BR112020007106A2 - two-component fiber three-dimensional lace material - Google Patents

Abstract

The present disclosure refers to a sheet. The sheet is composed of a three-dimensional random loop material that comprises a weft structure of an infinite continuous wound fibers connected by fusion at an infinite number of contact points to form an infinite number of loops. Each continuous fiber includes a component (1) which is an olefin-based polymer with a density of 0.86 g / c3 to 0.96 g / c3, and a component (2) which is an olefin-based polymer with a density of 0.86 g / c3 to 0.96 g / c3. The three-dimensional random loop material has an apparent density of 0.03 g / c3 to 0.08 g / c3.

Description

“TWO COMPONENT THREE-DIMENSIONAL FIBER TIE MATERIAL” BACKGROUND

[1] Articles such as abrasive pads (“scouring pads”) and mats produced from a plurality of random loops arranged in a three-dimensional (“3D”) orientation, random loops formed from polyester elastomer are known. Random loops are polymeric filaments linked together in an open non-woven weave. Mop filaments can be produced from a two-component polymeric material, typically a tough, durable polyester elastomer to apply an abrasive force to a surface.

[2] The 3D lace material based on polyester is resistant and abrasive, without flexibility and softness. Consequently, the technique recognizes the need for 3D loop material produced from materials other than polyester-based elastomers. There is still a need for random loop material produced from multi-component polymeric materials that has softness, flexibility, compression / elasticity and haptics suitable for cushioning and / or packaging applications.

SUMMARY

[3] The present disclosure refers to a sheet. The sheet is composed of a three-dimensional random loop material that comprises a weft structure of an infinite continuous wound fibers connected by fusion at an infinite number of contact points to form an infinite number of loops. Each continuous fiber includes a component (1) which is an olefin-based polymer with a density of 0.86 g / c3 to 0.96 g / c3, and a component (2) which is an olefin-based polymer with a density of 0.86 g / c3 to 0.96 g / c3. The three-dimensional random loop material has an apparent density of 0.03 g / c3 to 0.08 g / c3.

DEFINITIONS

[4] All references to the Periodic Table of Elements in this document must refer to the Periodic Table of Elements published and copyrighted by CRC Press, Inc.,

2003. In addition, any references to a Group or Groups must be to Groups or Groups reflected in this Periodic Table of Elements using the IUPAC system to enumerate groups. Unless stated otherwise, implied from context or routine in the technique, all components and percentages are based on weight. For the purposes of patent practice in the United States, the contents of any patent, patent application or publication referenced herein are incorporated into this document for reference in its entirety (or the equivalent US version thereof is hereby incorporated as a reference). of reference).

[5] The numerical ranges disclosed in this document include all values including the lower to the upper value. For ranges that contain explicit values (for example, 1, or 2, or 3 to 5, or 6, or 7) any sub-range between any two explicit values is included (for example, 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6 etc.).

[6] Unless stated otherwise or implied from the context or routine in the technique, all components and percentages are based on weight, and all test methods are current as of the filing date of this release.

[7] "Blend", "polymer blend" and similar terms are a composition of two or more polymers. Such a mixture can be miscible or not. This mix can be separated by phases or not. This mix may contain one or more domain configurations or not, as determined from transmission electronic spectroscopy, light scattering, x-ray scattering and any other method known in the art. Blends are not laminates, but one or more layers of a laminate can contain a blend.

[8] “Composition” and similar terms are a mixture of two or more materials. Pre-reaction, reaction and post-reaction mixtures are included in compositions, among which the latter will include reaction products and by-products, as well as unreacted components of the reaction mixture and decomposition products, if any, formed from the one or more components of the pre-reaction or reaction mixture.

[9] The terms "that comprises", "that includes", "that has" and its derivatives are not intended to exclude the presence of any additional component, step or procedure, regardless of whether it is specifically disclosed or not. In order to avoid any doubt, all compositions claimed using the term "comprise" may include any additive, adjuvant or additional compound, polymeric or not, unless stated otherwise. In contrast, the term, “which essentially consists of” excludes any other component, step or procedure from the scope of any following quote, except those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically outlined or listed.

[10] An “ethylene-based polymer” is a polymer that contains more than 50 weight percent polymerized ethylene monomer (based on the total weight of polymerizable monomers) and, optionally, can contain at least one comonomer. The ethylene-based polymer includes ethylene homopolymer and ethylene copolymer (meaning units derived from ethylene and one or more comonomers). The terms "ethylene-based polymer" and "polyethylene" are used interchangeably. Non-limiting examples of ethylene-based polymer (polyethylene) include low density polyethylene (LDPE) and linear polyethylene. Non-limiting examples of linear polyethylene include linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE), very low density polyethylene (VLDPE), multi-component ethylene-based copolymer (EPE), multi-block copolymer ethylene / α-olefin (also called olefin block copolymer (OBC)), single site catalyzed low density linear polyethylene (m-LLDPE), substantially linear or linear plastomers / elastomers, and high density polyethylene (HDPE) ). In general, polyethylene can be produced in gas-phase fluidized bed reactors, liquid-phase slurry process reactors or process reactors in liquid-phase solution, using a heterogeneous catalyst system, such as Ziegler- Natta, a homogeneous catalyst system, comprising ligand structures and Group 4 transition metals, such as metallocene, metal centered without metallocene, heteroaryl, heterovalent aryloxyether, phosphinimine and the like. Combinations of heterogeneous and / or homogeneous catalysts can also be used in single or double reactor configurations.

[11] “High density polyethylene” (or “HDPE”) is an ethylene homopolymer or an ethylene / α-olefin copolymer with at least one C4-C10 α-olefin comonomer or C4-C8 α-olefin comonomer and a density greater than 0.94 g / c3, or 0.945 g / c3, or 0.95 g / c3, or 0.955 g / c3 at 0.96 g / c3, or 0.97 g / c3 or 0, 98 g / c3. HDPE can be a monomodal copolymer or a multimodal copolymer. A "monomodal ethylene copolymer" is an ethylene / C4-C10 α-olefin copolymer that has a distinct peak in a gel permeation chromatography (GPC) that shows the molecular weight distribution. A "multimodal ethylene copolymer" is an ethylene / C4-C10 α-olefin copolymer that has at least two distinct peaks in a GPC showing the molecular weight distribution. Multimodal includes copolymer with two peaks (bimodal), as well as copolymer with more than two peaks. Non-limiting examples of HDPE include DOW ™ High Density Polyethylene (HDPE) resins (available from The Dow Chemical Company), ELITE ™ enhanced polyethylene resins (available from The Dow Chemical Company), CONTINUUM ™ bimodal polyethylene resins ( available from The Dow Chemical Company), LUPOLEN ™ (available from LyondellBasell), as well as HDPE products from Borealis, Ineos and ExxonMobil.

[12] An "interpolymer" is a polymer prepared by the polymerization of at least two different monomers. This generic term includes copolymers, commonly used to refer to polymers prepared from two different monomers and prepared from more than two different monomers, for example, terpolymers, tetrapolymers, etc.

[13] “Low density polyethylene” (or “LDPE”) consists of ethylene homopolymer, or an ethylene / α-olefin copolymer comprising at least one C3-C10 α-olefin, preferably C3-C4 which has a density of 0.915 g / cm3 to 0.940 g / cm3 and contains long chain branching with wide MWD. LDPE is typically produced by polymerization by high pressure free radicals (tubular reactor or autoclave with free radical initiator). Non-limiting examples of LDPE include MarFlex ™ (Chevron Phillips), LUPOLEN ™ (LyondellBasell), as well as LDPE products from Borealis, Ineos, ExxonMobil and others.

[14] “Linear low density polyethylene” (or “LLDPE”) is a linear ethylene / α-olefin copolymer that contains heterogeneous short chain branch distribution comprising units derived from ethylene and units derived from at least one comonomer of C3-C10 α-olefin or at least one C4-C8 α-olefin comonomer, or at least one C6-C8 α-olefin comonomer. LLDPE is characterized by little, if any, long chain branching, in contrast to conventional LDPE. LLDPE has a density of 0.910 g / cm3, or 0.915 g / cm3, or 0.920 g / cm3, or 0.925 g / cm3 to 0.930 g / cm3, or 0.935 g / cm3, or 0.940 g / cm3. Non-limiting examples of LLDPE include TUFLIN ™ low density linear polyethylene resins (available from The Dow Chemical Company), Dowlex ™ polyethylene resins (available from Dow Chemical Company), and Marlex ™ polyethylene (available from Chevron Phillips ).

