renewable polyester fibers with low density

专利摘要:
RENEWABLE POLYESTER FIBERS WITH LOW DENSITY. Fibers are provided that are formed by a thermoplastic compound that contains a renewable rigid polyester and presents a structure with voids and low density. To obtain such a structure, the renewable polyester is mixed with a polymeric curing additive, in which the curing additive can be dispersed as discrete physical domains, within a continuous matrix of the renewable polyester. The fibers are thus formed and then stretched or pulled at a temperature below the glass transition temperature of the polyester (i.e. "cold drawn"). Without the intention of limiting themselves by theory, these inventors believe that the deformation force and the stretching tension of the traction process causes the disintegration of the renewable polyester matrix, in the areas adjacent to the discrete domains. This creates a network of voids, (for example, micro-voids, nano-voids or a combination of them) located adjacent to the discrete domains, which, as a result of their close locations, can form a bridge between the void boundaries and act as internal structural hinges that help to stabilize the network and increase its power dissipation capacity.
公开号:BR112014019495B1
申请号:R112014019495-5
申请日:2013-01-28
公开日:2021-02-02
发明作者:Vasily A. Topolkaraev；Ryan J. Mceneany；Neil T. Scholl；Tom Eby
申请人:Kimberly-Clark Worldwide, Inc.；
IPC主号:

专利说明:

History of the invention
[001] Several attempts have been made to use renewable polyesters (eg, polylactic acid, "PLA") in fibers. However, the penetration of renewable polyesters on the market has been limited due to a density that is approximately 30% higher than conventional polyolefins, making them considerably more expensive. To help reduce the density of these polyesters, gaseous blowing agents are sometimes used to help create a "foamy" cell structure with a determined degree of porosity. Unfortunately, the processing and traction properties of the resulting cell structure are often compromised by the uncontrolled pore size and distribution. There are also other problems. Renewable polyesters, for example, have a relatively high glass transition temperature and usually demonstrate very high stiffness, while having low elongation / ductility at break. As an example, polylactic acid has a glass transition temperature of approximately 59 ° C and an elongation in tension (at break) of only approximately 5%. These low values of tensile elongation considerably limit the use of these polymers in fibers, in which a good balance between strength and ductility is necessary.
[002] Thus, currently, there is a need for renewable low-density polyester fibers that may still have good mechanical properties. Summary of the invention
[003] According to one of the embodiments of the present invention, a fiber formed from a thermoplastic compound is disclosed. The compound contains at least one rigid, renewable polyester, with a glass transition temperature of approximately 0 ° C or more, from approximately 1 wt% (weight percentage) to approximately 30 wt% of at least one polymeric curing additive, with based on the weight of the renewable polyester, and from approximately 0.1% to approximately 20% w in at least one interphasic modifier based on the weight of the renewable polyester. The thermoplastic compound has a morphology in which several discrete and empty primary domains are dispersed within a continuous phase, with the domains containing the polymeric hardening additive and with the continuous phase containing the renewable polyester. The fiber has a density of approximately 1.4 grams per cubic centimeter or less, and the average percentage volume of the compound that is occupied by the voids is approximately 20% to approximately 80% per cubic centimeter.
[004] According to another embodiment of the present invention, there is disclosed a method for forming a low density fiber which consists of forming a mixture containing a renewable rigid polyester and a polymeric curing additive, wherein the rigid renewable polyester has a glass transition temperature of approximately 0 ° C or more; extruding the mixture into a mold to form a fiber; and stretching the fiber to a temperature below the glass transition temperature of the renewable polyester to form a thermoplastic compound that contains a variety of void areas and a density of approximately 1.4 grams per cubic centimeter or less.
[005] In accordance with yet another embodiment of the present invention, there is disclosed a method for forming a non-woven mat consisting of the random deposit of a multiplicity of fibers forming a surface. The fibers can be formed from a mixture, as described herein. The method also consists of stretching the fibers before and / or after the formation of the non-woven blanket, in which the fibers are stretched at a temperature below the glass transition temperature of the renewable polyester, to form a thermoplastic compound that contains several voids and presents a density of approximately 1.4 grams per cubic centimeter or less.
[006] Other features and aspects of the present invention are discussed in more detail below. Brief description of the illustrations
[007] A complete and clarifying description of the present invention, including its best mode, directed to people with technical knowledge in the field, is demonstrated in more detail in the rest of the specification, which makes reference to the attached figures in which:
[008] Fig. 1 is a schematic illustration of a process that can be used in an embodiment of the present invention, to form fibers; and
[009] Fig. 2 is a schematic illustration of an embodiment of a fiber that can be formed according to the present invention.
[010] The repeated use of reference characters in this specification and in the drawings is intended to represent the same characteristics or elements, or analogues, of the present invention. Detailed description of representative embodiments
[011] Detailed references will be made to various embodiments of the invention, with one or more examples described below. Each example is provided for the purpose of explaining the invention, and not as a limitation on it. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention, without departing from the scope or spirit of the invention. For example, the features illustrated or described as part of one embodiment can be used in another embodiment, to obtain yet a third embodiment. Thus, it is intended that the present invention covers modifications and variations that are within the scope of the appended claims and their equivalents. Definitions
[012] As used herein, the term "fibers" refers to elongated extrudates formed by passing a polymer through a molding orifice, such as a mold. Unless mentioned otherwise, the term "fibers" involves both staple fibers with defined lengths and continuous filaments of great length. Long filaments can, for example, be much longer than the diameter, with length-to-diameter ratios (“aspect ratio”) greater than approximately 15,000 to 1 and, in some cases, approximately 50,000 to 1.
[013] As used herein, the term "monocomponent" refers to fibers formed from a polymer. Of course, this does not exclude fibers containing additives for color, antistatic properties, lubrication, hydrophilicity, liquid repellency, etc.
[014] As used herein, the term "multicomponent" refers to fibers formed from at least two polymers (e.g., bicomponent fibers) that are extruded from separate extruders. The polymers are arranged in distinct zones, positioned substantially and continuously through the cross section of the fibers. The components can be arranged in any desired configuration, such as core coating, side-by-side, pizza, island and so on. Various methods for the formation of multi-component fibers are described in U.S. Patent No. 4,789,592 to Taniguchi et al. and No. 5,336,552 by Strack et al., 5,108,820 by Kaneko et al., 4,795,668 by Kruege, et al., 5,382,400 by Pike et al., 5,336,552 by Strack et al., and 6,200,669 by Marmon et al. Multicomponent fibers with various irregular shapes can also be formed, such as those described in U.S. Patent No. 5,277,976 to Hogle et al., 5,162,074 to Hills, 5,466,410 to Hills, 5,069,970 to Largman et al ., and 5,057,368 by Largman et al.
[015] As used in this document, the term “non-woven blanket” refers to a blanket with a structure of individual fibers randomly interwoven, and not identifiable, as in a fabric. Non-woven blankets include, for example, meltblown blankets, heat-sealed blankets, carding blankets, wet blankets, airflow blankets, coform blankets, hydraulic matted blankets, etc. The base weight of non-woven blankets can generally vary, but it usually has 5 grams per square meter (“g / m2”) to 200 g / m2 and, in some embodiments, from approximately 10 g / m2 to approximately 150 g / m2 m2 and in other embodiments from 15 g / m2 to 100 g / m2.
[016] As used herein, the term "meltblown" blanket or layer generally refers to a non-woven blanket that is formed by a process in which a molten thermoplastic material is extruded through a variety of fine capillary molds, generally circular, such as fibers fused in gas streams (eg, air) of high speed convergence that attenuate the fibers of fused thermoplastic material to reduce their diameters, which may have a microfiber diameter. Consequently, the meltblown fibers are transported by the high-speed gas stream and deposited on a collecting surface to form a blanket of randomly scattered meltblown fibers. This process is published, for example, in US patents No. 3,849,241 by Butin et al .; 4,307,143 to Meitner et al .; and 4,707,398 by Wisneski et al. Meltblown fibers can be essentially continuous or non-continuous and are generally self-adhesive when deposited on a collecting surface.
[017] As used in this document, the term “heat-sealed” blanket or layer, refers to a non-woven blanket that has a small diameter and continuous filaments. The filaments are formed by the extrusion of molten thermoplastic material from a large number of thin capillaries, usually circular, from a die with the diameter of the extruded filaments and then quickly reduced, as by means of, for example, derivative printing and / or other known heat-sealing mechanisms. The production of heat-sealed blankets is described and illustrated, for example, in U.S. Patent No. 4,340,563 to Appel et al., 3,692,618 to Dorschner et al., 3,802,817 to Matsuki et al., 3,338,992 by Kinney, 3,341,394 by Kinney, 3,502,763 by Hartman, 3,502,538 by Levy, 3,542,615 by Dobo et al. and 5,382,400 by Pike et al. Generally, heat-sealed filaments are not self-adhesive when deposited on a collecting surface. Heat-welded filaments can sometimes have diameters of less than approximately 40 micrometers and often have a diameter between approximately 5 μm to approximately 20 micrometers. Detailed Description
[018] In general, the present invention is directed to fibers formed from a thermoplastic compound that contains a renewable rigid polyester and presents a structure with empty areas and low density. To obtain such a structure, the renewable polyester is mixed with a polymeric curing additive, in which the curing additive can be dispersed as discrete physical domains, within a continuous matrix of the renewable polyester. The fibers are thus formed and then stretched or pulled at a temperature below the glass transition temperature of the polyester (ie, "cold drawn"). Without the intention of limiting themselves by theory, these inventors believe that the deformation force and the stretching tension of the traction process causes the disintegration of the renewable polyester matrix, in the areas adjacent to the discrete domains. This creates a network of voids, (for example, micro-voids, nano-voids or a combination of them) located adjacent to the discrete domains, which, as a result of their close locations, can form a bridge between the void boundaries and act as internal structural “hinges” that help to stabilize the network and increase its energy dissipation capacity.
[019] The average percentage volume occupied by empty spaces within a given fiber volume unit can be relatively high, from approximately 20% to approximately 80% per cm3, in some embodiments from approximately 30% to approximately 70% , and in some embodiments, from approximately 40% to approximately 60% per cubic centimeter of the compound. The high volume of empty spaces can significantly decrease the density of the fibers. For example, fibers may have a density of approximately 1.4 grams per cubic centimeter (“g / cm3”) or less, in some embodiments from approximately 0.4 g / cm3 to approximately 1.1 g / cm3, and in some embodiments, from approximately 0.5 g / cm3 to approximately 0.95 g / cm3. These inventors also found that voids can be distributed quite evenly throughout the compound. For example, voids can be distributed in columns that are oriented in a direction normally perpendicular to the direction in which the tension is applied. These columns can generally be parallel to each other across the width of the composition. Without the intention of imposing theoretical limitations, it is believed that the presence of this network of homogeneously distributed voids may result in a significant dissipation of energy under load. This is a clear contrast to conventional techniques for creating voids that involve the use of blowing agents to initiate pore formation, which tends to result in uncontrolled pore distribution and poor mechanical properties.
[020] We will now describe several embodiments of this invention in more detail.
[021] I. Thermoplastic compound
[022] A. Renewable polyester
[023] Renewable polyesters typically make up approximately 70% pa to approximately 99% w, in some embodiments, approximately 75% to approximately 98% w, in other embodiments, approximately 80% to approximately 95% w of thermoplastic compound. Various renewable polyesters can normally be used in the thermoplastic compound, such as aliphatic polyesters such as polycaprolactone, polyesteramides, polylactic acid (PLA) and their copolymers, polyglycolic acid, polyalkylene carbonates (eg, polyethylene carbonate), poly- 3-hydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxybutyrate-co-4-hydroxybutyrate, copolymers of 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 polymers based on succinate (eg, polybutylene succinate, polybutylene succinate adipate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (eg, polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene adipate isophthalate, polybutylene adipate isophthalate etc.); aromatic polyesters (eg, polyethylene terephthalate, polybutylene terephthalate, etc.); and so on.
[024] Typically, the thermoplastic compound contains at least one renewable polyester that is rigid in nature and thus has a relatively high glass transition temperature. For example, the glass transition temperature ("Tg") can be approximately 0 ° C or more, in some embodiments, from approximately 5 ° C to approximately 100 ° C, in some embodiments, approximately 30 ° C to approximately 80 ° C and, in some embodiments, from approximately 50 ° C to approximately 75 ° C. Renewable polyester may also have a melting temperature of approximately 140 ° C to approximately 260 ° C, in some embodiments, from approximately 150 ° C to approximately 250 ° C and, in some embodiments, approximately 160 ° C at approximately 220 ° C. The melting temperature can be determined using differential scanning calorimetry (“DSC”) in accordance with the ASTM D-3417 standard. The glass transition temperature can be determined by dynamic mechanical analysis in accordance with ASTM E1640-09.
[025] A particularly suitable rigid polyester is polylactic acid, which can be derived from monomeric units of any lactic acid isomer, such as levorotatory lactic acid (“L-lactic acid”), dextrorotatory lactic acid (“D-lactic acid”) , meso-lactic acid or combinations of these. 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 extension agent can also be employed (for example, a diisocyanate compound, an epoxy compound or acid anhydride). The polylactic acid can be a homopolymer or a copolymer, such as one that contains monomeric units derived from L-lactic acid and monomeric units derived from D-lactic acid. While not required, the content ratio of one of the monomeric units derived from L-lactic acid and the monomeric unit derived from D-lactic acid is preferably approximately 85% per mol or more, in some embodiments, approximately 90% per mol or more and, in other embodiments, approximately 95% per mol or more. Various polylactic acids, each with a different ratio between the monomeric unit derived from L-lactic acid and the monomeric unit derived from D-lactic acid, can be mixed in any random percentage. Of course, polylactic acid can be mixed with other types of polymers (for example, polyolefins, polyesters, etc.).
[026] In a specific embodiment, polylactic acid has the following general structure:

[027] A specific example of a suitable polylactic acid polymer that can be used in the present invention is marketed by Biomer, Inc. of Krailling, Germany, under the name BIOMER ™ L9000. Other suitable polylactic acid polymers are commercially available from Natureworks LLC of Minnetonka, Minnesota (NATUREWORKS®) or Mitsui Chemical (LACEA®). Other suitable polylactic acids are described in U.S. Patent No. 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254 and 6,326,458, which are incorporated herein in their entirety as a reference for all purposes.
[028] Polylactic acid normally has an average molecular weight in number ("Mn") ranging from 40,000 g / mol to approximately 160,000 grams per mol; in some embodiments from 50,000 g / mol to approximately 140,000 grams per mol; and in other embodiments of 80,000 g / mol to approximately 120,000 grams per mol. Likewise, the polymer normally has an average molecular weight in number ("Mn") that ranges from approximately 80,000 g / mol to approximately 200,000 grams per mol; in some embodiments from 100,000 g / mol to approximately 180,000 grams per mol; and in other embodiments of 110,000 g / mol to approximately 160,000 grams per mol. The relationship between the average molecular weight by weight and the average molecular weight in number (“Mw / Mn”), that is, the "polydispersity index", is also relatively low. For example, the polydispersity index usually ranges from approximately 1.0 to 3.0; in some embodiments from 1.1 to 2.0 approximately, and in other embodiments, from 1.2 to 1.8 approximately. The numerical and weighted average molecular weights can be determined by methods known to those skilled in the art.
[029] Polylactic acid may also have an apparent viscosity of approximately 50 Pa ^ s to approximately 600 Pascal-seconds (Pa-s), in some embodiments of approximately 100 Pa ^ s to approximately 500 Pa ^ se, in other forms of carrying out approximately 200 Pa ^ s to approximately 400 Pa ^ s, as measured at a temperature of 190 ° C and a shear rate of 1000 s-1. The fluidity index of polylactic acid (on a dry basis) can also vary from approximately 0.1 to approximately 40 grams for 10 minutes; in some embodiments, from approximately 0.5 to approximately 20 grams for 10 minutes, and, in other embodiments, from approximately 5 to approximately 15 grams for 10 minutes, measured at a load of 2160 grams and at 190 ° C .
[030] Some types of pure polyester (for example, polylactic acid) can absorb water from an environment so that it has a moisture content of approximately 500 ppm to 600 parts per million ("ppm"), or even higher, based on in the dry weight of the initial polylactic acid. The moisture content can be determined in several ways, as is known in the art, in accordance with the ASTM D 7191-05 standard, as described below. Since the presence of water during melt processing can hydrolytically degrade the polyester and reduce its molecular weight, it is sometimes better to dry the polyester before mixing it. In most embodiments, for example, it is best for renewable polyester to have a moisture content of approximately 300 parts per million ("ppm") or less, in some embodiments, approximately 200 ppm or less, in some embodiments, from approximately 1 ppm to approximately 100 ppm, before mixing with the curing additive. The drying of the polyester can take place, for example, at a temperature of approximately 50 ° C to approximately 100 ° C and, in some embodiments, from approximately 70 ° C to approximately 80 ° C.
[031] B. Polymeric hardening additive
[032] As indicated above, the thermoplastic compound of the present invention also contains a polymeric curing additive. Due to its polymeric nature, the curing additive has a relatively high molecular weight which can help to improve the melting capacity and stability of the thermoplastic compound. Although not required, the polymeric curing additive can be immiscible with renewable polyester. In this way, the curing additive can be better spread as discrete phase domains within a continuous phase of the renewable polyester. The discrete domains are able to absorb energies resulting from an external force, which increases the stiffness and the total resistance of the resulting material. Domains can take a variety of different shapes, for example, elliptical, spherical, cylindrical, etc. In one embodiment, for example, the domains are quite elliptical in shape. The physical dimension of an individual domain is usually small enough to minimize the propagation of cracks in the polymeric material by applying an external stress, but large enough to initiate microscopic plastic deformation and to allow shear zones in particle inclusions or at the same time. around them.
[033] Although the polymers may be immiscible, the curing additive can still be selected having a solubility parameter that is relatively similar to that of renewable polyester. This can improve the interfacial compatibility and the physical interaction of the discrete and continuous phase boundaries and thus reduce the likelihood of the compound breaking. For this, the ratio of the renewable polyester solubility parameter to the hardener additive parameter is normally approximately 0.5 to approximately 1.5 and, in some embodiments, approximately 0.8 to approximately 1.2. For example, the polymeric curing additive may have a solubility parameter of approximately 15 to approximately 30 MJoules1 / 2 / m3 / 2 and, in some embodiments, approximately 18 to approximately 22 MJoules1 / 2 / m3 / 2, while polylactic acid can have a solubility parameter of approximately 20.5 MJoules1 / 2 / m3 / 2. The term “solubility parameter”, as used in this document, refers to the “Hildebrand Solubility Parameter”, which is the square root of the density of cohesive energy, calculated using the following equation:
on what:
[034] Δ Hv = heat of vaporization
[035] R = Ideal gas constant
[036] T = Temperature
[037] Vm = Molecular volume
[038] Hildebrand's solubility parameters for many polymers are also found in Wyeych's Solubility Handbook of Plastics (2004), included in this document as a reference.
[039] The polymeric curing additive can also have a fluidity index (or viscosity) to ensure that the resulting discrete domains and voids can be maintained properly. For example, if the curing rate of the curing additive is too high, it tends to flow and disperse uncontrollably during the continuous phase. This results in lamellar or plaque-like domains that are difficult to maintain and are likely to rupture prematurely. On the other hand, if the flow rate of the curing additive is too low, it will tend to agglutinate and form very large elliptical domains, which are difficult to disperse during mixing. This can cause an uneven distribution of the curing additive throughout the continuous phase. In this regard, the present inventors have found that the ratio of the curing index of the curing additive to the flow rate of the renewable polyester is normally approximately 0.2 to approximately 8, in some embodiments, approximately 0.5 to approximately 6 and, in other embodiments, from approximately 1 to approximately 5. The curing additive may, for example, have a melt index of approximately 0.1 to approximately 250 grams for 10 minutes, in some embodiments, from approximately 0.5 to approximately 200 grams for 10 minutes and, in other embodiments, approximately 5 to approximately 150 grams for 10 minutes, determined at a load of 2160 grams and at 190 ° C.
[040] In addition to the properties noted above, the mechanical characteristics of the polymeric curing additive can also be selected to achieve the desired increase in stiffness. For example, when a mixture of the renewable polyester and the curing additive is applied with an external force, shear flow zones and / or plastic flow can be initiated in and around the discrete phase domains as a result of stress concentrations. arising from a difference in the modulus of elasticity of the curing additive and the renewable polyester. Higher concentrations of stress promote a more intense localized plastic flow in the domains, allowing them to undergo considerable elongation when subjected to stress. These elongated domains allow the compound to behave more flexibly and softly than rigid polyester resin. To improve stress concentrations, the curing additive is selected in a way that it has a relatively low Young's modulus of elasticity, compared to renewable polyester. For example, the ratio of the modulus of elasticity of the renewable polyester to that of the curing additive is normally approximately 1 to approximately 250, in some embodiments, approximately 2 to approximately 100 and, in other embodiments, approximately 2 to approximately 50. The modulus of elasticity of the curing additive can, for example, vary from approximately 2 MPa to approximately 500 megapascals (MPa), in some embodiments from approximately 5 MPa to approximately 300 MPa and, in other embodiments , from approximately 10 MPa to approximately 200 MPa. On the other hand, normally the modulus of elasticity of polylactic acid is approximately 800 MPa approximately 2,000 MPa.
[041] In order to provide the desired increase in stiffness, the polymeric curing additive may also exhibit an elongation at break (that is, the percentage of elongation of the polymer at its pour point) greater than renewable polyester. For example, the polymeric curing additive of the present invention may exhibit an elongation at break of approximately 50% or more, in some embodiments, from approximately 100% or more, in some embodiments, from approximately 100% to approximately 2,000 % and, in other embodiments, from approximately 250% to approximately 1500%.
[042] Although a wide variety of polymeric additives with the properties identified above can be employed, especially suitable examples of such polymers (for example, polyethylene, polypropylene, polybutylene etc.); styrenic copolymers (for example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-butadiene-styrene, etc.); polytetrafluoroethylenes; polyesters (for example, recycled polyester, polyethylene terephthalate, etc.); polyvinyl acetates (for example, poly (ethylene vinyl acetate), polyvinyl chloride acetate, etc.); polyvinyl alcohols (for example, polyvinyl alcohol, poly (ethylene vinyl alcohol), etc.); polyvinyl butyral; acrylic resins (for example, polyacrylate, polymethylacrylate, polymethylmethacrylate, etc.); polyamides (for example, nylon); polyvinyl chlorides; polyvinylidene chlorides; polystyrenes, polyurethanes, etc. Suitable polyolefins may, for example, include ethylene polymers (for example, low density polyethylene (“PE-LD”), high density polyethylene (“HDPE”), linear low density polyethylene (“PELBD”) etc. ), propylene homopolymers (for example, syndiotactic, atactic, isotactic, etc.), propylene copolymers, and so on.
[043] In a given embodiment, the polymer is a propylene polymer such as homopolypropylene or a propylene copolymer. The propylene polymer can, for example, be formed from an isotactic polypropylene homopolymer or a copolymer containing an amount equal to or less than approximately 10% w of another monomer, that is, at least approximately 90% w of propylene. Such polymers can have a melting point of approximately 160 ° C to approximately 170 ° C.
[044] In yet another embodiment, the polyolefin can be a copolymer of ethylene or propylene with another α-olefin, such as C3-C20 α-olefin or C3-C12 α-olefin. Specific examples of suitable α-olefins are 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. The especially desired comonomers of α-olefin are 1-butene, 1-hexene and 1-octene. The ethylene or propylene content of these copolymers can vary from approximately 60% per mol to approximately 99% per mol, in some embodiments, from approximately 80% per mol to approximately 98.5% per mol and, in some embodiments , from approximately 87% per mol to approximately 97.5% per mol. The content of α-olefin can vary in the same way from approximately 1% to approximately 40% per mol, in some embodiments from approximately 1.5% to approximately 15% per mol and in other embodiments from approximately 2.5 % to 13% per mol.
[045] Examples of olefin copolymers for use in the present invention include ethylene-based copolymers, marketed under the name EXACT ™, from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are marketed under the name ENGAGE ™, AFFINITY ™, DOWLEX ™ (PELBD) and ATTANE ™ (PEUBD) from Dow Chemical Company of Midland, Michigan. Other suitable ethylene polymers are described in U.S. Patent No. 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 by Lai et al., which are incorporated herein in their entirety as a reference for all purposes. Propylene copolymers are marketed under the name VISTAMAXX ™ from ExxonMobil Chemical Co. of Houston, Texas; FINA ™ (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMER ™ marketed by Mitsui Petrochemical Industries; and VERSIFY ™, marketed by Dow Chemical Co. of Midland, Michigan. Other examples of suitable propylene polymers are described in U.S. Patent No. 6,500,563 to Datta et al .; 5,539,056 to Yang et al .; and 5,596,052 by Resconi et al., which are incorporated herein in their entirety as a reference for all purposes.
[046] A wide variety of known techniques can be employed to form the olefin copolymers. For example, olefin polymers can be formed using a free radical or a coordinating catalyst (for example, Ziegler-Natta). Typically, the olefin polymer is formed from a single site coordination catalyst, such as a metallocene catalyst. This catalyst system produces ethylene copolymers, in which the comonomer is randomly distributed within a molecular chain and uniformly distributed among the different molecular weight fractions. Metallocene-catalyzed polyolefins are described, for example, in U.S. Patent No. 5,571,619 to McAlpin et al .; 5,322,728 by Davis et al .; 5,472,775 to Obijeski et al .; 5,272,236 to Lai et al .; and 6,090,325 by Wheat et al., which are incorporated herein in their entirety as a reference for all purposes. Examples of metallocene catalysts include bis (n-butylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) scandium chloride, bis (indenyl) zirconium dichloride, methyl (dichloride) bis (methyl) dichloride titanium, bis (methylcyclopentadienyl) dichloride, zirconium, cobaltocene, cyclopentadienylthitanium trichloride, ferrocene, hafnocene dichloride, isopropyl dichloride (cyclopentadienyl, -1-flourenyl) zirconium, molybdenum, nichloride, nichloride, nichloride, nichloride, nichloride , zirconocene chloride hydride, zirconocene dichloride, etc. Polymers created using the metallocene catalyst usually have a narrow molecular weight range. For example, metallocene-catalyzed polymers may have polydispersity numbers (Mw / Mn) below 4, controlled short chain branch distribution and controlled isotacticity.
[047] Regardless of the materials used, the relative percentage of the polymeric curing additive in the thermoplastic compound is selected in order to achieve the desired properties without considerably affecting the resulting compound's ability to renew. For example, the curing additive is normally employed in the amount of approximately 1% per approximately 30% per, in some embodiments, approximately 2% per approximately 25% per, in other embodiments, approximately 5% per approximately 20% w of the thermoplastic compounds, based on the weight of the renewable polyesters used in the compound. The concentration of the curing additive in the entire thermoplastic compound can also form from approximately 0.1% to approximately 30%, in some embodiments, from approximately 0.5% to approximately 25%, in other embodiments, approximately 1% pa approximately 20% p.
[048] C. Interphasic modifier
[049] An interphasic modifier can also be used in the thermoplastic compound to reduce the degree of friction and connectivity between the hardening additive and the renewable polyester and, thus, increase the degree and uniformity of the detachment. In this way, the empty spaces can be distributed in a very homogeneous way throughout the compound. Typically, the shape of the modifier is liquid or semi-solid at room temperature (for example, 25 ° C), so that it has a relatively low viscosity, allowing it to be incorporated more quickly into the thermoplastic compound and easily migrated to the surfaces of the polymer. In this regard, the kinematic viscosity of the interphasic modifier is normally approximately 0.7 cs to approximately 200 centistokes ("cs"), in some embodiments of approximately 1 cs to approximately 100 cs and, in other embodiments, from approximately 1.5 dogs to approximately 80 dogs, determined at 40 ° C. In addition, the interphasic modifier is also normally hydrophobic, so that it has an affinity with the polymeric curing additive, resulting in a change in the interfacial tension between the renewable polyester and the curing additive. By reducing the physical forces at the interfaces between the polyester and the curing additive, it is believed that the hydrophobic and low-viscosity nature of the modifier can help facilitate the detachment of the polyester matrix. As used here, the term "hydrophobic" usually refers to material that has a contact angle between water and air of approximately 40 ° or more and, in some cases, approximately 60 ° or more. In contrast, the term "hydrophilic" usually refers to material that has a contact angle between water and air less than approximately 40 °. A suitable test to measure the contact angle is the ASTM D5725-99 (2008).
[050] Some suitable, low-viscosity hydrophobic interphase modifiers are, for example, silicones, silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, alkylene glycols (eg ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene polypropylene glycol, polybutylene glycol, etc.), alkane diols, (for example, Propane-1,3-diol, 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, etc. An especially suitable interphase modifier is polyester polyol, such as those sold under the trade name PLURIOL® WI by BASF Corp. Another particularly suitable modifier is the partially renewable ester, such as the one sold under the trade name HALLGREEN® IM by Hallstar.
[051] Although the actual amount may vary, the interphasic modifier is normally employed in the amount of approximately 0.1% pa to approximately 20% p, in some embodiments, of approximately 0.5% p to approximately 15% p, in other forms of realization, from approximately 1% to approximately 10% w of the thermoplastic compounds, based on the mass of renewable polyesters employed in the compound. The concentration of interphasic modifiers in the entire thermoplastic compound can likewise constitute approximately 0.05% pa to approximately 20% w, in some embodiments, approximately 0.1% pa to approximately 15% w, in other forms of approximately 0.5% pa to approximately 10% p.
[052] When the amounts observed above are used, the interphasic modifier has a characteristic that will allow it to migrate quickly to the interfacial surface of the polymers and facilitate the detachment without damaging the melting properties of the thermoplastic compound. For example, the interphasic modifier does not normally have a plasticizing effect on the polymer by reducing its glass transition temperature. In contrast, the present inventors have found that the glass transition temperature of the thermoplastic compound can be the same as that of the initial renewable polyester. In this regard, the ratio of the glass transition temperature of the compound to that of the polyester is normally approximately 0.7 to approximately 1.3, in some forms and carrying out approximately 0.8 to approximately 1.2 and, in other forms of realization, from approximately 0.9 to approximately 1.1. The thermoplastic compound can, for example, have a glass transition temperature of approximately 35 ° C to approximately 80 ° C, in some embodiments of approximately 40 ° C to approximately 80 ° C and, in other embodiments, of approximately 50 ° C to approximately 65 ° C. The fluidity index of the thermoplastic compound can also be similar to that of renewable polyester. For example, the fluidity index of the compound (on a dry basis) can be approximately 0.1 to approximately 70 grams for 10 minutes, in some embodiments from approximately 0.5 to approximately 50 grams for 10 minutes, and in others embodiments, from approximately 5 to approximately 25 grams for 10 minutes, determined at a load of 2160 grams and at a temperature of 190 ° C.
[053] D. Compatibilizer
[054] As indicated above, the polymeric curing additive is normally selected so that it has a solubility parameter relatively close to that of renewable polyester. Among other things, this can improve phase compatibility and increase the overall distribution of discrete domains within the continuous phase. However, in some embodiments, a compatibilizer can be used to further improve the compatibility between the renewable polyester and the polymeric curing additive. This may be desirable especially when the polymeric curing additive has a polar part, such as polyurethanes, acrylic resins, etc. When used, compatibilizers generally form approximately 0.5% per approximately 20% per, in some embodiments, approximately 1% per approximately 15% per, in other embodiments, approximately 1.5% per approximately 10% per of the thermoplastic compound. An example of a suitable compatibilizer is the functionalized polyolefin. The polar component can, for example, be provided by one or more functional groups, and the non-polar component can be provided by an olefin. The olefin component of the compatibilizer can normally be formed from any branched or linear α-olefin monomer, oligomer or polymer (including copolymers) derived from an olefin monomer, as described above.
[055] The functional group of the compatibilizer can be any group that provides a polar segment to the molecule. Especially suitable functional groups are maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, a reaction product of maleic anhydride and diamine, methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, etc. Maleic anhydride modified polyolefins are especially suitable for use in this invention. These modified polyolefins are usually formed by grafting maleic anhydride into a material of the polymeric structure. These maleatated polyolefins are marketed by EI du Pont de Nemours and Company under the name of Fusabond®, as the P series (chemically modified polypropylene), E series (chemically modified polyethylene), C series (chemically modified satin vinyl foam), A series (chemically modified ethylene acrylate copolymers or terpolymers) or the N series (chemically modified ethylene-propylene diene monomer ("EPDM") or ethylene-octene). As an alternative, maleated polyolefins are also marketed by Chemtura Corp. under the name of Polybond® and by the Eastman Chemical Company under the name of Eastman G series.
[056] In certain embodiments, the compatibilizer can also be reactive. An example of this reactive compatibilizer is the polyepoxide modifier that contains, on average, at least two oxirane rings per molecule. Without the intention of being limited by theory, it is believed that these polyepoxide molecules can induce a reaction of the renewable polyester under certain conditions, thus improving its melting capacity without greatly reducing the glass transition temperature. The reaction may involve chain extension, branching of side chains, graft, copolymer formation etc. Chain extension, for example, can occur through a variety of different reactive pathways. For example, the modifier may allow a nucleophilic reaction for ring opening by means of a renewable polyester carboxyl end group (esterification) or by means of a hydroxyl group (etherification). Reactions on the oxazoline side can occur and form stearamide organic functions. Through these reactions, the molecular weight of the renewable polyester can be increased to combat the degradation often seen during the melting process. Although it is desirable to induce a reaction with the renewable polyester as described above, the present inventors have found that too much reaction can cause crosslinking between the polyester structures. If this crosslinking is allowed to proceed to a considerable extent, the resulting polymer mixture may become brittle and difficult to mold into a film format with the desired properties of strength and elongation.
[057] In this sense, the present inventors have found that polyepoxide modifiers with relatively low epoxy functionality are especially effective, which can be quantified by their "epoxy equivalent weight". The epoxy equivalent weight reflects the amount of resin that contains a molecule in an epoxy group, and can be calculated by dividing the average molecular weight in number of the modifier by the number of epoxy groups in the molecule. The polyepoxide modifier of the present invention normally has an average molecular weight in number ranging from approximately 7,500 g / mol to approximately 250,000 grams per mol; in some embodiments, from approximately 15,000 g / mol to approximately 150,000 grams per mol and, in other embodiments, from approximately 20,000 g / mol to approximately 100,000 grams per mol, with a polydispersity index that generally ranges from 2, 5 to 7. The polyepoxide modifier may contain less than 50, in some embodiments, from 5 to 45 and, in other embodiments, from 15 to 40 epoxy groups. On the other hand, the epoxy equivalent weight may be less than approximately 15,000 grams per mol, in some embodiments from approximately 200 g / mol to approximately 10,000 grams per mol and in other embodiments from approximately 500 g / mol to approximately 7,000 grams per mol.
