Method for producing curled fibers

Abstract

To provide a process for forming fibers with an enhanced curling property.SOLUTION: There is provided a process comprising forming fibers having at least a first region and a second region, wherein the first region comprises an ethylene / α-olefin interpolymer composition characterized in that: a density is in a range of 0.930 to 0.965 g / cm3; a melt index (I2) is in a range of from 10 to 60 g / 10 minutes; a molecular weight distribution is in a range of from 1.5 to 2.6; a tan delta at 1 radian / second is at least 45; a low temperature peak and a high temperature peak on an elution profile via improved comonomer composition distribution (ICCD) procedure; and a full width at half maximum of the high temperature peak is less than 6.0°C and stretching the fibers to an elongation of at least 20% thereby increasing a curling property of the fiber. The process may further include forming a non-woven fabric from the fibers.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application is a continuation of U.S. Application No. 62 / 769,618, filed November 20, 2018. The benefit of which is claimed, and which is incorporated herein by reference in its entirety.

[0002] The field of the invention is curled fibers and methods for producing nonwoven fabrics having such fibers. and the method includes stretching. [Background technology]

[0003] Polyethylene-based fibers are used in consumer products, especially nonwoven fabrics. It is desirable for its drapeability and smoothness. Nonwovens are used in filters, medical applications, and It has many uses, such as disposal materials, diaper stock, etc. To reduce the weight of the final product In the literature, crimping or curling of the fibers has been proposed.

[0004] Forming fibers with enhanced curl (also known as crimp) and effectively It is still desirable to be able to do this efficiently. Summary of the Invention

[0005] By selecting specific materials for use in the multicomponent fibers, the inventors have They discovered that stretching these fibers enhanced the curl or crimp. Thus, disclosed herein is a method for producing a cellular membrane comprising at least a first region and a second region. The first region is a process including forming a fiber having a viscosity of 0.930 to 0.930. .965g / cm 3 Density in the range of 10~60g / 10min. I2), wherein I2 is an ethylene / α-olefin interpolymer composition characterized by: A Measured by STM D1238 at 190°C, 2.16 kg, and by GPC The ratio of the weight average molecular weight to the number average molecular weight (M w(GPC) / M n(GPC) ) The molecular weight distribution is in the range of 1.5 to 2.6, and the tan delta at 1 radian / second is small. The elution profile is at least 45 and is determined by the improved comonomer composition distribution (ICCD) method. The low-temperature peak and high-temperature peak on the ion exchanger and the full width at half maximum of the high-temperature peak are less than 6.0°C. This stretches the fiber to at least 20% elongation, thereby increasing the curl of the fiber. The process can further include forming a nonwoven fabric from the fibers, and the extension of the fibers can Stretching can occur before or after the nonwoven is formed. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 is an ICCD elution plot of the ethylene / α-olefin composition of Sample 1. DETAILED DESCRIPTION OF THE INVENTION

[0007] Producing fibers and / or nonwoven fabrics from fibers having first and second regions Disclosed herein is an efficient method for preventing fiber curl or deformation after drawing. are characterized by different responses to stretching and relaxation as the crimp increases. One of the areas where this is surprisingly good is when compared to certain other ethylene-based resin systems. It includes an ethylene / α-olefin interpolymer composition that provides curl or crimp. The stretching can occur before or after the nonwoven is formed.

[0008] Fibers useful in this process are said to have at least a first region and a second region. The fibers may be bicomponent fibers, or the fibers may be made of three or more components. The fiber may have a cross section consisting of one region surrounded by a sheath (multicomponent fiber). The multicomponent fiber may have a core-sheath configuration, which represents one region, the core. There may be one or more inner cores, one or more inner sheaths, and an outer sheath. The cross section of a part of the cross section, for example, a quarter, a third, or a half of the cross section, is an area, and the It can have a segmented pie configuration where two regions occupy the remainder of the cross section. In split fibers, the third or fourth region may occupy part of the pie cross section. Alternatively, the core-sheath configuration may be combined with a segmented pie. For example, the core may be , which may have two components in a segmented pie structure surrounded by a sheath. Alternatively, the third component may be contained within the first or second region of the sea-island structure. The portions may form a separate region within a first region that forms a core and is surrounded by a sheath. Each region of the fiber has a center of gravity, and the fiber itself also has a center of gravity. Centricity refers to the arithmetic mean of all points in the cross-sectional area of ​​the fiber or in a particular area of ​​the fiber. In the core-sheath case, the center of gravity of the core and the sheath is the same. The first and second regions have the same weight. The center of gravity of the first and second regions may be the same as the center of gravity of the entire fiber. Alternatively, the first and second regions may have different centers of gravity. At least one of these regions has a center of gravity that is different from the center of gravity of the fiber. can be done.