[15] “Ultra low density polyethylene” (or “ULDPE”) and “very low density polyethylene” (or “VLDPE”), each, is a linear ethylene / α-olefin copolymer that contains chain branch distribution heterogeneous short comprising units derived from ethylene and units derived from at least one C3-C10 α-olefin comonomer or at least one C4-C8 α-olefin comonomer or at least one C6-C8 α-olefin comonomer. Both ULDPE and VLDPE have a density of 0.885 g / c3, or 0.90 g / c3 to 0.915 g / c3. Non-limiting examples of ULDPE and VLDPE include ATTANE ™ ultra low density polyethylene resins (available from The Dow Chemical Company) and FLEXOMER ™ very low density polyethylene resins (available from The Dow Chemical Company).

[16] “Multi-component ethylene-based copolymer” (or “EPE”) comprises units derived from ethylene and units derived from at least one C3-C10 α-olefin comonomer, or at least one C4-C8 α comonomer -olefin, or at least one C6-C8 α-olefin comonomer, as described in USP patent references 6,111,023; USP

5,677,383; and USP 6,984,695. EPE resins have a density of 0.905 g / cm3, or 0.908 g / cm3, or 0.912 g / cm3, or 0.920 g / cm3 to 0.926 g / cm3, or 0.929 g / cm3, or 0.940 g / cm3 or 0.962 g / cm3. Non-limiting examples of EPE resins include ELITE ™ enhanced polyethylene (available from The Dow Chemical Company), SURPASS ™ polyethylene (PE) resins (available from Nova Chemicals), and SMART ™ (available from SK Chemicals Co.) .

[17] “Single site catalyzed low density linear polyethylenes” (or “m-LLDPE”) are linear ethylene / α-olefin copolymers that contain homogeneous short-chain branch distribution comprising ethylene-derived units and derivative units of at least one C3-C10 α-olefin comonomer, or at least one C4-C8 α-olefin comonomer, or at least one C6-C8 α-olefin comonomer. The m-LLDPE has a density of 0.913 g / cm3, or 0.918 g / cm3, or 0.920 g / cm3 to 0.925 g / cm3 or 0.940 g / cm3. Non-limiting examples of m-LLDPE include metallocene PE EXCEED ™ (available from ExxonMobil Chemical), m-LLDPE LUFLEXEN ™ (available from LyondellBasell) and m- LLDPE ELTEX ™ PF (available from Ineos Olefins & Polymers).

[18] “Ethylene plastomers / elastomers” are substantially linear or linear ethylene / α-olefin copolymers that contain homogeneous short-chain branch distribution comprising units derived from ethylene and units derived from at least one C3 – C10 α comonomer -olefin, or at least one C4 – C8 α-olefin comonomer, or at least one C6 – C8 α-olefin comonomer. Plastomers / ethylene elastomers have a density of 0.870 g / cm3, or 0.880 g / cm3, or 0.890 g / cm3 to 0.900 g / cm3, or 0.902 g / cm3, or 0.904 g / cm3, or 0.909 g / cm3, or 0.910 g / cm3 or 0.917 g / cm3. Non-limiting examples of ethylene plastomers / elastomers include AFFINITY ™ plastomers and elastomers (available from The Dow Chemical Company), EXACT ™ plastomers (available from ExxonMobil Chemical), Tafmer ™ (available from Mitsui), Nexlene ™ (available from SK Chemicals Co.) and Lucene ™ (available from LG Chem Ltd.).

[19] An "olefin-based polymer" as used herein is a polymer that contains more than 50 weight percent of polymerized olefin monomer (based on a total amount of polymerizable monomers) and, optionally , can contain at least one comonomer. Non-limiting examples of olefin-based polymer include ethylene-based polymer and propylene-based polymer.

[20] A “polymer” is a compound prepared by polymerisation monomers, whether of the same or a different type, which in the polymerized form provide the multiple and / or repetitive “units” or “mer units” that form a polymer. The generic term polymer, therefore, encompasses the term homopolymer, used, in general, to refer to polymers prepared from only one type of monomer, and the term copolymer used, in general, to refer to polymers prepared to from at least two types of monomers. This also covers all forms of copolymer, for example, random, block etc. The terms "ethylene polymer / α-olefin" and "propylene polymer / α-olefin" indicate the copolymer, as described above, prepared from the polymerization of ethylene or propylene, respectively, and one or more α-olefin monomers additional polymerisables. It is found that although a polymer is often referred to as "produced from" one or more specified monomers, "based on" a specified monomer or type of monomer, "containing" a specified monomer content, or the like, in this In this context, the term "monomer" is understood to refer to the polymerized remainder of the specified monomer and not to the unpolymerized species. In general, the polymers in this document are cited as based on "units" which are the polymerized form of a corresponding monomer.

[21] A “propylene-based polymer” is a polymer that contains more than 50 weight percent polymerized propylene monomer (based on the total amount of polymerizable monomers) and, optionally, can contain at least one comonomer.

TEST METHODS

[22] Apparent density. A sample material is cut into a square piece 38 cm × 38 cm (15 inches x 15 inches) in size. The volume of this part is calculated from the thickness measured at four points. The division of weight by volume gives the apparent density (an average of four measurements is made) with values reported in grams per cubic centimeter, g / cm³.

[23] Flexion stiffness. The flexural stiffness is measured according to DIN 53121, with 550 µm thick compression molded plates, using a Frank-PTI Flexion Tester. The samples are prepared by compression molding of resin granules according to the ISO 293 standard. The conditions for compression molding are chosen according to the ISO 1872 - 2007 standard. The average cooling rate of the foundry is 15 ° C / min Bending stiffness is measured in a 2-point bending configuration at room temperature with a span of 20 mm, a sample width of 15 mm and a bending angle of 40 °. Flexion is applied at 6 ° / second (s) and force readings are obtained from 6 to 600 s after the flexion is completed. Each material is evaluated four times with results reported in Newton's millimeters (“Nmm”).

13C NUCLEAR MAGNETIC RESONANCE (NMR)

SAMPLE PREPARATION

[24] Samples are prepared by adding approximately 2.7 g of a 50/50 mixture of tetrachloroethane-d2 / orthodichlorobenzene which is 0.025 M in chromium acetylacetonate (relaxation agent) to a 0.21 g sample in a 10 mm NMR tube. The samples are dissolved and homogenized by heating the tube and its content to 150 ° C.

ACQUISITION PARAMETERS OF DICE

[25] Data are collected using a 400 MHz Bruker spectrometer equipped with a high temperature Bruker Dual DUL cryoprobe. Data are obtained using 320 transients per data file, a 7.3 s pulse repetition delay (6 s delay + 1.3 s acquisition time), 90 degree excitation angles and decoupling reverse batch with a sample temperature of 125 ° C. All measurements were made on non-rotating samples in the locked mode. The samples are homogenized immediately before insertion into the heated NMR Sample changer (at 130 ° C) and are allowed to thermally equilibrate in the probe for 15 minutes before data acquisition.

CRYSTALLIZATION ELECTION FRACTIONING METHOD (CEF)

[26] The comonomer distribution analysis is performed with Crystallization Elution Fractionation (CEF) (PolymerChar, Spain) (B Monrabal et al., Macromol. Symp. 257, 71 to 79 (2007)). Orthodichlorobenzene

(ODCB) with 600 ppm of antioxidant butylated hydroxytoluene (BHT) is used as a solvent. Sample preparation is done with a self-sampler at 160 ° C for 2 hours under agitation at 4 mg / ml (unless otherwise specified). The injection volume is 300 μm. The temperature profile of CEF is: crystallization at 3 ° C / min from 110 ° C to 30 ° C, thermal equilibrium at 30 ° C for 5 minutes, elution at 3 ° C / min from 30 ° C to 140 ° C. The flow rate during crystallization is 0.052 ml / min. The flow rate during elution is 0.50 ml / min. The data is collected at a data point / second. The CEF column is packed by the Dow Chemical Company with 125 μm ± 6% glass beads (MO-SCI Specialty Products) with 0.32 cm (⅛ inch) stainless steel tubes. The glass beads are washed with acid by MO-SCI Specialty with the order from the Dow Chemical Company. The column volume is 2.06 ml. Column temperature calibration is performed using a mixture of Linear Polyethylene of Standard Reference Material NIST 1475a (1.0 mg / ml) and Eicosane (2 mg / ml) in ODCB. The temperature is calibrated by adjusting the elution heating rate so that the linear polyethylene NIST 1475a has a peak temperature at 101.0 ° C and Eicosane has a peak temperature at 30.0 ° C. The resolution of the CEF column is calculated with a mixture of linear polyethylene NIST 1475a (1.0 mg / ml) and hexacontane (Fluka, purum,> 97.0%, 1 mg / ml). A separation of NIST 1475a hexacontane and polyethylene reference line is obtained. The hexacontane area (from 35.0 to 67.0 ° C) for the NIST 1475a area from 67.0 to 110.0 ° C is 50 to 50, the amount of soluble fraction below 35.0 ° C is <1.8% by weight. The resolution of the CEF column is defined in the following equation: çã 1475 - = 1475 +

[27] where the column resolution is 6.0.