[058] The polyepoxide can be a linear or branched homopolymer or copolymer (for example, random, graft, block etc.) containing terminal epoxy groups, skeletal oxirane units and / or pendant epoxy groups. The monomers used to form these polyepoxides can vary. In a specific embodiment, for example, the polyepoxide modifier contains at least one epoxy-functional monomeric (meta) acrylic component. As used here, the term “(meta) acrylic” includes acrylic and methacrylic monomers, as well as salts or esters thereof, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meta) acrylic monomers can include, but are not limited to, those containing 1,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate and glycidyl itoconate.
[059] Poliepoxide normally has a relatively high molecular mass, as indicated above, so it can not only result in the extension of the renewable polyester chain, but also help to achieve the desired blend morphology. In this way, the resulting flow rate of the polymer can also vary from approximately 10 to approximately 200 grams for 10 minutes; in some embodiments; approximately 40 to approximately 150 grams for 10 minutes and; in other embodiments; from approximately 60 to approximately 120 grams for 10 minutes, determined at a load of 2160 grams and at a temperature of 190 ° C.
[060] If desired, other monomers can also be used in the polyepoxide to help achieve the desired molecular mass. Such monomers can vary and include, for example, ester monomers, (meta) acrylic monomers, olefin monomers, amide monomers, etc. In a given embodiment, for example, the polyepoxide modifier includes at least one linear or branched α-olefin monomer, such as those with 2 to 20 carbon atoms and, preferably, with 2 to 8 carbon atoms. Specific examples are ethylene, propylene, 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1- heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. The α-olefin comonomers specifically desired are ethylene and propylene.
[061] Another suitable monomer may include an (meta) acrylic monomer that is not epoxy-functional. Examples of such (meta) acrylic monomers can be methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-acrylate - butyl, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, acrylate methylcyclohexyl, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, methacrylate, methacrylate, methacrylate of n-amyl, n-hexyl methacrylate, i-amyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, methacrylate methacrylate cyclohexyl methacrylate , cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, methacrylate isobornyl, etc., as well as combinations of these.
[062] In a particularly desirable embodiment of the present invention, the polyepoxide modifier is a terpolymer formed from an epoxy-functional acrylic monomeric (meta) component, an α-olefin monomeric component and a monomeric (meta) component non-epoxy-functional acrylic. For example, the polyepoxide modifier can be poly (ethylene-co-methyl acrylate-co-glycidyl methacrylate), with the following structure:
where x, y and z are 1 or greater.
[063] The epoxy-functional monomer can be formed into a polymer, using several known techniques. For example, a monomer containing polar functional groups can be grafted onto the structure of a polymer in order to form a grafted copolymer. These grafting techniques are well known in the art and are described, for example, in U.S. Patent No. 5,179,164, which is incorporated herein in its entirety as a reference for all purposes. In other embodiments, a monomer containing epoxy-functional groups can be copolymerized with a monomer in order to form a random block or copolymer, using known free radical polymerization techniques, such as high pressure reactions, catalytic reaction systems Ziegler-Natta, single site catalytic reaction systems (eg metallocene) etc.
[064] The relative part of the monomeric components can be selected in order to achieve a balance between epoxy reactivity and fluidity index. More specifically, high levels of epoxy monomer can result in a good reactivity with the renewable polyester, but a very high content can reduce the flow rate in such a way that the polyepoxide modifier negatively affects the melt resistance of the polymer mixture. Thus, in most embodiments, the epoxy-functional acrylic (meth) monomer (s) are formed by approximately 1% w to approximately 25% w; in some embodiments, from approximately 2% w to approximately 20% w and, in other embodiments, from approximately 4% w to approximately 15% w of the copolymer. The α-olefin monomer (s) can also be formed by approximately 55% pa approximately 95% w, in some embodiments of 60% pa approximately 90% w and in other embodiments 65% pa 85 Approximately% p of the copolymer. When used, other monomeric components (for example, non-epoxy-functional acrylic (meta) monomers) can be formed by approximately 5% pa to approximately 35% p, in some embodiments of approximately 8% p to approximately 30% p in other forms of carrying out approximately 10% w to approximately 25% w of the copolymer. A specific example of a suitable polyepoxide modifier that can be used in this invention is marketed by Arkema under the name LOTADER® AX8950 or AX8900. LOTADER® AX8950, for example, has a flow rate of 70 to 100 g / 10 min and a glycidyl methacrylate monomer content of 7% to 11% w, a methyl acrylate monomer content of 13% to 17% eg an ethylene monomer content of 72% to 80% w.
[065] In addition to controlling the type and relative content of the monomers used to form the polyepoxide modifier, the overall weight percentage can also be controlled in order to achieve the desired benefits. For example, if the level of modification is very low, the desired increase in melt strength and mechanical properties may not be achieved. The present inventors have also found, however, that if the level of modification is very high, the formation of the fiber may be restricted due to strong molecular interactions (for example, crosslinking) and physical network formation by epoxy-functional groups. Thus, the polyepoxide modifier is normally employed in an amount of approximately 0.05% to approximately 10% w, in some embodiments of approximately 0.1% to approximately 8% w, in other embodiments of approximately 0.5 % pa approximately 5% p in other embodiments of approximately 1% pa approximately 3% w, based on the mass of polylactic acids employed in the compound. The polyepoxide modifier can also be formed by approximately 0.05% pa to approximately 10% w, in some embodiments of approximately 0.05% pa to approximately 8% w, in other embodiments of approximately 0.1% to approximately 5 % w and in other embodiments of approximately 0.5% w to approximately 3% w, based on the total mass of the compound.
[066] In addition to polyepoxides, other reactive compatibilizers can also be employed in the present invention, such as polymers functionalized with oxazoline, polymers functionalized with cyanide etc. When used, these reactive compatibilizers can be used within the concentrations indicated above for the polyepoxide modifier. In a specific embodiment, an oxazoline-grafted polyolefin can be employed, that is, a polyolefin grafted with a monomer contained in an oxazoline ring. Oxazoline can include 2-oxazolines, such as 2-vinyl-2-oxazoline (for example, 2-isopropenyl-2-oxazoline), 2-fatty acid-alkyl-2-oxazoline (for example, obtained from oleic acid ethanolamine, linoleic acid, palmitoleic acid, gadoleic acid, erucic acid and / or arachidonic acid) and combinations thereof. In another embodiment, oxazoline can be selected from ricinoloxazoline maleinate, undecyl-2-oxazoline, soya-2-oxazoline, ricinus-2-oxazoline and combinations thereof, for example. In another embodiment, oxazoline is selected from 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline and combinations thereof.
[067] E. Other components
[068] An advantageous aspect of the present invention is that good mechanical properties can be provided without the need for various conventional additives, such as blowing agents (for example, chlorofluorocarbons, hydrochlorofluorocarbons, hydrocarbons, carbon dioxide, etc.) and plasticizers ( for example, solid or semi-solid polyethylene glycol). In fact, the thermoplastic compound can be substantially free of these blowing and / or plasticizing agents. For example, blowing agents and / or plasticizers may be present in an amount of no more than approximately 1% w, in some embodiments, not more than approximately 0.5% w, in some embodiments, from 0.001% w to approximately 0.2% w thermoplastic compound. In addition, due to its tension-bleaching properties, as described in more detail below, the resulting composition can achieve an opaque color (e.g., white), without the need for conventional pigments, such as titanium dioxide. In certain embodiments, for example, pigments may be present in an amount of no more than approximately 1% w, in some embodiments not more than approximately 0.5% w, in other embodiments, approximately 0.001 % pa approximately 0.2% w of the thermoplastic compound. Obviously, a wide variety of ingredients can be used in the compound for several different reasons. For example, materials that can be used include, without limitation, catalysts, antioxidants, stabilizers, surfactants, waxes, solid solvents, fillers, nucleating agents (eg calcium carbonate, etc.), particulates and other materials added to in order to improve the processing capacity of the thermoplastic compound.
[069] II. Mixture
[070] The components of the thermoplastic compound can be mixed together, using any of a variety of known techniques. In one embodiment, for example, the components can be supplied separately or as a combination. For example, the components can first be dried and mixed together to form an essentially dry and homogeneous mixture, and can likewise be supplied simultaneously or sequentially to a melt processing device, which disperses the materials dispersively. Batch and / or continuous fusion processing techniques can be employed. For example, a mixer / kneader, Banbury mixer, Farrel continuous mixer, single screw extruders, double screw extruders, laminators, etc., to mix and process materials by melting. Especially suitable melt-processing devices may be a co-rotating twin screw extruder (for example, the ZSK-30 extruder marketed by Werner & Pfleiderer Corporation of Ramsey, New Jersey or a Thermo Prism ™ USALAB 16 extruder, marketed by Thermo Electron Corp ., Stone, England). These extruders can include supply and ventilation ports and provide a high intensity distributive and dispersive mix. For example, components can be introduced into the same feed ports as the twin screw extruder, or into other ports, and mixed by melting to form a very homogeneous melt. If desired, other additives can also be injected into the molten polymer and / or introduced separately into the extruder at a different point along its length.
[071] Regardless of the specific processing technique chosen, the resulting melted blended material typically contains curing additive domains with an axial dimension of one domain (e.g., length) of approximately 0.05 μm to approximately 30 μm, in some forms from approximately 0.1 μm to approximately 25 μm, in other embodiments from approximately 0.5 μm to approximately 20 μm, and in some embodiments from approximately 1 μm to approximately 10 μm. When used, the polyepoxide modifier may also be in the form of discrete domains distributed over a continuous polyester matrix. These "secondary" domains can have several different shapes, for example, elliptical, spherical, cylindrical, etc. However, regardless of shape, the size of an individual secondary domain, after mixing, is small to provide a larger surface area for the reaction with the renewable polyester. For example, the size of a secondary domain (for example, length) typically ranges from approximately 10 nm to approximately 1000 nanometers; in some embodiments, from approximately 20 nm to approximately 800 nanometers; in some embodiments, from approximately 40 nm to approximately 600 nanometers, and in other embodiments, from approximately 50 nm to approximately 400 nanometers. As indicated above, the curing additive also forms discrete domains within the polyester matrix, which are considered to be among the “primary” domains of the compound. It must also be understood that the domains can be formed by a combination of polyepoxide, curing additive and / or other components of the mixture.
[072] The degree of shear / pressure and heat can be controlled to ensure sufficient dispersion, but not so high as to adversely reduce the size of the discrete domains, making them unable to achieve the desired firmness and elongation. For example, mixing normally occurs at a temperature of approximately 180 ° C to approximately 260 ° C; in some embodiments, from approximately 185 ° C to approximately 250 ° C, and in other embodiments, from approximately 190 ° C to approximately 240 ° C. Likewise, the apparent shear rate during the melting process can vary from approximately 10 s-1 to approximately 3,000 seconds-1, in some embodiments, from approximately 50 s-1 to approximately 2,000 seconds-1 and, in other embodiments, from approximately 100 s-1 to approximately 1,200 seconds-1. The apparent shear rate is equal to 4Q / πR3, where Q is the volumetric flow rate (“m3 / s”) of the polymer melt and R is the radius (“m”) of the capillary (for example, extrusion) through which the molten polymer flows. Obviously, other variables, such as the residence time during the melting process, which is inversely proportional to the transfer rate, can also be controlled in order to achieve the desired degree of homogeneity.
[073] To achieve the desired shear conditions (eg rate, residence time, shear rate, melt processing temperature, etc.), the speed of the extruder rotations can be selected with a certain interval. Generally, an increase in the temperature of the product is observed with the increase in the rotation speed due to the additional input of mechanical energy in the system. For example, the speed of rotation can vary from approximately 50 rpm to approximately 300 revolutions per minute (“rpm”); in some embodiments, from approximately 70 rpm to approximately 500 rpm, and in other embodiments, from approximately 100 rpm to approximately 300 rpm. This can result in a temperature high enough to disperse the curing additive without adversely affecting the size of the resulting domains. The melt shear rate and, in turn, the degree to which the polymers are dispersed, can also be increased during the use of one or more distributive and / or dispersive mixing elements within the mixing section of the extruder. Among the single screw distributive mixers are, for example, Saxon, Dulmage, Cavity Transfer, etc. Likewise, suitable dispersive mixers can include bubble ring mixers, Leroy / Maddock, CRD, etc. As is known in the art, mixing can be further enhanced by using pins in the cylinder that create a bend by reorienting the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers and Vortex Intermeshing Pin (VIP) mixers.
[074] III. Fiber formation
[075] The fibers formed from the mixed thermoplastic compound can generally have any desired configuration, including single-component and multi-component (for example, a coating-core, wing-side, pizza, island, and so on) configuration. In some embodiments, the fibers may contain one or more additional polymers as a component (e.g., bicomposite) or constituent (e.g., biconstituent) to further increase strength and other mechanical properties. For example, the thermoplastic compound can form a coating component of a bicomponent coating / core fiber, while an additional polymer can form the core component, or vice versa. The additional polymer can be a thermoplastic polymer that is not generally considered to be renewable, such as polyolefins, e.g. eg, polyethylene, polypropylene, polybutylene, etc .; polytetrafluoroethylene; polyvinyl acetate; polyvinyl acetate chloride; polyvinyl butyral; acrylic resins, p. eg, polyacrylate, polymethylacrylate, polymethylmethacrylate, and so on; polyamides, e.g. , nylon; polyvinyl chloride; polyvinylidene chloride; polystyrene; polyvinyl alcohol; and polyurethanes. Most desirably, however, the additional polymer is renewable.
[076] Any of a number of processes can be used to form fibers according to the present invention. For example, the thermoplastic compound described above can be extruded through a die and cooled. In Fig. 1, for example, an embodiment of a method for forming fibers is shown in more detail. In this specific embodiment, the thermoplastic compound of the present invention can be inserted into an extruder 12 from a feed funnel 14. The mixture can be transferred to the feed funnel 14 by any conventional technique. Regardless, the mixture is generally intended to have a low moisture content to minimize hydrolytic degradation of renewable polyester, such as approximately 300 parts per million ("ppm") or less, in some embodiments, approximately 200 ppm or less, in some embodiments, from approximately 1 ppm to approximately 100 ppm. Such moisture contents can be achieved by drying, for example, at a temperature of approximately 50 ° C to approximately 100 ° C and, in some embodiments, from approximately 70 ° C to approximately 80 ° C.
[077] Extruder 12 is heated to a temperature sufficient to extrude the molten polymer. The extruded compound is then passed through a polymer 16 conduit through a die 18. For example, die 18 may contain a housing, containing a rotating assembly with several plates stacked on top of each other, with patterns of openings arranged in order to create flow paths to direct the polymer components. The die 18 may also have openings arranged in one or more rows. The openings form a downward facing filament extruder when the polymers are extruded through it. Process 10 also employs a cooling blower 20 in a position adjacent to the fiber curtain, extending from the die 18. The air originating in the cooling air blower 20 cools the fibers extending from the die 18. The air from cooling can be directed from one side of the fiber curtain, as shown in Fig. 1 or on both sides of the curtain.
[078] To form a fiber of the desired length, the cooled fibers are usually stretched and fused, as shown when using the fiber tensioning unit 22, in Fig. 1. The fiber tensioning units or vacuum cleaners, for use in melt spinning polymers are well known in the art. Fiber tensioning units suitable for use in the process of the present invention include a linear fiber vacuum cleaner of the type shown in U.S. Patent Nos. 3,802,817 and 3,423,255. Generally the fiber tensioning unit 22 contains a vertical elongation passage, whereby the fibers are pulled by the suction air that enters the sides of the passage and forcing the flow downwards through the passage. A heater or blower 24 supplies suction air to the fiber tensioning unit 22. The suction air pulls the fibers and the ambient air through the fiber tensioning unit 22. The gas flow causes the fibers to be stretched or attenuated, which increases the molecular orientation or crystallinity of the polymers that form the fibers. When using a fiber tensioning unit, the "tensile" rate can be selected to help achieve the desired fiber length. The "tensile" rate is the linear speed of the fibers after tensioning (for example, the linear speed of the godet 42 cylinder or a foraminous surface (not shown) divided by the linear speed of the fibers after extrusion). For example, the pull rate during the melt stretch can be calculated as follows: Pull rate = A / B where,
[079] A is the linear speed of the fiber after the melt stretch (that is, the speed of the godet) and is measured directly; and
[080] B is the linear speed of the extruded fiber and can be calculated as follows: Linear speed of the extruded fiber = C / (25 * π * D * E2) where,
[081] C is the speed of exit through a single orifice (grams per minute);
[082] D is the melted density of the polymer (grams per cubic centimeter); and
[083] And it is the diameter of the hole (in centimeters) through which the fiber is extruded. In some embodiments, the pull ratio can vary from approximately 20: 1 to approximately 4,000: 1, in some embodiments, from approximately 25: 1 to approximately 2,000: 1, in some embodiments, from approximately 50: 1 to approximately 1,000: 1 and, in some embodiments, from approximately 75: 1 to approximately 800: 1.
[084] Once formed, the fibers can be deposited through the outlet opening of the fiber tensioning unit 22 and transferred to a godet cylinder 42. If necessary, the fibers collected in the godet cylinder 42 can optionally be subjected to additional in-line processing and / or conversion steps (not shown), as will be understood by experts in the field. For example, fibers can be collected and then corrugated, textured and / or cut to an average fiber length in the range of approximately 3 mm to 80 mm, in some embodiments of approximately 4 mm to approximately 65 mm, and in some embodiments, from approximately 5 mm to approximately 50 mm. The cut fibers can then be incorporated into a non-woven blanket, as is known in the art, such as blankets by carding, blankets connected by airflow, etc. The fibers can also be deposited on a foraminous surface to form a non-woven blanket.
[085] Regardless of the specific way in which fibers are formed, the resulting fibers are thus stretched at a temperature below the glass transition temperature of the polyester ("cold drawn") to form the network of voids. Cold drawing can occur in the longitudinal direction (for example, machine direction), transverse direction (for example, machine cross direction), or a combination of them. The degree of stretching is generally selected in the present invention to ensure that the desired network of voids is achieved, but not in such a way that the mechanical properties of the resulting fibers are adversely impacted. In this regard, the fibers are normally stretched (for example, in the machine direction) to a "stretch ratio" of approximately 1.1 to approximately 3.5, in some embodiments of approximately 1.2 to approximately 3, 0 and, in other embodiments, from approximately 1.5 to approximately 2.5. The “stretch ratio” can be determined by dividing the length of the stretched fiber by its length before stretching. The stretch ratio can also vary to help achieve the desired properties, for example, the variation of approximately 5% to approximately 1,500% per minute of deformation, in some embodiments from approximately 10% to approximately 1,000% per minute of deformation. deformation and, in other embodiments, from approximately 100% to approximately 850% per minute of deformation. The fibers are generally kept at a temperature below the glass transition temperature of the renewable polyester during stretching. Among other things, this helps to ensure that the polyester chains are not altered in such a way that the web of voids becomes unstable. Typically, the fibers are stretched at a temperature of at least approximately 10 ° C, in some embodiments of at least approximately 20 ° C, and in other embodiments of at least approximately 30 ° C below of the glass transition temperature. For example, the fibers can be stretched at a temperature of at least approximately 0 ° C to approximately 50 ° C, in some embodiments of approximately 15 ° C to approximately 40 ° C, in other embodiments, of approximately 20 ° C to 30 ° C. If necessary, the fibers can be stretched without the application of external heat.
[086] The stretching of the fibers can occur in one or several stages. In one embodiment, for example, the stretch is completed in-line, without having to remove it for separate processing. In other cases, however, the fibers can be stretched to a certain extent in line, and then removed from the fiber forming machinery and subjected to an additional stretching step. Regardless, various stretching techniques can be employed, such as suction (for example, fiber tensioning units), tension frame stretching, biaxial stretching, multiaxial stretching, profile stretching, vacuum stretching, etc.
[087] Cold drawing in the manner described above generally results in the formation of empty spaces that have an axial dimension in the direction of the stretching (for example, longitudinal or in the machine direction) relatively small. For example, in one embodiment, the axial dimension of the voids may be approximately 5 micrometers or less, in some embodiments approximately 2 micrometers or less and, in other embodiments, approximately 25 nanometers to approximately 1 micrometer . In certain cases, the voids can be “micro-empty”, in the sense that at least one dimension of these voids is approximately 1 micrometer or more in size. For example, these microvazios may have a dimension in a direction orthogonal to the axial dimension (i.e., machine's cross-sectional direction) of approximately 1 micrometer or more, in some embodiments of approximately 1.5 micrometer or more and in other forms from approximately 2 micrometers to approximately 5 micrometers. This can result in an aspect ratio of the micro voids (the ratio of the axial dimension to the orthogonal dimension to the axial dimension) of approximately 0.1 to approximately 1, in some embodiments of approximately 0.2 to approximately 0.9 and , in other embodiments, from approximately 0.3 to approximately 0.8. Likewise, “nanovazios” can also be present, alone or in conjunction with microvazios. Each dimension of the nanovazios is generally less than approximately 1 micrometer and, in some embodiments, from approximately 25 nm to approximately 500 nanometers.
