[07] Fig. 2 is a perspective view of an embodiment of a coat that may include the fabric of the present invention;
[08] Fig. 3 is a top view of a lining for a shoe that may be formed from the fabric of the present invention;
[09] Fig. 4 is a cross-sectional view of the shoe lining of Fig. 3;
[10] Fig. 5 is a perspective view of an embodiment of insulation construction that may be formed from the fabric of the present invention and positioned adjacent an exterior wall;
[11] Fig. 6 is an SEM photomicrograph (1000X) of the fiber of Example 8 (polypropylene, polylactic acid and polyepoxide) after freeze fracturing in liquid nitrogen;
[12] Fig. 7 is an SEM photomicrograph (5000X) of the fiber of Example 8 (polypropylene, polylactic acid and polyepoxide) after freeze fracturing in liquid nitrogen; and
[13] Fig. 8 is an SEM photomicrograph (10,000X) of the fiber surface of Example 8 (polypropylene, polylactic acid and polyepoxide).
[14] The repeated use of reference characters in the present specification and in the figures is intended to represent the same or similar features or elements of the invention. Detailed Description of Representative Modalities
[15] Detailed references will be made to various embodiments 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 may 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 embodiment can be used in another embodiment to produce yet another embodiment. Thus, the present invention is intended to cover such modifications and variations as are within the scope of the appended claims and their equivalents.
[16] In general, the present invention is directed to a fabric that contains a plurality of fibers. Suitable fabrics may include, for example, woven fabrics, knits, non-woven fabrics (e.g. spunbond nets, meltblown nets, bonded carded nets), wet-laid, airflow nets (airlaid), absorbent nets (coform), hydraulically entangled nets, etc.), and so on. The fibers can be individual staple fibers or filaments (continuous fibers), as well as yarns formed from such fibers. Yarns may include, for example, multiple staple fibers that are twisted together (“twisted yarn”), filaments put together without twisting (“zero twist yarn”), filaments put together with a degree of twist, single filament with or without twist (“monofilament”), etc. The yarns may or may not be textured.
[17] Regardless of the specific nature of the tissue, it can serve a variety of functions. For example, the fibers are porous and define a porous network which, for example, can be from about 15% to about 80% per cm3, in some embodiments from about 20% to about 70%, and in some modalities, from about 30% to about 60% per cubic centimeter of fiber. The presence of such a high pore volume can allow the resulting fabric to be generally permeable to water vapours, thereby allowing such vapors to escape from the body during use. This water vapor permeability of fabric can be characterized by its relatively high water vapor transmission rate (“WVTR”), which is the rate at which water vapor penetrates a material as measured in units of grams. per square meter for 24 hours (g/m2/24 hrs). For example, the fabric may exhibit a WVTR of about 300 g/m2-24 hours or more, in some embodiments, about 500 g/m2-24 hours or more, in some embodiments, about 1000 g/m2-24 hours or more, and in some embodiments, from about 3,000 to about 15,000 g/m 2 -24 hours, as determined in accordance with ASTM E96/96M-12, Procedure B or INDA IST-70.4 Test Procedure (01) . In addition to allowing the passage of vapors, the relatively high pore volume of the fibers also significantly decreases the density of the fibers, which may allow the use of lighter, more flexible materials that still achieve good 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 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 .
[18] Despite being highly porous and generally permeable to water vapour, the present inventors have nevertheless discovered that the porous network can be considered a “closed cell” network, such that a tortuous path between a substantial part of the pores. Such a structure can help to restrict the flow of fluids through the tissue so that it can be generally impermeable to fluids (eg, liquid water). In this regard, the fabric may have a relatively high hydrostatic pressure value of about 50 centimeters ("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.
[19] A substantial portion of the pores in the fibers may also be of a “nanoscale” size (“nanopores”), such as those with an average cross-sectional dimension of about 800 nanometers or less, in some embodiments, of about 1 to about 500 nanometers, in some embodiments from about 5 to about 450 nanometers, in some embodiments from about 5 to about 400 nanometers, and in some embodiments from about 10 to about 100 nanometers. The term "transverse dimension" generally refers to a characteristic dimension (e.g., width or diameter) of a pore, which is substantially orthogonal to its major axis (e.g., length) and also normally orthogonal to the direction of the applied stress during the stretch. Such nanopores may, for example, constitute about 15% by volume or more, in some embodiments, about 20% by volume or more, in some embodiments, from about 30% by volume to 100% by volume, and in some modalities, from about 40% by volume to about 90% by volume of the total volume of pores in the fibers. The presence of this high degree of nanopores can substantially decrease thermal conductivity, as fewer cell molecules are available within each pore to collide and transfer heat. Thus, the fibers can also serve as thermal insulation to help limit the degree of heat transfer through the fabric.
[20] To this end, the fabric may exhibit relatively low thermal conductivity, such as about 0.40 watts per meter-kelvin ("W/m-K") or less, in some embodiments, about 0.20 W/mK or less, in some embodiments, about 0.15 W/mK or less, in some embodiments, 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 fabric is able to achieve these low values of thermal conductivity at relatively low thicknesses, which can allow the fabric to have a greater degree of flexibility and conformability, as well as reduce the space it takes up. For this reason, fabric can also exhibit a relatively low “thermal admittance”, which is equal to the thermal conductivity of the material divided by its thickness and is given in units of watts per square meter-kelvin (“W/m2K”). For example, the fabric may exhibit 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 embodiments, from about 40 to about 200 W/m2K. Actual tissue thickness may depend on its specific shape, but typically ranges from about 50 micrometers to about 100 millimeters, in some embodiments from about 100 micrometers to about 50 millimeters, in some embodiments from about 200 micrometers to about 25 millimeters, and in some embodiments, from about 500 micrometers to about 5 millimeters.
[21] Unlike conventional techniques, the present inventors have found that the porous fibers of the present invention can be formed without the use of gas blowing agents. This is due, in part, to the unique nature of the material's components, as well as the matter from which it is formed. More particularly, the porous fibers can be formed of a thermoplastic composition containing a continuous phase that includes a matrix polymer, microinclusion additive and nanoinclusion additive. Additives can be selected so that they have a different elastic modulus than the matrix polymer. In this way, the microinclusion and nanoinclusion additives can be rendered dispersed within the continuous phase as discrete microscale and nanoscale phase domains, respectively. The present inventors have discovered that the microscale and nanoscale phase domains are capable of uniquely interacting when subjected to a strain and stretching force (e.g. stretching) to create a network of pores, a substantial part of which has a nanoscale size. That is, it is believed that the stretching force can initiate zones of intensive localized shear and/or zones of stress intensity (e.g. normal stresses) near 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. Namely, however, localized shear intensity and/or stress zones can also be created close to discrete nanoscale phase domains that overlap the microscale zones. Such overlapping shear intensity and/or stress zones further cause debonding to occur in the polymer matrix, thereby creating a substantial number of nanopores adjacent to the nanoscale domains and/or the microscale domains. Furthermore, because the pores are located adjacent to the discrete domains, a bridge can be formed between the pore boundaries that act as internal structural “hinges” that help to stabilize the network and increase its energy dissipation capacity. Among other things, this increases the flexibility of the resulting fabric and allows it to be more moldable.
[22] Various embodiments of the present invention will now be described in more detail. I. Thermoplastic Composition A. Matrix Polymer
[23] As indicated above, the thermoplastic composition may contain a continuous phase that contains one or more matrix polymers, which typically constitute from about 60% by weight to about 99% by weight, in some embodiments, from about 75% by weight. % 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 may be generally employed, such as polyesters, polyolefins, styrenic polymers, polyamides, etc. In certain embodiments, for example, polyesters may be employed in the composition to form the polymer matrix. Any of a variety of polyesters may be generally employed, such as aliphatic polyesters such as polycaprolactone, polyesteramides, polylactic acid (PLA) and its copolymers, polyglycolic acid, polyalkylene carbonates (e.g. 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-hydroxydecanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate, and aliphatic based polymers of succinate (e.g. polybutylene succinate, polybutylene adipate succinate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (e.g., polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene isophthalate adipate, polybutylene isophthalate adipate, etc.); aromatic polyesters (e.g. polyethylene terephthalate, polybutylene terephthalate, etc.); and so on.
[24] In certain cases, the thermoplastic composition may contain at least one polyester that is rigid in nature and thus has a relatively high glass transition temperature. For example, the glass transition temperature ("Tg") can be from about 0 °C or higher, in some embodiments from about 5 °C to about 100 °C, in some embodiments from about 30 °C at about 80°C, and in some embodiments, from about 50°C to about 75°C. The polyester may also have a melt temperature of from about 140°C to about 300°C, in some embodiments from about 150°C to about 250°C, and in some embodiments from about 160°C. at about 220°C. The melting temperature can be determined using differential scanning calorimetry (“DSC”) in accordance with ASTM D-3417. The glass transition temperature can be determined by dynamic mechanical analysis in accordance with ASTM E1640-09.
[25] A particularly suitable rigid polyester is polylactic acid, which can generally be derived from the monomer units of any isomer of lactic acid, such as levorotatory lactic acid (“L-lactic acid”), dextrorotatory lactic acid (“D- lactic acid”), meso-lactic acid or combinations thereof. The monomer 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 extending agent (e.g., a diisocyanate compound, an epoxy compound, or acid anhydride) may also be employed. The polylactic acid can be a homopolymer or a copolymer, such as one that contains monomer units derived from L-lactic acid and monomer units derived from D-lactic acid. Although not required, the content ratio of one of the L-lactic acid-derived monomer units and the D-lactic acid-derived monomer unit is preferably about 85 mol% or more, in some embodiments, about 90 % by mol or more and, in other embodiments, about 95% by mol or more. Various polylactic acids, each with a different ratio between the monomer unit derived from L-lactic acid and the monomer 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 (eg polyolefins, polyesters, etc.).
[26] In a specific embodiment, polylactic acid has the following general structure:

[27] 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 (LACEATM). Still other suitable polylactic acids may be described in U.S. Patent. US. 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254; and 6,326,458.
[28] Polylactic acid typically has a number average molecular weight ("Mn") that ranges from about 40,000 to about 180,000 grams per mole, in some embodiments from about 50,000 to about 160,000 grams per mole, and in some embodiments from about 50,000 to about 160,000 grams per mole. in some embodiments, from about 80,000 to about 120,000 grams per mole. Likewise, the polymer typically also has a weight average molecular weight ("Mw") that ranges from about 80,000 to about 250,000 grams per mole, in some embodiments from about 100,000 to about 200,000 grams per mole, and in some embodiments from about 100,000 to about 200,000 grams per mole. in some embodiments, from about 110,000 to about 160,000 grams per mole. The ratio of weight average molecular weight to number average molecular weight ("Mw/Mn"), i.e. the "polydispersity index", is also relatively low. For example, the polydispersity index typically ranges from about 1.0 to about 3.0, in some embodiments from about 1.1 to about 2.0, and in some embodiments from about 1.2 at about 1.8. The weight average and weight average molecular weight numbers can be determined by methods known to those skilled in the art.
[29] Polylactic acid may also have an apparent viscosity of from 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 Pa2s, 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 range from about 0.1 to about 40 grams per 10 minutes, in some embodiments from about 0.5 to about 20 grams per 10 minutes. , and, in some embodiments, from about 5 to about 15 grams per 10 minutes, determined at a load of 2160 grams and at 190°C.
[30] Some types of pure polyester (e.g. 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 starting polylactic acid. Moisture content can be determined in a variety of ways as is known in the art, such as in accordance with 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 prior to blending. In most embodiments, for example, it is desired that the polyester have a moisture content of about 300 parts per million ("ppm") or less, in some embodiments, about 200 ppm or less, in some embodiments, of about 1 to about 100 ppm, prior to mixing with the microinclusion and nanoinclusion additives. Drying of the polyester can occur, for example, at a temperature of from about 50°C to about 100°C and, in some embodiments, from about 70°C to about 80°C. B. Microinclusion Additive
[31] As indicated above, in certain embodiments of the present invention, the microinclusion and/or nanoinclusion additives may be dispersed within the continuous phase of the thermoplastic composition. As used herein, the term "micro-inclusion additive" generally refers to any amorphous, crystalline or semi-crystalline material that is capable of being dispersed within the polymer matrix in the form of discrete domains of a microscale size. For example, prior to drawing, domains may have an average cross-sectional dimension of about 0.05 μm to about 30 μm, in some embodiments, from about 0.1 μm to about 25 μm, in some embodiments, from about 0.1 μm to about 25 μm. 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 (e.g., width or diameter) of a domain that is substantially orthogonal to its principal axis (e.g., length) and also substantially orthogonal to the direction of the applied stress during the stretch. While normally formed from the microinclusion additive, it should be understood that the microscale domains may also be formed from a combination of the microinclusion and nanoinclusion additives and/or other components of the composition.
[32] 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 may be generally immiscible with the matrix polymer. In this way, the additive can be better spread out as discrete phase domains within a continuous phase of the matrix polymer. Discrete domains are able to absorb energy from an external force, which increases the stiffness and overall strength 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 normally small enough to minimize the propagation of cracks through the fibers after external stress is applied, but large enough to initiate microscopic plastic deformation and allow for zones of shear intensity and/or stress. tension around or at the particle inclusions.
[33] Although the polymers may be immiscible, the microinclusion additive may nevertheless be selected for having 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 composite breakdown. In this regard, the ratio of the solubility parameter for the matrix polymer to that of the additive is typically from 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 from 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 can 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 cohesive energy density and is calculated according to the following equation:
where: Δ Hv = heat of vaporization R = Ideal gas constant T = Temperature Vm = Molecular volume
[34] Hildebrand solubility parameters for various polymers are also available from the Solubility Handbook of Plastics, by Wyeych (2004), which is incorporated herein by reference.
[35] The microinclusion additive may also have a certain melt flow rate (or viscosity) to ensure that the discrete domains and resulting pores can be properly maintained. For example, if the melt flow rate of the additive is too high, it tends to flow and disperse uncontrollably through the continuous phase. This results in lamellar or plate-like domains or co-continuous phase structures that are difficult to maintain and also likely to crack prematurely. On the other hand, if the melt flow rate of the additive is too low, it will tend to clump together and form very large elliptical domains, which are difficult to disperse during mixing. This may cause uneven distribution of the additive throughout the continuous phase. In this regard, the present inventors have found that the ratio of the melt flow rate of the microinclusion additive to the melt flow rate of the matrix polymer is normally from about 0.2 to about 8, in some embodiments, of from about 0.5 to about 6 and, in some embodiments, from about 1 to about 5. The microinclusion additive may, for example, have a melt flow rate of from about 0.1 to about 250 grams per 10 minutes, in some embodiments from about 0.5 to about 200 grams per 10 minutes, and in some embodiments from about 5 to about 150 grams per 10 minutes, determined at a load of 2160 grams and the 190°C.
[36] In addition to the properties noted above, the mechanical characteristics of the microinclusion additive can also be selected to achieve the desired increase in stiffness. For example, when a mixture of matrix polymer and microinclusion additive is applied with an external force, stress concentrations (e.g. including normal or shear stress) and shear and/or plastic producing zones may be initiated around and in the discrete phase domains as a result of stress concentrations arising from a difference in the elastic modulus of the additive and matrix polymer. Higher stress concentrations promote more intense localized plastic flow in the domains, allowing them to become significantly elongated when stresses are applied. Such elongated domains allow the composition to exhibit a more flexible and softer behavior than the matrix polymer, such as when the matrix 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 elastic modulus of the matrix polymer to that of the additive is typically from about 1 to about 250, in some embodiments from about 2 to about 100, and in some embodiments from about 2 to about 50. The modulus of elasticity of the microinclusion additive can, for example, range 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 normally from about 800 MPa to about 3000 MPa.
[37] While a wide variety of microinclusion additives having the properties identified above may be employed, particularly suitable examples of such additives may also include synthetic polymers such as polyolefins (e.g. polyethylene, polypropylene, polybutylene, etc.); styrene copolymers (e.g. styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-butadiene-styrene, etc.); polytetrafluoroethylenes; polyesters (eg recycled polyester, polyethylene terephthalate, etc.); polyvinyl acetates (e.g. poly(ethylene vinyl acetate), polyvinyl acetate and chloride, etc.); polyvinyl alcohols (e.g. polyvinyl alcohol, poly(ethylene vinyl) alcohol, etc.); polyvinyl butyrals; acrylic resins (e.g. polyacrylate, polymethylacrylate, polymethylmethacrylate, etc.); polyamides (e.g. nylon); polyvinyl chlorides; polyvinylidene chlorides; polystyrenes; polyurethanes; etc. Suitable polyolefins may, for example, include ethylene polymers (e.g. low density polyethylene ("LDPE"), high density polyethylene ("HDPE"), linear low density polyethylene ("LLDPE"), etc.), propylene homopolymers (eg syndiotactic, atactic, isotactic, etc.), propylene copolymers, and so on.
[38] In one embodiment, the polymer is a propylene polymer, such as homopolypropylene, or a propylene copolymer. The propylene polymer may, for example, be formed of a substantially isotactic polypropylene homopolymer or 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 the propylene. Such homopolymers may have a melting point of from about 160°C to about 170°C.
[39] In yet another embodiment, the polyolefin may be a copolymer of ethylene or propylene with another α-olefin, such as C3-C12 α-olefin or C3-C12 α-olefin. 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. Particularly desired α-olefin comonomers are 1-butene, 1-hexene and 1-octene. The ethylene or propylene content of such copolymers can range from about 60 mol% to about 99 mol%, in some embodiments from about 80 mol% to about 98.5 mol%, and in some modalities, from about 87% by mol to about 97.5% by mol. The α-olefin content can range 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% by mol to about 13% by mol.
[40] Examples of olefin copolymers for use in the present invention include ethylene-based copolymers available under the designation EXACT™ from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are available under the names ENGAGE™, AFFINITY™, DOWLEX™ (LLDPE) and ATTANE™ (ULDPE) from the Dow Chemical Company of Midland, Michigan. Other suitable ethylene polymers are described in U.S. Patents. US. 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 names VISTAMAXX™ from ExxonMobil Chemical Co. from Houston, Texas; FINA™ (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMER™ available from Mitsui Petrochemical Industries; and VERSIFY™, available from Dow Chemical Co. from Midland, Michigan. Suitable polypropylene homopolymers may include polypropylene from Exxon Mobil 3155, resins from Exxon Mobil Achieve™, and resin from Total M3661 PP. Other examples of suitable propylene polymers are described in U.S. Patents. US. 6,500,563 to Datta et al.; 5,539,056 to Yang et al.; and 5,596,052 to Resconi et al.
[41] A wide variety of known techniques can be generally employed to form olefin copolymers. For example, olefin polymers can be formed using a free radical or a coordination catalyst (eg 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 evenly distributed among 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 to Davis et al.; 5,472,775 to Obijeski et al.; 5,272,236 to Lai et al.; and 6,090,325 to 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, bis(methylcyclopentadienyl)titanium dichloride, dichloride bis(methylcyclopentadienyl)zirconium, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafnocene dichloride, isopropyl(cyclopentadienyl,-1-fluorenyl)zirconium dichloride, molybdocene dichloride, nickelocene, niobocene dichloride, ruthenocene, titanocene dichloride, 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 (Mw/Mn) numbers below 4, controlled distribution of short chain branching, and controlled isotacticity.
[42] Regardless of the materials employed, 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 typically employed in an amount of from 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 (matrix polymer(s). 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
[43] As used herein, the term "nanoinclusion additive" generally refers to any amorphous, crystalline or semi-crystalline material that is capable of being dispersed within the polymer matrix in the form of discrete domains of a nanoscale size. For example, before stretching, domains may have an average cross-sectional dimension of about 1 to about 500 nanometers, in some embodiments from about 2 to about 400 nanometers, and in some embodiments from about 5 to about 400 nanometers. of 300 nanometers. For example, the nanoinclusion additive is normally employed in an amount of 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, 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 polymer(s)). The concentration of the nanoinclusion 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.
[44] The nanoinclusion additive may be polymeric in nature and have a relatively high molecular weight to help improve the melt strength and stability of the thermoplastic composition. To enhance its ability to become dispersed in the nanoscale domains, the nanoinclusion additive can also be selected from materials that are generally compatible with the matrix polymer and the microinclusion additive. This can be particularly useful when the matrix polymer or microinclusion additive has a polar moiety, such as a polyester. An example of such a nanoinclusion additive is a functionalized polyolefin. The polar compound can, for example, be provided by one or more functional groups, and the nonpolar component can be provided by an olefin. The olefin compound of the nanoinclusion additive may generally be formed from any branched or linear α-olefin monomer, oligomer, or polymer (including copolymers) derived from an olefin monomer, as described above.
[45] The functional group of the nanoinclusion additive can be any group, segment and/or molecular block that provides a polar component to the molecule and is not compatible with the matrix polymer. Examples of non-polyolefin compatible segment and/or molecular blocks may include acrylates, styrenics, polyesters, polyamide, 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, and the like. Maleic anhydride modified polyolefins are particularly suitable for use in the present invention. These modified polyolefins are typically formed by grafting maleic anhydride onto a polymeric backbone material. These maleated polyolefins are available from EI du Pont de Nemours and Company under the name Fusabond®, such as P series (chemically modified polypropylene), E series (chemically modified polyethylene), C series (chemically modified ethylene vinyl acetate), A series (chemically modified ethylene acrylate copolymers or terpolymers), or N series (chemically modified ethylene-propylene, ethylene-propylene diene monomer ("EPDM") or ethylene-octene). Alternatively, maleated polyolefins are also available from Chemtura Corp. under the designation of Polybond® and Eastman Chemical Company under the designation of Eastman series G.
[46] In certain embodiments, the nanoinclusion additive may also be reactive. An example of such a reactive nanoinclusion additive is a polyepoxide that contains, on average, at least two oxirane rings per molecule. Without intending to be bound by theory, it is believed that these polyepoxide molecules can induce a reaction of the matrix polymer (e.g. polyester) under certain conditions, thereby improving their melt strength without significantly reducing the melt temperature. 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 may allow a nucleophilic reaction to ring opening through a terminal carboxyl group of a polyester (esterification) or through a hydroxyl group (etherification). Oxazoline side reactions can occur to form esteramide moieties. Through these reactions, the molecular weight of the matrix polymer can be increased to counteract degradation frequently during the melting process. While 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 polymer backbones. If such crosslinking was allowed to proceed to a significant extent, the resulting polymer blend could become brittle and difficult to process into a material with the desired strength and elongation properties.