[28] Density is measured according to ASTM D 792 with reported values in grams per cubic centimeter, or g / cm³.

[29] Differential Scanning Calorimetry (DSC). Differential Scanning Calorimetry (DSC) is used to measure the melting and crystallization behavior of a polymer over a wide temperature range.

For example, TA Instruments' Q1000 DSC, equipped with an RCS (refrigerated cooling system) and a self-sampler is used to perform this analysis.

During the test, a 50 ml / min nitrogen purge gas flow is used.

Each sample is pressed by melting in a thin film at about 175 ° C; the molten sample is then cooled to room temperature (approximately 25 ° C). The film sample is formed by pressing a “0.1 to 0.2 gram” sample at 175 ° C at 10.34 Mpa (1,500 psi) and 30 seconds to form a “0.254 mm to 0.508 mm film (0.1 to 0.2 mil thick) ”. A specimen of 3 to 10 mg and 6 mm in diameter was extracted from the cooled, weighed polymer, placed in a light aluminum container (about 50 mg) and closed with crimp.

The analysis was then carried out to determine its thermal properties.

The thermal behavior of the sample is determined by grading the sample temperature up and down to create a heat flow versus temperature profile.

First, the sample was quickly heated to 180 ° C and kept isothermal for five minutes in order to remove its thermal history.

Then, the sample was cooled to -40 ° C at a cooling rate of 10 ° C / minute and kept isothermal at -40 ° C for five minutes.

The sample was then heated to 150 ° C (this is the “second heat” rise) at a heating rate of 10 ° C / minute.

The cooling and second heating curves are recorded.

The cooling curve is analyzed by defining the baseline parameters from the start of crystallization to -20 ° C.

The heat curve is analyzed by defining the baseline parameters of -20 ° C until the end of the fusion.

The values determined are peak melting temperature (Tm), peak crystallization temperature (Tc), crystallization onset temperature (Tc onset), melting heat (Hf) (in Joules per gram),% crystallinity calculated for polyethylene samples using:% crystallinity for PE =

((Hf) / (292 J / g)) x 100 and the% crystallinity calculated for polypropylene samples using:% crystallinity for PP = ((Hf) / 165 J / g)) x 100. The heat of fusion (Hf) and peak melting temperature are reported from the second heat curve. The peak crystallization temperature and the initial crystallization temperature are determined from the cooling curve.

[30] Elastic Recovery. Resin pellets are compression molded following ASTM D4703, Annex A1, Method C, to a thickness of approximately 0.127 to 0.254 mm (5 to 10 mil). Geometry microtensile test specimens, as detailed in ASTM D1708, are drilled from the molded sheet. The test specimens are conditioned for 40 hours prior to testing in accordance with Procedure A of Practice D618.

[31] The samples are tested on a screw-driven tensile tester using flat rubber-faced grips. The handle separation is adjusted to 22 mm, equal to the measurement length of microtensile specimens. The sample is extended to a traction of 100% at a rate of 100% / min and maintained for 30 s. The crosshead is then returned to the original handle separation at the same rate and maintained for 60 s. The sample is then subjected to traction to 100% at the same traction rate as 100% / min.

[32] Elastic recovery can be calculated as follows: çã "á $% & çã '-' () = 100%% & çã '

[33] The melt flow rate (MFR) is measured according to ASTM D 1238, Condition of 280 ° C / 2.16 kg (g / 10 minutes).

[34] The melt index (MI) is measured in accordance with ASTM D 1238, Condition 190 ° C / 2.16 kg (g / 10 minutes).

[35] "Melting point" or "Tm", as used in this document (also called melting peak with reference to the shape of the plotted DSC curve), is typically measured by the DSC technique

(Differential Scanning Calorimetry) to measure the peaks or melting points of polyolefins, as described in document No. USP 5,783,638. It should be noted that many mixtures comprising two or more polyolefins will have more than one melting point or peak, many individual polyolefins will comprise only one melting point or peak.

[36] Molecular Weight Distribution (Mw / Mn) is measured using Gel Permeation Chromatography (GPC). In particular, conventional GPC measurements are used to determine the average weight molecular weight (Mw) and the number average molecular weight (Mn) of the polymer and to determine the Mw / Mn. The gel permeation chromatographic system consists of a Polymer Laboratories Model PL-210 instrument or a Polymer Laboratories Model PL-220 instrument. The column and carousel compartments are operated at 140 ° C. Three 10-micron Mixed-B columns from Polymer Laboratories are used. The solvent is 1,2,4 trichlorobenzene. The samples are prepared at a concentration of 0.1 gram of polymer in 50 millimeters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). The samples are prepared by gently shaking for 2 hours at 160 ° C. The injection volume used is 100 microliters and the flow rate is 1.0 ml / minute.

[37] The GPC column set calibration is performed with 21 polystyrene standards of narrow molecular weight distribution with molecular weights in a range of 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least one decade of separation between individual molecular weights. Standards are purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards are prepared in 0.025 grams in 50 milliliters of solvent for molecular weights greater than or equal to

1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80 ° C with gentle agitation for 30 minutes. Mixtures of narrow patterns are performed first and in decreasing order of the highest molecular weight component to minimize degradation. The standard peak molecular weights of polystyrene are converted to molecular weights of polyethylene using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): Mpolypropylene = 0.645 (Mpolystyrene).

[38] Calculations in equivalent molecular weight of polypropylene are performed using Viscotek TriSEC Version 3.0 software.

BRIEF DESCRIPTION OF THE DRAWINGS

[39] Figure 1 is a perspective view of a sheet of three-dimensional random loop material according to one embodiment of the present disclosure.

[40] Figure 1A is an enlarged perspective view of Area 1A in Figure 1.

[41] Figure 2 is a cross-sectional view of a two-component fiber in a side-by-side configuration according to one embodiment of the present disclosure.

[42] Figure 3 is a cross-sectional view of a two-component fiber in a sheath-core configuration according to one embodiment of the present disclosure.

[43] Figure 3A is a cross-sectional view of a two-component fiber in an eccentric sheath-core configuration according to one embodiment of the present disclosure.

[44] Figure 4 is a cross-sectional view of a two-component fiber in an island-at-sea configuration according to one embodiment of the present disclosure.

[45] Figure 5 is a cross-sectional view of a two-component fiber in a segmented pie configuration according to one embodiment of the present disclosure.

[46] Figure 6 is a cross-sectional view of a two-component fiber in a tip-core configuration according to one embodiment of the present disclosure.

[47] Figure 7 is a cross-sectional view of a two-component fiber in a segmented ribbon configuration according to one embodiment of the present disclosure.

DETAILED DESCRIPTION

[48] This disclosure provides a sheet. The sheet is composed of a three-dimensional random loop material (or "3DRLM"). 3DRLM includes a fabric structure of a multitude of continuous coiled fibers joined by melting at various points of contact to form an infinite number of loops. Each continuous fiber includes a component (1) which is an olefin-based polymer with a density of 0.86 g / c3 to 0.96 g / c3. Each continuous fiber also includes a component (2) which is an olefin-based polymer with a density of 0.86 g / c3 to 0.96 g / c3. 3DRLM has an apparent density of 0.03 g / c3 to 0.08 g / c3. THE LEAF

[49] Figure 1 shows that a sheet 10 is composed of a three-dimensional random loop material 14. The sheet 10 has a geometric shape. A "geometric shape", as used in this document, is a three-dimensional shape or a three-dimensional configuration that has a length, a width and a height. The geometric shape can be a regular three-dimensional shape, an irregular three-dimensional shape and combinations thereof. Non-limiting examples of regular three-dimensional shapes include cube, prism, sphere, cone and cylinder. The sheet can be solid or hollow. It is understood that when the geometric shape of the leaf is a prism, the prism may have a cross-sectional shape that is a regular polygon or an irregular polygon with three, four, five, six, seven, eight, nine, 10 or more sides. It is also understood that when the geometric shape of the sheet is a cylinder,

the cylinder may have a cross-sectional shape which is an ellipse or a circle. B. RANDOM TIE MATERIAL

THREE-DIMENSIONAL

[50] Sheet 10 is composed of a three-dimensional random loop material 30. As shown in Figure 1A, a “three-dimensional random loop material” (or “3DRLM”) is a mass or structure of an infinite number of loops 32 formed allowing the continuous fibers 34 to wrap, allowing the respective loops to come into contact in a molten state and to be bonded by heat, or otherwise bonded by casting at the contact points 36. Even when a great deal of stress to cause significant deformation is provided, the 3DRLM 30 absorbs the tension with the entire network structure composed of three-dimensional random bonds fused by fusion, deforming; and once the tension is stopped, the elastic flexibility of the polymer manifests to allow the original shape of the structure to be recovered. When a mesh structure composed of continuous fibers produced from a known non-elastic polymer is used as a cushioning material, plastic deformation is developed and recovery cannot be achieved, thus resulting in low heat resistance durability. When the fibers are not bonded by melting at the contact points, the shape cannot be maintained and the structure does not change its shape entirely, resulting in a fatigue phenomenon due to the concentration of stress, degrading durability and resistance to deformation . In certain embodiments, the fusion link is the state in which all contact points are fused.