[088] In addition to forming a void network as described above, stretching can also significantly increase the axial dimension of the primary domains, so that they have a generally elongated and linear shape. For example, elongated domains may have an axial dimension of approximately 10% or more, in some embodiments from approximately 20% to approximately 500% and, in some embodiments, from approximately 50% to approximately 250% greater than the axial dimension of the domains before stretching. The axial dimension after stretching can, for example, vary from approximately 1 μm to approximately 400 μm, in some embodiments from approximately 5 μm to approximately 200 μm and, in some embodiments, from approximately 10 μm to approximately 150 μm. The domains can be relatively thin and thus have a small dimension in a direction orthogonal to the axial dimension (that is, transversal dimension). For example, the cross-sectional dimension can be from approximately 0.02 μm to approximately 75 micrometers, in some embodiments from approximately 0.1 μm to approximately 40 micrometers and, in other embodiments, from approximately 0.4 μm to approximately 20 micrometers. This can result in an aspect ratio of the domains (the ratio of the axial dimension to the orthogonal dimension to the axial dimension) of approximately 2 to approximately 150, in some embodiments of approximately 3 to approximately 100, and in other embodiments , from approximately 4 to approximately 50.
[089] As a result of the domain structure with empty and elongated spaces obtained from cold drawing, the present inventors also found that the resulting composition can expand evenly in volume when drawn in the longitudinal direction, which translates to a low "Poisson's ratio", as determined according to the following equation: Poisson's ratio = - Transverse E / E longitudinal where Etransversal is the transversal deformation of the material and Elongitudinal is the longitudinal deformation of the material. More specifically, the Poisson's ratio of the material can be approximately 0 or even negative. For example, the Poisson's ratio can be approximately 0.1 or less, in some embodiments of approximately 0.08 or less and in other embodiments of approximately -0.1 to approximately 0.04. When the Poisson's ratio is zero, there is no contraction in the transverse direction when the material is expanded in the longitudinal direction. When the Poisson's ratio is negative, the transverse or lateral dimensions of the material also expand when the material is stretched in the longitudinal direction. In this way, materials with a negative Poisson's ratio can exhibit an increase in width when stretched in the longitudinal direction, which can result in increased energy absorption in the transverse direction.
[090] Cold stretching can also create one or more neck regions located along the longitudinal axis of the fiber, which are spaced between neckless regions. These neck-forming regions may contain fewer voids than regions without a neck, which allows the fiber to maintain a high degree of strength, even if the overall low density is low and the void volume is high. Neck-forming fibers can also have a non-uniform cross-sectional diameter along their longitudinal axis, which can provide a variety of different benefits, such as a greater surface area, etc. The number of neck-forming regions can generally vary and be controlled based on the selected stretch ratio. However, generally the number of neck-forming regions can vary from approximately 1 to approximately 400 necks per centimeter, in some embodiments from approximately 2 to approximately 200 necks per centimeter, and in some embodiments, from approximately 5 to approximately 50 necks per centimeter. The number of necked regions can be determined from the following equation: N = (1 - L2) / (L1 + L2) where N is the number of necked regions, L1 is the average length of a neck-shaped region and L2 is the average length of a region without a neck (includes transition from the neck region to the neckless region). In Fig. 2, for example, an example of a fiber 200 is shown that contains neck-shaped regions 202 spaced between regions without neck-formation 204, where the length of neck-shaped regions 202 is shown as the length " L1 "and the length of the regions without neck formation 204 is shown as the length" L2 ".
[091] Even at the very low densities achieved by the present invention, the resulting fibers are not as fragile as the pure polymer and, therefore, can deform when stretched instead of breaking. The fibers can therefore continue to function as load-bearing members, even after the fiber has shown considerable elongation. In this respect, the fibers of the present invention may have better "peak elongation" properties, that is, the percentage of elongation of the fiber at its maximum load. For example, the fibers of the present invention may exhibit a peak elongation of approximately 50% or more; in some embodiments of approximately 100% or more; in other embodiments of approximately 200% to approximately 1,500%; and in some embodiments, from approximately 400% to approximately 800%, as determined according to the ASTM D638-10 standard at 23 ° C. These stretches can be achieved for fibers that have a wide range of average diameters, ranging from approximately 0.1 μm to approximately 50 micrometers, in some embodiments of approximately 1 μm to approximately 40 micrometers, in some embodiments of approximately 2 μm to approximately 25 micrometers, and in other embodiments, from approximately 5 μm to approximately 15 micrometers.
[092] While having the ability to stretch under tension, the fibers of the present invention can also remain relatively strong. For example, fibers can exhibit a peak tensile stress of approximately 25 MPa to approximately 200 Megapascals ("MPa"); in some embodiments, from approximately 50 MPa to approximately 150 MPa; and in other embodiments, from approximately 60 MPa to approximately 150 MPa, as determined according to ASTM D638-10 at 23 ° C. Another parameter that is indicative of the relative strength of the fibers of the present invention is "toughness", which indicates the tensile strength of a fiber expressed as the strength per unit of linear density. For example, the fibers of the present invention can have a toughness of approximately 0.75 to approximately 6.0 grams of strength ("gf") per denier; in some embodiments, from approximately 1.0 to approximately 4.5 gf per denier; and in other embodiments, from approximately 1.5 to approximately 4.0 gf per denier. The denier of the fibers may vary depending on the desired application. Typically, fibers are formed to have a denier per filament (ie, the unit of linear density equal to the mass in grams per 9,000 meters of fiber) less than approximately 6; in some embodiments, less than approximately 3; and, in other embodiments, from approximately 0.5 to approximately 3.
[093] If desired, the fibers of the present invention can be subjected to one or more additional production steps before and / or after cold drawing. Examples of such processes include, for example, notch roller drawing, embossing, coating, etc. The fibers can also be surface treated using any of a variety of known techniques to improve their properties. For example, high-energy beams (for example, plasma, x-rays, electron beams, etc.) can be used to remove or reduce any surface layer that forms on the fibers, to change polarity, porosity, topography of the surface, etc. If desired, this surface treatment can be used alternatively before and / or after cold stretching the fibers.
[094] The fibers can also be incorporated into a fabric, such as textile fabric, knitted fabric, non-woven blanket, etc. For example, the fibers can also be formed in a non-woven mat structure, depositing the fibers randomly on a forming surface (optionally with the aid of a vacuum) and making the resulting mat adhere using any technique. known. The non-woven web can be formed before or after the fibers are stretched. In certain embodiments, for example, it may be desired to form a non-woven mat from a plurality of fibers, and thereafter stretch the fibers by stretching the non-woven mat to the desired extent to form the web of voids . In an alternative embodiment, a continuously forming surface can simply be positioned below a fiber suction unit that stretches the fibers to the desired extent, before forming the mat.
[095] Once formed, the non-woven blanket can then be joined using any conventional technique, such as with an adhesive or autogenously (for example, fusion and / or self-adhesion of the fibers without the application of external adhesives). Autogenic adhesion, for example, can be obtained through contact with the fibers while they are semi-melted or sticky, or by simply mixing resin and / or solvent adherent with polymers used in the formation of the fibers. Autogenic adhesion techniques can include ultrasonic welding, thermal bonding, airflow adhesion, calender welding, and so on. For example, the mat can be glued or modeled with a pattern by means of a thermomechanical process, in which the mat is passed between a pressure roller and a heated roller with designs. The patterned roll can have any embossed pattern, which will create the properties or appearance of the blanket. It is preferable that the patterned roller determines an embossed pattern that establishes several adhesion sites, which, in turn, define an adhesion area between approximately 2% and approximately 30% of the total area of the roller. Some examples of adherence patterns include, for example, those described in U.S. Patent No. 3,855,046 to Hansen et al., U.S. Patent No. 5,620,779 to Levy et al., U.S. Patent No. 5,962,112 to Haynes et al., US patent No. 6,093,665 to Sayovitz et al., As well as US design patents No. 428,267 to Romano et al .; 390,708 from Brown; 418,305 by Zander et al .; 384,508 by Zander et al .; 384,819 to Zander et al .; 358,035 by Zander et al .; and 315,990 by Blenke, et al. The pressure between the rollers can be approximately 5 to approximately 2,000 pounds per linear inch. The pressure between the rollers and the temperature of the rollers is balanced to obtain the desired properties or appearance of the blanket, while maintaining the fabric properties. As is known to experts in the field, the required temperature and pressure can vary, depending on several factors, including, among others, the area of adhesion of the pattern, the properties of the polymer, the properties of the fiber and the properties of the nonwoven. .
[096] In addition to heat-sealed blankets, several other non-woven blankets can also be formed from the thermoplastic composition, in accordance with the present invention, such as meltblown blankets, blankets by carding and consolidation by pressure and heat, blankets arranged in a wet way , airflow blankets, co-formed blanket, hydraulic matted blankets, etc. For example, the thermoplastic compound can be extruded by means of several fine molding capillaries in a converging flow of high-speed gas (for example, air) that attenuate the fibers to reduce their diameters. Consequently, the meltblown fibers are transported by the high-speed gas stream and deposited on a collecting surface to form a blanket of randomly scattered meltblown fibers. Optionally, the polymer can be transformed into a blanket by carding, placing bales of fibers formed from the thermoplastic compound in a collector, which separates the fibers. Then, the fibers are sent by means of a combing or carding unit, which separates and aligns the fibers in the machine direction, to form a fibrous nonwoven web arranged in the machine direction. Once formed, the non-woven mat is usually stabilized by means of one or more adhesion techniques.
[097] If desired, the nonwoven web can also be a compound that contains a combination of the fibers of the thermoplastic compound and other types of fibers (for example, cut fibers, filaments, etc.). For example, additional thermoplastic synthetic fibers can be used, such as those formed from polyolefins, for example, polyethylene, polypropylene, polybutylene, etc .; polytetrafluoroethylene; polyesters, for example, polyethylene terephthalate and so on; 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; polyurethanes; polylactic acid; etc. If desired, renewable polymers can also be used. Some examples of known synthetic fibers include two-component coating and core fibers, marketed by KoSa Inc. of Charlotte, North Carolina, under the designations T-255 and T-256, both using polyolefin coating, or T-254, which features low melting copolyester coating. Still other known two-component fibers that can be used include those marketed by Chisso Corporation of Moriyama, Japan, or Fibervisions LLC of Wilmington, Delaware. Polylactic acid cut fibers can also be used, such as those marketed by Far Eastern Textile, Ltd. in Taiwan.
[098] The compound may also contain cellulose fibers, such as celluloses with a longer average fiber length, celluloses with a shorter average fiber length, or combinations of these. An example of pulp fiber with lanugo with a longer average length is hardwood kraft cellulose fibers. Hardwood kraft cellulose fibers are derived from coniferous trees and include cellulose fibers such as, among others, species from the north, west and south, including redwood, red cedar, hemlock, Douglas fir, true fir, pine ( for example, southern pine), pea (for example, pea mariana) bamboo, combinations of these, and so on. Hardwood kraft cellulose fibers can be used in the present invention. An example of southern hardwood kraft cellulose fibers, suitable for the present invention, are those sold by the Weyerhaeuser Company, which has offices in Federal Way, Washington, under the trade name "NF-405". Another cellulose suitable for use in the present invention is a bleached sulphated wood cellulose, containing mainly hardwood fibers, marketed by Bowater Corp., which has offices in Greenville, South Carolina, under the trade name of CoosAbsorb S cellulose. low medium length can also be used in the present invention. An example of low medium-length cellulose fibers is kraft cellulose fibers from conifers. Coniferous kraft cellulose fibers are derived from deciduous trees and include cellulose fibers such as, among others, eucalyptus, acer, birch, aspen, etc. Eucalyptus kraft cellulose fibers may be particularly desirable to increase softness, luster, opacity and to change the pore structure of the sheet to increase its absorption capacity. Bamboo or cotton fibers can also be used.
[099] Non-woven compounds can be formed using several known techniques. For example, the nonwoven compound can be a "co-formed material" that contains a stabilized mixture or matrix of thermoplastic compound fibers and an absorbent material. For example, it is possible to manufacture co-formed materials by means of a process in which at least one meltblown mold head is disposed close to a chute, through which absorbent materials are added to the mat during its formation. Such absorbent materials may include, but are not limited to, cellulose fibers, superabsorbent particles, organic and / or inorganic absorbent materials, cut staple polymer fibers, and so on. The relative percentages of the absorbent material can vary over a wide range, depending on the desired characteristics of the nonwoven compound. For example, the nonwoven compound can contain approximately 1 wt% to approximately 60 wt%; in some embodiments, from 5% w to approximately 50% w; and in other embodiments, from approximately 10 wt% to approximately 40 wt% thermoplastic compound fibers. The compound can likewise contain from approximately 40 wt% to approximately 99 wt%; in some embodiments, from 50% w to approximately 95% w; and in other embodiments, from approximately 60 wt% to approximately 90 wt% absorbent material. Some examples of these co-formed materials are disclosed in U.S. Patents No. 4,100,324 to Anderson et al .; 5,284,703 to Everhart et al .; and 5,350,624 by Georger, et al.
[100] Non-woven laminates can also be formed in the present invention, in which one or more layers are formed from the thermoplastic compound. For example, the nonwoven web of one layer can be a heat seal containing a thermoplastic compound, while the nonwoven web of another layer contains thermoplastic compound, other renewable polymers and / or any other type of polymer (such as polyolefins). In one embodiment, the non-woven laminate contains a meltblown layer disposed between two heat-sealed layers, to form a heat-sealed / meltblown / heat-sealed laminate (“SMS”). If desired, heat-sealed layers can be formed from the thermoplastic compound. The meltblown layer can be formed from the thermoplastic compound, other renewable polymers and / or any other polymers (such as polyolefins). There are several techniques for forming SMS laminates described in U.S. Patent No. 4,041,203 to Brock et al .; 5,213,881 by Timmons et al .; 5,464,688 by Timmons et al .; 4,374,888 to Bornslaeger; 5,169,706 by Collier et al .; and 4,766,029 by Brock et al., as well as in US patent application publications No. 2004/0002273 by Fitting et al. Of course, the non-woven laminate may have other configurations and have other numbers of meltblown and heat-welded layers, as desired, such as heat-welded / meltblown / meltblown / heat-welded (“SMMS”) and heat-welded / meltblown (“SM”) laminates, etc. Although the weight of the non-woven laminate can be obtained tailored to the desired application, it usually ranges from approximately 10 g / m2 to approximately 300 grams per square meter (g / m2); in some embodiments, from approximately 25 g / m2 to approximately 200 g / m2; and in some embodiments, from approximately 40 g / m2 to approximately 150 g / m2.
[101] If desired, fibers, nonwoven blanket, etc. they can also be annealed to help ensure the desired shape is maintained. Annealing normally occurs at temperatures above the glass transition temperature of the renewable polyester, such as temperatures of approximately 65 ° C to approximately 120 ° C; in some embodiments from approximately 70 ° C to approximately 110 ° C; and in other embodiments, from approximately 80 ° C to approximately 100 ° C. The fibers can also be surface treated using any of several known techniques in order to improve their properties. For example, high energy beams (for example, plasma, x-rays, electron beams, etc.) can be used to remove or reduce any surface layer that forms on the fibers, to change the polarity of the surface, to weaken a layer superficial etc. If desired, this surface treatment can be used before and / or after cold stretching the fibers.
[102] IV. Article (s)
[103] The fibers and / or a blanket formed from them can be used in a wide variety of applications. For example, fibers can be incorporated into "medical articles", such as clothing, absorbent surgical drapes, face masks, head guards, surgical guards, foot guards, sterilization wraps, heating blankets, heating pads, among others. Of course, the fibers can also be used in several other products. For example, fibers can be incorporated into an "absorbent article" capable of absorbing water or other fluids. Examples of some absorbent articles, among others: absorbent articles for personal care, such as diapers, training pants, absorbent panties, incontinence products, feminine hygiene products (for example, sanitary napkins etc.), bathing suits, baby wipes , and so on; medical absorbent articles, such as clothing, fenestration materials, bed linings, dressings, absorbent surgical drapes and medical wipes; paper towels for heavy cleaning in kitchens, articles of clothing, and so on. Suitable materials and processes for forming such products are well known to those skilled in the art. Absorbent articles, for example, usually include a highly liquid-impermeable layer (for example, outer covering), a liquid-permeable layer (for example, body-contact coating, expandable layer, etc.) and an absorbent core. In one embodiment, for example, a nonwoven blanket formed with the fibers of the present invention can be used to form an outer cover of an absorbent article. If desired, the non-woven blanket can be laminated to form a liquid-impermeable, permeable or vapor-impermeable film.
[104] The present invention can be better understood by referring to the following examples. Testing methods
[105] Flow rate:
[106] The fluidity index (“MFR”) is the weight of a polymer (in grams) forced through the hole of an extrusion rheometer (0.0825 inch diameter) when subjected to a load of 2160 grams for 10 minutes, usually at 190 ° C or 230 ° C. Unless otherwise indicated, the flow rate is measured according to the test method ASTM D1239, with an extrusion plastomer from Tinius Olsen.
[107] Thermal properties:
[108] The glass transition temperature (Tg) can be determined by dynamic mechanical analysis (DMA) in accordance with ASTM E1640-09. TA Instrument A Q800 can be used. Experimental runs can be performed on the stress / stress geometry, in a temperature analysis mode in the range of -120 ° C to 150 ° C with a heating rate of 3 ° C / min. The frequency of the voltage amplitude can be kept constant (2 Hz) during the test. Three (3) independent samples can be tested to obtain an average glass transition temperature, which is defined by a peak value of the tan δ curve, where tan δ is defined as the ratio between the loss modulus and the modulus of modulus. storage (tan δ = E ”/ E ').
[109] The melting temperature can be determined using differential scanning calorimetry (DSC). The differential scanning calorimetry equipment can be a DSC Q100 differential scanning calorimeter, which can be prepared with a liquid nitrogen cooling accessory and UNIVERSAL ANALYSIS 2000 analysis software (version 4.6.6), both marketed by TA Instruments Inc. of New Castle, Delaware. To avoid direct handling of the samples, tweezers and other tools can be used. The samples can be placed on an aluminum plate and weighed with an accuracy of 0.01 milligrams on an analytical balance. A lid can be placed over the material sample on the plate. Usually, the beans can be placed directly on the weighing pan.
[110] The differential scanning calorimetry equipment can be calibrated using an Indian metal standard and a baseline correction can be made, as described in the equipment's operating manual. The material sample can be placed in the test chamber of the differential scanning calorimetry equipment to be tested, and an empty plate can be used as a reference. All tests can be performed by purging 55 cubic centimeters per minute of nitrogen (industrial grade) in the test chamber. For resin grain samples, the heating and cooling program is a two-cycle test, which started with equilibrating the chamber with -30 ° C, followed by a first heating period, at a rate of 10 ° C per minute until the temperature of 200 ° C, followed by an equilibrium of the sample at 200 ° C for three minutes, followed by a first cooling period of 10 ° C per minute, until a temperature of -30 ° C, followed by the equilibrium of the sample at -30 ° C for 3 minutes, and then a second heating period, at a rate of 10 ° C per minute to a temperature of 200 ° C. With fiber samples, the heating and cooling program can be a one-cycle test that starts with the chamber balance at -25 ° C, followed by a heating period at a rate of 10 ° C per minute up to a temperature of 200 ° C. ° C, followed by a sample equilibrium at 200 ° C for 3 minutes, and then a cooling period at the rate of 10 ° C per minute to a temperature of -30 ° C. All tests are performed by purging 55 cubic centimeters per minute of nitrogen (industrial grade) in the test chamber.
[111] The results can be evaluated using the UNIVERSAL ANALYSIS 2000 analysis software, which identifies and quantifies the glass transition temperature (Tg) of the inflection, the endothermic and exothermic peaks and the areas under the peaks in the DSC traces. The glass transition temperature can be identified as the region of the drawn line where there was a clear change in the curve, and the melting temperature can be determined by using an automatic inflection calculation.
[112] Traction properties:
[113] Tensile properties can be determined according to ASTM 638-10 at 23 ° C. For example, individual specimens of fiber may initially be reduced in length (for example, cut with scissors) by 38 mm and be arranged separately on a black velvet cloth. 10 to 15 specimens can be collected in this way. The fiber specimens can then be placed in a straight line on a rectangular paper structure, with external dimensions of 51 mm x 51 mm and internal dimensions of 25 mm x 25 mm. The ends of each fiber specimen can be attached to the structure, carefully attaching the ends of the fibers to the sides of the structure with adhesive tape. Each fiber specimen can then be measured, in the relatively shorter external dimension, using a conventional laboratory microscope, properly calibrated and adjusted with 40X magnification. The fiber dimension can be recorded as the diameter of the fiber specimen. The structure assists in the assembly of the ends of the fiber samples, in the upper and lower fixations of a tensile tester with constant extension rate, in order to avoid excessive damage in the fiber samples.
[114] A constant rate of the type of extension of the tensile tester and an appropriate load cell can be employed in the test. The load cell can be chosen (for example, 10N) so that the test value is between 10% and 90% of the total load scale. The tensile tester (ie, MTS SYNERGY 200) and the load cell can be obtained from MTS Systems Corporation, of Eden Prairie, Michigan. The specimens of fiber in the structure can then be placed between the claws of the tensile tester, such that the ends of the fibers are caught in the claws of the tensile tester. Then, the edges of the paper structure that extend parallel to the length of the fibers can be cut, so that the tensile tester applies the test force only to the fibers. The fibers can then be subjected to a tensile test, with a pull rate and claw speed of 12 inches per minute. The resulting data can be analyzed using the TESTWORKS 4 software, from MTS Corporation, with the following test parameters:

[115] The toughness values can be expressed in terms of strength per denier. Peak elongation (% of stress at break) and peak stress are also calculated.
[116] Expansion ratio, density and percentage void volume
[117] To determine the expansion rate, density and percentage void volume, the width (Wi) and thickness (Ti) of the specimen were initially measured before cold drawing. The length (Li) before stretching was also determined by measuring the distance between two marks on the specimen's surface. Consequently, the specimen was cold drawn to begin emptying. Specimen width (Wf), thickness (Tf) and length (Lf) were measured to the nearest 0.01 mm using a Digimatic Caliper caliper (Mitutoyo Corporation). The volume (Vi) before cold drawing was calculated by Wi x Ti x Li = Vi. The volume (Vf) after cold drawing was calculated by Wf x Tf x Lf = Vf. The expansion rate (Φ) was 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 of empty volume (% Vv) was calculated by:% Vv = (1 - 1 / Φ) x 100.
[118] Moisture content
[119] The moisture content can be determined using the Arizona Instruments Computrac Vapor Pro moisture analyzer (Model No. 3100) in accordance with ASTM D 7191-05, hereby incorporated in its entirety as a reference for all purposes. The test temperature (§X2.1.2) can be 130 ° C, the sample size (§X2.1.1) can be 2 g to 4 grams, and the emptying time of the bottle (§X2.1.4) can be 30 seconds. In addition, the closure criterion (§X2.1.3) can be defined as a “prediction” mode, which means that the test is terminated when the internally programmed criterion (which mathematically calculates the moisture content at the end point) is reached. EXAMPLE 1
[120] PLA 6201 D (NatureWorks®, flow rate 10 g / 10 minutes at 190 ° C) was centrifuged at 240 ° C at a yield of 0.40 grams per hole per minute, through a die of diameter 0 , 6 mm. The fibers were collected in free fall (gravity only as stretching force) and then tested for mechanical properties at a pull rate of 50 millimeters per minute. No volume expansion was observed in PLA fibers, since PLA fibers failed to deform at rupture of only 3.8%. EXAMPLE 2
[121] A mixture of 85.3% w of polylactic acid (PLA 6201D, Natureworks®), 9.5% w of a curing additive and 1.4% w of a polyepoxide modifier and 3.8% w of a interfacial modifier (PLURIOL® WI 285 from BASF) was spun in fibers. The curing additive was Vistamaxx ™ 2120 (ExxonMobil), which is a polyolefin copolymer / elastomer with a melt index of 29 g / 10 min (190 ° C, 2160 g) and a density of 0.866 g / cm3. The polyepoxy modifier was poly (ethylene-co-methyl acrylate-co-glycidyl methacrylate) (Lotader® AX8900, Arkema), with a melt index of 70 to 100 g / 10 min (190 ° C / 2160 g), a content glycidyl methacrylate of 7% per 11% w, a methyl acrylate content of 13% per 17% w, and an ethylene content of 72% per 80% w. The polymers were introduced in a double screw and coil extruder (ZSK-30, diameter 30 mm, length 1328 mm) for compounds manufactured by Werner and Pfleiderer Corporation, of Ramsey, New Jersey. The extruder had 14 zones, numbered consecutively from 1 to 14 starting from the feed funnel to the die. The first drum zone No. 1 received the resins via a gravimetric feeder, with a total yield of 15 pounds per hour with PLURIOL® WI285 added via an injection pump in drum zone No. 2. The matrix used to expel the resin had 3 die openings (6mm in diameter) separated by 4mm. After formation, the expelled resin was cooled on a conveyor belt cooled by a fan and transformed into grains by a Conair granulator. The screw speed of the extruder was 200 revolutions per minute ("rpm"). The grains were then fed by overflow in a single screw extruder at 240 ° C, melted and passed through a melting pump at a rate of 0.40 grams per orifice per minute through a 0.6 mm diameter die. mm. The fibers were collected in free fall (gravity only as stretching force) and then tested for mechanical properties at a pull rate of 50 millimeters per minute. The fibers were then cold drawn at 23 ° C in an MTS Synergie Tensile frame at a speed of 50 mm / min. The fibers were stretched to predefined deformations of 50%, 100%, 150%, 200% and 250%.
[122] After stretching, expansion rate, void volume and resulting density were calculated for various strain rates, as shown in the tables below.

