polyolefinic material, absorbent article, and method for forming a polyolefinic material

专利摘要:
LOW DENSITY POLYOLEFINIC MATERIAL A polyolefinic material is given which is formed by solid state stretching of a thermoplastic compound, containing a continuous phase that includes a polyolefinic matrix polymer and nanoinclusion additive. The nanoinclusion additive is dispersed in the continuous phase in the form of discrete nanoscale phase domains. During stretching, the nanoscale phase domains are able to interact with the matrix in a unique way to create a nanopore network.
公开号:BR112015028913B1
申请号:R112015028913-4
申请日:2014-06-06
公开日:2020-11-10
发明作者:Vasily A. Topolkaraev；Ryan J. Mceneany；Antonio J. Carrillo
申请人:Kimberly-Clark Worldwide, Inc.；
IPC主号:

专利说明:

Related requests
[1] This application claims priority over temporary orders with serial numbers 61 / 833,980, submitted on June 12, 2013, and 61 / 907,572, submitted on November 22, 2013, which are incorporated herein in full for purposes of reference. History of the Invention
[2] Significant efforts have been made to produce low density polyolefin materials to improve the use of natural resources and reduce the carbon footprint of finished products. The typical approach to producing such low-density materials is through the formation of polymeric foam using physical or chemical blowing agents, which create pores filled with gas through the volume. Chemical expansion agents are compounds that undergo a chemical reaction with the release of gas that creates the pore structure through the mass of the polymer. Physical expansion agents are usually compressed gases that are dispersed in the polymer and that expand, creating the cells. Regardless, typical foaming processes induce low molecular orientation as cell formation occurs when the polymer is in the molten state. This prevents the polymer from hardening, which usually occurs at temperatures well above the polymer's melting temperature or glass transition temperature, resulting in products with low mechanical strength. In addition, typical foaming processes generate large cell sizes, such as greater than 100 pm. This reduces the melt strength, thus leading to breakages in high-speed production processes, with high deformation rates (for example, fiber spinning, film formation, molding, etc.).
[3] Thus, there is currently a need for an improved technique in the formation of low density polyolefinic materials. Summary of the Invention
[4] According to one of the embodiments of the present invention, a polyolefinic material formed by a stretch of thermoplastic composition containing a continuous phase is disclosed which includes a polyolefin matrix polymer, where a nano-inclusion additive is dispersed in the continuous phase in the form of discrete domains. A porous network is defined in the compound that includes a plurality of nanopores having an average cross-sectional dimension of about 800 nanometers or less. The thermoplastic composition has a density of about 0.90 g / cm3 or less.
[5] Other properties and aspects of the present invention will be discussed in more detail below. Brief description of the illustrations
[6] 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: Fig. 1 is an SEM photomicrograph of the injection molded sample, not stretched from Example 1 (polypropylene and alkoxylated alcohol) after freeze fracture in liquid nitrogen; Fig. 2 is an SEM photomicrograph of the injection molded sample, drawn from Example 1 (polypropylene and alkoxylated alcohol) after freeze fracture in liquid nitrogen; Fig. 3 is a SEM photomicrograph of the injection molded and stretched sample of Example 2 (polypropylene and polylactic acid) after freeze fracture in liquid nitrogen; A Fig. 4 is a SEM photomicrograph of the injection molded and stretched sample of Example 2 (polypropylene and polylactic acid) after fracture by freezing in liquid nitrogen; 5 is a stress-strain curve of the stretched sample of Example 2; Fig. 6 is a SEM photomicrograph of the injection molded, unstretched sample of Example 3 (polypropylene, polylactic acid and polyepoxide) after fracture by freezing in nitrogen Fig. 7 is a SEM photomicrograph of the injection molded and stretched sample of Example 3 (polypropylene, polylactic acid, and polyepoxide) after freezing fracture in liquid nitrogen; Fig. 8 is a stress-strain curve of the stretched sample of Example 3; Fig. 9 is a SEM photomicrograph (1,000X) of the fiber of Example 4 (polypropylene, polylactic acid and polyepoxide) after fracture by freezing in liquid nitrogen; Fig. 10 is a photomicrograph by SEM (5,000X) of the fiber of Example 4 (polypropylene, polylactic acid and polyepoxide) after freeze fracture in liquid nitrogen; Fig. H is a SEM photomicrograph (10,000X) of the fiber surface of Example 4 (polypropylene, poly acid lactic and polyepoxide); Fig-12 is a SEM photomicrograph (5,000X) of the cross-sectional area (polished and engraved with chloroform) of the injection molded bar of Example 5; Fig-13 is a SEM photomicrograph (10,000X) the cross-sectional area (polished and etched with chloroform) of the injection molded bar of Example 5; Fig-14 is a SEM photomicrograph (5,000X) of the fractured region by freezing, along the axial direction of the injection molded stretched bar. Example 5; Fig-15 is a SEM photomicrograph (20,000X) of the fractured region by freezing, along the axial direction of the injection molded stretched bar of Example 5; Fig-16 is a SEM photomicrograph (10,000X) of the freeze-fractured transverse area, along the axial direction of the non-stretched injection molded bar of Example 6; Fig-17 is a SEM photomicrograph (5,000X) of the freeze-fractured transverse area, along the axial direction of the bar injection molded form of Example 6.
[7] Fig-18 is a SEM photomicrograph of the Example 10 film surface, taken at 14.243X magnification; Fig-19 is a SEM photomicrograph of the Example 10 film (cut in the plane of the machine direction) ) taken at a magnification of 5,382X; Fig-20 is a SEM photomicrograph (4,270X) of the fiber of Example 16 after freezing fracture in liquid nitrogen; Fig-21 is a SEM photomicrograph (9,170X) of fiber of Example 16 after freeze fracture in liquid nitrogen; Fig- 22-23 is an SEM photomicrograph of the fiber of Example 17 after freeze fracture in liquid nitrogen; Fig. 24 is an SEM photomicrograph of the fiber from Example 18 after freezing fracture in liquid nitrogen; eA Fig- 25 is a SEM photomicrograph of the joined frame of Example 18. Detailed Description of Representative Embodiments
[8] Detailed references will be made to various configurations of the invention, with one or more examples described below. Each example is provided by way of explanation of the invention, without limitation to the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment, can be used in another application to produce yet another embodiment. Thus, it is intended that the present invention covers modifications and variations that are within the scope of the attached claims and their equivalents.
[9] In general, the present invention is directed to a polyolefinic material (eg film, fibrous material, molded article, etc.) that is formed by drawing a thermoplastic composition (for example, drawing in solid state) containing a continuous phase that includes a polyolefin matrix polymer. The compound also contains a nano-inclusion additive that is at least partially incompatible with the polyolefin matrix polymer, so that it becomes dispersed in the continuous phase as discrete nanoscale phase domains. During stretching, when the compound is subjected to a strain and strain stress, the present inventors have found that these discrete nanoscale phase domains are able to interact in a unique way to create a pore network. For example, it is believed that the stretching stress can initiate localized intensive shear zones and / or stress intensity zones (for example, normal stresses) close to the discrete phase domains, as a result of the stress concentrations that result from the incompatibility. of the materials. These zones of shear intensity and / or stress cause a certain initial detachment in the polyolefin matrix adjacent to the domains. Once the initial pores are formed, the matrix located between domains can plastically deform to create stretched internal areas that narrow locally and harden with tension. This process allows the formation of pores through the mass of the compound that grows in the direction of stretching, thus leading to the formation of a porous network, while the molecular orientation leads to the hardening by tension that increases the mechanical resistance.
[10] Through the aforementioned techniques, an exclusive porous network can be formed in the polyolefinic material, so that the percentage volume occupied by the pores in a given unitary volume of material can be from 15% to 80% per cm3, in some embodiments. about 20% to about 70%, and in some embodiments, from about 30% to about 60% per cubic centimeter of the material. For example, the compound may have a density of about 0.90 grams per cubic centimeter ("g / cm3") or less, in some embodiments about 0.85 g / cm3 or less, in some embodiments 0.80 g / cm3 or less, in some embodiments from 0.10 g / cm3 to about 0.75 g / cm3, and in some embodiments from about 0.20 g / cm3 to about 0 , 70 g / cm3. A substantial portion of the pores in the porous network are also "nanoscale" size, as are those having an average cross-sectional dimension of about 800 nanometers or less, in some embodiments of about 5 to about 700 nanometers and, in other embodiments, from about 10 to about 500 nanometers. The term "transverse dimension" generally refers to a characteristic dimension (for example, width or diameter) of a pore, which is substantially perpendicular to its major axis (for example, length) and also typically substantially orthogonal to the direction of applied stress during stretching. Nanopores can also have an average axial dimension within the range of about 100 to 5000 nanometers, in some embodiments from about 50 to about 2000 nanometers, and in some embodiments, from about 100 nanometers to about 1000 nanometers. The "axial dimension" is the dimension in the direction of the major axis (for example, length), which is usually in the direction of the stretch. Such nanopores can, for example, constitute about 15% by vol. about 20% by vol. or more; in some embodiments, 30% by vol. about 100% by vol .; and in other embodiments, about 40% by vol. about 90% by vol. of the total pore volume in the polyolefin material.
[11] In addition to reduced density, the porosnanoporous structure can also provide a variety of different benefits to the resulting polyolefin material. For example, such a structure can help to restrict the flow of fluids through the material and generally be impermeable to liquids (eg, liquid water), thus allowing the material to insulate a water penetrating surface. In this regard, the polyolefin material may have a relatively high hydrostatic charge of about 50 cm ("cm") or more, in some embodiments about 100 cm or more, in some embodiments, about 150 cm or more, and in some embodiments, from about 200 cm to about 1000 cm, as determined according to ATTCC 127-2008. Other beneficial properties can also be achieved. For example, the resulting polyolefin material can generally be permeable to water vapor. The permeability of the material to water vapor can be characterized by its relatively high water vapor transmission rate (“TTVA”), which is the rate at which water vapor enters the material, as measured in units of grams per square meter for 24 hours (g / m2 / 24 h). For example, the polyolefin material may exhibit a TTVA of about 300 g / m2- 24 hours or more, in some embodiments about 500 g / m2-24 hours or more, in some embodiments about 1,000 g / m2 m2-24 hours or more, and in other embodiments, from about 3,000 to about 15,000 g / m2-24 hours, as determined in accordance with ASTM E96 / 96M-12, Procedure B or INDA Test IST Procedure -70.4 (01). The polyolefin material can also act as a thermal barrier that has a relatively low thermal conductivity, such as about 0.40 watts per meter-Kelvin ("W / mK") or less, in some embodiments about 0.20 W / mK or less, in some embodiments of about 0.15 W / mK or less, in some embodiments of about 0.01 to about 0.12 W / mK, and in some embodiments , from about 0.02 to about 0.10 W / mK. Notably, the material is able to achieve these low thermal conductivity values with relatively low thicknesses, which can allow the material to have a greater degree of flexibility and moldability, as well as reducing the space it occupies in an article. For this reason, the polyolefin material may also have a relatively low "thermal intake", which is equal to the thermal conductivity of the material divided by its thickness and is given in units of watts per square meter-Kelvin ("W / m2K"). For example, the material may have a thermal intake of about 1000 W / m2K or less, in some embodiments from about 10 to about 800 W / m2K, in some embodiments from about 20 to about 500 W / m2K, and in some embodiments, from about 40 to about 200 W / m2K. The actual thickness of the polyolefin material may depend on its particular shape, but it generally ranges from about 5 micrometers to about 100 millimeters, in some embodiments from about 10 micrometers to about 50 milliliters, in some embodiments of about from 200 micrometers to about 25 millimeters.
[12] We will now describe several forms of this invention in more detail. Thermoplastic compositionPolyolefin matrix
[13] Polyolefins typically constitute about 60% weight to about 99% by weight, in some embodiments, from about 60% by weight to about 98% by weight and, in other embodiments, by about 80% by weight to about 95% by weight of the thermoplastic composition. The polyolefin can also have a melting temperature of about 100DC to about 220DC, in some embodiments, from about 120DC to about 200 ° C, and, in some embodiments, from about 140 ° C to about 180 ° C. The melting temperature can be determined by means of differential scanning calorimetry (differential scanning calorimetry-DSC, according to ASTM D-3417. Suitable polyolefins may, for example, include ethylene polymers (eg 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. 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 about 10% of the mass of another monomer, that is, at least about 90% of the mass of propylene. These homopolymers can have a melting point of about 140 ° C at about 170 ° C.
[14] Of course, other polyolefins can also be used in the compound of the present invention. In yet another embodiment, for example, 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 a-olefin comonomers are 1-butene, 1-hexene and 1-octene. The ethylene or propylene content of such copolymers can vary from about 60% per mol to about 99% per mill, in some embodiments from 80% per mol to about 98.5% and in other embodiments of 87% by mol to about 97.5% by mol. The content of alpha olefin can vary from about 1% per mol to about 40% per mol, in some embodiments from 1.5% per mol to about 15% and in some embodiments from 2.5 % per mol to about 13% per mol.
[15] 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 to Lai, et al. 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. Suitable polypropylene homopolymers can also include Exxon Mobil 3155 polypropylene, Exxon Mobil Achieve ™ resins and Total M3661 PP resin. Other examples of suitable propylene polymers are described in U.S. Patent No. 6,500,563 to Datta et al .; 5,539,056 to Yang et al .; and 5,596,052 for Resconi et al
[16] A wide variety of known techniques can be used to form 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 by 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 for Davis et al .; 5,472,775 to Obijeski et al .; 5,272,236 to Lai et al .; and 6,090,325 for Wheat, et al. Examples of metallocene catalysts include bis (n-butylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) scandium chloride, bis (indenyl) zirconium dichloride, methyl (dichloride) bis (methylene chloride) dichloride , bis (methylcyclopentadienyl) zirconium dichloride, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafnocene dichloride, isopropyl dichloride (cyclopentadienyl, -l-flourenyl) zirconium, molybdenum dichloride, nichloride, nichloride, niqu zirconocene chloride hydride, zirconocene dichloride and so on. Polymers created using the metallocene catalyst usually have a narrow molecular weight range. For example, metallocene-catalyzed polymers can have polydispersity numbers (Mw / Mn) below 4, controlled short-chain branching distribution and controlled isotacticity.
[17] As used here, the term "nanoinclusion additive" generally refers to a material capable of being dispersed in the polymer matrix in the form of discrete domains with a nanoscale size. For example, before stretching, the domains may have an average cross-sectional dimension of about 1 to about 1000 nanometers, in some embodiments from about 5 to about 800 nanometers and, in other embodiments, from about 10 to about 500 nanometers, and in some embodiments from about 20 to about 200 nanometers. The domains can have several different shapes, such as elliptical, spherical, cylindrical, plate-shaped, tubular, etc. In one embodiment, for example, the domains are quite elliptical in shape. The nanoinclusion additive is generally used in an amount of about 0.05% by weight to about 20% by weight, in some embodiments, from about 0.1% by weight to about 10% by weight and, in other embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase polyolefin matrix. The concentration of the nano-inclusion additive in the entire thermoplastic composition can also be from about 0.01% to about 15% by weight, in some embodiments, from about 0.05% to about 10% by weight and, in other embodiments, from about 0.3% to about 6% by weight.
[18] The nanoinclusion additive is partially incompatible with apoliolefin in the sense that it can be distributed substantially uniformly within the polyolefin matrix, but in the form of discrete domains. Such partial incompatibility can be obtained in several ways. In certain embodiments, for example, the nano-inclusion additive may have a non-polar component (e.g., olefin) that is compatible with the polyolefinic matrix and allows it to be uniformly distributed therein. However, the additive can also include a polar component that is incompatible with the polyolefin matrix, thus allowing integration or separation in discrete domains. Such a component may include high or low molecular weight polar segments or molecular blocks, ionic groups, charged or uncharged polar domains and / or polar molecular groups. Alternatively, the additive may be entirely non-polar in nature, but have certain physical properties that still allow the formation of discrete domains. For example, in certain embodiments, the nanoinclusion additive may be compatible or miscible with the polyolefin above a certain temperature, however, phase separation at temperatures lower than the critical temperature of the solution. In this way, the nano-inclusion additive can form a stable mixture with the polyolefin in the molten phase, however, as the temperature decreases, the continuous phase crystallizes and secretes so that the nano-inclusion additive separates by phase, coalesces and forms domains in separate nanoscale.
[19] The state or particular form of the nano-inclusion additive is not critical as long as the desired domains can be formed. For example, in some embodiments, the nano-inclusion additive can be in the form of a liquid or semi-solid at room temperature (for example, 25 ° C). Such a liquid can be easily dispersed in the matrix to form a metastable dispersion, and then quenched to preserve the size of the domain by reducing the temperature of the mixture. The kinematic viscosity of such a liquid or semi-solid material is generally about 0.7 to about 200 centistokes ("cs"); in some embodiments, from about 1 to about 100 dogs; and in some embodiments, from about 1.5 to about 80 dogs, determined at 40 ° C. Suitable liquids or semi-solids can include, for example, silicones, silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, alkylene glycols (for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, polyethylene glycol, , diols alkanes, (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-l, 3-cyclobutanediol, etc.), oxides amine (for example, octyldimethylamine oxide), fatty acid esters, fatty acid amides (eg oleamide, erucamide, stearamide, ethylene bis (stearamide), etc.), mineral and vegetable oils, etc. A particularly suitable liquid or semi-solid is polyester polyol, such as those sold under the trade name PLURIOL® WI by BASF Corp.
[20] In still other embodiments, the non-inclusion additive is in the form of a solid, which can be amorphous, crystalline or semi-crystalline. For example, the nanoinclusion additive can be polymeric and have a relatively high molecular weight which can help to improve melt strength and stability of the thermoplastic composition. As indicated above, the nanoinclusion additive is partially incompatible with the polyolefin matrix. An example of such an additive is a microcrystalline polyolefin wax, which is typically derived from ethylene and / or C3-C10-alkyl-1-enes, such as from propylene, 1-butene, 1-pentene, 1-hexene , 1-heptene, 1-octene, 1-nonene and 1-decene. Microcrystalline waxes generally have a relatively low melting temperature, such as from about 30 ° C to about 150 ° C; in some embodiments from about 50 ° C to about 140 ° C, and in some embodiments, from about 80 ° C to about 130 ° C. At low melting temperatures, the wax can form a miscible mixture with the polyolefin when in the molten phase, but with decreasing temperature and crystallization or solidification of the polymer, the wax will separate and coalesce forming separate nanoscale domains.
[21] Another example of a polymeric nanoinclusion additive is a functionalized polyolefin that contains both a polar and a non-polar component. The polar component, for example, can be provided by one or more functional groups, and the non-polar component can be provided by an olefin. The olefin component of the nanoinclusion additive can normally be formed of any branched or linear α-olefin monomer, oligomer or polymer (including copolymers) derived from an olefin monomer, as described above. The functional group of the nanoinclusion additive can be any group, segment and / or molecular block that provides a polar component to the molecule and is not compatible with the polyolefin matrix polymer. Examples of segment and / or molecular blocks not compatible with polyolefin may include acrylates, styrenes, polyesters, polyamides, etc. The functional group may be ionic in nature and comprise charged metal ions. 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 the present invention. These modified polyolefins are usually formed by grafting maleic anhydride into a material of the polymeric structure. These maleated 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, maleatated polyolefins are also marketed by Chemtura Corp, under the name Polybond®, by Eastman Chemical under the name Eastman G series and Arkema, under the name Orevac®.