[51] A non-limiting method for the production of 3DRLM 30 includes the steps of (a) heating a molten olefin-based polymer to a temperature of 10 ° C to 140 ° C higher than the melting point of the polymer in a typical melt extruder; (b) discharge the molten interpolymer in a downward direction from a nozzle with multiple holes to form loops allowing the fibers to fall naturally (due to gravity). The polymer can be used in combination with a thermoplastic elastomer, non-elastic thermoplastic polymer or a combination thereof. The distance between the nozzle surface and the starting conveyors installed in a cooling unit to solidify the fibers, the viscosity of the polymer, the diameter of the orifice and the quantity to be discharged are the elements that determine the diameter of the loop and the fineness of the fibers. The loops are formed by holding and allowing the melted fibers supplied to reside between a pair of starting conveyors (belts or rollers) placed in a cooling unit (the distance between them being adjustable), placing the loops thus formed in contact by adjusting the distance between the holes for this purpose, in such a way that the ties in contact are connected by heat, or connected by casting in another way, insofar as they form a three-dimensional random loop structure. Then, the continuous fibers, in which the contact points were connected by heat as the loops form a three-dimensional random loop structure, are taken continuously to a cooling unit for solidification to provide a network structure. After that, the structure is cut to a desired length and shape. The method is characterized in that the olefin-based polymer is melted and heated to a temperature between 10 ° C to 140 ° C higher than the melting point of the interpolymer and released downward in a molten state from a nozzle with multiple holes. When the polymer is discharged at a temperature below 10 ° C higher than the melting point, the fiber supplied becomes cold and less fluid to result in insufficient heat bonding of the fiber contact points.

[52] Properties, such as the diameter of the loop and the fineness of the fibers that make up the structure of the damping network provided in this document, depend on the distance between the nozzle surface and the speed of the starting conveyor installed in a cooling unit. to solidify the interpolymer, melt viscosity of the interpolymer, diameter of the orifice and the amount of interpolymer to be delivered therefrom. For example, a reduced amount of the interpolymer to be delivered and a lower melt viscosity, greater distance between the nozzle and the conveyor and greater speed of the conveyor on delivery result in less fineness of the fibers and smaller average loop diameter of the random loop. On the contrary, a shortened distance between the surface of the nozzle and the starting conveyor installed in the cooling unit to solidify the interpolymer results in a slightly greater fineness of the fiber and a larger average loop diameter of the random loop. The orifice diameter also influences the fiber diameter and the loop diameter. A smaller orifice diameter produces finer fibers and a smaller loop diameter. A larger orifice diameter produces a larger fiber diameter and a larger loop diameter. These conditions in combination provide the desired fineness of 111.11 dtex (100 denier) to 111,111.11 dtex (100,000 denier) continuous fibers and an average random loop diameter of up to 100 mm, or 1 millimeter (mm), or 2 mm, or 10 mm to 25 mm or 50 mm. By adjusting the distance to the aforementioned conveyor, the thickness of the structure can be controlled while the heat-bonded network structure is in a molten state and a structure with a desirable thickness and a flat surface formed by the conveyors can be obtained. Too high a conveyor speed results in failure to heat contact points, since cooling occurs before heat connection. On the other hand, a very slow speed can cause a higher density resulting from the excessively long stay of the melt. In some embodiments, the distance to the conveyor and the speed of the conveyor must be selected in such a way that the desired apparent density of 0.005 to 0.1 g / cm³ or 0.01 to 0.05 g / cm³ can be achieved.

[53] In one embodiment, 3DRLM 30 has one, some or all of the properties (i) to (v) below:

[54] (i) an apparent density of 0.016 g / c3 or 0.024 g / c3 or 0.03 g / c3 or 0.040 g / c3 or 0.050 g / c3 or 0.060 g / c3 to 0.070 g / c3 or 0.080 g / c3, or 0.090 g / c3 or 0.100 g / c3 or 0.150 g / c3 and / or

[55] (i) a fiber diameter of 0.1 mm, or 0.5 mm, or 0.7 mm, or 1.0 mm, or 1.5 mm to 2.0 mm, or 2.5 mm , or 3.0 mm; and / or

[56] (iii) a thickness (machine direction) of 1.0 cm, 2.0 cm or 3.0, cm or 4.0 cm or 5.0 cm or 10 cm or 20 cm to 25 cm or 30 cm or 35 cm or 40 cm or 45 cm or 50 cm; and / or

[57] (iv) a fiber with a linear density of 1,000 dpf, or 5,000, or 10,000 to 20,000, or 30,000 dpf.

[58] It is understood that the thickness of the 3DRLM 30 will vary based on the application of the sheet.

[59] 3DRLM 30 is formed in a three-dimensional geometric shape to form a leaf (that is, a prism). 3DRLM 30 is an elastic material that can be compressed and stretched and returned to its original geometric shape. An “elastic material”, as used in this document, is a rubber-like material that can be compressed and / or stretched and which expands / retracts very quickly to approximately its original shape / length when the force exerting compression and / or the stretch is released. The three-dimensional random loop material 30 has a "neutral state" when no compressive forces and no stretching forces are transmitted to the 3DRLM 30. The three-dimensional random loop material 30 has "a compressed state" when a compressive force is transmitted to the 3DRLM 30. 3DRLM 30. The three-dimensional random loop material 30 has “a stretched state” when a stretching force is transmitted to the 3DRLM

30. C. COMPONENT (1)

[60] Each continuous fiber 34 in 3DRLM 30 is composed of a component (1) and a component (2). Component (1) is an olefin-based polymer with a density of 0.86 g / c3 to 0.96 g / c3. The component (1)

is a non-functionalized olefin-based polymer. A "non-functionalized olefin-based polymer" is an olefin-based polymer without a functional group. In other words, the non-functionalized olefin-based polymer consists only of carbon and hydrogen atoms and is free of heteroatoms. A "heteroatom" is an atom other than carbon or hydrogen. Non-limiting examples of heteroatoms are carbon-free atoms of Groups IV, V, VI and VII of the Periodic Table. Non-limiting examples of heteroatoms include: F, N, O, P, B, S and Si.

[61] The component olefin-based polymer (1) can be an ethylene-based polymer, a propylene-based polymer and mixtures thereof. The component olefin-based polymer (1) has a density of 0.86 g / c3 to 0.96 g / c3, or a density of 0.90 g / c3 or 0.91 g / c3 or 0.92 g / c3 or 0.93 g / c3 to 0.94 g / c3, or 0.95 g / c3, or 0.96 g / c3. In one embodiment, component (1) is an ethylene-based polymer with a density of 0.90 g / c3, or 0.91 g / c3, or 0.92 g / c3, or 0.92 g / c3 , or 0.93 g / c3 to 0.94 g / c3, or 0.95 g / c3, or 0.96 g / c3 and the ethylene-based polymer is not functionalized, as disclosed above. The ethylene-based polymer can be an ethylene homopolymer or an ethylene / α-olefin copolymer. Α-olefin is a C3-C20 α-olefin, or a C4-C12 α-olefin, or a C4-C8 α-olefin. Non-limiting examples of suitable α-olefin comonomers include propylene, butene, methyl-1-pentene, hexene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, cyclohexyl-1-propene (allyl cyclohexane), vinyl cyclohexane and combinations thereof.

[62] In one embodiment, component (1) is a high density polyethylene (HDPE) which is an ethylene / C4-C8 α-olefin copolymer.

[63] In one embodiment, component (1) is a low density linear polyethylene which is an ethylene / C4-C8 α-olefin copolymer.