[0009] Each region has a 2% secant modulus E and a yield stress σ y Different materials with The 2% secant modulus of each region, the yield strength of each region, or both may differ from each other. The difference between the yield stress of the material in the first and second regions divided by the yield stress of the second region is at least 0.4, or at least 0.45, or at least 0.5, or at least It may be 0.55 or at least 0.6, and may be 1.0 or less. The difference between the 2% secant modulus of the material in the first region and the 2% secant modulus of the material in the second region divided by the 2% secant modulus of the material in the second region is at least 0.4 or at least 0.45, or at least 0.5 or at least The first yield stress may be 0.55 or may be 1.0 or less. The quotient of the second yield stress divided by the second 2% secant modulus is subtracted from the quotient of the second yield stress divided by the second 2% secant modulus Absolute value of something, |σ y1 / E1-σ y2 / E2| / (σ y2 / E2) must be at least 0. 01, or at least 0.02, or at least 0.05, or at least 0.0 7, or at least 0.1, but not more than 1.0, or not more than 0.8, or 0. 7 or less, or 0.5 or less, or 0.4 or less, or 0.3 or less, where E1 is the 2% secant modulus of the first region material and E2 is the 2% secant modulus of the second region material. is the linear modulus, and σ y1 is the yield stress of the first region material, and σ y2 is the second domain material The 2% secant modulus and yield stress are measured by the axial strain test in accordance with ASTM D638. It is measured on extruded samples.

[0010] Ethylene / α-olefin interpolymer composition Interpolymers are polymers of two, three, or more monomers. This means that the polymer is a copolymer, terpolymer, etc. The first monomer is ethylene. The second monomer is an α-olefin. The olefin has at least 3 carbon atoms, e.g., up to 20, up to 10, or The α-olefin comonomers may have up to 8 carbon atoms. 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-octene Examples include, but are not limited to, 1-decene, 1-decene, and 4-methyl-1-pentene. Optionally, the third, fourth, or more monomers may be α-olefins. The interpolymer composition is bimodal and has different molecular weights, as described in more detail below. At least two different molecular weights and / or different densities and / or ICCD elution Combining two ethylene / α-olefin interpolymers having different peaks It can be easily prepared by

[0011] The interpolymer can be a random interpolymer. At least 50 mole percent based on the total number of moles of repeat units in the terpolymer or at least 60 mole percent or at least 70 mole percent ethylene-based The interpolymer may comprise repeating units. 99.9 or less, or 99.5 or less, or 99 or less, based on the total number of moles of the unit; is 95 or less, or 90 or less, or 85 or less mole percent ethylene repeat units The interpolymer may comprise a total mole fraction of repeat units in the interpolymer. Based on the number, at least 0.1 or at least 0.5 or at least 1 or less At least 5 or at least 10 mole percent of α-olefin repeat units (i.e., The interpolymer may contain a second and optionally a third and fourth monomer. The number of moles of repeat units in the interpolymer is 50 or less, or 30 or less, based on the total number of moles of repeat units in the interpolymer. percent or less of α-olefinic repeat units (i.e., secondary and optionally tertiary and and a fourth monomer).

[0012] These ethylene / α-olefin interpolymer compositions, in certain embodiments, and at least 0.930 g / cm 3 and 0.965 g / cm 3 Less than or equal to 0.9 60 or less, or 0.955 or less, or 0.950 or less, or 0.945 or less, or is 0.940g / cm 3 It is characterized by the following density: Density is measured according to ASTM D79 2. Two-component compositions containing the disclosed ethylene / α-olefin interpolymers The fibers can exhibit higher curvatures. The bimodal polymer composition has a curvature of about 0.900 to about 0.940g / cm 3 and a low density fraction having a density in the range of at least about 0.950 g / cm 3の The granular material can be characterized by a high density fraction having a density of 0.1 to 0.25.