[47] In this regard, the present inventors have found that polyepoxides with a 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 one molecule of an epoxy group, and can be calculated by dividing the number average molecular weight of the modifier by the number of epoxy groups in the molecule. The polyepoxide of the present invention typically has a number average molecular weight of from about 7,500 to about 250,000 grams per mole, in some embodiments from about 15,000 to about 150,000 grams per mole, and in some embodiments from about 20,000 to about 20,000 to about 150,000 grams per mole. about 100,000 grams per mole, with a polydispersity index ranging from 2.5 to 7. The polyepoxide may contain less than 50, in some embodiments, 5 to 45, and in some embodiments, 15 to 40 epoxy groups. In turn, the epoxy equivalent weight can 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 mole
[48] The polyepoxide can be a linear or branched (eg, random, graft, block, etc.) homopolymer or copolymer 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 (meth)acrylic monomeric 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 may 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 isoconate.
[49] Polyepoxide normally has a relatively high molecular weight, as indicated above, so it can not only result in chain extension, but also achieve the desired blend morphology. The resulting melt flow rate of the polymer is thus typically within a range of from 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 embodiments from about 40 to about 150 grams for 10 minutes. some embodiments, from about 60 to about 120 grams for 10 minutes, determined at a load of 2160 grams and at a temperature of 190°C.
[50] If desired, additional monomers can also be employed in the polyepoxide to help achieve the desired molecular weight. These monomers can 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 from 2 to 20 carbon atoms and preferably from 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. Particularly desired α-olefin comonomers are ethylene and propylene.
[51] Another suitable monomer may include a (meth)acrylic monomer that is not epoxy-functional. Examples of such (meth)acrylic monomers may 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, i-butyl methacrylate, methacrylate of n-amyl, n-hexyl methacrylate, i-amyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, crotyl methacrylate, cyclohexyl methacrylate , cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, isobornyl methacrylate, etc., good as a comb inactions of the same.
[52] In a particularly desirable embodiment of the present invention, the polyepoxide is a terpolymer formed of an epoxy-functional (meth)acrylic monomeric component, an α-olefin monomeric component, and a non-epoxy-functional (meth)acrylic monomeric 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.
[53] The epoxy-functional monomer can be made into a polymer using a variety of known techniques. For example, a monomer containing polar functional groups can be grafted onto the backbone 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. At the. 5,179,164. In other embodiments, a monomer containing epoxy-functional groups can be copolymerized with a monomer to form a block or random copolymer using known free radical polymerization techniques, such as high pressure reactions, Ziegler-Natta catalyst reaction systems, reaction with single-site catalyst (eg metallocene), etc.
[54] The relative portion of the monomeric component(s) can be selected to strike a balance between epoxy reactivity and melt flow rate. More specifically, a high content of epoxy monomer can result in good reactivity with the matrix polymer, but too high a content can reduce the melt flow rate such that the polyepoxide negatively affects the melt strength of the epoxy blend. polymer. Thus, in most embodiments, the epoxy-functional (meth)acrylic monomer(s) constitute(s) from about 1% by weight to about 25% by weight, in some embodiments, 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) may 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. weight and, in some embodiments, from about 65% by weight to about 85% by weight of the copolymer. When employed, other monomeric components (e.g., 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 glycidyl methacrylate monomer content of 7 wt. of methyl from 13% by weight to 17% by weight, and an ethylene monomer content from 72% by weight to 80% by weight. Another suitable polyepoxide is commercially available from DuPont under the name ELVALOY® PTW, which is a terpolymer of ethylene, butyl acrylate, and glycidyl methacrylate and has a melt flow rate of 12 g/10 min.
[55] 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 desired benefits. For example, if the level of modification is too low, the desired increase in melt strength and mechanical properties may not be achieved. The present inventors have also discovered, however, that if the level of modification is too high, processing can be restricted due to strong molecular interactions (eg, cross-linking) and physical network formation by the epoxy-functional groups. Thus, the polyepoxide is normally employed in an amount of from 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 matrix polymer employed in the composition. The polyepoxide may also constitute from 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.
[56] Other reactive nanoinclusion additives can also be employed in the present invention, such as oxazoline functionalized polymers, cyanide functionalized polymers, etc. When employed, such reactive nanoinclusion additives can be employed within the concentrations noted above for the polyepoxide. In a specific embodiment, an oxazoline-grafted polyolefin may be employed, i.e., a polyolefin grafted with a monomer containing an oxazoline ring. The oxazoline may include a 2-oxazoline, such as 2-vinyl-2-oxazoline (e.g. 2-isopropenyl-2-oxazoline), 2-graxo-alkyl-2-oxazoline (e.g. obtainable from oleic acid ethanolamine , linoleic acid, palmitoleic acid, gadoleic acid, erucic acid and/or arachidonic acid) and combinations thereof. In another embodiment, the oxazoline can be selected from ricinoloxazoline maleinate, undecyl-2-oxazoline, soy-2-oxazoline, ricin-2-oxazoline and combinations thereof, for example. In yet another embodiment, the oxazoline is selected from 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline and combinations thereof.
[57] Nanofillers can also be used, such as carbon black, carbon nanotubes, carbon nanofibers, nanoclays, metallic nanoparticles, nanosilica, nanoalumina, etc. Nanoclays are particularly suitable. The term "nanoclay" generally refers to nanoparticles of a clay material (a naturally occurring mineral, an organically modified mineral, or a synthetic nanomaterial), which typically have a platelet structure. Examples of nanoclays 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 empirical formula of Al2Si2O5 (OH)4), halloysite (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 nanoclays include, but are not limited to, mixed metal hydroxide nanoclay, double layered hydroxide nanoclay (e.g., sepiocite), laponite, hectorite, saponite, indonite, etc.
[58] If desired, the nanoclay can 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 which 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), methyl benzyl bis[hydrogenated tallow] ammonium chloride (MB2HT). ), methyl tris[hydrogenated tallow alkyl] chloride (M3HT), etc. Examples of commercially available organic nanoclays may include, for example, Dellite® 43B (Laviosa Chimica of 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 nanofiller can be blended with a carrier resin to form a masterbatch that enhances the additive's compatibility with the other polymers in the composition. Particularly suitable carrier resins include, for example, polyesters (e.g. polylactic acid, polyethylene terephthalate, etc.); polyolefins (e.g. ethylene polymers, propylene polymers, etc.); and so on, as described in more detail above.
[59] In certain embodiments of the present invention, various nanoinclusion additives may be employed in combination. For example, a first nanoinclusion additive (e.g., polyepoxide) may be dispersed in the form of 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 embodiments, from about 80 to about 300 nanometers. A second nanoinclusion additive (e.g. nanofiller) may also be dispersed in the form of domains that are smaller than the first nanoinclusion 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 embodiments from about 5 to about 40 nanometers. When employed, the first and/or second nanoinclusion additives typically constitute 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 (matrix polymer(s)). The concentration of the first and/or second nanoinclusion additives 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 0.1% by weight to about 8% by weight of the thermoplastic composition. D. Other Components
[60] A wide variety of ingredients can be used in the composition for many different reasons. For example, in a specific embodiment, an interphase modifier may also be employed in the thermoplastic composition to help reduce the degree of friction and connectivity between the microinclusion additive and the matrix polymer and thereby increase the degree and uniformity of debonding. . 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 (eg, 25°C) so that it has a relatively low viscosity, allowing it to be more easily incorporated into the thermoplastic composition and more readily migrate to the polymer surfaces. In this regard, the kinematic viscosity of the interphase modifier is typically about 7 x 10-7 to about 2 x 10-4 m2/s (about 0.7 to about 200 centistokes ("cs")), in some cases. embodiments, from about 1 x 10 -6 to 1 x 10 -4 m2/s (from about 1 to about 100 cs) and, in some embodiments, from about 1.5 x 10 -6 to 8 x 10 -5 m2/s (from about 1.5 to about 80 cs), determined at 40 °C. Furthermore, the interphase 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 low viscosity, hydrophobic nature of the modifier can help facilitate debonding. As used herein, the term "hydrophobic" typically refers to a material that has a contact angle of water and air of about 40° or more, and in some cases of about 60° or more. In contrast, the term “hydrophilic” typically refers to a material that has a contact angle of water and air of less than about 40°. A suitable test to measure contact angle is ASTM D5725-99 (2008).
[61] Suitable low viscosity, hydrophobic interphase modifiers may include, for example, silicones, silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, alkylene glycols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.), alkane diols (e.g. 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 (e.g. octyldimethylamine oxide), fatty acid esters, fatty acid amides (e.g. oleamide, erucamide, stearamide, ethylene 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 that commercially available under the Hallstar name HALLGREEN® IM.
[62] When employed, the interphase modifier can 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 interphase 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.
[63] When employed in the amounts noted above, the interphase modifier will have a characteristic that allows it to easily migrate to the interfacial surface of polymers and facilitate debonding without impairing the overall melting properties of the thermoplastic composition. For example, the interphase modifier does not normally have a plasticizing effect on the polymer by reducing its glass transition temperature. On the contrary, the present inventors have discovered that the glass transition temperature of the thermoplastic composition can be substantially equal to that of the initial matrix polymer. In this regard, the ratio of the glass temperature of the composition to that of the matrix polymer is normally from about 0.7 to about 1.3. in some embodiments, from about 0.8 to about 1.2, and in some embodiments, from about 0.9 to about 1.1. The thermoplastic composition may, 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 40°C to about 80°C. 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 from 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 per 10 minutes, determined at a load of 2160 grams and at a temperature of 190°C.
[64] Compatibility agents 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 chemical moieties of maleic anhydride. An example of a maleic anhydride compatibilizer is polypropylene-grafted maleic anhydride, which is commercially available from Arkema under the names Orevac™ 18750 and Orevac™ CA 100. When employed, the compatibilizers can constitute from 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.
[65] Other suitable materials that can also be used in the thermoplastic composition, such as catalysts, antioxidants, stabilizers, surfactants, waxes, solid solvents, fillers, nucleating agents (e.g. 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 various conventional additives such as blowing agents (e.g. chlorofluorocarbons, hydrochlorofluorocarbons, hydrocarbons, carbon dioxide, supercritical carbon dioxide, nitrogen, etc.) and plasticizers (eg solid or semi-solid polyethylene glycol). Indeed, the thermoplastic composition may generally be free of blowing agents and/or plasticizers. For example, the blowing agents and/or plasticizers can be present in an amount of not more than about 1% by weight, in some embodiments, not more than about 0.5% by weight, and in some embodiments, of about 0.5% by weight. from 0.001% by weight to about 0.2% by weight of the thermoplastic composition. Furthermore, 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, the pigments may be present in an amount of not more than about 1% by weight, in some embodiments, not more than about 0.5% by weight, and in some embodiments, of about 0.001 % by weight to about 0.2% by weight of the thermoplastic composition. II. fibers
[66] Fibers formed from the thermoplastic composition can generally have any desired configuration, including single-component and multi-component (e.g., coating-core 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 (e.g., bi-component) or constituent (e.g., bi-constituent) to further enhance strength and other mechanical properties. For example, the thermoplastic composition can form a cladding component of a bicomponent cladding/core fiber, while an additional polymer can form the core component, or vice versa. The additional polymer may 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.
[67] Any of a variety of processes can be used to form fibers in accordance with the present invention. For example, the thermoplastic composition described above can be extruded through a die and cooled. Referring to Fig. 1, for example, an embodiment of a method for forming fibers is shown in more detail. In this specific embodiment, the thermoplastic composition of the present invention may be fed into an extruder 12 from a funnel 14. To form the initial thermoplastic composition, the components are typically blended using any one of a variety of known techniques. In one embodiment, for example, the components may be provided separately or in combination. For example, the components may first be dry blended to form an essentially homogeneous dry blend, and may be fed simultaneously or sequentially to a melt processing device which dispersively blends the materials. Batch and/or continuous melt processing techniques may be employed. For example, a mixer/kneader, Banbury mixer, Farrel continuous mixer, single screw extruder, twin screw extruder, rolling mills, etc. can be used to mix and melt materials. Particularly suitable melt processing devices may be a co-rotating twin screw extruder (e.g. 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 feed and vent ports and provide high-intensity distributive and dispersive mixing. For example, the components can be fed into the same feed ports as the twin screw extruder and melt blended to form a substantially homogeneous melt 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.