[64] In one embodiment, the component olefin-based polymer (1) is a propylene-based polymer with a density of 0.90 g / c3 to 0.96 g / c3 and the propylene-based polymer is non-functionalized, as disclosed above. The propylene-based polymer can be a propylene homopolymer or a propylene / α-olefin copolymer. Α-olefin is a C2 α-olefin, or a C4-C20 α-olefin or a C4-C12 α-olefin or a C4-C8 α-olefin. D. COMPONENT (2)

[65] Each continuous fiber 34 in 3DRLM 30 is composed of a component (1) and a component (2). Component (2) is a non-functionalized olefin-based polymer with a density of 0.86 g / c3 to 0.96 g / c3, or 0.86 g / c3 or 0.87 g / c3 to 0, 88 g / c3 or 0.89 g / c3. Component (2) is a polymeric material different from component (1).

[66] In one embodiment, component (2) is a non-functionalized ethylene-based polymer that is an ethylene / α-olefin polymer with a density of 0.86 g / c3 or 0.87 g / c3 at 0 , 88 g / c3 or 0.89 g / c3. The ethylene / α-olefin copolymer can be a random ethylene / α-olefin polymer or a multi-block polymer of ethylene / α-olefin. Α-olefin is a C3-C20 α-olefin, or a C4-C12 α-olefin or a C4-C8 α-olefin. Non-limiting examples of suitable α-olefin comonomers include propylene, butene, methyl-1-pentene, hexene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, cyclohexyl-1-propene (allyl cyclohexane), vinyl cyclohexane and combinations thereof.

[67] In one embodiment, component (2) is an ethylene / C4-C8 α-olefin copolymer that is an elastomer. An "elastomer", as used herein, refers to a rubber-like polymer that can be stretched to at least twice its original length and which retracts very quickly to approximately its original length when the force exerting the stretch is released . An elastomer has an elastic modulus of about 10,000 psi (68.95 MPa) or less and an elongation generally greater than 200% in the non-crosslinked state at room temperature using the ASTM D638 - 72 method. component (2) is an “ethylene-based elastomer” which is an elastomer composed of at least 50% by weight of ethylene-derived units.

[68] In one embodiment, component (2) is an ethylene / C4-C8 α-olefin copolymer with a comonomer distribution constant (CDC) in the range of more than 45 to less than 400, the copolymer of ethylene / C4-C8 α-olefin with a total of less than 120 units of unsaturation / 1,000,000 C (hereinafter “CDC45-ethylene copolymer”). Non-limiting examples of suitable CDC45-ethylene copolymer are found in US Patent Nos. 8372931 and 8829115, the entire contents of which are incorporated herein by reference.

[69] In one embodiment, the CDC45-ethylene copolymer has one, some or all of the following properties (i) to (iv) below:

[70] (i) a density of 0.86 g / c3, or 0.87 g / c3 to 0.88 g / c3, or 0.89 g / c3; and / or

[71] (ii) a zero shear viscosity ratio (ZSVR) of at least 2; and / or

[72] (iii) less than 20 vinylidene unsaturation units / 1,000,000 C; and / or

[73] (iv) a bimodal molecular weight distribution.

[74] In one embodiment, component (2) is an ethylene-based polymer that is a multi-block copolymer of ethylene / α-olefin. The term “ethylene / α-olefin multiple block copolymer” refers to a ethylene / C4-C8 α-olefin multiple block copolymer consisting of ethylene and a copolymerizable C4-C8 α-olefin comonomer in polymerized form ( and optional additives), in which the polymer is characterized by multiple blocks or segments of two polymerized monomer units that differ in chemical or physical properties, the blocks joined (or covalently linked) in a linear manner, that is, a polymer comprising chemically differentiated units that are joined end to end with respect to polymerized ethylene functionality.

The ethylene / α-olefin multi-block copolymer includes the block copolymer with two blocks (diblock) and more than two blocks (multiple blocks). C4-C8 α-olefin is selected from butene, hexene and octene. The ethylene / α-olefin multi-block copolymer is free of, or otherwise excludes, styrene (i.e., it is free of styrene) and / or aromatic vinyl monomer and / or conjugated diene. When reference is made to quantities of “ethylene” or “comonomer” in the copolymer, it is understood that it means polymerized units of the same. In some embodiments, the multi-block copolymer of ethylene / α-olefin can be represented by the following formula: (AB) n; where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or higher, "A" represents a rigid block or segment and "B" represents a soft block or segment. The As and Bs are linked, or covalently linked, in a substantially linear or linear manner, as opposed to a substantially branched or substantially star shape. In other modalities, blocks A and B are randomly distributed along the polymer chain. In other words, block copolymers do not normally have a structure as follows: AAA-AA-BBB-BB. In one embodiment, the multi-block copolymer of ethylene / α-olefin does not have a third type of block, which comprises a different comonomer (or comonomers). In another embodiment, each of blocks A and B has monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor block B comprises two or more subsegments (or sub-blocks) of different composition, such as a tip segment, which has a substantially different composition than the rest of the block.

[75] Preferably, ethylene comprises the major molar fraction of the entire ethylene / α-olefin multiple block copolymer, i.e., ethylene comprises at least 50% by weight of the entire ethylene / α-olefin multiple block copolymer. More preferably, ethylene comprises at least 60% by weight, at least 70% by weight, or at least 80% by weight,

wherein the substantial remainder of the entire multi-block copolymer of ethylene / α-olefin comprises the C4-C8 α-olefin comonomer. In one embodiment, the multi-block copolymer of ethylene / α-olefin contains 50% by weight to 90% by weight of ethylene, or 60% by weight to 85% by weight of ethylene or 65% by weight to 80% by weight of ethylene. For many ethylene / octene multi-block copolymers, the composition comprises an ethylene content greater than 80% by weight of the entire ethylene / octene multi-block copolymer and an octene content of 10% by weight at 15% by weight or 15% by weight to 20% by weight of the entire multi-block copolymer.

[76] The multi-block copolymer of ethylene / α-olefin includes various amounts of "rigid" and "soft" segments. "Rigid" segments are blocks of polymerized units in which ethylene is present in an amount greater than 90% by weight or 95% by weight or greater than 95% by weight or greater than 98% by weight, based on the weight of the polymer , up to 100% by weight. In other words, the content of comonomers (monomer content in addition to ethylene) in the rigid segments is less than 10% by weight or 5% by weight or less than 5% by weight or less than 2% by weight, based on weight polymer, and can be as low as zero. In some embodiments, the rigid segments include all or substantially all units derived from ethylene. "Soft" segments are blocks of polymerized units where the content of comonomers (content of monomers other than ethylene) is greater than 5% by weight or greater than 8% by weight, greater than 10% by weight or greater than 15% by weight, based on the weight of the polymer. In one embodiment, the comonomer content in the soft segments is greater than 20% by weight, greater than 25% by weight, greater than 30% by weight, greater than 35% by weight, greater than 40% by weight, greater than 45 % by weight and greater than 50% by weight or greater than 60% by weight and can be up to 100% by weight.

[77] Soft segments can be present in a 1 wt% ethylene / α-olefin multi-block copolymer to 99 wt% total weight of the ethylene / α-olefin or multi-block copolymer

5% by weight to 95% by weight, 10% by weight to 90% by weight, 15% by weight to 85% by weight, 20% by weight to 80% by weight, 25% by weight to 75 % by weight, from 30% by weight to 70% by weight, from 35% by weight to 65% by weight, from 40% by weight to 60% by weight, or from 45% by weight to 55% by weight total ethylene / α-olefin multi-block copolymer. On the other hand, the rigid segments can be present in similar ranges. The weight percentage of the soft segment and the weight percentage of the rigid segment can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed, for example, in document No. US

7,608,668, entitled “Ethylene / α-Olefin Block Inter-Polymers”, filed on March 15, 2006, in the name of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global Technologies Inc., the disclosure of which is hereby incorporated by reference in its entirety for reference. In particular, the percentages by weight of the hard and soft segment and the comonomer content can be determined, as described in column 57 to column 63 of document No. USP 7.608.668.

[78] The ethylene / α-olefin multiple-block copolymer comprises two or more chemically distinct regions or segments (called "blocks") joined (or covalently linked) in a linear fashion, that is, contains chemically differentiated units that are joined together end to end with respect to polymerized ethylene functionality, rather than pending or grafted. In one embodiment, the blocks differ in the amount or type of comonomer incorporated, density, amount of crystallinity, size of crystallite attributable to a polymer of such composition, type or degree of stratification (isotactic or syndiotactic), regioregularity or regio-irregularity, amount of branching (including long chain branching or hyper-branching), homogeneity or any other chemical or physical property. In comparison to the block interpolymers of the prior art, including interpolymers produced by sequential addition of monomer,

fluxional catalysts or anionic polymerization techniques, the present multi-block copolymer of ethylene / α-olefin is characterized by unique polymeric polydispersity distributions (PDI or Mw / Mn or MWD), polydispersed block length distribution and / or number distribution polydispersed block, due, in one embodiment, to the effect of the transfer agent (or transfer agents) in combination with multiple catalysts used in its preparation.