[0013] These ethylene / α-olefin interpolymer compositions have a molecular weight of 10 to 60 g / 10 It can be characterized by a melt index (I2) in the range of AST min. Measured at 190°C and 2.16 kg according to M D1238. The ratio of I10 to AS may be less than 6.9 or 6.8 or 6.7, where I10 is less than AS Measured at 190°C and 10 kg according to TM D1238. Lower I10 / I2 The ratio may exhibit lower long chain branching resulting in better spinnability / processability.

[0014] These ethylene / α-olefin interpolymer compositions have a viscosity of 2.6 or less, or 0.5 or less, and at least 1.5 or at least 1.7, or at least 2.0 The ratio of the weight average molecular weight to the number average molecular weight (M w(GPC) / M n(GPC) ) The polymer can be characterized by its molecular weight distribution according to the method described below. The interpolymer composition having a molecular weight distribution in the range is preferably a copolymer of an interpolymer having a higher molecular weight distribution and an interpolymer having a higher molecular weight distribution. It is believed to have better processability (e.g., fiber spinning) than terpolymers. The olefin / α-olefin interpolymer has an M greater than (I10 / I2)-4.63. w( GPC) / M n(GPC) can be characterized by

[0015] The ethylene / α-olefin interpolymer composition was 15,000 g / mol, 20 ,000 g / mol, or a lower limit of 30,000 g / mol to 100,000 g / mol, 1 with a weight average molecular weight of 20,000 g / mol, or up to an upper limit of 150,000 g / mol It is possible. M z(GPC) / M w(GPC) is less than 3.0 or less than 2.0 A bimodal polymer composition has an ICCD elution ratio of 2.0 or greater than 1.0. The high temperature fraction may show two different peaks below 70,000 g / mol or below 50,000 g / mol. The high temperature fraction may have a peak position molecular weight of at least 150 g / mol or less. and having a peak position molecular weight of at least 20,000 g / mol or at least 20,000 g / mol. The low temperature fraction may have a molecular weight of at least 30,000, or at least 40,000, or The low temperature fraction may have a peak position molecular weight of at least 50,000 g / mol. , 250,000, or 200,000, or 150,000 g / mol or less peaks It can have a positional molecular weight.

[0016] These ethylene / α-olefin interpolymer compositions exhibit a low characterized by a tan delta of at least 45 or at least 50. In addition, these ethylene / α-olefin interpolymers have a viscosity of 1 rad / Tan delta at 100 rad / s and 190°C vs. tan delta at 100 rad / s and 190°C The ratio can be characterized by a ratio of at least 12. These properties are This can be measured by dynamic mechanical analysis (DMS).

[0017] These ethylene / α-olefin interpolymer compositions have improved comonomer - At least two points between 35℃ and 110℃ on the elution profile of the composition distribution (ICCD) It can be characterized by distinct peaks with distinct valleys (smaller peaks) between the peaks. (at least 10% reduction compared to the peak height of the peak) and the peak position is at least Each peak must be spaced 10° apart. are separated by

[0018] The peak temperature of the low temperature peak may be at least 50°C or at least 60°C. The peak temperature of the high temperature peak may be at least It may be 90°C or at least 95°C, 110°C, or 105°C or 100°C The present inventors have found that a low-temperature peak in the range of 50 to 75°C produces curled fibers. It has been found that this can be particularly useful in preparing

[0019] The weight fraction of the low temperature peak fraction is at least 25 or at least 30, and less than 65, or less than 60 or 55 weight percent The weight fraction of the high temperature peak fraction may be less than 1000 ppm based on the total weight of the eluted polymer. , at least 35 or at least 40, or at least 45 and 75 weight percent It can be less than 10 ...

[0020] The full width at half maximum of the high temperature peak may be less than 6.0°C. The narrow peak of the high density fraction is Ultra-high or ultra-low molecular weight species that can interfere with performance or produce extractables It shows a narrower composition distribution.

[0021] The ethylene / alpha olefin composition is less than 0.5 (i.e., less than 50%), 0.3 (3 0%), 0.25 (less than 25%), 0.22 (less than 22%), or less than 0.2 (2 0%).