EXAMPLE 3
[123] The fibers were formed as described in Example 2, with the exception that they were collected at a collection roller speed of 100 meters per minute, resulting in a pull rate of 77. The fibers were collected and tested for properties mechanics at a pull rate of 50 millimeters per minute. The fibers were then cold drawn at 23 ° C in an MTS Synergie Tensile frame at a speed of 50 mm / min. The fibers were stretched to predefined deformations of 50%, 100%, 150%, 200% and 250%. After stretching, expansion rate, void volume and the resulting density were calculated for various strain rates, as shown in the tables below.

EXAMPLE 4
[124] The fibers were formed as described in Example 2, except that the mixture contained 84.6 wt% polylactic acid (PLA 6201D, Natureworks®), 9.4 wt% Vistamaxx ™ 2120 hardening additive (ExxonMobil ), 1.3% wt of polyepoxide modifier (Lotader® AX8900, Arkema), and 4.5% wt of the HALLGREEN® IM-8830 interfacial modifier from Hallstar. HALLGREEN® IM-8830 was added by means of the injection pump inside drum zone no. 2. The fibers were collected at 240 ° C, 0.40 ghm and under free fall. EXAMPLE 5
[125] The fibers were formed as described in Example 4, with the exception that they were collected at a collection roller speed of 100 meters per minute, resulting in a tensile rate of 77. The fibers were then cold drawn at 23 ° C in an MTS Synergie Tensile frame at a speed of 50 mm / min. The fibers were stretched to a predefined strain of 100%. EXAMPLE 6
[126] The fibers were formed as described in Example 2, except that the mixture contained 85.3 wt% polylactic acid (PLA 6201D, Natureworks®), 9.5 wt% resin hardening additive Exceed ™ 3512CB ( ExxonMobil), 1.4% wt of polyepoxide modifier (Lotader® AX8900, Arkema), and 3.8% wt of interfacial modifier (PLURIOL® WI 285 from BASF). PLURIOL® WI285 was added via an injection pump into drum zone no. 2. The fibers were collected at 240 ° C, 0.40 ghm and under free fall. EXAMPLE 7
[127] The fibers were formed as described in Example 6, with the exception that they were collected at a collection roller speed of 100 meters per minute, resulting in a tensile rate of 77. The fibers were then cold drawn at 23 ° C in an MTS Synergie Tensile frame at a speed of 50 mm / min. The fibers were stretched to a predefined strain of 100%. EXAMPLE 8
[128] The fibers were formed as described in Example 2, except that the mixture contained 85.3 wt% polylactic acid (PLA 6201D, Natureworks®), 9.5 wt% Escorene ™ UL EVA 7720 curing additive (ExxonMobil), 1.4% wt of polyepoxide modifier (Lotader® AX8900, Arkema), and 3.8% wt of interfacial modifier (PLURIOL® WI 285 from BASF). PLURIOL® WI285 was added via an injection pump into drum zone no. 2. The fibers were collected at 240 ° C, 0.40 ghm and under free fall. EXAMPLE 9
[129] The fibers were formed as described in Example 8, with the exception that they were collected at a collection roller speed of 100 meters per minute, resulting in a tensile rate of 77. The fibers were tested for mechanical properties at a pull rate of 50 millimeters per minute. The fibers were then cold drawn at 23 ° C in an MTS Synergie Tensile frame at a speed of 50 mm / min. The fibers were stretched to a predefined strain of 100%. EXAMPLE 10
[130] The fibers were formed as described in Example 2, except that the mixture contained 83.7 wt% polylactic acid (PLA 6201D, Natureworks®), 9.3 wt% Vistamaxx ™ 2120 hardening additive (ExxonMobil ), 1.4% w of polyepoxide modifier (Lotader® AX8900, Arkema), 3.7% w of internal interfacial modifier (PLURIOL® WI 285 from BASF) and 1.9% w 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 an injection pump into drum zone no. 2. The fibers were collected at 240 ° C, 0.40 ghm and under free fall. EXAMPLE 11
[131] The fibers were formed as described in Example 10, with the exception that they were collected at a collection roller speed of 100 meters per minute, resulting in a tensile rate of 77. The fibers were collected and tested for mechanical properties at a pull rate of 50 millimeters per minute. The fibers were then cold drawn at 23 ° C in an MTS Synergie Tensile frame at a speed of 50 mm / min. The fibers were stretched to a predefined strain of 100%.
[132] After stretching, the expansion rate, void volume and density were calculated for Examples 6, 7, 9 and 11 as shown in the tables below.