[68] Regardless of the specific processing technique chosen, the resulting melt-blended composition may contain microscale domains of the microinclusion additive and nanoscale domains of the nanoinclusion 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 typically 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 embodiments, 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 (e.g. extruder) through which the molten polymer flows. Of course, other variables, such as residence time during melt processing, which is inversely proportional to the production rate, can also be controlled to achieve the desired degree of homogeneity.
[69] To achieve the desired shear conditions (e.g. rate, dwell time, shear rate, melt processing temperature, etc.), the speed of the extruder screw(s) can be selected with a certain range. Generally, an increase in product temperature is observed with increasing screw speed due to the additional input of mechanical energy into the system. For example, screw speed can range from about 50 to about 600 revolutions per minute ("rpm"), in some embodiments, from about 70 to about 500 rpm, and in some embodiments, from about 100 to about 500 rpm. about 300 rpm. This can result in a temperature that is high enough to disperse the microinclusion additive without adversely affecting 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 when using one or more distributive and/or dispersive mixing elements within the mixing section of the extruder. Distributive mixers suitable for single screw extruders may include, for example, Saxon, Dulmage, Cavity Transfer mixers, etc. Accordingly, 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 the use of barrel pins 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. ).
[70] Referring again to Fig. 1, extruder 12 can be heated to a temperature sufficient to extrude molten polymer. The extruded composite is then passed through a polymer duct 16 to a die 18. For example, the die 18 may include a housing containing a swivel assembly with a plurality of plates stacked on top of each other and with a pattern of openings arranged to create pathways. flow to direct the polymer components. Die 18 may also have openings arranged in one or more rows. The openings form a descending extruder curtain of filaments as polymers are extruded through it. The process 10 also employs a cooling blower 20 positioned adjacent to the fiber curtain, extending from the spinneret 18. Air originating in the cooling air blower 20 cools the fibers extending from the spinneret 18. Cooling can be directed to one side of the fiber curtain, as shown in Fig.1, or to both sides of the fiber curtain.
[71] To form a fiber of the desired length, the cooled fibers are generally melt drawn, such as a fiber drawing unit 22 in Fig. 1. Stretching units or fiber aspirators for use in melt spinning polymers are well known in the art. Suitable fiber drawing units in the process for the present invention include a linear fiber aspirator of the type shown in U.S. Patent. US. 3,802,817 and 3,423,255. The fiber stretching unit 22 generally includes an elongated vertical passageway through which the fibers are drawn in by drawing in air from the sides of the passageway and flowing down the passageway. A heater or blower 24 supplies the suction air to the fiber stretching unit 22. The suction air draws the fibers and ambient air through the fiber stretching unit 22. The flow of gas causes the fibers to stretch. or decrease, which increases the molecular orientation or crystallinity of the fiber-forming polymers. When employing a fiber stretch unit, the “pull” rate can be selected to help achieve the desired fiber length. The "pull" ratio is the linear velocity of the fibers after drawing (e.g., the linear velocity of the godet cylinder 42 or a foraminous surface (not shown) divided by the linear velocity of the fibers after extrusion). For example, the pull rate during melt stretching can be calculated as follows: Pull Rate = A/B where, A is the linear speed of the fiber after melt stretching (e.g. godet speed) and is measured directly; and B is the linear velocity of the extruded fiber and can be calculated in this way: Linear velocity of the extruded fiber = C/(25*π*D*E2) where, C is the production through a single hole (grams per minute); D is the melt density of the polymer (grams per cubic centimeter); and E is the diameter of the hole (in centimeters) through which the fiber is extruded. In certain embodiments, the pull ratio can be from about 20:1 to about 4000:1, in some embodiments from about 25:1 to about 2000:1, and in some embodiments from about 50: 1 to about 1000:1, and in some embodiments, from about 75:1 to about 800:1.
[72] Once formed, the fibers can be deposited through the outlet opening of the fiber drawing unit 22 and into a godet cylinder 42. If desired, the fibers collected in the godet cylinder 42 can optionally be subjected to further processing. in additional series and/or conversion steps (not shown), as will be understood by those skilled in the art. For example, fibers may be collected and then curled, textured and/or cut to an average fiber length in the range of about 3 to 80 millimeters, in some embodiments, from about 4 to about 65 millimeters, and in some modalities, from about 5 to about 50 millimeters.
[73] Regardless of the specific way in which the fibers are formed, the desired porous network can be formed by stretching the resulting fibers in a subsequent step, or during fiber formation. Various stretching techniques can be employed, such as aspiration (eg fiber stretching units), extensible frame stretching, biaxial stretching, multiaxial stretching, profile stretching, vacuum stretching, etc. The degree of stretch depends, in part, on the nature of the material being stretched, but is generally selected to ensure that the desired porous network is achieved. For example, the fibers may be stretched (e.g., in the machine direction) at a pull ratio of 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 ratio can be determined by dividing the length of the stretched material by its length before stretching. The pull rate can also be varied to help achieve desired properties, such as within the range of about 5% to about 1500% per minute of strain, in some embodiments, from about 20% to about 1000% per minute. minute of strain, and in some embodiments, from about 25% to about 850% per minute of strain. The fibers can be maintained at a temperature below the glass temperature of the matrix polymer and microinclusion additive during drawing. Among other things, this helps to ensure that the polymer chains are not altered to such a degree that the porous network becomes unstable. For example, the fibers can be drawn at a temperature that is 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. of the matrix polymer. For example, the fibers can be stretched at a temperature from about 0°C to about 50°C, in some embodiments from about 15°C to about 40°C, and in some embodiments from about 20°C. C to about 30°C. If desired, the composition is stretched without the application of external heat (e.g., heated rollers).
[74] Stretching in the manner described above can result in the formation of pores that have a relatively small transverse dimension in the stretch direction (eg longitudinal or machine direction). For example, pores can be formed to have a “nanoscale” dimension (“nanopores”). For example, nanopores may have an average cross-sectional dimension of about 800 nanometers or less, in some embodiments, from about 1 to about 500 nanometers, in some embodiments, from about 5 to about 450 nanometers, in some embodiments , from about 5 to about 400 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 transverse dimension of about 0.5 to about 30 micrometers, in some embodiments from about 1 to about 20 micrometers, and in some embodiments from about 1 to about 20 micrometers. some embodiments, from about 2 micrometers to about 15 micrometers. The micropores and/or nanopores can be of any regular or irregular shape, such as spherical, elongated, etc. In certain cases, the axial dimension of the micropores and/or nanopores may be greater than the transverse dimension so that the aspect ratio (the ratio of the axial dimension to the transverse dimension) is from about 1 to about 30, in some cases. embodiments, from about 1.1 to about 15, and in some embodiments, from about 1.2 to about 5. The "axial dimension" is the dimension in the principal axis direction (e.g., length), which it is normally in the stretch direction.
[75] The present inventors have also found that pores (eg, micropores, nanopores, or both) can be distributed substantially homogeneously 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 stress is applied. These columns can generally be parallel to each other across the entire width of the material. Without intending to be bound 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 (eg 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 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 (eg, 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.
[76] In addition to forming a porous network, stretching can also significantly increase the axial dimension of microscale domains so that they have a generally linear, elongated shape. For example, elongated microscale domains can have an average axial dimension that is about 10% or more, in some embodiments, from about 20% to about 500%, and in some embodiments, from about 50% to about 500%. 250% greater than the axial dimension of the domains before stretching. The axial dimension after stretching may, for example, range from about 0.5 to about 250 micrometers, in some embodiments from about 1 to about 100 micrometers, in some embodiments from about 2 to about 50 micrometers. micrometers, and in some embodiments, from about 5 to about 25 micrometers. Microscale domains can also be relatively thin and thus have a small cross-sectional dimension. For example, the cross-sectional 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 10 micrometers. 5 micrometers. This can result in an aspect ratio for the first domains (the ratio of the axial dimension to the transverse dimension) of from about 2 to about 150, in some embodiments from about 3 to about 100, and in some embodiments, from about 3 to about 100. about 4 to about 50.
[77] As a result of the porous and elongated structure of the domain, the present inventors have found that the resulting fibers can be uniformly expanded in volume when stretched lengthwise, which is reflected by a low “Poisson coefficient”, as determined accordingly. with the following equation: Poisson's coefficient = - Etransverse / Elongitudinal where Etransverse is the transverse strain of the material and Elongitudinal is the longitudinal strain of the material. More specifically, the Poisson ratio of the material can be approximately 0 or even negative. For example, the Poisson ratio can be about 0.1 or less, in some embodiments about 0.08 or less, and in some embodiments, from about -0.1 to 0.04. When Poisson's ratio is zero, there is no contraction in the transverse direction when the material is expanded in the longitudinal direction. When Poisson's ratio is negative, the transverse or lateral dimensions of the material also expand when the material is stretched lengthwise. Materials with a negative Poisson's ratio may thus exhibit an increase in width when stretched in the longitudinal direction, which can result in greater energy absorption in the cross-direction.
[78] The resulting fibers may have excellent mechanical properties for use in the fabric of the present invention. For example, fibers can deform after force is applied, rather than breaking. The fibers can thus continue to function as load-bearing members even after the fiber has exhibited substantial elongation. In this respect, the fibers are able to show better “peak elongation properties”, that is, the percentage elongation of the fiber at its peak load. For example, the fibers of the present invention can 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 in some embodiments, from about 400% to about 800%, as determined in accordance with ASTM D638-10 at 23°C. These elongations can be obtained for fibers that have a wide range of average diameters, such as those ranging from about 0.1 to about 50 micrometers, in some embodiments, from about 1 to about 40 micrometers, in some embodiments. , from about 2 to about 25 micrometers, and in some embodiments, from about 5 to about 15 micrometers.
[79] While possessing the ability to stretch under force, the fibers can also remain relatively strong. For example, the fibers can have peak elastic stresses from 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 60 to about 300 MPa. about 200 MPa, as determined in accordance with ASTM D638-10 at 23°C. Another parameter that is indicative of the relative strength of the fibers of the present invention is "tenacity", which indicates the tensile strength of a fiber expressed as the force per unit of linear density. For example, the fibers of the present invention may have a tenacity from about 0.75 to about 6.0 grams-force ("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. Fibers are typically shaped to have a denier per filament (i.e., the linear density unit equal to the mass in grams per 9000 meters of fiber) of less than about 6, in some embodiments, less than about 3, and in some modalities, from about 0.5 to about 3.
[80] If desired, the fibers can be subjected to one or more additional processing steps before and/or after being drawn. Examples of such processes include, for example, roller traction in grooves, embossing, coating, etc. In certain embodiments, the fibers may also be annealed to help ensure they maintain the desired shape. Annealing typically occurs at temperatures at or above the glass transition temperature of the polymer matrix, such as at about 40°C to about 120°C, in some embodiments, from about 50°C to about 100°C. , and in some embodiments, from about 70°C to about 90°C. The fibers can also be surface treated using any of a variety of known techniques to improve their properties. For example, high energy beams (e.g. plasma, x-rays, electron beam, etc.) can be used to remove or reduce any layers of skin, to alter surface polarity, porosity, topography, to weaken a surface layer, etc. If desired, such a surface treatment can be used before and/or on stretching. III. Fabric Construction
[81] The whole fabric may be formed from the fibers, or the fabric may be a composite whose fibers are used in a component and/or laminate, where the fibers are used in a layer. In either case, the fabric can sometimes be a composite that employs additional material(s) in conjunction with the fibers of the present invention. Any of a variety of materials can generally be employed in combination with the fibers 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, bast fiber, silk, aromatic polyamides (e.g. Nomex® or Kevlar®), aliphatic polyamides (e.g. nylon), rayon, lyocell, etc.; elastic fibers, such as those formed from elastoesters (e.g., REXE™ from Teijin), lastol (e.g., Dow XLA™), spandex (e.g., Lycra® from 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 interspaced 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 copolymer of ethylene/α-olefin. Elastic textile fibers are particularly suitable for use in fabrics that have a stretch-like characteristic.