[79] In one embodiment, the multi-block copolymer of ethylene / α-olefin is produced in a continuous process and has a polydispersity index (Mw / Mn) of 1.7 to 3.5, or 1.8 to 3, or 1.8 to 2.5, or 1.8 to 2.2. When produced in a batch or semi-blended process, the multi-block ethylene / α-olefin copolymer has Mw / Mn of 1.0 to 3.5, or 1.3 to 3, or 1.4 to 2, 5, or from 1.4 to 2.

[80] In addition, the multi-block ethylene / α-olefin copolymer has a PDI (or Mw / Mn) that fits a Schultz-Flory distribution instead of a Poisson distribution. The present multi-block copolymer of ethylene / α-olefin has a polydispersed block distribution, as well as a polydispersed block size distribution. This results in the formation of polymeric products with enhanced and distinguishable physical properties. The theoretical benefits of a polydispersed block distribution were previously modeled and discussed in Potemkin, Physical Review E (1998) 57 (6), pages 6,902 to 6,912, and Dobrynin, J. Chem. Phvs. (1997) 107 (21), pages 9,234 to 9,238.

[81] In one embodiment, the present multi-block copolymer of ethylene / α-olefin has a more likely distribution of block lengths.

[82] In an additional embodiment, the multi-block copolymer of ethylene / α-olefin of the present disclosure, especially those produced in a polymerization reactor in continuous solution, has a more likely distribution of block lengths. In one embodiment of this disclosure, copolymers of multiple ethylene / α-olefin blocks are defined as having:

[83] (A) Mw / Mn of about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius and a density, d, in grams / cubic centimeter, where the values numerical values of Tm and d correspond to the relation:

[84] Tm> -2,002.9 + 4,538.5 (d) - 2,422.2 (d) 2 and / or

[85] (B) Mw / Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, ∆H in J / g, and a delta amount, ∆T, in defined degrees Celsius as the temperature difference between the highest peak of the DSC and the highest peak of the Crystallization Analysis Fractionation (“CRYSTAF”), in which the numerical values of ∆T and ∆H have the following relationships:>

[86] ∆T> -0.1299 ∆H + 62.81 for ∆H greater than zero and up to 130 J / g

[87] ∆T ≥ 48 ° C for ∆H greater than 130 J / g, where the peak of CRYSTAF is determined using at least 5% of the cumulative polymer and, if less than 5% t of the polymer has a CRYSTAF identifiable peak, then the CRYSTAF temperature is 30 ° C; and / or

[88] (C) elastic recovery, Re, in percentage at 300 percent traction and 1 cycle measured with a compression molded film of ethylene / α-olefin interpolymer and has a density, d, in grams / cubic centimeter, where the numerical values of Re ed satisfy the following relationship when the ethylene / α-olefin interpolymer is substantially free of the cross-linked phase:

[89] Re> 1,481 to 1,629 (d); and / or

[90] (D) has a molecular fraction that elutes between 40 ° C and 130 ° C when fractioned with the use of TREF, in which the fraction is characterized by having a molar comonomer content of at least 5% higher than that of a fraction of comparable random ethylene interpolymer that elutes between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer (or comonomers) and has a melt index, density and molar comonomer content (based on the entire the polymer) within 10% of those of the ethylene / α-olefin interpolymer; and / or

[91] (E) has a storage module at 25 ° C, G '(25 ° C) and a storage module at 100 ° C, G' (100 ° C), where the ratio of G '(25 ° C) to G '(100 ° C) is in the range of 1: 1 to 9: 1.

[92] The ethylene / α-olefin multiple block copolymer may also have:

[93] (F) a molecular fraction that elutes between 40 ° C and 130 ° C when fractioned using TREF, where the fraction has characteristics of a block index of at least 0.5 and up to 1 and a distribution molecular weight, Mw / Mn, greater than 1.3; and / or

[94] (G) mean block index greater than zero and up to 1.0 and a molecular weight distribution, Mw / Mn greater than 1.3.

[95] It is understood that the multi-block copolymer of ethylene / α-olefin can have any, any, all or any combination of properties (A) to (G). The Block Index can be determined, as described in detail in document No. USP 7.608.668 incorporated into this document as a reference for this purpose. The analytical methods for determining properties (A) to (G) are disclosed, for example, in document No. USP 7.608.668, Column 31 line 26 to Column 35, line 44, which is incorporated into this document as a reference for that end.

[96] In one embodiment, the multi-block copolymer of ethylene / α-olefin has rigid segments and soft segments, is free of styrene, consists only of (i) ethylene and (ii) a C4-C8 α-olefin (and optional additives) and is defined as having a Mw / Mn of 1.7 to 3.5, at least one melting point, Tm, in degrees Celsius and a density, d, in grams / cubic centimeter, where the numerical values of Tm ed correspond to the relation:

[97] Tm> -2,002.9 + 4,538.5 (d) - 2,422.2 (d) 2,

[98] where the density, d, is 0.850 g / cm3, or 0.860 g / cm3, or 0.870 g / cm3 to 0.875 g / cm3, or 0.877 g / cm3, or 0.880 g / cm3 or 0.890 g / cm3 ; and the melting point, Tm, is 110 ° C or 115 ° C or 120 ° C to 125 ° C or 130 ° C or 135 ° C.

[99] In one embodiment, the multi-block copolymer of ethylene / α-olefin is a multi-block copolymer of ethylene / 1-octene (consisting only of comonomers of ethylene and octene) and has one, some or all of the properties Next:

[100] (i) an Mw / Mn of 1.7 or 1.8 to 2.2 or 2.5 or 3.5; and / or

[101] (ii) a density of 0.860 g / cm3, or 0.865 g / cm3, or 0.870 g / cm3, or 0.877 g / cm3, or 0.880 g / cm3; and / or

[102] (iii) a melting point, Tm, of 115 ° C, or 118 ° C, or 119 ° C, or 120 ° C to 120 ° C, or 123 ° C, or 125 ° C; and / or

[103] (iv) a melting index (MI) of 0.1 g / 10 min, or 0.5 g / 10 min to 1.0 g / 10 min, or 2.0 g / 10 min, or 5 g / 10 min, or 10 g / 10 min; and / or

[104] (v) 50 to 85% by weight of soft segment and 40 to 15% by weight of rigid segment; and / or

[105] (vi) 10 mol%, or 13 mol%, or 14 mol%, or 15 mol% to 16 mol%, or 17 mol%, or 18 mol%, or 19% in mol, or 20 mol% of C4 – C12 α-olefin in the soft segment; and / or

[106] (vii) from 0.5 mol%, or 1.0 mol%, or 2.0 mol%, or 3.0 mol% to 4.0 mol%, or 5 mol% , or 6 mol, 7 mol%, or 9 mol% octene in the rigid segment; and / or

[107] (viii) an elastic recovery (Re) of 50% or 60% to 70% or 80% or 90% at a deformation rate of 300% min-1 at 21 ° C measured in accordance with ASTM D 1708 ; and / or

[108] (ix) a polydispersed distribution of blocks and a polydispersed distribution of block sizes.

[109] In one embodiment, the multi-block copolymer of ethylene / α-olefin is a multi-block copolymer of ethylene / octene. The ethylene / octene multi-block copolymer is sold under the tradename INFUSE ™, available from The Dow Chemical Company, Midland, Michigan, USA.

[110] In one embodiment, the multi-block copolymer of ethylene / α-olefin is selected from INFUSE ™ 9817, INFUSE ™ 9500 and INFUSE ™ 9530, available from The Dow Chemical Company.

[111] In one embodiment, the multi-block copolymer of ethylene / α-olefin is INFUSE ™ 9817.

[112] Ethylene / α-olefin multi-block copolymers can be produced through a chain transport process, as described in US No. 7,858,706, which is incorporated by reference into this document. In particular, suitable chain transport agents and related information are listed in Column 16, line 39 through Column 19, line 44. Suitable catalysts are described in Column 19, line 45 through Column 46, line 19 and suitable cocatalysts in Column 46 , line 20 to Column 51, line 28. The process is described throughout the document, but particularly in Column 51, line 29 to Column 54, line 56. The process is also described, for example, in the following documents in:

7,608,668; USP 7,893,166; and USP 7,947,793.

[113] The base ethylene / α-olefin multiple block copolymer may comprise more than one ethylene / α-olefin multiple block copolymer.