[0022] The ethylene / α-olefin interpolymer composition has a molecular weight of less than 100, preferably less than 30 It may have a comonomer distribution constant (CDC) of ∼80.

[0023] The ethylene / α-olefin interpolymer composition has a β-olefin copolymer ratio greater than 0.20 or greater than 0. More than 0.25, or more than 0.30, or more than 0.35, or more than 0.40 A molecular weighted comonomer distribution index greater than, or greater than 0.45, or greater than 0.50 MWCDI can be characterized by conventional gel permeation chromatographs. is a measure of the slope of comonomer incorporation as a function of molecular weight obtained from fluoropolymerization. When MWCDI is greater than 0.25 (molecular weight range 20,000 to 200,000 g / mol), the resin structure is significantly more comonomer-incorporated at the high molecular weight end of the distribution. It is believed to have reverse comonomer incorporation.

[0024] The ethylene / α-olefin interpolymer compositions disclosed herein contain a small amount of long It can be characterized by chain branching (LCB), which is the zero shear viscosity ratio (ZSV Specifically, ZSVR is less than 1.35 or less than 1.30. Possible. ZSVR can be at least 1.10.

[0025] The ethylene / α-olefin interpolymer composition comprises 1 Determined by H-NMR less than 230, or less than 210, or less than 190, or less than 170, or 15 It can be characterized by a vinyl saturation number per 1,000,000 carbon atoms less than 0. Cut.

[0026] Ethylene / α-olefin interpolymer compositions prepared using any conventional polymerization process Such conventional polymerization processes may include one or more conventional reactors. , for example, loop reactors, isothermal reactors, stirred tank reactors, parallel and serial batch reactors, and / or any combination thereof, Such polymerization processes include, but are not limited to, those known in the art. Any type of reactor or reactor configuration may be used to conduct gas phase, solution, or slurry polymerization. or any combination thereof.

[0027] Generally, the solution phase polymerization process is carried out at a temperature in the range of 115 to 250°C, for example, 115 to 200°C. At temperatures in the range of 300 to 1000 psi, e.g., 400 to 750 psi. , one or more well-stirred reactors, for example, one or more isothermal loop reactors or one In a double reactor, for example, the temperature in the first reactor is 1 The second reactor temperature may be in the range of 15 to 190°C, or 115 to 150°C. The temperature may be in the range of 50 to 200°C, or 170 to 195°C. The temperature in the reactor can be in the range of 115 to 190°C, or 115 to 150°C. The residence time in the phase polymerization process is typically 2 to 30 minutes, for example, 10 to 20 minutes. The catalyst comprises ethylene, a solvent, hydrogen, one or more catalyst systems, optionally one or more cocatalysts, and and optionally one or more comonomers are continuously fed into one or more reactors. The solvent includes, but is not limited to, isoparaffins. Solvents were purchased from ExxonMobil Chemical Co. (Houston, Texas). The resulting ethylene / α-olefin copolymer is commercially available from Sigma-Aldrich under the name ISOPAR E. The mixture of ethylene / α-olefin interpolymer and solvent is removed from the reactor. The solvent is typically recovered in a solvent recovery unit, i.e., a heat exchanger, to isolate the interpolymer. It is recovered via an exchanger and a gas-liquid separator drum and then recycled to the polymerization system.

[0028] The ethylene / α-olefin interpolymer compositions can be prepared in a dual reactor system, e.g., a dual reactor system. It can be produced by solution polymerization in a loop reactor system, where ethylene and and optionally one or more α-olefins are polymerized in the presence of one or more cocatalysts. In addition, one or more promoters may be present.

[0029] Ethylene / α-olefin interpolymers can be produced in a single reactor system, e.g., a single loop. It can be produced by solution polymerization in a reactor system, where ethylene and any Optionally, one or more α-olefins are polymerized in the presence of one or more cocatalysts. Two different catalysts can be used in the system. One or both of the two different catalysts can be The bimodal interpolymer composition has the formula (I) as shown below. This makes it possible to manufacture

[0030] Exemplary catalysts suitable for producing the first ethylene / α-olefin interpolymer include: The catalyst system may be a catalyst system comprising a precatalyst component comprising a metal-ligand complex of formula (I): [ka]