[22] In certain embodiments, the polymeric additive may also be reactive. An example of this reactive nano inclusion additive is a polyepoxide that contains, on average, at least two axirane rings per molecule. Without claiming to be limited by theory, it is believed that such polyepoxide molecules can be subjected to a reaction (for example, chain extension, side chain branches, graft, copolymer formation, etc.) with certain components of the compound to improve melt strength without significantly reducing the glass transition temperature. The reactive additive can also provide compatibility between polyolefin and other more polar additives, such as micro-inclusion additives, and can improve dispersion uniformity and reduce the size of micro-inclusion additives. For example, as will be described in more detail below, certain embodiments of the present invention may employ a polyester as a microinclusion additive. In such embodiments, the reactive nanoinclusion additive may allow a nucleophilic reaction for ring opening through a polyester carboxyl end group (esterification) or through a hydroxyl group (etherification). Reactions on the oxazoline side can occur to form amide ester parts. Through these reactions, the molecular weight of the matrix polymer can increase in order to counteract the degradation that is often observed 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 can become brittle and difficult to process in a material with the desired strength and elongation properties.
[23] In this sense, the present inventors have found that polyepoxides with a relatively low epoxy resource 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 of the present invention normally has an average molecular weight in number ranging from about 7,500 to about 250,000 grams per mole; in some embodiments, from about 15,000 to about 150,000 grams per mole, and in other embodiments, from about 20,000 to about 100,000 grams per mole, with a polydispersity index ranging from 2.5 to 7 The polyepoxide may contain less than 50, in some embodiments, from 5 to 45 and, in other embodiments, from 15 to 40 epoxy groups. In turn, the epoxy equivalent weight can be less than about 15,000 grams per mol; in some embodiments, from about 200 to about 10,000 grams per mole, and in other embodiments, from about 500 to about 7,000 grams per mole.
[24] The polyepoxide can be a homopolymer or copolymer or branched (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 contains at least one epoxy-functional monomeric (meta) acrylic component. As used here, the term “(meta) acrylic” includes acrylic and meta-acrylic monomers, as well as salts or esters thereof, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meta) acrylic monomers can include, without limitation, 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.
[25] Poliepoxide typically has a relatively high molecular weight, as indicated above, so it can not only result in chain extension, but also help to achieve the desired blend morphology. Thus, the resulting flow rate of the polymer can thus vary from about 10 to about 200 grams for 10 minutes; in some embodiments, from about 40 to about 150 grams for 10 minutes and, in other embodiments, from about 60 to about 120 grams for 10 minutes, determined at a load of 2,160 grams and a temperature 190 ° C.
[26] Polyepoxide generally also includes at least one linear or branched α-olefin monomer, such as those with 2 to 20 carbon atoms and preferably 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 specifically desired α-olefin comonomers are ethylene and propylene. Another suitable monomer may include an acrylic (meta) 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 , cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, isobornyl methacrylate, etc., good with o combinations of these.
[27] In a particularly desirable embodiment of the present invention, polyepoxide is a terpolymer formed from an epoxy-functional monomeric (meta) acylic component, an alphaolefin monomeric component and a non-epoxy-functional acrylic monomeric (meta) component . For example, the polyepoxide can be poly (ethylene-methyl co-acrylate-co-glycidyl methacrylate), with the following structure:
where x, y and z are 1 or greater.
[28] The epoxy-functional monomer can be transformed into a polymer using several known techniques. For example, a monomer containing polar functional groups can be grafted onto a polymer structure to form a grafted copolymer. Such grafting techniques are well known in the art and described, for example, in U.S. Patent No. 5,179,164. In other embodiments, a monomer containing epoxy-functional groups can be copolymerized with a monomer to form a random block or copolymer using known free radical polymerization techniques, such as high pressure reactions, Ziegler-catalytic reaction systems Natta, single site catalyst reaction systems (eg metallocene), etc.
[29] 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 polylactic acid, but a very high content can reduce the melt flow rate, such that the polyepoxide modifier will negatively affect the melt resistance of the mixture. polymer. Thus, in most embodiments, epoxy-functional (meta) acrylic monomers form about 1% to about 25% by weight, in some embodiments, from about 2% to about 20% by weight and , in other embodiments, from about 4% to about 15% by weight of the copolymer. Alphaolefin monomers can also comprise from about 55% to about 95% by weight; in some embodiments; from about 60% to about 90% by weight and; in other embodiments; from about 65% to about 85% by weight of the copolymer. When used, other monomeric components (for example, non-epoxy-functional (meta) acrylic monomers) can make up from about 5% to about 35% by weight, in some embodiments, from about 8% to about 30% % by weight and, in other embodiments, from about 10% to about 25% by weight of the copolymer. A specific example of a suitable polyepoxide that can be used in this invention is marketed by Arkema under the name of LOTADER® AX8950 or AX8900. LOTADER® AX8950, for example, has a melt index of 70 to 100 g / 10 min and has a 7% to 11% by weight glycidyl methacrylate monomer content, a 13% methyl acrylate monomer content at 17% by weight, and an ethylene monomer content of 72% to 80% by weight. Another suitable polyepoxide commercially available from DuPont under the name ELVALOY® PTW, which is a terpolymer of ethylene, butyl acrylate and glycidyl methacrylate and has a melt index of 12 g / 10 min.
[30] In addition to controlling the type and relative content of the monomers used to form the polyepoxide, the overall weight percentage can also be controlled to achieve the desired benefits. For example, if the level of modification is very low, the desired increase in melt strength and mechanical properties may not be achieved. The present inventors have also found, however, that if the level of modification is too high, processing may be restricted due to strong molecular interactions (eg, crosslinking) and physical network formation by epoxy-functional groups. Thus, polyepoxide is normally used in an amount of about 0.05% to about 10% by weight; in some embodiments, from about 0.1% to about 8% by weight, in other embodiments, from about 0.5% to about 5% by weight, and in other embodiments, from about 1% to about 3% by weight, based on the mass of polylactic acids used in the compound. Polyepoxide can also constitute about 0.05% to about 10% by weight; in some embodiments, from about 0.05% to about 8% by weight, in other embodiments, from about 0.1% to about 5% by weight and, in other embodiments, from about 0.5% to about 3% by weight, based on the total weight of the compound.
[31] Other reaction nano-inclusion additives can also be used in the present invention, such as polymers functionalized with oxazoline, polymers functionalized with cyanide, etc. When used, these reactive nano-inclusion additives can be used within the concentrations indicated above for the polyepoxide. In a specific embodiment, an oxazoline-grafted polyolefin can be employed, i.e., a polyolefin grafted with a monomer containing 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, soy-2-oxazoline, castor-2-oxazoline and combinations thereof, for example. In yet another embodiment, oxazoline is selected from 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline and combinations thereof.
[32] In certain embodiments of the present invention, multiple nano-inclusion additives can be used in combination. For example, a first nanoinclusion additive (e.g., polyepoxide) can be dispersed in the form of domains having an average cross-sectional dimension of about 50 to about 500 nanometers, in some embodiments of about 60 to about 400 nanometers and, in other embodiments, from about 80 to about 300 nanometers. A second nano-inclusion additive can also be dispersed in the form of domains that are smaller than the first nano-inclusion additive, such as those having an average cross-sectional dimension of about 1 to about 50 nanometers, in some embodiments of about 2 to about 45 nanometers, and in some embodiments from about 5 to about 40 nanometers. When used, the first and / or second nanoinclusion additive generally comprises from about 0.05% to about 20% by weight, in some embodiments, from about 0.1% by weight to about 10% % by weight and, in other embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase (matrix polymers). The concentration of the first and / or second nano-inclusion additive in the entire thermoplastic composition can also be formed from about 0.01% to about 15% by weight, in some embodiments, from about 0.05% to about from 10% by weight and, in other embodiments, from about 0.1% to about 8% by weight of the thermoplastic composition.
[33] Nanocharges can optionally be used for the second nano-inclusion additive, examples of which include carbon black, carbon nanotubes, carbon nanofibers, clays, metallic nanoparticles, nanosilica, nanoalumina, etc. Nano-clays are especially suitable. The term "nano-clay" generally refers to nanoparticles of a clay material (a naturally occurring mineral, an organically modified mineral or a synthetic nanomaterial), which typically has a platelet structure. Examples of nanoclay include, for example, montmorillonite (2: 1 layered smectite clay structure), bentonite (aluminum phyllosilicate formed mainly by montmorillonite), kaolinite (aluminosilicate 1: 1 having a lamellar structure and the empirical formula A 2Si2O5 (OH ) 4), Haloisite (aluminosilicate 1: 1 having a tubular structure and empirical formula A12Si2O5 (OH) 4), etc. An example of a suitable nanoclay is Cloisite®, which is a montmorillonite nanoclay and is commercially available from Southern Clay Products, Inc. Other examples of synthetic nanoclay include, but are not limited to, a mixed metal hydroxide, hydroxide nanoclay. double layer (eg sepiocite), laponite, hectorite, saponite, indonite, etc.
[34] If desired, the nanoclay may contain a surface treatment to help improve compatibility with the matrix polymer (eg, polyester). The surface treatment can be organic or inorganic. In one embodiment, an organic surface treatment is obtained by the relationship of the organic cation to the clay. Suitable organic cations may include, for example, organoquaternary ammonium compounds that are capable of exchanging cations with clay, such as dimethyl-bis [hydrogenated tallow] ammonium chloride (2M2HT), benzyl methyl bis [hydrogenated tallow] chloride ammonium (MB2HT), methyl tris [hydrogenated tallow alkyl] (M3HT) chloride, etc. Examples of commercially available organic nanoclay may include, for example, Dellite® 43B (Laviosa Chimica from Livorno, Italy), which is a montmorillonite clay modified with hydrogenated tallow dimethyl benzyl ammonium. Other examples include Cloisite® 25A and Cloisite® 30B (Southern Clay Products) and Nanofil 919 (Sod Chemie). If desired, the nanocharge can be mixed with a base resin to form a base mixture that increases the compatibility of the additive with the other polymers in the compound. Particularly suitable base resins include, for example, polyesters (for example, polylactic acid, polyethylene terephthalate, etc.); polyolefins (for example, ethylene polymers, propylene polymers, etc.); and so on, as described in more detail above.
[35] The polymeric curing additive can also have a certain viscosity (or fluidity index) to ensure that the resulting discrete domains and voids can be maintained properly. For example, if the viscosity of the nano-inclusion additive is too low (or the flow rate is too high), it will tend to flow and disperse uncontrollably during the continuous phase. This results in lamellar domains similar to a cocontinuous plate or phase structure, difficult to maintain and likely to rupture prematurely. On the other hand, if the viscosity is too high (or the flow rate is too low), it will tend to clump together and form large elliptical domains, which are difficult to disperse during mixing. This may cause an irregular distribution of the nano-inclusion additive throughout the continuous phase. In this sense, the ratio of the polyolefin fluidity index to the fluidity index of a polymeric nanoinclusion additive, for example, can vary from 0.2 to about 8; in some embodiments, from about 0.5 to about 6; and in other embodiments of about 1 to about 5. The nano-inclusion additive can, for example, have a flow rate (on a dry basis) of about 0.1 to about 100 grams for 10 minutes; in some embodiments, from about 0.5 to about 50 ranges per 10 minutes, and in other embodiments, from about 5 to about 15 grams per 10 minutes, determined at a load of 2,160 grams and the a temperature of at least about 40 ° C above the melting temperature (eg 190 ° C) according to ASTM D1238. The polyolefin can likewise have a flow rate (on a dry basis) of about 0.5 to about 80 grams for 10 minutes; in some embodiments, from about 1 to about 40 grams for 10 minutes and; in other embodiments, from about 5 to about 20 grams for 10 minutes, determined at a load of 2,160 grams and at a temperature 40 ° C above the melting temperature (eg 230 ° C) according to the ASTM DI238 standard. Microinclusion additive
[36] Although not required, the compound of the present invention can also employ a microinclusion additive. As used herein, the term "microinclusion additive" generally refers to a material capable of being dispersed in the polymer matrix in the form of discrete domains having a microscale size. For example, prior to stretching, the domains may have an average cross-sectional dimension of about 0.1 pm to about 25 pm, in some embodiments from about 0.5 pm to about 20 pm, and in other forms from about 1 pm to about 10 pm. When employed, the present inventors discovered that the micro and nanoscale phase domains were able to interact in a unique way when subjected to a strain and elongation force (eg, stretching), to create a pore network. For example, it is believed that the stretching stress can initiate localized intensive shear zones and / or stress intensity zones (for example, normal stresses) close to the discrete microscale phase domains as a result of the stress concentrations that result incompatibility of materials. These zones of shear intensity and / or tension cause a certain initial detachment in the polyolefin matrix adjacent to the microscale domains. Notably, however, the shear intensity and / or localized stress zones created close to the nanoscale discrete phase domains can coincide with the microscale zones to cause even more detachment in the polymer matrix, thus creating a substantial number of nanopores adjacent to the nanoscale and / or microscale domains.
[37] The particular nature of the micro-inclusion additive is not critical, and may include liquids, semi-solids or solids (eg amorphous, crystalline or semi-crystalline). In certain embodiments, the microinclusion additive is polymeric in nature and has a relatively high molecular weight which can help to improve the melt strength and stability of the thermoplastic composition. Generally, the microincluding additive polymer may be generally incompatible with the matrix polymer. In this way, the additive can be better spread as discrete phase domains within a continuous phase of the matrix polymer. The discrete domains are able to absorb energies resulting from an external force, which increase the stiffness and the total resistance of the resulting material. The domains can have several different shapes, such as elliptical, spherical, cylindrical, plate-shaped, tubular, 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 allow shear zones in particle inclusions or at the around them.
[38] The polymeric microinclusion additive can have a fluidity index (or viscosity) to ensure that the resulting discrete domains can be maintained properly. For example, if the flow rate of the additive is too high, it tends to flow and disperse uncontrollably during the continuous phase. This results in lamellar domains similar to a cocontinuous plate or phase structure, difficult to maintain and likely to rupture prematurely. On the other hand, if the flow rate of the additive is very low, it will tend to agglutinate and form very large elliptical domains, which are difficult to disperse during mixing. This may cause an irregular distribution of the additive throughout the continuous phase. Accordingly, the present inventors have found that the ratio of the microinclusion additive melt index to the matrix polymer melt index is normally about 0.5 to about 10, in some embodiments, about 1 at about 8 and, in other embodiments, from about 2 to about 6. The micro-inclusion additive can have, for example, a melt index of about 5 to about 200 grams for 10 minutes, in some embodiments of about 20 to about 150 grams for 10 minutes and, in other embodiments, of about 40 to about 100 grams for 10 minutes, determined at a load of 2160 grams and at a temperature of at least about 40 ° C above its melting temperature (eg 210 ° C).
[39] In addition to the properties noted above, the mechanical characteristics of the micro-inclusion additive can also be selected to achieve the desired porous network. For example, applied with an external force, stress concentrations (eg, including normal and shear stresses) and shear flow zones and / or plastic flow can be initiated in and around the discrete phase domains , as a result of stress concentrations that arise from a difference in the elastic modulus of the additive and the matrix polymer. Higher concentrations of stress promote a more intense localized plastic flow in the domains, allowing them to undergo considerable elongation when subjected to stress. These elongated domains allow the compound to have a more flexible and soft behavior. To improve stress concentrations, the microinclusion additive can be selected so that it has a relatively high Young's modulus of elasticity, compared to the polyolefinic matrix. For example, the ratio of the modulus of elasticity of the additive to that of the polyolefin matrix is generally from about 1 to about 250, in some embodiments from about 2 to about 100, and in other embodiments, from about from 2 to about 50. The modulus of elasticity of the micro-inclusion additive can, for example, vary from about 200 to about 3,500 megapascals (MPa), in some embodiments from about 300 to about 2,000 MPa and, in other embodiments, from about 400 to about 1500 MPa. In contrast, the modulus of elasticity of the polyolefin, for example, can vary from about 100 to about 1,500 megapascals (MPa), and in some embodiments from about 200 to about 1000 MPa. Alternatively, the modulus of elasticity of the micro-inclusion additive may be less than the modulus of elasticity of the polyolefin matrix. The modulus of elasticity can, for example, vary from about 10 MPa to about 100 MPa, and optionally, from about 20 MPa to about 80 MPa.
[40] Although a wide variety of micro-inclusion additives can be employed and which have the properties identified above, particularly suitable examples of such additives may include styrenic copolymers (eg, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene -ethylene-butadiene-styrene, etc.); fluoropolymers, such as polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), etc .; polyvinyl alcohols; polyvinyl acetates; polyesters, such as aliphatic polyesters such as polycaprolactone, polyesteramides, polylactic acid (PEA) and its 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-hydroxydecanoic, poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate, and succinate-based aliphatic polymers (e.g., polybutylene succinate, polybutylene succinate adipate, polyethylene succinate , etc.); aliphatic-aromatic copolyesters (for example, polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene adipate isophthalate, polybutylene adipate isophthalate, etc.); aromatic polyesters (for example, polyethylene terephthalate, polybutylene terephthalate, etc.); and so on.
[41] Micro-inclusion additives are generally considered to be particularly rigid, to the extent that they have a relatively high glass transition temperature. For example, the glass transition temperature ("Tg") can be from about 0 ° C or more, in some embodiments from about 5 ° C to about 100DC, in some embodiments, from about 30 ° C to about 80 ° C, and in some embodiments, from about 50 ° C to about 75 ° C. The glass transition temperature can be determined by dynamic mechanical analysis in accordance with ASTM El640-09.
[42] 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”), mesolactic acid or combinations thereof. Monomeric units can also be formed by anhydrides of any isomer of lactic acid, including L-lactide, D-lactide, mesolactide 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). Polylactic acid can be a homopolymer or a copolymer, such as one containing monomeric units derived from L-lactic acid and monomeric units derived from D-lactic acid. Although not required, the content ratio of one of the monomeric units derived from L-lactic acid and the monomeric unit derived from D-lactic acid is preferably about 85% per mol or more, in some embodiments , of about 90% per mol or more and, in other embodiments, of about 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.).
[43] In a specific embodiment, polylactic acid has the following general structure:

[44] In a specific example of a suitable polylactic acid polymer that can be used in the current invention is marketed by Biomer, Inc. of Krailling, Germany) under the name BIOMER ™ L9000. Other suitable polylactic acid polymers are available from Natureworks LLC of Minnetonka, Minnesota (NATUREWORKS®) or Mitsui Chemical (LACEA®). Still other suitable polylactic acids can be 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 included in their entirety in this document, by reference, for all purposes.
[45] Polylactic acid typically has an average molecular weight in number ("Mn") ranging from about 40,000 to about 180,000 grams per mole; in some embodiments, of about
[46] 50,000 to about 160,000 grams per mole and, in other embodiments, from about 80,000 to about 120,000 grams per mole Likewise, the polymer usually has an average molecular weight in number ("Mn") that varies from about 80,000 to about 250,000 grams per mole; in some embodiments, from about 100,000 to about
[47] 200,000 grams per mol and, in other embodiments, from about 110,000 to about 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 typically ranges from about 1.0 to about 3.0; in some embodiments from about 1.1 to about 2.0 and, in other embodiments, from about 1.2 to about 1.8. The average molecular masses in number and weight can be determined by methods known to those of skill in the art.
[48] Some types of pure polyester (for example, polylactic acid) can absorb water from an environment in a way that has a moisture content of about 500 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 ASTM D 7191-05, as described below. Since the presence of water during melt processing can hydrolytically degrade the polyester and reduce its molecular weight, it is sometimes 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 about 300 parts per million ("ppm") or less, in some embodiments, about 200 ppm or less, in some embodiments, from about 1 to about 100 ppm, before mixing with the microinclusion additive. The drying of the polyester can take place, for example, at a temperature of about 50 ° C to about 100 ° C and, in some embodiments, from about 70 ° C to about 80 ° C.
[49] Regardless of the materials used, the relative percentage of the microinclusion additive in the thermoplastic composition is selected to achieve the desired properties without considerably affecting the resulting compound. For example, the microinclusion additive is normally used in an amount of about 1% by weight to about 30% by weight, in some embodiments, from about 2% by weight to about 25% by weight and, in other embodiments, from about 5% by weight to about 20% by weight of the thermoplastic composition, based on the weight of the polyolefinic matrix employed in the compound. The concentration of the micro-inclusion additive in the entire thermoplastic composition can also be formed from about 0.1% by weight to about 30% by weight, in some embodiments, from about 0.5% to about 25% by weight and, in other embodiments, from about 1% to about 20% by weight.
[50] A wide variety of ingredients can be used in the compound for several different reasons. For example, in a particular embodiment, an interphasic modifier can also be employed in the thermoplastic composition to help reduce the degree of friction and connectivity between the nano-inclusion and / or micro-inclusion additive and the polyolefin matrix, and thus increase the degree and uniformity of take-off. In this way, the pores can be distributed more evenly throughout the compound. The shape of the modifier can be 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 composition and easily migrated to the polymer surfaces. By reducing the physical forces at the interfaces of the polyolefin matrix and the additive, it is believed that the hydrophobic and low viscosity nature of the modifier can help facilitate take-off. As used here, the term "hydrophobic" usually refers to material that has a contact angle of water and air of about 40 ° or more and, in some cases, about 60 ° or more. In contrast, the term "hydrophilic" usually refers to material that has a contact angle of water and air less than about 40 °. A suitable test for measuring the contact angle is ASTM D5725-99 (2008).
[51] Although not necessary, the interphasic modifier may be particularly suitable in embodiments where a micro-inclusion additive is used and where the nano-inclusion additive is a solid (for example, polymeric material). Suitable hydrophobes, low viscosity interphasic modifiers may include, for example, the aforementioned liquids and / or semi-solids. A particularly suitable interphase modifier is polyether polyol, as the commercially available product under the name PLURIOL® WI from Basf Corp. Another particularly suitable modifier is the partially renewable ester, marketed under the trade name HALLGREEN® IM by Hallstar.
[52] When used, the interphasic modifier may comprise from about 0.1% to about 20% by weight, in some embodiments, from about 0.5% by weight to about 15% by weight and , in other embodiments, from about 1% by weight to about 10% by weight of the thermoplastic composition, based on the weight of the continuous phase polyolefin matrix. The concentration of interphasic modifiers in the entire thermoplastic composition can likewise be formed from about 0.05% to about 20% by weight, in some embodiments from about 0.1% to about 15% by weight and, in other embodiments, from about 0.5% to about 10% by weight. In the quantities noted above, the interphasic modifier will have a feature that allows it to migrate quickly to the interfacial surface of the polymers and facilitate detachment without damaging the melting properties of the thermoplastic composition. For example, the flow rate of the thermoplastic composition can also be similar to that of the polyolefin matrix. For example, the fluidity index of the compound (on a dry basis) can be about 0.1 to about 250 grams for 10 minutes, in some embodiments of about 0.5 to about 200 ranges for 10 minutes and, in other embodiments, from about 5 to about 150 grams for 10 minutes, determined at a load of 2,160 grams and at a temperature of 190 ° C according to the ASTM D1238 standard.
[53] Compatibility agents can also be used to improve interfacial adhesion and reduce the interfacial tension between the domain and the matrix, thus allowing the formation of small domains during mixing. Examples of suitable compatibilizing agents may include, for example, epoxy functionalized copolymers or maleic anhydride chemical parts. An example of a maleic anhydride compatibilizing agent is polypropylene-grafted maleic anhydride, which is commercially available from Arkema under the trade names Orevac ™ 18750 and Orevac ™ CA 100. When used, compatibilizing agents can consist of about 0.05% to about 10% by weight, in some embodiments, from about 0.1% by weight to about 8% by weight and, in other embodiments, from about 0.5% by weight. weight at about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase polyolefin matrix.
[54] Other suitable materials that can also be used in the thermoplastic composition, such as catalysts, antioxidants, stabilizers, surfactants, waxes, solid solvents, fillers, nucleating agents, particulates, flocs and other materials added in order to improve the processing capacity and mechanical properties of the thermoplastic composition. Regardless, a beneficial aspect of the current 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, nitrogen, etc.). pore initiation charge of inorganic oxides (eg calcium carbonate). In fact, the thermoplastic composition can be considerably free of blowing agents and / or pore-initiating inorganic oxide fillers. For example, blowing agents and / or fillers may be present in an amount not exceeding about 1% by weight, in some embodiments not exceeding about 0.5% by weight and, in other embodiments, from about 0.001% to about 0.2% by weight of the thermoplastic composition. In addition, due to the stress-bleaching properties, as described in more detail below, the resulting compound can achieve an opaque color (eg, white) without the need for conventional pigments, such as titanium dioxide. In certain embodiments, for example, pigments can be present in an amount of no more than about 1% by weight, in some embodiments no more than about 0.5% by weight and in other embodiments from about 0.001% to about 0.2% by weight of the thermoplastic composition. POLYOLEFINE MATERIAL
[55] The polyolefinic material of the present invention can generally be formed by drawing the thermoplastic composition. To form the initial thermoplastic composition, the components are generally mixed using one of several known techniques. In one embodiment, for example, the components can be supplied separately or as a combination. For example, the components can be mixed dry to form an essentially homogeneous dry mixture and can be supplied simultaneously or in sequence in a melt-processing apparatus that mixes 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. can be used to mix and process materials by melting. Especially suitable melt-processing apparatus 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 mixture. 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.
[56] Regardless of the particular processing technique chosen, the resulting mixed and melted compound generally contains nanoscale domains of the nano-inclusion additive and, optionally, microscale domains of the micro-inclusion additive. The degree of shear / pressure and heat can be controlled to ensure sufficient dispersion, but not so high as to negatively reduce the size of the discrete domains, making them unable to achieve the desired properties. For example, mixing generally occurs at a temperature of about 180 ° C to about 300 ° C, in some embodiments of about 185 ° C to about 250 ° C, and in some embodiments, of about from 190 ° to about 240 ° C. Likewise, the apparent shear rate during processing can vary from about 10 seconds-1 to about 3000 seconds-1, in some embodiments from about 50 seconds-1 to about 2000 seconds-1, and in some embodiments, from about 100 seconds-1 to about 1200 seconds-1. The apparent shear rate can be equal to 4Q / πR3, where Q is the volumetric flow rate (“m3 / s”) of the polymer melt and R is the radius (“m”) of the capillary (for example, matrix 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.
[57] To achieve the desired shear conditions (for example, rate, residence time, shear rate, melt processing temperature, etc.), the speed of the extruder rotations can be selected within a certain range. Generally, an increase in the temperature of the product is observed with increasing speed of rotation due to the additional input of mechanical energy into the system. For example, the speed of rotation can vary from about 50 to about 600 revolutions per minute ("rpm"), in some embodiments, from about 70 to about 500 rpm and, in other embodiments, from about 100 to about 300 rpm. This can result in a temperature high enough to disperse the first nanoinclusion additive without negatively affecting the size of the resulting domains. The melt shear rate and, in turn, the degree to which the additives are dispersed, can also be increased 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, the 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 on 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.
[58] Regardless of the particular way it is shaped, the compound can be stretched in the longitudinal direction (for example, machine direction), the cross direction (for example, machine direction), etc., or also a combination of them, to form a porous network. If desired, the compound can be drawn in line, as it is formed in a film, fiber, etc. Alternatively, the compound can be stretched in its solid state after being formed into a film, fiber, etc., before and / or after lamination on other optional materials. By "solid state" stretching, it is generally understood that the compound is maintained at a temperature below the melting point of the polyolefin matrix polymer. Among other things, this helps to ensure that the polymer chains are not altered in such a way that the pore network becomes unstable. For example, the compound can be drawn at a temperature of about -50 ° C to 150 ° C, in some embodiments between about -40 ° C to about 140 ° C, and in some embodiments, at from about -20 ° C to about 100 ° C, and in some embodiments, from about 0 ° C to about 50 ° C. In certain cases, the drawing temperature can also optionally be at least about 10 ° C, in some embodiments at least about 20 ° C, and in some embodiments, at least about 30 ° C below the glass transition temperature of the component with the highest glass transition temperature (eg micro-inclusion additive). In such embodiments, the compound can be drawn at a temperature of about 0 ° C to about 50 ° C; in some embodiments, from about 15 ° C to about 40 ° C; and in some embodiments, from about 20 ° C to about 30 ° C.
[59] To achieve the desired stretch, the thermoplastic composition can be formed into a precursor form, stretched and then converted to the desired material (eg, film, fiber, molded article, etc.). In one embodiment, the precursor form may be a film having a thickness of about 1 to about 5,000 micrometers, in some embodiments of about 2 to about 4,000 micrometers, in some embodiments of about 5 at about 2,500 micrometers, in other embodiments from about 10 to about 500 micrometers. As an alternative to forming a precursor shape, the thermoplastic composition can also be drawn in place as it is shaped into the desired shape for the polyolefinic material. In one embodiment, for example, the compound can be stretched as it is formed into a film or fiber.
[60] Regardless, several stretching techniques can be used, such as suction (for example, fiber stretching units), tension frame stretching, biaxial stretching, multiaxial stretching, profile stretching, vacuum stretching, etc. In one embodiment, for example, the compound is stretched with a machine-oriented advisor ("OSM"), such as those marketed by Marshall and Wiliams, Co. of Providence, Rhode Island. OSM units generally have several draft cylinders (for example, 5 to 8) that progressively stretch and thin the film towards the machine. The compound can be drawn in discrete single or multiple discrete drawing operations. It should be noted that some of the cylinders in an OSM apparatus may not be operating at higher progressive speeds. To stretch the compound in the manner described above, it is generally preferable that the OSM cylinders are not heated. However, if desired, one or more cylinders can be slightly heated to facilitate the stretching process, as long as the temperature of the compound remains below the ranges noted above.
[61] The degree of stretching depends in part on the nature of the material being drawn (eg fibers, films, etc.). The compound is generally stretched (for example, in the machine direction) to a "stretch ratio" of about 1.1 to about 3.5, in some embodiments of about 1.2 to about 3, 0 and, in other embodiments, from about 1.3 to about 2.5. The stretching rate is determined by dividing the length of the stretched material by its length before stretching. The stretch rate can also be varied to help achieve the desired properties, for example, the variation of about 5% to about 1500% per minute of deformation, in some embodiments from about 20% to about from 1,000% per minute of deformation and, in other embodiments, from about 25% to about 850% per minute of deformation. Although the compost is typically stretched without the application of external heat (eg, heated cylinders), that heat can optionally be used to improve processing capacity, reduce the drawing force, increase the drawing rates, and improve the uniformity of the drawing. fiber.
[62] Stretching the method described above can result in the formation of a transverse dimension in "nanoscale" ("nanopores"), such as about 800 nanometers or less; in some embodiments, from about 5 to about 700 nanometers and; in other embodiments, from about 10 to about 500 nanometers. Nanopores can also have an average axial dimension (eg length) of about 100 to 5000 nanometers; in some embodiments, from about 50 to about 2000 nanometers; and in some embodiments, from about 100 nanometers to about 1000 nanometers. Micropores can also be formed during stretching, having an average cross-sectional dimension of about 0.2 micrometers or more; in some embodiments about 0.5 micrometers or more, and in other embodiments about 0.5 micrometers to about 5 micrometers. In certain cases, the axial dimension of the micropores and / or nanopores can be greater than the transverse dimension, so that the ratio (ratio of the axial dimension to the transverse dimension) is from about 1 to about 30; in some embodiments, from about 1.1 to about 15; and in other embodiments, from about 1.2 to about 5. For example, the axial dimension of the micropores can be 1 micrometer or more; in some embodiments about 1.5 micrometers or more; and, in other embodiments, from about 2 to about 30 micrometers.
[63] Regardless of the particular size, presentinventors have also found that pores (eg, nanopores, micropores, nanopores or both) can be distributed evenly throughout the material. For example, pores can be distributed in columns oriented in a direction normally perpendicular to the direction in which the tension is applied. These columns can generally be parallel to each other over the entire width of the material. Without the intention of imposing theoretical limitations, it is believed that the presence of this homogeneously distributed porous network can result in a high thermal resistance, as well as good mechanical properties (eg, energy dissipation under load and impact resistance) ). There is a stark contrast to conventional pore creation techniques that involves the use of a blowing agent, which tends to result in uncontrolled pore distribution and low quality mechanical properties.
[64] In addition to forming a porous network, stretching can also significantly increase the axial dimension of the domains, so that they have a generally elongated and linear shape. For example, elongated microscale domains may have an average axial dimension of about 10% or more, in some embodiments from about 20% to about 500% and, in some embodiments, about 50% about 250% larger than the axial dimension of the domains before stretching. The axial dimension (e.g., length) after stretching can, for example, vary from about 1 pm to about 400 pm, in some embodiments from about 5 pm to about 200 pm and in some ways from about 10 µm to about 150 µm. The microscale domain can also be relatively thin, and thus have a small cross-sectional dimension, which can be from about 0.02 to about 20 micrometers, in some embodiments from about 0.1 to about 10 micrometers and, in other embodiments, from about 0.4 to about 5 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) from about 2 to about 150, in some embodiments from about 3 to about 100, and in other embodiments, from about 4 to about 50. Due to their small size, nanoscale domains are generally not stretched in the same way as microscale domains. Thus, nanoscale domains can have an average axial dimension (eg, length), from about 1 to about 1000 nanometers, in some embodiments from about 5 to about 800 nanometers, and in others embodiments, from about 10 to about 500 nanometers, and in some embodiments from about 20 to about 200 nanometers.