[114] In one embodiment, component (2) is a propylene-based plastomer or elastomer. A "propylene-based plastomer or elastomer" (or "PBPE") is a propylene / ethylene copolymer and includes at least 50% by weight of propylene-derived units and up to 15% by weight of ethylene comonomer. All individual values and subintervals from 1% by weight to 15% by weight are included and disclosed in this document. For example, the ethylene content can range from a lower limit of 1 or 3 or 4 or 5 or 6 or 7% by weight to an upper limit of 8 or 9 or 10 or 11 or 12, or 13 or 14 or 15% in weight.

[115] PBPE is produced by the polymerization of propylene and ethylene in the presence of a Group IV metal complex of a polyvalent aryloxyether catalyst. The Group IV metal complex catalyst of a polyvalent aryloxyether gives PBPE unique properties. In one embodiment, PBPE is characterized as having substantially isotactic propylene sequences. “Substantially isotactic propylene sequences” means that the sequences have an isotactic triad (mm) measured by 13C NMR greater than 0.85, or greater than 0.90, or greater than 0.92 or greater than 0 , 93. Isotactic triads refer to the isotactic sequence in terms of a triad unit in the copolymer molecular chain determined by 13C NMR spectroscopy.

[116] PBPE has a B value less than 1.0 or less than 0.99 or less than 0.98 or less than 0.97. The term “B value” is a measure of randomness and measures the distribution of propylene and ethylene across the polymeric chain of PBPE. B values range from 0 to 2. The higher the B value, the more the distribution of ethylene in the copolymer alternates. The lower the B value, the more obstructed or grouped is the distribution of ethylene in the propylene / ethylene copolymer of PBPE.

[117] The B value, as described by Koenig (Spectroscopy of Polymers American Chemical Society, Washington, DC, 1992) is calculated as follows.

[118] B is defined for a propylene / ethylene copolymer as: f (EP + PE) B = 2 • FE • FP,

[119] where f (EP + PE) = the sum of the dyad fractions of EP and PE; and Fe and Fp = molar fraction of ethylene and propylene in the copolymer, respectively. The dyad fraction can be derived from triad data according to: f (EP + PE) = [EPE] + [EPP + PPE] / 2 + [PEP] + [EEP + PEE] / 2. B values can be calculated for other copolymers, in a similar way, by assigning the respective copolymer dyads. For example, calculating the B value for a propylene / 1-octene copolymer uses the following equation: f (OP + PO) B = 2 • FO • FP.

[120] For PBPE polymers produced with a Group IV metal complex of a polyvalent aryloxyether catalyst, B values are less than 1.0. In one embodiment, PBPE has a B value of 0.90, or 0.92, or 0.93, or 0.94 for 0.95, or 0.96, or 0.97, or 0.98, or 0.99. This means that, for PBPE produced with the Group IV metal complex of a polyvalent aryloxy catalyst, the propylene block length is not only relatively long for a given percentage of ethylene, but also a substantial amount of long sequences of three or more sequential ethylene inserts are present in the PBPE.

[121] PBPE has a total unsaturation, per mol of propylene, of 0.01% to 0.03%. Total unsaturation per mole of propylene is measured by 1H NMR analysis, as described below. 1H NMR ANALYSIS

[122] Samples were prepared by adding approximately 3.25 g of a 50/50 mixture of tetrachloroethane-d2 / perchlorethylene that has 0.0015 M of chromium acetylacetonate (relaxation agent) to 0.130 g of the sample in one 10 mm NMR tube. The samples are dissolved and homogenized by heating the tube and its contents to 110 ° C. The data is collected using a 400 MHz Bruker spectrometer, equipped with a high temperature Bruker Dual DUL cryoprobe. Unsaturation data is collected using

4 scans per data file, a pulse repetition delay of 15.6 seconds, with a sample temperature of 120 ° C. The acquisition is performed using a spectral width of 10,000 Hz and a file size of 16K data points. The pre-saturation experiment is performed with a modified pulse sequence, lc1prf2.zz1, using 100 scans per data file.

CALCULATIONS

[123] Propylene H moles

[124] Mole fraction of propylene * (integral area δ 3.5 to 0.2 ppm)

[125] Total moles of propylene 6

[126] mol% of vinyl unsaturation / mol of propylene 100 ∗ /

[127] mol% Cis / Trans / mol of propylene 100 ∗ /

[128] mol% of tri-substituted unsaturation / mol of propylene 100 ∗ 3 μm

[129] mol% of vinylidene unsaturation / mol of propylene 100 ∗ /

[130] Total mol% of unsaturation / mol of propylene% mol / +8 of e +% mol 3 í +8 + /

[131] PBPE has a crystallinity in the range of 1% by weight to 40% by weight. For example, crystallinity can be 10% by weight at 15 or 20 to 25 or 30 or 35 or 40% by weight. Crystallinity is measured by the DSC method, as described below in the test methods section. The propylene / ethylene copolymer includes units derived from propylene units and polymeric units derived from ethylene comonomer and optional C4-C10 α-olefin. Exemplary comonomers are C2 and C4 to C10 α-olefins; for example, C2, C4, C6 and C8 α-olefins.

[132] In one embodiment, PBPE has a melting heat (Hf) of 10 J / g to 65 J / g.

[133] In one embodiment, PBPE has a density of 0.860 g / c3 to 0.890 g / c3, or 0.860 g / c3 to 0.870 g / c3, or 0.860 g / c3 to 0.865 g / c3.

[134] In one embodiment, PBPE has a melting temperature, Tm, of 50 ° C to 100 ° C, or 60 ° C to 90 ° C, or 60 ° C to 80 ° C, or 65 ° C to 75 ° Ç.

[135] In one embodiment, PBPE has a weight average molecular weight (Mw) of 20,000 to 50,000 g / mol, in addition to 24,000 to 50,000 g / mol.

[136] In one embodiment, PBPE has an Mw / Mn of 2.0 to 4.0, plus 2.0 to 3.5, plus 2.0 to 3.0, plus 2.0 to 2 , 5.

[137] In one embodiment, PBPE has one, some or all of the following properties:

[138] (i) 80% by weight to 99% by weight of units derived from propylene and 20% by weight to 1% by weight of units derived from ethylene; and / or

[139] (ii) an isotactic triad (mm) measured by 13 C NMR greater than 0.92; and / or

[140] (iii) a Koenig B value of 0.93 to 0.97; and / or

[141] (iv) unsaturation in% in total mol of propylene from 0.018% to 0.025%, in addition to 0.019% to 0.025%; and / or

[142] (v) a density of 0.860 g / c3 or 0.865 g / c3 to 0.870, or 0.875 or 0.880 g / c3; and / or

[143] (vi) a melting temperature, Tm of 60 ° C to 75 ° C, additionally 60 ° C to 72 ° C, additionally 60 ° C to 70 ° C; and / or

[144] (vii) a heat of fusion (Hf) from 40 J / g to 80 J / g; and / or

[145] (viii) a crystallinity of 5% to 15%, in addition to 5% to 10%; and / or

[146] (ix) an Mw of 20,000 to 50,000 g / mol, additionally from 25,000 to 50,000 g / mol, additionally from 30,000 to 50,000 g / mol; and / or

[147] (x) an Mw / Mn of 2.0 to 3.0, in addition to 2.0 to 2.7, in addition to 2.0 to 2.5.

[148] PBPE can comprise two or more modalities disclosed in this document.

[149] In one embodiment, for each fiber, component 1 has a first melting temperature, Tm1, and component (2) has a second melting temperature, Tm2. The components (1) and (2) in each fiber have a change with respect to Tm, ΔTm, from 0 to 10. The term “ΔTm”, as used in this document, is the absolute value of the difference between the melting temperature of component (1), Tm1 and the melting temperature of component (2), Tm2, where the melting temperature is reported in ° C. The term ΔTm is defined by Equation (2) below. Equation (2) ΔTm = | Tm1-Tm2 | = 0 ° C to 10 ° C.

[150] In one embodiment, ΔTm is 0 ° C or 1 ° C or 2 ° C or 3 ° C or 4 ° C to 5 ° C or 6 ° C or 7 ° C or 8 ° C, or 9 ° C or below 10 ° C.

[151] In one embodiment, the fibers have a side-by-side configuration. Figure 2 shows a sectional view of fiber 134. In fiber 134, component (1) forms a first side 140 of fiber 134. Component (2)

forms a second side 142 of fiber 134. The first side 140 (component (1)) and the second side 142 (component (2)) extend along the length of fiber 134 and are integral and inseparable.