[0031] In formula (I), M is selected from titanium, zirconium, or hafnium. metal, the metal being in the +2, +3, or +4 formal oxidation state, and n being 0, 1 , or +2, and when n is 1, X is a monodentate or bidentate ligand, and n When is 2, each X is a monodentate ligand, the same or different, and the metal-ligand complex is , the overall charge is neutral, and each Z is -O-, -S-, -N(R N )-, or -P(R P )-, and L is independently selected from (C1-C 40 ) hydrocarbylene or (C1- C 40 ) heterohydrocarbylene, and R N and R P is (C1-C 30 ) Hydroca Lubill or (C1-C 30 ) heterohydrocarbyl, where (C-C 40 ) Hydrocarbylene is a linker of 1 to 10 carbon atoms connecting two Z groups in formula (I). or (C1-C 40 ) Heterohydr The locarbylene has a linker skeleton of 1 to 10 atoms that connects the two Z groups of formula (I). and a moiety comprising: (C1-C 40 ) Heterohydrocarbylene 1 to 10 atoms Each of the 1 to 10 atoms of the linker backbone is independently a carbon atom or a heteroatom. , where each heteroatom is independently O, S, S(O), S(O)2, Si(R C )2, Ge(R C )2, P(R C ), or N(R C ) where, independently, each R C teeth, (C1-C 30 ) hydrocarbyl or (C-C 30 ) heterohydrocarbyl, R 1 and R 8 is -H(C1-C40 ) hydrocarbyl, (C1-C 40 ) Heterohydr locarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2- , (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N ) -, (R N )NC(O)-, a halogen, and a group represented by formula (II), formula (III), or formula ( IV). [ka]

[0032] In formulas (II), (III), and (IV), R 31-35 , R 41-48 ,Ma or R 51-59 Each of (C1-C 40 ) hydrocarbyl, (C1-C 40 ) Hetero Hydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N ) 2. -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O) -, R C S(O)2-, (R C )2C=N-, R C C(O)O-, RC OC(O)-, R C C(O)N(R N )-, (R N )2NC(O)-, halogen, or -H independently selected, but R 1 or R 8 At least one of the formula (II), formula (III), or or a radical having formula (IV), wherein R C、 R N , and R P is defined above. That is exactly right.

[0033] In formula (I), R 2-4 , R 5-7 , or R 9-16 Each of (C1 -C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3 , -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C ,- SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2 C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) 2 is independently selected from N-C(O)-, halogen, or -H, wherein R C、 R N , and BiR P is as defined above.

[0034] The catalyst system comprising the metal-ligand complex of formula (I) is useful for activating metal-based catalysts in olefin polymerization reactions. The catalyst may be catalytically activated by any technique known in the art for activating a catalyst. For example, those containing a metal-ligand complex of formula (I) may be prepared by contacting the complex with an activating cocatalyst or The catalyst or complex may be made catalytically active by combining it with an activating cocatalyst. The activating cocatalyst used in this invention is alkylaluminum, polymer or oligomer. Alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymers, Non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions) One activation technique is bulk electrolysis. Combinations of one or more of these are also contemplated. The term "aluminum alkyl" refers to Monoalkylaluminum dihydride or monoalkylaluminum dihalide, di Alkyl aluminum hydride or dialkyl aluminum halide, or trialuminum Examples of polymeric or oligomeric alumoxanes include: Methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylaluminum-modified methylalumoxane butylalumoxane.

[0035] The Lewis acid activator (cocatalyst) may be one to three (C1 -C 20 ) Group 13 metal compounds containing hydrocarbyl substituents. Examples of compounds include tri((C1-C 20 )hydrocarbyl)-substituted aluminum, or Ri((C1-C 20 )hydrocarbyl)-boron compounds, tri((C-C 20 ) Hydro Carbyl)-boron compounds, tri((C1-C 10 ) alkyl) aluminum, tri(( C6-C 18 )aryl)boron compounds, and halogenated (including perhalogenated) derivatives of Other examples of Group 13 metal compounds include tris(fluoro-substituted phenyl)borane, The activating cocatalyst is tris(pentafluorophenyl)borane. 20 ) hydrocarbyl borates (e.g., trityl tetrafluoroborate) or tri ((C1-C 20 )hydrocarbyl)ammonium tetra((C1-C 20 ) Hydrocal bis(octadecyl)methylammonium tetrakis(pentafluorobenzoate)borane (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorobenzoate) As used herein, the term "ammonium" includes The term is ((C1-C 20 ) Hydrocarbyl) 4N + , ((C1-C 20 ) Hydro Karubi Lu) 3N(H) + , ((C1-C 20 )hydrocarbyl)2N(H)2 + , (C1-C2 0) Hydrocarbyl N(H)3 + , or N(H)4 + means a nitrogen cation, each of which is (C1-C 20 When two or more hydrocarbyls are present, they may be the same or different. It's fine.