[65] Due to its unique and beneficial properties, the polyolefin material resulting from the present invention is well suited for use on a wide variety of different types of articles, such as an absorbent article, packaging film, barrier film, medical products (for example, example, surgical gowns, masks, head cover, surgical cap, shoe cover, sterilization wrap, thermal blanket, heating pad, etc.), and so on. For example, the polyolefin material can be incorporated into an "absorbent product" capable of absorbing water or other fluids. Examples of some absorbent articles, among others: absorbent articles for personal care, such as diapers, training diapers, absorbent panties, incontinence products, feminine hygiene products (eg sanitary napkins, menstrual pads, 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 molding 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, the polyolefin material can be in the form of a fibrous material (e.g., nonwoven fabric) and used to form an outer covering of an absorbent article. If desired, the nonwoven web can be laminated to a liquid-impermeable film, which will be permeable or impervious to vapors. The polyolefinic material may also be in the form of a film that is used on an absorbent article, such as a liquid-impermeable film of the outer cover, which is either vapor-permeable or vapor-impermeable.
[66] Therefore, a particular embodiment of an absorbent article that can employ the polyolefinic material of the present invention, will now be described in more detail. For example, an absorbent product may include a main body portion containing an topsheet, an outer cover or a backsheet, an absorbent core positioned between the backsheet and the topsheet and two flaps extending on each longitudinal side of the portion of main body. The top sheet defines a surface of the absorbent product, facing the body. The absorbent core is positioned inwardly from the outer perimeter of the absorbent product, and includes a side facing the body, positioned adjacent to the top sheet, and a surface facing the clothing, positioned adjacent to the back sheet. In a particular embodiment of the present invention, the backsheet is a film formed of a polyolefinic material of the present invention and is generally impermeable to liquids and, optionally, vapor permeable. The film used to form the backsheet can also be laminated with one or more nonwoven webs as described above.
[67] The top sheet is generally designed to contact the user's body and is liquid permeable. The topsheet may surround the absorbent core in order to completely cover the absorbent product. Alternatively, the topsheet and the backsheet can extend beyond the absorbent core and join peripherally, totally or partially, using known techniques. Usually, the upper and posterior sheets are joined by means of adhesives, by ultrasound, or any other joining method known in the art. The top sheet is hygienic, clean in appearance and relatively opaque to hide body discharges collected and absorbed by the absorbent core. The top sheet also exhibits good penetration and rewetting characteristics, allowing discharges to penetrate quickly through the top sheet and forward to the absorbent core, but not allowing body fluid to return through the top sheet and contact the user's skin . For example, some suitable materials that can be used for the topsheet include non-woven materials, perforated thermoplastic films or a combination thereof. A non-woven fabric made of polyester, polyethylene, polypropylene, bicomponent, nylon, rayon or similar fibers can be used. For example, there is a preference for a uniform white spunbond material as the color exhibits good properties to disguise the periods that pass through it. U.S. Patent No. 4,801,494 to Datta, et al. and 4,908,026 to Sukiennik, et al. have several other cover materials that can be used in the present invention.
[68] The topsheet may also contain a variety of openings formed through it, to allow body fluid to reach the absorbent core more quickly. The openings can be arranged evenly or randomly throughout the top sheet or they can be arranged only in the narrow longitudinal strip positioned along the longitudinal axis of the absorbent product. The openings allow the rapid penetration of body fluids into the absorbent core. The size, shape, diameter and number of openings can vary to meet the specific needs of each person.
[69] The absorbent product may also contain an absorbent core positioned between the top sheet and the back sheet. The absorbent core can be formed by a single absorbent member or by a compound containing different and separate absorbent members. It should be understood, however, that any number of absorbent members can be used in the present invention. For example, in one embodiment, the absorbent core may contain an absorption member positioned between the topsheet and a transfer delay member. The absorption member can be made of a material capable of rapidly transferring, in the z direction, the body fluid received by the topsheet. The absorption member can, in general, have any desired shape and / or size. In one embodiment, the absorption member has a rectangular shape, with a length equal to or less than the total length of the absorbent product, and a width less than the width of the absorbent product. For example, a length of between about 150 mm to about 300 mm and a width of between about 10 mm to about 60 mm can be used.
[70] It is possible to use a variety of different materials for the absorption member, in order to perform the functions described above. The material can be synthetic, cellulosic, or a combination of synthetic and cellulosic materials. For example, cellulose fabrics formed by airflow may be suitable for use on the absorption member. The cellulose fabric formed by airflow can have a weight ranging from about 10 grams per square meter (g / m2) to about 300 g / m2 and, in some embodiments, between about 100 g / m2 at about 250 g / m2. In one embodiment, the airflow-formed cellulose fabric has a basis weight of about 200 g / m2. The fabric formed by airflow can be formed from short and / or long fibers of wood. The air flow tissue has a fine pore structure and provides excellent evaporation capacity, especially for menstruation.
[71] If desired, the transfer delay member can be positioned vertically below the absorption member. The transfer retarding member can contain a material less hydrophilic than the other absorbent members and can, in general, be characterized as quite hydrophobic. For example, the transfer retarding member may be a fibrous non-woven mat composed of a relatively hydrophobic material, such as polypropylene, polyethylene, polyester or the like, and may also be composed of a mixture of these materials. An example of a suitable material for the transfer retarding member is a spunbond weft composed of multilayer polypropylene fibers. Other examples of materials suitable for transfer delay members include spunbond wefts composed of polypropylene fibers which can be circular, trilobal or polilobal in cross shape and which can be hollow or solid structures. Normally, blankets are joined, for example, by thermal bonding, above 3% to about 30% of the blanket area. Other examples of suitable materials that can be used on the transfer delay member are described in U.S. Patent No. 4,798,603 to Meyer, et al. and 5,248,309 for Serbiak, et al. To adjust performance, the transfer delay member can also be treated with a selected amount of surfactant, to increase its initial water absorption capacity.
[72] The transfer delay member can, in general, have any size, such as a size of about 150 mm to about 300 mm. Normally, the length of the transfer delay member is almost equal to the length of the absorbent product. The transfer delay member may also be equal in width to the absorption member, but is generally wider. For example, the width of the transfer delay member can be between about 50 mm to about 75 mm, and especially about 48 mm. The transfer delay member normally weighs less than other absorbent members. For example, the weight of the transfer delay member is usually less than about 150 grams per square meter (g / m2) and, in some embodiments, between about 10 g / m2 to about 100 g / m2. In a specific embodiment, the transfer delay member is formed by a spunbond weft with a weight of about 30 g / m2.
[73] In addition to the aforementioned members, the absorbent core may also include a composite absorbent member, such as a shaped material. In that case, fluids can be transferred from the transfer delay member to the composite absorbent member. The composite absorbent member may be formed separately from the absorption member and / or the transfer delay member, or may be formed simultaneously with them. In one embodiment, for example, the composite absorbent member may be formed in the transfer delay member or the absorption member, which acts as a carrier during the co-forming process described above.
[74] Polyolefinic material can also be used in a wide variety of other types of articles. Non-limiting examples include, for example, insulation materials for refrigeration units (for example, refrigerators, freezers, vending machines, etc.); automotive components (for example, front and rear seats, headrests, armrests, door panels, rear shelves / package trays, steering wheels and interior trim, panels, etc.); building panels and sections (for example, roofs, wall cavities, floors, etc.); clothing (for example, coats, shirts, pants, gloves, aprons, overalls, shoes, boots, socks, head accessories, insoles, etc.); furniture and clothes (for example, sleeping bags, comforters, etc.); liquid storage / transfer systems (for example, tubes or tankers of liquid hydrocarbons / gas, liquid nitrogen, oxygen, hydrogen, or crude oil); extreme environments (for example, under water or space); food products and beverages (for example, glasses, coasters, plates, etc.); containers and bottles; and so on. Polyolefin material can also be used in a "garment", which is generally intended to include any article that is shaped to fit a part of a body. Examples of such articles include, but are not limited to, clothing (for example, shirts, pants, jeans, pants, skirts, jackets, clothing for physical, athletic, aerobic, swimwear, cycling jerseys or shorts, swimsuit / swim trunks, running clothing , wetsuit, bodysuit, etc.), shoes (for example, shoes, socks, boots, etc.), protective clothing (for example, fireman's jacket), accessories (for example, belts, bra straps, side panels, gloves, socks, leggings, orthopedic appliances, etc.), underwear (for example, underwear, T-shirts, etc.), compression clothing, draped clothing (for example, kilts, thongs, togas, ponchos, coats, shawls, etc.), and so on.
[75] The polyolefin material can also be used in several other articles for any particular application. For example, when considering automotive applications, the polyolefin material can be used in fibrous articles or as solid moldings. For example, fibers of the polyolefin material can be beneficially used in articles that can improve the comfort and / or aesthetics of a vehicle (for example, coverings and / or trim for visors, loudspeaker covers and cases, seat coverings , sliding agents for seals and supports for seat coverings, carpets and carpet reinforcement including carpet support, car mats and support for car mats, seat belt coverings and fastenings, floor and ceiling lining, shelf panels rear, ceiling and support coverings, upholstery support, decorative fabrics in general, etc.), materials that can provide general insulation at temperature and / or noise (for example, column padding, door upholstery, ceiling linings, general soundproof and insulating materials, noise-proof enclosures, body parts, windows, roofs and sunroofs, tire reinforcements, etc.) and filter / engine materials (eg example, fuel filters, oil filters, battery separators, cabin air filters, transmission tunnel materials, fuel tanks, etc.).
[76] Solid moldings that include polyolefinic material can be used to improve automotive safety components. For example, the polyolefin material can be integrated into passive safety components, such as deformation zones on the rear, front and / or side of a vehicle; inside the car's safety cell, as a component of the airbag or steering wheel (for example, a deformable steering column); as a load barrier; or as a component of a pedestrian safety system (for example, as a component of the bumper, hood, window frame, etc.).
[77] The low density of the polyolefin material can provide weight saving benefits in automotive applications. For example, the polyolefinic material can be a component of the structure of an automobile, including, without limitation, the hood, bumpers and / or bumper supports, the lid of the luggage compartment and / or compartment, and the underside of the vehicle body.
[78] Such a wide application of the polyolefin material is applicable to a wide variety of fields, and is not intended to be limited in any way to the automotive sector. For example, polyolefin material can be used in the transport industry in any suitable application, including, without limitation, aerospace applications (eg, airplanes, helicopters, space transport, military aerospace devices, etc.), marine applications (boats, ships , passenger vehicles), trains, and so on. The polyolefinic material can be used in transport applications in any desired shape, for example, in fibrous articles or solid moldings, in aesthetic applications, for temperature and / or acoustic insulation, in filter and / or engine components, safety components, etc.
[79] The present invention can be better understood with reference to the following examples. Test methods index of fluidity:
[80] The fluidity index ("MFR") is the weight of a polymer (diagrams) forced through an extrusion rheometer orifice (diameter 0.0825 inches) when subjected to a load of 2,160 grams in 10 minutes , usually at 190 ° C, 210 ° C or 230 ° C, unless otherwise specified. The fluidity index is measured according to the ASTM D1238 test method with a Tinius Olsen extrusion plastomer. Thermal properties:
[81] The glass transition temperature (Tg) can be determined by means of dynamic mechanical analysis (DMA), according to the ASTM El640-09 standard. A TA Instruments Q800 instrument can be used. Experimental tests can be performed on voltage / voltage geometry, in a temperature sweep mode in the range of -120 ° C to 150 ° C with a heating rate of 3 ° C / min. The voltage amplitude frequency can be kept constant (2 Hz) during the test. Three (3) independent samples can be tested to obtain an average glass transition temperature, which is defined by the peak value of the tangent curve o, where the tangent o is defined as the ratio of the loss module to the storage module. (tangent o = E ”/ E ').
[82] The melting temperature can be determined using differential scanning calorimetry (DSC). The differential scanning calorimeter can be a DSC Q100 calorimeter, which has been equipped with a liquid nitrogen cooling accessory and UNIVERSAL ANALYSIS 2000 analysis software (version 4.6.6), which are available from TA Instruments Inc. of New Castle , Delaware. To avoid handling samples directly, tweezers or other instruments are used. The samples are placed in an aluminum pan and weighed to the nearest 0.01 milligram on an analytical balance. A lid is folded over the sample material over the pan. Usually, the resin grains are placed directly on the weighing pan.
[83] The calorimetry differential scanning equipment is calibrated using an Indian metal standard, and a basic correction is made, as described in the equipment's operating manual. The material sample is placed in the test chamber of the calorimetry differential scanning equipment to be tested and an empty plate is used as a reference. All tests are performed with the application of 55 cubic centimeters per minute of nitrogen (industrial grade) on the test chamber. For resin grain samples, the heating and cooling program is a 2-cycle test, which started with the chamber balance at -30 ° C, followed by a first heating period up to a rate of 10 ° C per minute to a temperature of 200 ° C, followed by a sample equilibrium at 200 ° C for 3 minutes, followed by a first cooling period of 10 ° C per minute to a temperature of -30 ° C, followed by the sample equilibrium 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. All tests are performed with the application of 55 cubic centimeters per minute of nitrogen (industrial grade) on the test chamber.
[84] The results are evaluated using the UNIVERSAL ANALYSIS 2000 analysis software, which identifies and quantifies the inflection glass transition temperature (Tg), the endothermic and exothermic peaks and the areas under the peaks in the DSC graphs. The glass transition temperature is identified as the region in the narrative line where a clear change in slope has occurred, and the melting temperature is determined by an automatic inflection calculation. Stress properties of the molded article:
[85] The module was determined using an MTS 810 hydraulic tension table to extract bones from Type I injection molded dogs, as described in ASTM D638-10 (samples extracted at a rate of 50 mm / min or 87.7% min of deformation). The tension frame fixings can have a nominal length of 115 mm. Peak stress, breaking stress, elongation to failure and energy per volume to failure were determined using an MTS Synergie 200 tension board for removing bone from Type V dogs, injection molded, as described in ASTM D638- 10 (samples extracted at a rate of 8.4 mm / min or 87.7% min of deformation). The tension frame fixings can have a nominal length of 25.4 mm. In each test, the specimens were conditioned at 23 ° C ± 2 ° C and with a relative humidity of 50% ± 10% for a minimum period of 40 hours. The test conditions were 23 ° C ± 2 ° C and 50% ± 10% relative humidity. Five (5) specimens were tested for each compound. A computer program (eg, TestWorks) 4 was used to collect the data during the test and to generate a stress curve in relation to a strain curve, from which the mean modules, peak of tension, tensile strength, elongation to failure and energy per volume to failure. Film tension properties:
[86] The films were tested for detention properties (maximum stress, modulus, deformation at rupture and energy by volume at rupture) in an MTS Synergie 200 stress frame. The test can be performed in accordance with ASTM D638- 10 (at about 23 ° C). Film samples can be cut into a dog bone shape with a central width of 3.0 mm before testing. Dog bone film samples can be held in place by means of fasteners on the MTS Synergie 200 device with a length of the part to be measured 18.0 mm. The film samples can be stretched at a pull speed of 5.0 in / min until rupture occurs. Five samples of each film can be tested in the machine direction (MD) and in the cross direction (CD). A computer program (eg, TestWorks 4) can be used to collect data during the test and generate a stress versus strain curve, from which various properties can be determined, including modulus, maximum stress, elongation and energy to break. Fiber tension properties:
[87] The voltage 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 millimeters 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 shortest 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 to the fiber samples.
[88] A constant rate of the type of traction tester extension 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:

[89] The toughness values can be expressed in terms of gram strength per denier. Peak elongation (% of stress at break) and peak stress are also calculated.
[90] The peak load of a weft can be determined using a 2 "x 6" strip cut along the length (MD) and width (CD). The test can be performed on a universal tensile tester equipped with two 1 "x3" rubber-coated fixings. The length can be 76 ± 1 mm (3 ± 0.04 "). Density and percentage of empty volume:
[91] To determine density and percentage of empty volume, width (Wi) and thickness (Ti) of the specimen were initially measured before stretching. The length (Li) before drawing can also be determined by measuring the distance between two marks on the specimen surface. Consequently, the specimen must have stretched to initiate the formation of pores. Sample width (Wf), thickness (Tf) and length (Lf) can be measured as close to 0.01 mm using a Digimatic Caliper caliper (Mitutoyo Corporation). The volume (Vi) before drawing can be calculated by Wi x Ti x Li = Vi. The volume (Vf) after stretching can also be calculated by Wf x Tf x Lf = Vf. The density (Pf) can be calculated by Pf = P / cl, where Pi is the density of the precursor material; and the percentage of empty volume (% Vv) was calculated by:% Vv = (1 - 1 / <1) x 100. Hydrostatic pressure test ("Hydrohead"):
[92] The hydrostatic pressure test is a measure of the resistance of a material to water penetration in the liquid state under a static pressure and is performed according to the AATCC Test Method 127-2008. The results of each sample can be averaged and recorded in centimeters (cm). A higher value indicates greater resistance to water penetration. Water vapor transmission rate (“TTVA”)
[93] The test used to determine the TTVA of a material may vary based on the nature of the material. One technique for measuring the TTVA value is ASTM E96 / 96M-12, Procedure B. Another method involves using the INDA Test Procedure IST-70.4 (01). The INDA test procedure is summarized as follows. A dry chamber is separated from a wet chamber of known temperature and humidity by a permanent protective film and the sample material to be tested. The purpose of the protective film is to define a definite air gap and to calm or calm the air in the air gap while it is characterized. The dry chamber, the protective film and the wet chamber form a diffuser cell, in which the test film is sealed. The sample holder is known as the Permatran-W model 100K manufactured by Mocon / Modem Controls, Inc., Minneapolis, Minnesota. A first TTVA test of the protective film and air gap between the evaporator assembly is performed, generating 100% relative unity. The water vapor diffuses through the air gap and the protective film and then mixes with the dry gas flow, proportional to the water vapor concentration. The electrical signal is routed to a computer for processing. The computer calculates the transmission rate of the air gap and the protective film and stores the value for later use.
[94] The transmission rate of the protective film and air gap is stored in the computer as CalC. The sample material is then sealed in the test cell. Again, the water vapor diffuses through the air gap into the protective film and the test material, and then mixes with the dry gas stream that sweeps the test material. Also, again, the mixing is conducted to the steam sensor. The computer then calculates the transmission rate for the combination of air gap, protective film and test material. This information is then used to calculate the baud rate at which the unit is transmitted by the test material according to the equation:

[95] The water vapor transmission rate ("TTVA") is then calculated as follows:
where, F = the flow of water vapor in cm3 per minute; psat (T) = the density of water in the saturated air at a temperature T; RH = the relative humidity in specific places in the cell; A = the transversal area of the cell; ePsat (T) = the saturated vapor pressure of the water vapor at temperature Conductive properties
[96] Thermal conductivity (W / mK) and thermal resistance (nrK / W) can be determined according to the ASTM E-1530-11 standard ("resistance to the thermal transmission of materials by the protected heat flow meter technique. ") using an Anter Unitherm Model 2022 tester. The desired test temperature can be 25 ° C and the applied load can be 0.17 MPa. Before testing, the sample can be conditioned for +40 hours at a temperature of 23 ° C (+2 ° C) and a relative humidity of 50% (+ 10%). The thermal intake (W / m2K) can also be calculated by dividing the thermal resistance by 1. Porosity Frazier:
[97] Frazier porosity was measured in a Frazier® low-pressure and low differential pressure tester (FAP-LP) by cutting an 8 "strip (measured along the machine's direction) from a sample and folding the sample as an accordion (in the transverse direction) to obtain six layers. EXAMPLE 1
[98] A precursor mixture was made, and contained 95% by weight of isotactic propylene homopolymer (M3661, melt index 14 g / 10 at 230 ° C and melting temperature of 150 ° C, Total Petrochemicals) in combination with 5 % by weight of alkoxylated alcohol (Pluriol® WI 285, BASF). The components were composed in a double screw extruder with corotation (ZSK-30 from Werner and Pfleiderer, with a diameter of 30 mm and a C / D = 44). The extruder had seven heating zones. The temperature in the extruder ranged from 180 ° C to 220 ° C. The polymer was fed gravimetrically into the extruder hopper at 15 pounds per hour and the liquid was injected into the drum via a peristaltic pump. The extruder was operated at 200 revolutions per minute (“rpm”). In the last section of the drum (front), a die with three 6 mm diameter holes was used to form the extrudate. The extrudate was air-cooled on a conveyor belt with ventilation and molded into pellets by a Conair pelletizer. The injected samples (ASTM D638 Type 1) were made from the precursor mixture using a Boy 22D injection molding machine with 3 heating sections. The temperature in the heating sections ranged from 185 to 220 ° C. The injection retention pressure time varied from 14s to 24s, the cooling time from 12s to 23s, cycle time varied from 22s to 43s, and the mold temperature was fixed at about 21 ° C.
[99] Once formed, the samples were drawn on a tension tester 810 Material Test System, at a tensile speed of 25 mm / min at 25 ° C. To analyze the material's morphology, both stretched and unstretched injection molded bars were fractured by freezing in liquid nitrogen. The fractured surfaces were coated with layers with gold-palladium alloy, and analyzed using a Jeol 6490LV Scanning Electron Microscope in high vacuum. The results are shown in Fig. 1. As shown in Fig. 1, Pluriol® WI 285 can initially form liquid nanodomains in the polypropylene matrix that have a width of about 50 to 500 nanometers. Fig. 2 shows an example of a fractured surface by freezing the stretched molded bar containing liquid domains, seen perpendicular to the long axis of the narrow area. As shown, a porous network is formed in the polypropylene matrix and contains nanopores with a width of 100 to 500 nanometers and a length of 2 to 5 micrometers. EXAMPLE 2
[100] A precursor mixture was formed from 92.5% polypropylene (M3661, Total Petrochemicals) weight and 7.5% by weight polylactic acid (PLA 6252, melt index 70 to 85 g / 10 min at 210 ° C, NatureWorks®) in the manner described in Example 1. Injected samples were also formed and tested before and after stretching, as described in Example 1. The results are shown in Figs. 3-4. As shown in Fig. 3, the mixture exhibited a relatively large domain size. In stretching, as shown in Fig. 4, larger domain sizes tended to form relatively long, relatively large pores. A stress-strain curve was also generated for the stretched sample and is shown in Fig. 5. As shown, the mixture showed a premature and random failure. EXAMPLE 3
[101] A precursor mixture was formed from about 91.8% by weight of polypropylene (M3661, Total Petrochemicals) 7.4% by weight of PLA 6252, and 0.7% by weight of a polyepoxide as described in Example 1. The polyepoxy was poly (ethylene-co-methyl acrylate-co-glycidyl methacrylate) (LOTADER® AX8900, Arkema), with a melt flow rate of 6 g / 10 min (190 ° C / 2160 g) , a glycidyl methacrylate content of 8% by weight, a methyl acrylate content of 24% by weight, and an ethylene content of 68% by weight. Injected samples were also formed and tested before and after stretching, as described in Example 1. The results are shown in Figs. 6-7. As shown in Fig. 6, the mixture exhibited a relatively small domain size. After stretching, as shown in Fig. 7, the small domain sizes of the mixture tended to form relatively small pores. A stress-strain curve was also generated for the stretched sample and is shown in Fig. 8. As shown, the mixture showed good mechanical properties, similar to that of pure polypropylene. In addition, a section of the narrow region of the stretched molded bar was cut and then submerged in hexane (density 0.65 g / cc). It was observed that the narrow region of the stretched molded bars floated in hexane, which suggested that the density is less than 0.65 g / cc. EXAMPLE 4
[102] The fiber was produced from the precursor mixture of Example 3 using a Davis-Standard fiber spinning line equipped with a 0.75 inch single-screw extruder and 16-hole die with 0.6 mm diameter. The fibers were collected in different proportions of stretch. The adoption speed varied from 1 to 1000 m / min. The temperature of the extruder ranged from 175 ° C to 220 ° C. The fibers were stretched in a tensile tester at 300 mm / min up to 400% stretch at 25 ° C. To analyze the morphology of the materials, the fibers were fractured by freezing in liquid nitrogen and analyzed using a Jeol 6490LV Scanning Electron Microscope in high vacuum. The results are shown in Fig. 9-11. As shown, the spheroidal pores are formed in such a way that they are highly elongated in the direction of stretching. Both nanopores (—50 nanometers wide, -500 nanometers long) and micropores (~ 0.5 micrometers wide, -4 micrometers long) were formed. EXAMPLE 5
[103] A mixture of 93% by weight of polypropylene (Total M3661) and 7% by weight of Lotader® AX8900) was composed in a double screw extruder with co-rotation (ZSK-30 from Werner and Pfleiderer, with a diameter of 30 mm and a C / D = 44). The extruder had seven heating zones. The temperature in the extruder ranged from 180 ° C to 220 ° C. The polymer was fed gravimetrically into the extruder hopper at 15 pounds per hour. The extruder was operated at 200 revolutions per minute (“rpm”). In the last section of the drum (front), a die with three 6 mm diameter holes was used to form the extrudate. The extrudate was air-cooled on a conveyor belt with ventilation and molded into pellets by a Conair pelletizer. The injected samples (ASTM D638 Type 1) were obtained in a Boy 22D injection molding machine with 3 heating sections. The temperature of the heating sections ranged from 185 to 220 ° C. To analyze the material's morphology, the non-stretched molded bars were cut with a razor blade and the cross-sectional area was polished using aluminum oxide polishing discs with sizes ranging from 1 to 0.05 microns. To extract the Lotader® AX8900, the polished samples were soaked in chloroform for 12 hours.
[104] The results are shown in Figs. 12-15. Figs. 12-13 show the polished surface of the PPM3661 / Lotader® AX8900 mixture. The cavities observed on the polished surface correspond to the spaces that were occupied by the Lotader® domains. The narrow region of the injection molded and stretched bars was also fractured by freezing in liquid nitrogen. The surfaces were coated with layers with gold-palladium alloy, and analyzed using a Jeol 6490LV Scanning Electron Microscope in high vacuum. Figs. 14-15 show the narrow region fractured by freezing along the axial direction of the stretched injection molded bar. EXAMPLE 6
[105] A mixture of 91.1 wt% polypropylene (Total M3661), 7.4 wt% polylactic acid (NatureWorks 6251), and 1.5% Lotader® AX8900) were compounded in the extruder and the conditions described in Example 5. In this case, 5% of Pluriol® WI 285 was then injected into the drum via a peristaltic pump. Injection molded bars were prepared as described above. The non-stretched bars and the narrow region of the stretched bars were fractured by freezing in liquid nitrogen. The fractured surfaces were coated with layers with gold-palladium alloy, and analyzed using a Jeol 6490LV Scanning Electron Microscope in high vacuum. The results are shown below in Figs. 16-17. EXAMPLE 7
[106] A mixture of materials was formed, which contained 91.5% by weight of polypropylene (Total Petrochemicals M-3661), 7.5% by weight of polylactic acid (NatureWorks Ingeo 6251D), and 1.0% by weight of a polyepoxide modifier (Arkema Lotader AX8900). This mixture was then mixed by melting by means of a twin screw extruder at 220 ° C to form a homogeneous polymer mixture. The molten polymer mixture was extruded through a multifilament matrix, quenched by water, and cut into a pellet from the underwater pelletizing system, such as those available from Gala Industries of Eagle Rock, Virginia. The composite pellet was then fed into a single screw extruder (24: 1 length to diameter ratio) with a molten film matrix. The materials were melted at a temperature of 220 ° C and extruded through a film mold in which a mold roll at a temperature of 25 ° C. A melt stretch force was applied to the melt film to reduce the thickness from about 177 to 203 micrometers. EXAMPLE 8
[107] A film was formed as described in Example 7, except that the thickness was 254 to 279 micrometers. EXAMPLE 9
[108] The film of Example 7 was stretched in a solid state in a tensile frame (eg, Sintech 1 / S frame available from MTS Systems), at a speed of 50 millimeters per minute at 300% deformation. After stretching, it was determined that the film length increased 5.2 times in the machine direction and the film width decreased by 20%. EXAMPLE 10
[109] The film of Example 8 was stretched in a solid state in a tensile frame (eg, Sintech 1 / S frame available from MTS Systems), at a speed of 50 millimeters per minute at 300% deformation. After stretching, it was determined that the film length increased 5.6 times in the machine direction and the film width decreased by 20%. SEM microphotographs of the film are shown in Figs. 18-19. Various mechanical properties of the stretched films of Examples 9 and 10 were tested. The results are shown in the table below.
EXAMPLE 11
[110] A film was formed as described in Example 7, except that the thickness was 48 to 55 micrometers. EXAMPLE 12
[111] A mixture of materials was formed, and contained 78% by weight of polypropylene (Total Petrochemicals M-3661), 15% by weight of polylactic acid (NatureWorks Ingeo 625ID), and 7.0% by weight of a polyepoxide modifier (Arkema Lotader AX8900). This mixture was then mixed by melting by means of a twin screw extruder at 220 ° C to form a homogeneous polymer mixture. The molten polymer mixture was extruded through a multifilament matrix, quenched by water, and cut into a pellet from the underwater pelletizing system, such as those available from Gala Industries of Eagle Rock, Virginia. The composite pellet was then fed into a single screw extruder (24: 1 length to diameter ratio) with a molten film matrix. The materials were melted at a temperature of 220 ° C and extruded through a film mold in which a mold roll at a temperature of 25 ° C. A melt stretch force was applied to the melt film to reduce the thickness from about 48 to 55 micrometers. EXAMPLE 13
[112] A film was formed as described in Example 12, except that the thickness was 70 to 80 micrometers. EXAMPLE 14
[113] A film was formed as described in Example 12, except that the thickness was 120 to 132 micrometers. EXAMPLE 15
[114] A precursor mixture was made, and contained 91.8% by weight of isotactic propylene (M3661, melt index of 14 g / 10 at 230 ° C and melting temperature of 150 ° C, Total Petrochemicals), 7.45 % polylactic acid (PLA) (Ingeo 6251D, melt index 70-85 g / 10 at 210 ° C, Natureworks) and 0.75% polyepoxide matching agent (Arkema Lotader® AX8900). The polyepoxide modifier was poly (ethylene-co-methyl acrylate-co-glycidyl methacrylate) (Lotader® AX8900, Arkema), with a melt index of 5-6 g / 10 min (190 ° C / 2,160 g), a content glycidyl methacrylate of 7% to 11% by weight, a methyl acrylate content of 13% to 17% by weight, and an ethylene content of 72% to 80% by weight. The components were composed in a double screw extruder with corotation (ZSK-30 from Werner and Pfleiderer, with a diameter of 30 mm and a C / D = 44). The extruder had seven heating zones. The temperature in the extruder ranged from 180 ° C to 220 ° C. The polymer was fed gravimetrically into the extruder hopper at 6.8 kilograms per hour (15 pounds per hour). The extruder was operated at 200 revolutions per minute (“rpm”). In the last section of the drum (front), a die with three 6 mm diameter holes was used to form the extrudate. The extrudate was air-cooled on a conveyor belt with ventilation and molded into pellets by a Conair pelletizer. EXAMPLE 16
[115] The bicomponent fibers were produced in a line of bicomponent fibers equipped with 2 single screw extruders (1.25 in. In diameter). The bicomponent fibers had a 30/70 sheath / core configuration, in which the sheath was formed 100% by weight of polypropylene (M3661, Total Petrochemicals) and the core was formed from the mixture of Example 15. The extruders fed the polymeric compounds of the sheath and core in a 288 capillary die, 0.5 mm in diameter and 4: 1 in length / diameter ratio (C / D). The fibers were spun at a rate of 8 kg / h at a spinning speed of 660 meters per minute and collected in bobbins for the post-stretching process. The extrusion temperature profile of the sheath and core was as follows: Zone 1 = 220 ° C, zone 2 = 225 ° C, zone 3 = 230 ° C, Zone 4 = 240 ° C, and Wiring bundle = 240 ° C. The fibers produced by melt spinning were stretched at room temperature (25 ° C) to 200% between two Godet rollers (single-stage stretch) at a speed of 1200 meters per nunuto. The fibers were then pleated (19 pleats per inch) and cut to a length of 38 mm. The fibers were cut with a razor in liquid nitrogen and analyzed using scanning electron microscopy. The fractured surface was coated with gold-palladium in a Denton Vaccum Desk V crackle system, using 15 mA by 75 s and analyzed using SEM in Field Emission Quanta 650. The results are shown below in Figs. 20-21. Various fiber properties have also been tested as provided in the table below.