[82] In a specific embodiment, for example, the fabric is a woven or knitted composite that contains yarns formed by a combination of the fibers and textile fibers (eg, elastic fibers). A stretchable composite fabric may, for example, be formed from yarns formed from elastic textile fibers and yarns formed from fibers of the present invention, which may be relatively inelastic in nature. In a fabric, for example, the elastic yarns can be oriented in the direction in which the stretch exists, such as the filler yarn in woven stretch fabrics. Alternatively, the fabric may be formed from yarns which are themselves a composite of fibers of the present invention and textile fibers (e.g., elastic fibers). Stretchable composite yarns can, for example, be formed by single or double winding elastic fibers with a yarn formed from the fibers of the present invention, coating (i.e., spinning into a core) an elastic fiber with staple fibers formed from according to the present invention, mixing and tangling the elastic yarns and yarns formed by the fibers of the present invention (e.g., with a jet of air), twisting the elastic fibers and yarns formed by the fibers of the present invention, etc. Composite fabrics can also be formed that employ a combination of textile yarns and yarns formed from a blend of textile fibers and fibers of the present invention. III. articles
[83] The fabric of the present invention can be used in a wide variety of article types. Non-limiting examples of such articles include, for example, panels and building sections (e.g., roofs, wall cavities, basements, etc.); Clothing parts; furniture and bedding (eg sleeping bags, blankets, etc.); extreme environments (eg submarine or space); food and beverage products (eg cups, cup holders, plates, etc.); and so on. As used herein, for example, the term "articles of clothing" is generally intended to include any article that is shaped to fit a part of the body. Examples of such articles include, without limitation, clothing (e.g., shirts, pants, jeans, baggy pants, skirts, coats, sportswear, athletic, aerobic, and exercise clothing, swimwear, cycling shirts or shorts, swimming/swimwear, running wear, wetsuit, leotard, etc.), footwear (e.g. shoes, socks, boots, etc.), protective clothing (e.g. firefighter coat), clothing accessories (e.g. e.g. belts, bra straps, side straps, gloves, socks, leggings, braces, etc.), underwear (e.g. underwear, t-shirts, etc.), compression garments, draped garments ( e.g. petticoats, togas, ponchos, cloaks, shawls, etc.), and so on.
[84] When employed in garments, the fabric of the present invention may form the entire garment or simply be located within a part or region of the garment. Referring to Fig. 2, for example, an embodiment of a garment 200 (i.e., coat) that includes a body part 220, sleeves 222, and a collar 224 attached to the body part. In this specific embodiment, the garment 200 is formed of a laminate 202 that includes an outer layer 212 and an inner layer 214, which defines a body-facing surface 225. The outer layer 212 also includes a front closure 226 that includes fasteners 228, or alternatively a slide fastener (not shown). If desired, the outer layer 212 and/or the inner layer 214 may be formed from the fabric of the present invention. However, in certain embodiments, the outer wall 212 can be another material, such as nylon, polyester, cotton, or blends thereof. In still other embodiments, the garment 200 is formed entirely from the fabric of the present invention.
[85] In still other embodiments of the present invention, the fabric of the present invention may be used in footwear. The fabric can be used to form the entire shoe or simply as a lining. Referring to Figs. 3-4, for example, an embodiment of a lining 100 for a shoe that may be formed from the fabric of the present invention is shown. In this specific embodiment, the liner 100 contains an insulating layer 112, which may be formed from the fabric of the present invention, and which is wrapped within the backing layers 114 and 116. Typically, the insulating layer 112 is cut and then arranged in an upper surface 113 of the first backing layer 114. The liner 100 is completed by arranging the second backing layer 116 having a garment material 118 laminated to an upper surface 122 of a layer of fibers 120 to define an outward facing surface. body 113. The periphery of the first and second backing layers 114 and 116 may be hermetically sealed by an ultrasonic or high frequency welder to surround the insulation layer 112. The liner 100 may also include a front region 125 that includes the layers tops and bottoms joined together with no insulating material 112 between them. This front region includes raised contour lines 127 with cut lines along which the lining 100 can be trimmed to fit various shoe sizes. In still other embodiments, the thermal liner 100 is formed entirely from the fibers of the present invention.
[86] In still other embodiments of the present invention, the fabric of the present invention may be used in insulation in constructions. For example, fabric can be employed as a “protective membrane” material that acts as an external covering for the building and is located adjacent to an external surface (eg wall, roof, etc.) of the building. For example, such materials can be applied to the exterior surface and/or an exterior cladding (eg, sides, bricks, stone, masonry, stucco, concrete varnish, etc.) prior to installation and located adjacent to them. Referring to Fig. 5, for example, an embodiment is shown in which building insulation is applied to the exterior wall. Typically, building insulation is employed after the walls have been built and all cladding and veneering details have been installed. Building insulation is preferably applied before the doors and windows have been fitted into the framed openings and prior to the installation of the primary wallcovering. In the illustrated embodiment, a first insulation of construction 300 is applied to the wall assembly 340. As shown, a roll of insulation material can be unrolled. Building insulation 300 is secured to exterior wall mount 340 with fasteners such as staples or nails. Building insulation may be trimmed around each frame opening with appropriate additional detailing applied per window/door manufacturer's code and/or standards. Once installed, an exterior cladding can be applied/installed over the building insulation if desired.
[87] The fabric can be used in a wide variety of articles within any specific application. For example, the fabric can be used in automotive applications. By way of example, the fabric can be beneficially used in articles that can enhance the comfort and/or aesthetics of a vehicle (e.g. lining and/or upholstery for sun visors, compartments and speaker covers, seat coverings, slip sealing agents, and seats for seat coverings, carpet and carpet reinforcement, including carpet backing, car mats and car mat bases, seat belt coverings, car floor coverings and linings trunk, ceiling linings and bases, tapestry bases, general decorative fabrics, etc.), materials that can provide general temperature and/or sound insulation (e.g. column upholstery, infills for door adornments, linings for hood, general soundproofing and insulating materials, sound dampers, etc.) and engine/filtration materials (e.g. fuel filters, oil filters, battery separators, engine air filters, cabin, etc.).
[88] The tissue can be used beneficially in a wide variety of fields. For example, the fabric can be used in the general transportation industry and is not limited to automotive applications. The fabric can be used in any transportation application, including, without limitation, air and space applications (e.g. airplanes, helicopters, space transports, military aerospace devices, etc.), marine applications (boats, ships, recreational vehicles). ), trains, and so on. The fabric can be used in transport applications in any desired shape, for example in aesthetic applications, for thermal and/or sound insulation, in filtration and/or motor components, in safety components, etc.
[89] The present invention can be better understood with reference to the following examples. Test Methods Hydrostatic Pressure Test ("Hydrostatic Load"):
[90] Hydrostatic pressure testing is a measure of a material's resistance to penetration by liquid water under static pressure and is performed in accordance with Test Method AATCC 127-2008. Results for each sample can be averaged and recorded in centimeters (cm). A higher value indicates greater resistance to water penetration. Water Vapor Transmission Rate (“WVTR”):
[91] The test used to determine the WVTR of a material may vary based on the nature of the material. One technique for measuring the WVTR value is ASTM E96/96M-12, Procedure B. Another method involves the use of the INDA Test Procedure IST-70.4 (01). The INDA test procedure is summarized as follows. A dry chamber is separated from a wet chamber of known temperature and humidity by a permanent protective film and the sample material to be tested. The purpose of the protective film is to define a definite air gap and calm or quiet the air in the air gap while it is characterized. The dry chamber, protective film and wet chamber form a diffusion cell, in which the test film is sealed. The sample holder is known as the Permatran-W Model 100K manufactured by Mocon/Modem Controls, Inc., Minneapolis, Minnesota. A first test is made of the WVTR of the protective film and the air gap between the evaporator assembly, generating 100% relative humidity. The water vapor diffuses through the air gap and the protective film and then mixes with the dry gas stream, proportional to the water vapor concentration. The electrical signal is routed to a computer for processing. The computer calculates the transmission rate of the air gap and protective film and stores the value for later use.
[92] The baud rate of the protective film and the air gap is stored in the computer as CalC. The sample material is then sealed in the test cell. Again, the water vapor diffuses through the air gap into the protective film and test material, and then mixes with the dry gas stream that sweeps through the test material. Also, again, the mixture is led to the vapor sensor. The computer then calculates the transmission rate from the combination of air gap, protective film and test material. This information is then used to calculate the transmission rate at which moisture is transmitted through the test material according to the equation: TR-1 test material = TR-1 test material, protective film, air gap – TR film protective air gap
[93] The water vapor transmission rate (“WVTR”) is then calculated as follows:
where, F = the flow of water vapor in cm3 per minute; psat(T) = the density of water in saturated air at a temperature T; RH = the relative humidity at specific locations in the cell; A = the cross-sectional area of the cell; and Psat(T) = the saturated vapor pressure of water vapor at temperature T. Conductive Properties:
[94] Thermal conductivity (W/mK) and thermal resistance (m2K/W) can be determined in accordance with ASTM E-1530-11 (“Resistance to Thermal Transmission of Materials by the Guarded Heat Flow Meter Technique”) using a Anter Unitherm model 2022 tester. The target test temperature can be 25 °C and the applied load can be 0.17 MPa. Prior to testing, samples can be conditioned for 40+ hours at a temperature of 23 °C (+2 °C) and relative humidity of 50% (+10%). Thermal admittance (W/m2K) can also be calculated by dividing 1 by thermal resistance. Melting Flow Rate:
[95] 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 at 10 minutes, typically at 190 °C, 210 °C, or 230 °C. Unless otherwise noted, melt flow rate is measured according to ASTM test method D1239 with a Tinius Olsen Extrusion Plastometer. Thermal Properties:
[96] The glass transition temperature (Tg) can be determined by dynamic-mechanical analysis (DMA) according to ASTM E1640-09. A TA Instruments Q800 instrument can be used. Experimental runs can be performed in stress/stress geometry, in a temperature sweep mode in the range of -120°C to 150°C with a heating rate of 3°C/min. The force amplitude frequency 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 of the loss modulus to the loss modulus. storage (tangent δ = E”/E').
[97] The melting temperature can be determined using differential scanning calorimetry (DSC). The differential scanning calorimeter may be a DSC Q100 differential scanning calorimeter, which can be prepared with a liquid nitrogen cooling accessory and a UNIVERSAL ANALYSIS 2000 analysis software program (version 4.6.6), both available from T.A. Instruments Inc. of New Castle, Delaware. To avoid direct handling of samples, tweezers and other tools can be used. Samples can be placed on an aluminum plate and weighed to within 0.01 milligram on an analytical balance. A lid can be placed over the material sample in the dish. Normally, resin pellets can be placed directly on the weighing pan.
[98] The differential scanning calorimeter can be calibrated using an indium metal standard and a baseline correction can be made as described in the differential scanning calorimeter operating manual. 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 with 55 cubic centimeters per minute nitrogen purge (industrial grade) in the test chamber. For resin pellet samples, the heating and cooling program is a 2-cycle test that started with chamber equilibration 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 equilibration of the sample at 200 °C for 3 minutes, followed by a first period of cooling at a cooling rate of 10 °C per minute, to 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 may be a 1-cycle test that begins with chamber equilibration at -25 °C, followed by a period of heating at a heating rate of 10 °C per minute at a temperature of 200 °C, followed by equilibration of 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 performed with a nitrogen purge of 55 cubic centimeters per minute (industrial grade) in the test chamber.
[99] Results can be evaluated using the UNIVERSAL ANALYSIS 2000 analysis software program, which identifies and quantifies the glass transition temperature (Tg) of inflection, endothermic and exothermic peaks, and areas under the peaks on DSC plots. . 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. Elastic Properties:
[100] Elastic properties can be determined according to ASTM 638-10 at 23 °C. For example, individual fiber samples can initially be shortened (eg, cut with scissors) to 38 millimeters in length, and placed separately on a black velvet cloth. 10 to 15 samples can be collected this way. The fiber samples can then be mounted in a substantially straight condition on a rectangular paper frame, with external dimensions of 51mm x 51mm and internal dimensions of 25mm x 25mm. The ends of each fiber sample can be operatively secured to the frame by carefully securing the fiber ends to the sides of the frame with adhesive tape. Each fiber sample can then be measured for its relatively shorter, outer, cross-fiber dimension using a conventional laboratory microscope, which can be properly calibrated and adjusted at 40X magnification. The cross fiber dimension can be recorded as the diameter of the individual fiber sample. The frame helps to mount the ends of the fiber samples to the top and bottom fixtures of a constant rate stretch-type elastic tester so as to avoid excessive damage to the fiber samples.
[101] A constant rate of elastic tester extension type and an appropriate load cell can be employed in the test. The load cell can be chosen (eg 10N) so that the test value is between 10-90% of the full scale of the load. The elastic tester (ie MTS SYNERGY 200) and load cell are available from MTS Systems Corporation of Eden Prairie, Michigan. The fiber samples in the frame assembly can then be mounted between the grips of the stretch tester, such that the fiber ends are operatively held by the grips of the stretch tester. Then the sides of the paper frame that run parallel to the length of the fiber can be cut or otherwise separated so that the stretch tester applies the test force to the fibers only. The fibers can then be subjected to a pull test, with a pull rate and grip speed of 12 inches per minute. The resulting data can be analyzed using a TESTWORKS 4 software program from MTS Corporation with the following test setup:

[102] Tenacity values can be expressed in terms of gram-force per denier. Peak elongation (% force at break) and peak stress can also be calculated. Expansion Ratio, Density and Percent Pore Volume:
[103] To determine the expansion ratio, the density and the 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 surface of the sample. Consequently, the sample could be stretched to start emptying. The width (Wf), thickness (Tf) and length (Lf) of the sample could then be measured to the nearest 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 ratio (Φ) could be calculated by Φ = Vf/Vi; the density (Pf) was 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:
[104] Moisture content can be determined using an Arizona Instruments Computrac Vapor Pro moisture analyzer (Model #3100) substantially in accordance with ASTM D 7191-05, which is incorporated in its entirety herein 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 vial purge time (§X2.1.4) can be of 30 seconds. In addition, the final criteria (§X2.1.3) can be set to 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
[105] The ability to form fibers for use in a fabric has been demonstrated. Initially, a blend of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of a microinclusion additive, 1.4% by weight of a nanoinclusion additive, and 3.8 % by weight of the interfacial modifier (PLURIOL® WI 285 from BASF) was twisted into fibers. The microinclusion additive was Vistamaxx™ 2120 (ExxonMobil), which is a polyolefin/elastomer copolymer with a melt flow rate 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 70-100 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 polymers were fed into a co-rotating twin screw extruder (ZSK-30, diameter 30 mm, length 1328 mm) for compounds which were manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey. The extruder had 14 zones, numbered sequentially from 1-14, from the hopper to the mold. The first zone of keg #1 received the resins through the gravimetric feeder with a total throughput of 15 pounds per hour with PLURIOL® WI285 added via injection pump in the keg zone #2. The mold used to extrude the resin had 3 mold openings (6 millimeters in diameter) that were 4 millimeters apart. After forming, the extruded resin was cooled on a fan cooled conveyor belt and formed into pellets by a Conair pelletizer. The extruder screw speed was 200 revolutions per minute (“rpm”). The pellets were then fed into a single screw extruder at 240 °C, melted and passed through a melt pump at a rate of 0.40 grams per hole per minute through a 0.6 mm diameter die. .
[106] The fibers were collected in free fall (gravity only as tensile force) and then tested for mechanical properties at a tensile rate of 50 millimeters per minute. The fibers were then cold drawn at 23°C on an MTS Synergie elastic frame at a rate of 50 mm/min. The fibers were stretched at pre-set strengths of 50%, 100%, 150%, 200% and 250%. After stretching, expansion ratio, void volume and density were calculated for various force ratios as shown in the tables below.