[0036] The neutral Lewis acid activator (cocatalyst) combination includes tri((C1-C4) alkyl) Aluminum and trihalides ((C6-C 18 )aryl)boron compounds, especially thiazolinone Tris(pentafluorophenyl)borane or its mixture with neutral Lewis acids and polymers. and combinations with mono- or oligomeric alumoxanes, and single neutral Lewis acids, especially tri- Combinations of tris(pentafluorophenyl)borane with polymeric or oligomeric alumoxanes. (Metal-ligand complex): (Tris(pentafluorophenylborane) (Group 4 metal-ligand complexes): (tris(pentafluoro) The molar ratio of (phenylborane):(alumoxane) is 1:1:1 to 1:10:3 In another embodiment, it is 1:1:1.5 to 1:5:10.

[0037] A catalyst system comprising a metal-ligand complex of formula (I) can be activated by the addition of one or more cocatalysts, e.g. cation-forming promoter, strong Lewis acid, or a combination thereof. Suitable activating cocatalysts include polymers, or oligomeric aluminoxanes, especially methylaluminoxane, as well as inert, compatible Examples of suitable cocatalysts include modified methyl Aluminoxane (MMAO), Bis(hydrogenated tallow alkyl)methyl, Tetrakis(penta Fluorophenyl)borate (1 - ) amines, and combinations thereof, , but not limited to these.

[0038] One or more of the foregoing activating cocatalysts may be used in combination with one another. The best combination is tri((C 1- C4)hydrocarbyl)aluminum, tri((C1- C4) Hydrocarbyl) borane or ammonium borate and oligomer or polymer The total molar ratio of one or more metal-ligand complexes of formula (I) to one or more alumoxane compounds is 1:1. The ratio of the number of moles of the catalyst to the total number of moles of one or more activating cocatalysts is 1:10,000 to 100:1. For example, the ratio may be at least 1:5000, or at least 1:1000, and The ratio of alumoxane to activating cocatalyst may be 10:1 or less, or 1:1 or less. When used as a metal-containing alumoxane, preferably the number of moles of alumoxane used is The number of moles of the ligand complex may be at least 100 times the number of moles of the tris(pentafluorophenyl) When the (phenyl)borane is used alone as an activating cocatalyst, one or more metal- The moles of tris(pentafluorophenyl)borane used relative to the total number of moles of the ligand complex. The ratio may be 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The activating cocatalyst is generally present in an amount approximately equal to the total molar amount of one or more metal-ligand complexes of formula (I). They are used in equal molar amounts.

[0039] Fibers and Nonwovens At least 75%, or at least 80%, or at least 8% of the first component of fiber 5%, or at least 90%, or at least 95%, or at least 97%, or or at least 98%, or at least 99%, or 100% (all by weight) ) may be an ethylene / α-olefin interpolymer. may be additional components such as one or more other polymers and / or one or more additives. Other polymers may be other polyethylenes (e.g., polyethylene homopolymer or ethylene / α-olefin interpolymers), propylene-based polymers (e.g., polypropylene Pyrene homopolymer, propylene-ethylene copolymer, or propylene / α-olefin The amount of other polymers can be up to 25%. Additives include antistatic agents, color enhancers, dyes, lubricants, TiO2 or CaC Fillers such as O3, opacifiers, nucleating agents, processing aids, pigments, primary antioxidants, secondary antioxidants, Processing aids, UV stabilizers, anti-blocking agents, slip agents, tackifiers, flame retardants, antibacterial agents , odor reducing agents, antifungal agents, and combinations thereof. The ethylene / α-olefin interpolymer composition does not contain such additives. based on the weight of the ethylene / α-olefin interpolymer composition, such additives The total weight of the mixture is about 0.01, or 0.1, or 1 to about 25, or about 20, or may be present in a mixture of about 15 or about 10 weight percent.