EXAMPLE 12
[133] The fibers of Example 10 were stretched on an MTS Synergie Tensile frame, at a speed of 50 mm per minute at 250% deformation. This opened the void structure making the fiber white. A one-inch sample was then cut from the white, tensioned area of the fiber. The new fiber was then tested as described above. The density was estimated at 0.75 grams per cubic centimeter and the pull rate for the tensile test was 305 mm / min. EXAMPLE 13
[134] The fibers of Example 3 were heated in an oven at 50 ° C for 30 minutes for the annealing of the fiber. EXAMPLE 14
[135] The fibers of Example 3 were heated in an oven at 90 ° C for 5 minutes for annealing the fiber and inducing crystallization. EXAMPLE 15
[136] The fibers were formed as described in Example 8, with the exception that they were collected at a collection roller speed of 500 meters per minute. This resulted in a traction rate of 387. EXAMPLE 16
[137] The fibers were formed as described in Example 8, with the exception that they were collected at a collection roller speed of 1000 meters per minute. This resulted in a pull rate of 775. EXAMPLE 17
[138] The fibers of Examples 1 to 16 were tested for mechanical properties at a pull rate of 50 millimeters per minute. The results are shown in the table below.

[139] Although the invention has been described in detail with respect to the specific embodiments of it, it would be good for experts in the field, after reaching an understanding of the above, to be able to easily conceive changes, variations and equivalents of such embodiments. Therefore, the scope of the present invention must be assessed as that of the appended claims and their equivalents.