EXAMPLE 2
[107] The fibers were formed as described in Example 1, with the exception that they were collected at a take-up roller speed of 100 meters per minute, resulting in a tensile ratio of 77. The fibers were then tested for mechanical properties at a pull rate of 50 millimeters per minute. The fibers were then cold drawn at 23°C on an MTS Synergie elastic frame at a rate of 50 mm/min. The fibers were stretched at pre-set strengths of 50%, 100%, 150%, 200% and 250%. After stretching, expansion ratio, void volume and density were calculated for various force ratios as shown in the tables below.

EXAMPLE 3
[108] The fibers were formed as described in Example 1, except that the blend consisted of 83.7% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.3% by weight of Vistamaxx™ 2120, 1.4% by weight of Lotader® AX8900, 3.7% by weight of PLURIOL® WI 285, and 1.9% by weight of hydrophilic surfactant (Masil SF-19). PLURIOL® WI285 and Masil SF-19 were premixed in a 2:1 ratio (WI-285:SF-19) and added via injection pump into barrel zone #2. Fibers were collected at 240 °C, 0.40 ghm and under free fall. EXAMPLE 4
[109] The fibers were formed as described in Example 3, with the exception that they were collected at a take-up roller speed of 100 meters per minute, resulting in a tensile ratio of 77. The fibers were then tested for mechanical properties at a pull rate of 50 millimeters per minute. The fibers were then cold drawn at 23°C on an MTS Synergie elastic frame at a rate of 50 mm/min. The fibers were stretched to a pre-set strength of 100%. After stretching, expansion ratio, void volume and density were calculated as shown in the tables below.
EXAMPLE 5
[110] The fibers of Example 2 were stretched on an MTS Synergie elastic frame at a rate of 50 millimeters per minute at 250% strength. This opened up the void structure and made the fiber white. A one-inch sample was then cut from the tensioned white area of the fiber. The new fiber was then tested as described above. The density was estimated to be 0.75 grams per cubic centimeter and the pull rate for the elastic test was 305 mm/min. EXAMPLE 6
[111] The fibers from Example 2 were heated in an oven at 50°C for 30 minutes for fiber annealing. EXAMPLE 7
[112] The fibers of Example 2 were heated in an oven at 90 °C for 5 minutes for fiber annealing and for inducing crystallization.
[113] The fibers from Examples 1-7 were then tested for mechanical properties at a tensile rate of 50 millimeters per minute. The results are shown in the table below.
EXAMPLE 8
[114] The ability to form fibers for use in a fabric has been demonstrated. Initially, a precursor mixture was formed by 91.8% by weight of isotactic propylene homopolymer (M3661, melt flow rate of 14 g/10 at 210 °C and melt temperature of 150 °C, Total Petrochemicals), 7 .4% by weight of polylactic acid (PLA 6252, melt flow rate 70 to 85 g/10 min at 210°C, Natureworks®), and 0.7% by weight of a polyepoxide. The polyepoxide was poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) (LOTADER® AX8900, Arkema) having a melt flow rate of 6 g/10 min (190 °C/2160 g), a glycidyl methacrylate of 8% by weight, methyl acrylate content of 24% by weight, and ethylene content of 68% by weight. The components were compounded in a co-rotating twin screw extruder (Werner and Pfleiderer ZSK-30 with a diameter of 30 mm and an L/D=44). The extruder had seven heating zones. The temperature in the extruder ranged from 180°C to 220°C. The polymer was gravimetrically fed into the extruder into the hopper at 15 pounds per hour and the liquid was injected into the keg using a peristaltic pump. The extruder was operated at 200 revolutions per minute (RPM). In the last section of the barrel (front), a mold with 3 holes of 6 mm in diameter was used to form the extrudate. The extrudate was air cooled on a conveyor belt and pelleted using a Conair pelletizer.
[115] The fiber was then produced from the precursor blend using a Davis-Standard fiber spin line equipped with a 0.75 inch single screw extruder and a 16-hole spinneret with a diameter of 0.6 mm. Fibers were collected at different tensile ratios. The shortening speed ranged from 1 to 1000 m/min. The extruder temperature ranged from 175 °C to 220 °C. The fibers were stretched in an elastic testing machine at 300 mm/min to 400% elongation at 25 °C. To analyze the morphology of the material, the fibers were broken by freezing in liquid nitrogen and analyzed using a Jeol 6490LV scanning electron microscope in high vacuum. The results are shown in Fig. 6-8. As shown, spheroid pores are formed which are elongated in the stretching direction. Both nanopores (~50 nanometers wide, ~500 nanometers long) and micropores (~0.5 micrometers wide, ~4 micrometers long) were formed.
[116] While the invention has been described in detail with respect to its specific embodiments, it will be appreciated that those skilled in the art, after gaining an understanding of the foregoing, can readily devise alterations, variations, and equivalents of these embodiments. In that sense, the scope of the present invention should be evaluated as that of the appended claims and any equivalents thereto.