[152] In one embodiment, the fibers have a core-sheath configuration. Figure 3 shows a sectional view of fiber 234. In fiber 234, a core 240 is formed from component (1). A sheath 242, formed from component (2) encompasses, or otherwise surrounds, core 240 along the length of fiber 234. In other words, core 240 extends concentricly within sheath 242 along the length of fiber length 234. Core 240 and sheath 242 extend along the length, or along the entire length, of fiber 234 and are integral and inseparable.

[153] In one embodiment, each fiber comprises from 5% by volume, or 10% by volume, or 20% by volume, or 30% by volume to 40% by volume, or 50% by volume of the sheath (component 2) and a reciprocal volume% of the core, or from 95% volume or 90% volume or 80% volume or 70% volume to 60% volume or 50% volume of the core (component 1) based on the total fiber volume.

[154] In one embodiment, the core component (1) is an ethylene-based polymer and the sheath component (2) is an ethylene-based polymer. Thus, sheet 10 of 3DRLM is composed exclusively of polymer based on ethylene. In an additional embodiment, the core which is an ethylene-based polymer includes re-ground polyethylene or also known as recycled polyethylene. An “all polyethylene” sheet 10 is advantageous, as it promotes recycling.

[155] In one embodiment, the core includes an additive mixed with the olefin-based polymer component (1). Non-limiting examples of suitable additive include stabilizer, processing aid, filler, coloring pigment, sound blocking agent, crosslinking agent,

foaming agent, flame retardant, UV inhibitor, antimicrobial agent and combinations thereof.

[156] In one embodiment, core 240 is centrally located within sheath 242, as shown in Figure 3.

[157] In one embodiment, Figure 3A shows a fiber 234a that has a core-sheath configuration, where a core 240a (composed of component (1)) is not centrally located within sheath 242a (composed of the component (two)).

[158] In one embodiment, the fibers have an island configuration in the sea. Figure 4 shows a sectional view of a fiber 334 composed of a plurality of cores 340 (formed from the component (1)). The plurality of cores 340 are separated from each other and are arranged in a sheath 342 composed of component (2). The plurality of cores 340 forms distinct "islands" within the "sea", which is sheath 342. The component material (2) of sheath 342 separates the plurality of cores from each other. The component material (2) of sheath 342 also surrounds, or otherwise surrounds, the plurality of cores 340. The cores of plurality 340 (“islands”) and sheath 242 (“sea”) extend along the length , or along the entire length, of fiber 334, and are integral and inseparable.

[159] In one embodiment, the fibers have a segmented pie configuration. Figure 5 shows a sectional view of a fiber 434 composed of a plurality of first pie segments 440. The first pie segments are composed of the component (1). Fiber 434 also includes a plurality of second pie segments 442. The second pie segments 442 are comprised of component (2). Each pie segment 440, 442 extends from a central point of the fiber and extends radially outward to the outer surface of the fiber, as shown in Figure 5. Fiber volume 434 is filled by an alternating arrangement of the first segment of pie 440 and the second pie segment

442. The first 440 pie segments and the second pie segments

442 alternates extend along the length, or along the entire length, of fiber 434 and are integral and inseparable.

[160] In one embodiment, the fibers have a tip-core configuration. Figure 6 shows a sectional view of a fiber 534 having a core 540. The core 540 is composed of component (1). The fiber 534 includes a plurality of tip portions 542. The tip portions 542 are composed of component (2). The core 540 and the tip portions 542 extend along the length, or along the entire length of the fiber 534, and are integral and inseparable.

[161] In one embodiment, the fibers have a segmented ribbon configuration. Figure 7 shows a fiber 634 that has a plurality of first segments of ribbon 640. The first segments of ribbon 640 are composed of component (1). Fiber 634 also includes a plurality of second tape segments 642. The second tape segments are comprised of component (2). Each segment of tape 640, 642 extends a first side of the fiber to an opposite side of the fiber, as shown in Figure 7. The volume of fiber 634 is filled by an alternating arrangement of the first segments of tape 640 and the second segments of tape 642 The first alternating tape segments 440 and second alternate tape segments 442 extend along the length, or along the entire length, of the fiber 634, and are integral and inseparable.

[162] By way of example, and not by way of limitation, some modalities of this disclosure will now be described in detail in the Examples below.

EXAMPLES

[163] A 3DRLM sheet is composed of fibers with a core-sheath configuration, as shown in Figure 3. The core is composed of component (1) which is an ethylene-octene copolymer with a density of 0.917 g / c3 , sold under the trade name DOWLEX 2517, available from The Dow Chemical Company. The fibers include 90% by volume of the core. The sheath is composed of component (2) which is an ethylene / C4-C8 α-olefin copolymer which is an ethylene-CDC45 copolymer and has a density of 0.86 g / c3 to 0.89 g / c3. The fibers include 10% by volume of the sheath. The core-sheath fiber described in this paragraph is referred to below as Fiber 1.

[164] The 3DRLM sheet composed of Fiber 1 is a sheet made entirely of polyethylene and exhibits bond strength of (1) an average maximum force (in Newtons, N) of 110 Newtons (N) to 120 N and a limit of average elasticity from 91 N to 100 N.

[165] Specifically, this disclosure is not intended to be limited to the modalities and illustrations contained therein, but includes modified forms of such modalities, including portions of the modalities and combinations of elements of different modalities, according to the scope of the claims to be made. follow.

Claims (15)

1. Sheet characterized by the fact that it comprises: a three-dimensional random loop material that comprises a weft structure of an infinity of continuous two-component coiled fibers linked by fusion at an infinity of contact points to form an infinity of loops; wherein each continuous two-component fiber comprises: a component (1) which is an olefin-based polymer having a density of 0.90 g / c3 to 0.96 g / c3; a component (2) which is an olefin-based polymer having a density of 0.86 g / c3 to 0.89 g / c3; and the three-dimensional random loop material has an apparent density of 0.03 g / c3 to 0.08 g / c3. 2. Sheet according to claim 1, characterized by the fact that the component olefin-based polymer (1) is an ethylene-based polymer that has a density of 0.91 g / c3 to 0.94 g / c3; and the component olefin-based polymer (2) is an ethylene-based polymer with a density of 0.86 g / c3 to 0.89 g / c3. Sheet according to either of claims 1 or 2, characterized in that the component (1) has a first melting temperature, Tm1, and the component (2) has a second melting temperature, Tm2, in that the difference between Tm1 and Tm2 is ΔTm; and ΔTm is from 0 ° C to 10 ° C. 4. Sheet according to any one of claims 1 to 3, characterized in that the component (1) is selected from the group consisting of a linear low density polyethylene and a high density polyethylene (HDPE). 5. Sheet according to any one of claims 1 to 3, characterized in that the component (1) is a polymer based on propylene. 6. Sheet according to any one of claims 1 to 5, characterized by the fact that component (2) is an ethylene / C4-C8 α-olefin copolymer that has a Comonomer Distribution Constant in the range of more than 45 to less than 400, where the composition has a total of less than 120 units of unsaturation / 1,000,000 C. 7. Sheet according to any one of claims 1 to 5, characterized in that the component (2) is a multi-block copolymer of ethylene / C4-C8 α-olefin. 8. Sheet according to any one of claims 1 to 5, characterized in that the component (2) is a plastomer based on propylene or elastomer (PBPE). 9. Sheet according to any one of claims 1 to 8, characterized by the fact that the continuous two-component fibers are in the form of a two-component sheath-core fiber, in which the core is the component (1 ) and the sheath is the component (2). 10. Sheet, according to claim 9, characterized by the fact that each fiber comprises from 5% by volume to 50% by volume of the sheath and 95% by volume to 50% by volume of the core based on the total volume of the sheath. fiber. 11. Sheet according to claim 10, characterized in that the component (1) of the core is an ethylene-based polymer and the component (2) of the sheath is an ethylene-based polymer. 12. Sheet according to claim 11, characterized by the fact that the component (1) of the core is an ethylene / C4-C8 α-olefin copolymer that has a density of 0.90 g / c3 to 0.96 g / c3; and component (2) of the sheath is an ethylene / C4-C8 α-olefin copolymer having a density of 0.86 g / c3 to 0.89 g / c3. 13. Sheet, according to claim 9, characterized by the fact that an additive is mixed with the olefin-based polymer component (1). 14. Sheet, according to claim 13, characterized by the fact that the additive is selected from the group consisting of stabilizer, processing aid, filler, coloring pigment, sound blocking agent, crosslinking agent, foam, flame retardant, UV inhibitor, antimicrobial agent and combinations thereof. 15. Sheet according to any one of claims 1 to 8, characterized in that the fibers of two continuous components are in a configuration selected from the group consisting of a side-by-side configuration, a core-sheath configuration , a configuration of islands in the sea, a segmented pie configuration, a tip-core configuration and a segmented ribbon configuration.