[116] A 100 g / m2 air-flow carded and bonded weave (TABCW) was also formed with a blend of fibers from Example 16 (70% by weight and two-component sheath / core fibers, PE / PP ( 30% by weight.) The web was formed on a Truetzschler High-Speed Card EWK 413 equipped with an Asselin Profile 415-FD card and a Fleissner oven (NC State University). The carded web was connected by air flow at 260 ° F and the final thickness was 5.5 mm. EXAMPLE 17
[117] A precursor polymeric mixture was prepared as described in Example 15 and contained 93% by weight of polypropylene matrix (M3661, Total Petrochemicals) and 7% by weight of Lotader® AX8900. Hollow bicomponent fibers were produced in a bicomponent fiber line equipped with 2 single screw extruders (1.25 in. In diameter). The bicomponent fibers had a 50/50 sheath / core configuration, in which the sheath was formed 100% by weight of polypropylene (Achieve 3854) and the core was formed from the mixture described above. The extruders fed the polymeric compounds from the sheath and core into a 72 capillary die with 4C segment design. The fibers were spun at a rate of 2 kg / h at a spinning speed of 198 meters per minute and collected in reels for the post-stretching process. The extrusion temperature profile of the sheath and core was as follows: Zone 1 = 220 ° C, Zone 2 = 225 ° C, Zone 3 = 230 ° C, Zone 4 = 240 ° C, and Wiring bundle = 240 ° Ç. The fiber was quenched in a water bath located 35 cm below the die. The fibers produced by melt spinning were stretched at room temperature (25 ° C) to 200% between two Godet rollers (single-stage stretch) at a speed of 1200 meters per minute. The fibers were cut with a razor blade in liquid nitrogen and analyzed using scanning electron microscopy. The fractured surface was coated with gold-palladium in a Denton Vaccum Desk V crackle system, using 15 mA by 75 s and analyzed using SEM in Field Emission Quanta 650. The results are shown below in Figs. 22-23. Several properties of the fibers were also tested as provided in the table below.
EXAMPLE 18
[118] A precursor mixture was formed, as described in Example 15, except that the material was produced using a 64 mm coil-fired twin screw extruder at a production rate of 270 kilograms per hour (600 pounds per hour) and at a temperature of 220 ° C. The molten polymer mixture was extruded through a multifilament matrix, quenched by water, and cut into a pellet from the underwater pelletizing system, such as those available from Gala Industries of Eagle Rock, Virginia. A single-component fiber was formed from the mixture at a rate of 22.5 kilograms per hour on a single-component fiber spinning line (FiberVisions) equipped with a 1.25 24 C / D single screw extruder and two rows, each having 675 round capillaries (1,350 in total), 0.35 mm in diameter and 4: 1 C / D ratio. The speed of rotation was 435 meters per minute. The heating zones of extruder 7 and the temperature profile of the spinning beam were maintained at 220 ° C. The spinning line was equipped with a single-sided airflow cooling box and the air temperature was 21 ° C. The fibers drawn by melting were collected in 5-pound spools without cold drawing. The oriented fusion fibers had a denier of 10.7 per filament.
[119] The fibers were 100% stretched at a speed of 50 meters per minute, in a stretch unit consisting of three five-roller benches (quintets). The temperature of the first quintet was maintained at 50 ° C and the second and third quintets were maintained at a temperature of 25 ° C. The fibers were pleated and cut to 1.5 inches. The wiring finish was adjusted before the cutting unit to 0.5%. The fibers were cut with a razor blade in liquid nitrogen and analyzed using scanning electron microscopy. The fractured surface was coated with gold-palladium in a Denton Vaccum Desk V crackle system, using 15 mA by 75 s and analyzed using SEM in Field Emission Quanta 650. The results are shown below in Fig. 24. Various properties of the fibers were also tested as provided in the table below