权利要求:
Claims (14)
[0001]
1. Fabric, characterized in that it comprises a plurality of porous fibers, wherein the fibers are formed of a thermoplastic composition containing a continuous phase that includes a polyolefin matrix polymer, and wherein further a microinclusion additive and an additive are dispersed within the continuous phase in the form of discrete domains, wherein a porous network that includes a plurality of nanopores with an average transverse dimension of 800 nanometers or less is defined in the composition; wherein the nanoinclusion additive is selected from styrenic copolymers, polytetrafluoroethylenes; polyesters; polyvinyl acetates; polyvinyl alcohols; polyvinyl butyrals; acrylic resins; polyamides; polyvinyl chlorides; polyvinylidene chlorides; polystyrenes, and polyurethanes; and wherein the nanoinclusion additive is present in the amount of 0.05% to 10% by weight of the thermoplastic composition, based on the weight of the continuous phase.
[0002]
2. Fabric according to claim 1, characterized in that the fabric exhibits a water vapor transmission rate of 300 g/m2-24 hours or more, a thermal conductivity of 0.02 to 0.10 watts per meterkelvin, and/or a hydrostatic head value of 50 centimeters or more, determined in accordance with AATCC Test Method 127-2008.
[0003]
3. Fabric according to any one of the preceding claims, characterized in that the ratio between the solubility parameter for the matrix polymer and the solubility parameter for the microinclusion additive is from 0.5 to 1.5, the ratio of the melt flow rate for the matrix polymer to the melt flow rate of the microinclusion additive is 0.2 to 8, and/or the ratio between the Young's modulus of elasticity of the matrix polymer and the Young's modulus of elasticity of the microinclusion additive is 1 to 250.
[0004]
Fabric according to any one of the preceding claims, characterized in that the nanoinclusion additive is polymeric, preferably a functionalized polyolefin, such as a polyepoxide.
[0005]
5. Fabric according to any one of the preceding claims, characterized in that the microinclusion additive constitutes from 1% by weight to 30% by weight of the composition, based on the weight of the continuous phase, wherein the continuous phase constitutes from 60% by weight to 99% by weight of the thermoplastic composition; and/or wherein the nano-inclusion additive constitutes from 0.5% by weight to 5% by weight of the composition, based on the weight of the continuous phase.
[0006]
Fabric according to any one of the preceding claims, characterized in that the thermoplastic composition further comprises an interphase modifier, such as a silicone, a silicone-polyether copolymer, an aliphatic polyester, an aromatic polyester, an alkylene glycol. , an alkane diol, an amine oxide, a fatty acid ester, or a combination thereof, preferably wherein the interphase modifier constitutes from 0.1% by weight to 20% by weight of the composition based on the weight of the continuous phase .
[0007]
7. Fabric according to claim 6, characterized in that the interphase modifier has a kinematic viscosity of 7 x 10-7 to 2 x 10-4 m2/s (0.7 to 200 centistokes), determined at a temperature of 40°C; and/or wherein the interphase modifier is hydrophobic.
[0008]
8. Fabric according to any one of the preceding claims, characterized in that the microinclusion additive is in the form of microscale domains and the nanoinclusion additive is in the form of nanoscale domains, wherein the nanoscale domains have a average cross-sectional dimension from 1 nanometer to 500 nanometers.
[0009]
9. Fabric, according to any one of the preceding claims, characterized in that the porous network also includes micropores, and in which the micropores have an average transverse dimension of 1 to 30 micrometers.
[0010]
10. Fabric, according to claim 18, characterized in that the micropores have an aspect ratio of 1 to 30.
[0011]
11. Fabric, according to any one of the preceding claims, characterized in that the total volume of pores of the fibers is from 15% to 80% per cubic centimeter; wherein the nanopores constitute 20% by volume or more of the total pore volume of the fibers; and/or wherein the thermoplastic composition has a density of 1.2 grams per cubic centimeter or less.
[0012]
12. Fabric according to any one of the preceding claims, characterized in that the fabric is a non-woven fabric, or a fabric or knit that contains a plurality of yarns, at least a part of the yarns including the fibers porous.
[0013]
13. Fabric, according to claim 12, characterized in that the fabric is a compound that also contains textile fibers, such as generally inelastic textile fibers, and/or elastic textile fibers, such as elastoester, lastol, spandex, or a combination of them.
[0014]
14. Fabric, according to claim 13, characterized in that the compound includes yarns formed from a combination of porous fibers and textile fibers, and/or yarns formed by porous fibers and yarns formed by textile fibers.

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同族专利:

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CN105264128B|2017-10-17|

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JP2016527406A|2016-09-08|

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MX2015016526A|2016-04-15|

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CN105264128A|2016-01-20|

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WO2014199274A1|2014-12-18|

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EP3008231A1|2016-04-20|

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AU2014279701B2|2017-06-01|

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AU2014279701A1|2016-01-21|

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EP3008231A4|2016-09-14|

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BR112015029507A2|2017-07-25|

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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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2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-07-20| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-08-24| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-12-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-01-25| 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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US201361833985P| true| 2013-06-12|2013-06-12|

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US61/833,985|2013-06-12|

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US201361907552P| true| 2013-11-22|2013-11-22|

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