权利要求:
Claims (15)
[0001]
1. Fiber formed by a thermoplastic composition, characterized by the fact that the thermoplastic compound comprises: 70% by weight or more, based on the total weight of the thermoplastic composition, of at least one renewable rigid polyester with a glass transition temperature of 0 ° C or higher, and preferably from 50 ° C to 75 ° C; from 1% to 30% by weight of at least one polymeric curing additive, based on the weight of the renewable polyester; from 0.1% to 20% by weight of at least one interphasic modifier, based on the weight of the renewable polyester, where the interphasic modifier is hydrophobic; and at least one polyepoxide modifier; in which the thermoplastic compound has a morphology in which several discrete and empty primary domains are dispersed within a continuous phase, with the domains containing the polymeric hardening additive and with the continuous phase containing the renewable polyester, in which the voids are located adjacent domains; where the fiber has a density of 1.4 grams per cubic centimeter or less, and preferably 0.5 grams per cubic centimeter to 0.95 grams per cubic centimeter; wherein the average percentage volume of the composition that is occupied by the voids is 20% to 80% per cubic centimeter, and preferably 40% to 60% per cubic centimeter; and where the hydrophobic interphasic modifier has an angle of contact with water in air of 40 ° or more.
[0002]
2. Fiber according to claim 1, characterized by the fact that the proportion of voids is 0.1 to 1; and / or voids contain a combination of micro voids and nano voids.
[0003]
3. Fiber according to any one of the preceding claims, characterized by the fact that the renewable polyester is a polylactic acid; and / or the renewable polyester constitutes 75 to 98% by weight of the thermoplastic composition.
[0004]
4. Fiber according to any of the preceding claims, characterized by the fact that the ratio between the renewable polyester solubility parameter and the polymeric curing additive solubility parameter is 0.5 to 1.5, the ratio between the flow rate of the renewable polyester and the flow rate of the polymeric curing additive is 0.2 to 8, and the ratio between the Young's modulus of the renewable polyester and the Young's modulus of the polymeric curing additive is 2 to 500.
[0005]
Fiber according to any one of the preceding claims, characterized in that the polymeric curing additive includes a polyolefin, such as a propylene homopolymer, alpha-olefin / propylene copolymer, ethylene / alpha-olefin copolymer, or a combination of these.
[0006]
6. Fiber according to any one of the preceding claims, characterized by the fact that the interphasic modifier has a kinematic viscosity of 0.7 to 200 centistokes, determined at a temperature of 40 ° C; and / or the ratio of the glass transition temperature of the thermoplastic composition to the glass transition temperature of the renewable polyester is 0.7 to 1.3.
[0007]
7. Fiber according to any one of the preceding claims, characterized by the fact that the interphasic modifier is a silicone, silicone-polyether copolymer, aliphatic polyester, aromatic polyester, alkylene glycol, alkane diol, amine oxide, fatty acid ester or a combination of these.
[0008]
8. Fiber according to any of the preceding claims, characterized by the fact that the polyepoxide modifier includes an epoxy-functional monomeric (meta) acrylic component.
[0009]
9. Non-woven blanket, characterized by the fact that it comprises the fiber as defined in any one of claims 1 to 8.
[0010]
10. Absorbent article comprising an absorbent core positioned between a liquid-permeable layer and a generally liquid-impermeable layer, characterized by the fact that it comprises the non-woven mat as defined in claim 9.
[0011]
11. Method for forming low density fiber, characterized by the fact that it comprises: forming a mixture containing a renewable rigid polyester, such as a polylactic acid, a polymeric hardening additive, such as a polyolefin, a hydrophobic interphasic modifier, and a polyepoxide modifier, in which the renewable rigid polyester has a glass transition temperature of 0 ° C or higher and is present in the mixture in an amount of 70% by weight or more; extruding mixture through a mold to form the fiber; and stretching the fiber to a temperature below the glass transition temperature of the renewable polyester, preferably at a temperature of at least 10 ° C below the glass transition temperature of the renewable polyester, to form a thermoplastic composition that has a morphology in which several discrete and empty primary domains are dispersed within a continuous phase, in which the voids are located adjacent to the domains; wherein the thermoplastic composition has a density of 1.4 grams or less per cubic centimeter, and preferably 0.5 grams per cubic centimeter to 0.95 grams per cubic centimeter; where the average percentage volume of fiber that is occupied by voids is 20% to 80% per cubic centimeter; and where the hydrophobic interphasic modifier has an angle of contact with water in air of 40 ° or more.
[0012]
Method according to claim 11, characterized in that it further comprises the annealing of the fiber stretched at a temperature above the glass transition temperature of the renewable polyester.
[0013]
Method according to claim 11, characterized in that the mixture comprises at least one interphasic modifier and / or a polyepoxide modifier that includes an epoxy-functional monomeric (meta) acrylic component.
[0014]
Method according to claim 11, characterized in that the mixture is generally free of gaseous swelling agents.
[0015]
15. Method for forming a non-woven blanket, characterized by the fact that it comprises: forming a mixture containing a renewable rigid polyester, a polymeric hardening additive, a hydrophobic interphasic modifier, and a polyepoxide modifier, in which the renewable rigid polyester it has a glass transition temperature of 0 ° C or higher and is present in the mixture in an amount of 70% by weight or more; extruding the mixture through a mold to form several fibers; randomly deposit the stretched fibers on a surface to form a non-woven blanket; and stretching the fibers before and / or after the formation of the non-woven blanket, where the fibers are stretched at a temperature below the glass transition temperature of the renewable polyester, to form a thermoplastic composition that has a morphology in which several discrete primary domains and voids are dispersed within a continuous phase, in which the voids are located adjacent to the domains; wherein the thermoplastic composition has a density of 1.4 grams per cubic centimeter or less; and where the hydrophobic interphasic modifier has an angle of contact with water in air of 40 ° or more.

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同族专利:

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公开号 | 公开日

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RU2014135462A|2016-04-10|

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EP2820175A2|2015-01-07|

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MX354160B|2018-02-14|

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CN104093891B|2017-04-12|

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JP6168526B2|2017-07-26|

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KR101964486B1|2019-07-31|

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KR20140123061A|2014-10-21|

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AU2013217362B2|2016-10-20|

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JP2015508848A|2015-03-23|

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US20210180216A1|2021-06-17|

---

CN104093891A|2014-10-08|

---

EP2820175A4|2015-11-04|

---

AU2013217362A1|2014-07-24|

---

US10858762B2|2020-12-08|

---

WO2013118019A3|2013-11-07|

---

RU2620415C2|2017-05-25|

---

WO2013118019A2|2013-08-15|

---

MX2014009542A|2014-11-10|

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US20130210308A1|2013-08-15|

---

EP2820175B1|2019-11-27|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-02-02| 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 28/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/370,952|US10858762B2|2012-02-10|2012-02-10|Renewable polyester fibers having a low density|

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US13/370,952|2012-02-10|

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PCT/IB2013/050729|WO2013118019A2|2012-02-10|2013-01-28|Renewable polyester fibers having a low density|

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