[120] Carded and thermally bonded wefts (30 g / m2) were also produced in a carding line. In order to thermally bind attracts, a diamond union pattern was used, as shown in Fig.25. The calender temperature was 150 ° C and the carding speed was 250 feet per minute. Various properties of the web were then tested, as provided below.


[121] While the invention is described in detail with respect to the specific embodiments thereof, it will be noted that those skilled in the art, by gaining an understanding of the above, can easily conceive of changes and variations of equivalents for these forms of achievement. Therefore, the scope of the present invention must be assessed as that of the appended claims and their equivalents.

权利要求:
Claims (17)
[0001]
1. Polyolefinic material, characterized by being formed from a thermoplastic composition, in which the thermoplastic composition contains a continuous phase that includes a polyolefin matrix polymer and a nano-inclusion additive dispersed in the continuous phase, in the form of discrete domains, in which a porous network is defined in the composition that includes a plurality of nanopores that have an average transverse dimension of 800 nanometers or less, where the transverse dimension is orthogonal to the main axis of the nanopore, where the compound has a density of 0.90 g / cm3 or less; where the nano-inclusion additive is a polymer having a non-polar component; where the polyolefin matrix is a propylene homopolymer, propylene / a-olefin copolymer, ethylene / a-olefin copolymer or a combination of where the composition further comprises a microinclusion additive dispersed in the continuous phase, in the form of discrete domains; and the microinclusion additive is a polymer.
[0002]
2. Polyolefin material according to claim 1, characterized by the fact that the nanopores have an average cross-sectional dimension of 5 to 700 nanometers, and / or in which the nanopores have an average axial dimension of 100 to 5000 nanometers.
[0003]
3. Polyolefinic material according to claim 1 or 2, characterized by the fact that the polyolefinic matrix polymer which has a melt index of 0.5 to 80 grams for 10 minutes, determined at a load of 2160 grams and at 230 ° C, according to ASTM D1238; and / or where the polyolefin matrix polymer is a propylene homopolymer, propylene / a-olefin copolymer, ethylene / a-olefin copolymer or a combination thereof, preferably where the polyolefin matrix polymer is a propylene homopolymer substantially isotactic or a copolymer containing at least 90% by weight of propylene.
[0004]
4. Polyolefinic material according to any one of the preceding claims, characterized by the fact that the continuous phase constitutes 60% by weight to 99% by weight of the thermoplastic composition, and / or in which the nano-inclusion additives constitute 0.05% to 20% of the composition based on the weight of the continuous phase.
[0005]
5. Polyolefin material according to any one of the preceding claims, characterized by the fact that the nanoinclusion additive is a functionalized polyolefin containing a polar and a non-polar component.
[0006]
6. Polyolefin material according to any one of the preceding claims, characterized by the fact that the nano-inclusion additive which has a melt index of 0.1 to 100 grams for 10 minutes, determined at a load of 2160 grams and at a temperature of about 40 ° C above the melting temperature (eg 190 ° C) according to ASTM Dl238; and / or where the ratio of the flow rate of the polyolefin matrix polymer to the flow rate of a polymeric nanoinclusion additive is 0.2 to 8.
[0007]
7. Polyolefinic material according to any one of the preceding claims, characterized by the fact that the nanoscale additive is in the form of nanoscale domains, in which the nanoscale domains have an average cross-sectional dimension of 1 nanometer to 1000 nanometers.
[0008]
8. Polyolefinic material according to any one of the preceding claims, characterized by the fact that the microinclusion additive is a copolymer of styrene, fluoropolymer, polyvinyl alcohol, polyvinyl acetate or a polyester; preferably in which the polymer is a polylactic acid.
[0009]
9. Polyolefin material according to claim 8, characterized by the fact that the microinclusion additive has a glass transition temperature of 0 ° C or more, determined by means of dynamic-mechanical analysis (DMA), according to the ASTM standard El 640-9; hear that the microinclusion additive has a melt index of 5 to 200 grams for 10 minutes; determined at a load of 2160 grams and at a temperature of about 210 ° C, wherein the ratio of the flow rate of the micro-inclusion additive to the flow rate of the polyolefin matrix polymer is 0.5 to 10; hear that the ratio of Young's modulus of the polyolefin matrix polymer to the Young's modulus of the microinclusion additive is 1 to 250; where Young's modulus is determined according to ASTM D638-10.
[0010]
10. Polyolefin material according to claim 8, characterized by the fact that the microinclusion additive is in the form of microscale domains that have an average axial dimension of 1 micrometer to 400 micrometers; or wherein the microinclusion additive constitutes from 1% by weight to 30% by weight of the composition, based on the weight of the continuous phase.
[0011]
11. Polyolefinic material according to any one of the preceding claims, characterized by the fact that the thermoplastic composition further comprises an interphasic modifier.
[0012]
12. Polyolefinic material according to any one of the preceding claims, characterized by the fact that the porous network that still includes micropores.
[0013]
13. Polyolefin material according to any of the preceding claims, characterized by the fact that the total pore volume of the polyolefin material is 15% to 80% per cubic centimeter; and / or that the nanopores make up 20% by vol. or more of the total pore volume of the polyolefin material; and / or that the thermoplastic composition has a density of 0.85 g / cm3 or less.
[0014]
14. Polyolefinic material according to any of the preceding claims, characterized by the fact that the thermoplastic composition is generally free of blowing agents and / or pore-initiating inorganic oxide fillers.
[0015]
15. Absorbent article comprising the polyolefinic material as defined in any of the preceding claims, characterized in that the absorbent article includes a substantially liquid-impermeable layer, a liquid-permeable layer and an absorbent core.
[0016]
An absorbent article according to claim 15, characterized by the fact that the substantially liquid-impermeable layer includes the polyolefinic material; preferably in which the liquid impermeable layer includes a nonwoven web material laminated to a film, and in which film which includes the polyolefinic material.
[0017]
17. Method for forming a polyolefinic material as defined in any one of claims 1 to 14, the method characterized by the fact that it comprises: forming a thermoplastic composition containing the polyolefinic matrix polymer and the nanoincluding additive; e stretching the thermoplastic composition in a solid state; preferably at a stretch rate of 1.1 to 3.0.

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AU2018228336A1|2017-02-28|2019-09-05|Kimberly-Clark Worldwide, Inc.|Techinque for forming porous fibers|

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TWI647113B|2017-09-01|2019-01-11|財團法人工業技術研究院|Sound absorbing material|

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CN109577100B|2018-12-18|2021-08-24|广州泽田餐饮用品实业有限公司|Photooxygenically degradable polyethylene coated paper and preparation method and application thereof|

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TWI733421B|2020-04-24|2021-07-11|南亞塑膠工業股份有限公司|Waterproof and breathable membrane, waterproof and breathable fabric, and method for manufacturing the same|

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

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

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2020-08-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/06/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361833980P| true| 2013-06-12|2013-06-12|

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US61/833,980|2013-06-12|

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US201361907572P| true| 2013-11-22|2013-11-22|

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US61/907,572|2013-11-22|

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PCT/IB2014/062015|WO2014199268A1|2013-06-12|2014-06-06|Polyolefin material having a low density|

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