[0040] Other regions may comprise different polyolefins or polyesters, for example Other areas include polypropylene-based polymers, polypropylene, polyethylene terephthalate The remainder of the second region may be one or more The other polymers may be additional components such as other polymers and / or one or more additives. - Polypropylene or polyester (with or without additives as mentioned above) Another polymer, such as polyethylene terephthalate or polybutylene terephthalate, The polymer may be a polyethylene or another polyester. Possible additives include antistatic agents. , color enhancers, dyes, lubricants, fillers such as TiO2 or CaCO3, opacifiers, Nucleating agents, processing aids, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, Anti-blocking agents, slip agents, tackifiers, flame retardants, antibacterial agents, odor reducing agents, antifungal agents, and and combinations thereof. The copolymer interpolymer composition is an ethylene / α-olefin copolymer containing such an additive. about 0.01, or about 0.1, or 1 based on the weight of the copolymer interpolymer composition About 25, or about 20, or about 15, or about 10 weight percent of such The composition may contain a mixture of additives.

[0041] the weight ratio of the first component or region to the second component or region is at least 5 / 95; and is at least 10 / 90, or at least 20 / 80, or at least 30 / 70, Or it may be at least 40 / 60, but not more than 95 / 5, or 90 / 10, or less may be 80 / 20 or less, or 70 / 30 or less, or 60 / 40 or less.

[0042] The fibers taught herein can be formed by any conventional spinning technique. The fibers disclosed herein can have one or more of the following characteristics: At least 5 micrometers, or at least 10 micrometers, and 50 micrometers The fibers may have a diameter of less than 100 micrometers or less than 30 micrometers. The denier per filament may range from 50g / 9000m to less than 50g / 9000m. All individual values ​​and subranges less than m are included herein and disclosed herein, and examples are not intended to limit the scope of the present invention. For example, the denier per filament can be set to lower limits of 0.1, 0.5, 1, 5, 10, 15, 17, 20, 25, 30, 33, 40, or 44g / 9000m~Upper limit 0.5, 1, 5, 10, 15, 17, 20, 25, 30, 33, 40, 44, or 50g / 9000 For example, the fiber may have a per filament density in the range of less than 40 g / 9000 m. The fibers may have a denier in the range of less than 30 g / 9000 m of filament. The fibers may have a denier per meter or may have a fiber weight in the range of less than 20g / 9000m. The fibers may have a denier per lament or may be in the range of less than 10 g / 9000 m. The fibers may have a denier per filament of 0.5 to 10 g / 9. The filament may have a denier per filament in the range of 000 to 1000 m.

[0043] Bicomponent fibers are made by forcing air through tiny orifices in a metal plate called a spinneret. or other gases, where they are cooled and solidified to form the continuous A bicomponent fiber is formed. The continuous fiber is then passed through a set of rotating rollers having different rotational speeds. The fibers are guided into the rollers or godets and stretched between them. Between the sets, at least 20%, or at least 30%, or at least 40%, or The fibers can be stretched to an elongation of at least 50% or at least 75%. 00% or less, or 700% or less, or 600% or less, or 500% or less, or 4 00% or less, or 250% or less, or 200% or less, or 150% or less, or 1 The fiber can be stretched to an elongation of up to 0.5%. The stretching is performed on the fiber at ambient temperature. can be done.

[0044] The fibers can be chopped into short fibers, or they can be drawn after chopping. Stretching before cutting is effective. Cut fibers have a length of at least 0.2, or At least 0.5 or at least 1 cm and no more than 16 or 12 or 10 cm The resulting short fibers can then be processed in a carded web process, an airlaid process, or the like. The bonding process can be thermal calendering, adhesive bonding, etc. bonding process, hot air bonding process, needle punch process, hydroentanglement process, and It may be a combination of these, but is not limited to these.

[0045] Bicomponent fibers are made by forcing air through tiny orifices in a metal plate called a spinneret. or other gases, where they are cooled and solidified to form the continuous Bicomponent fibers are formed. The solidified fibers are pneumatically drawn through an air stream and then The nonwoven web can be laid on a conveyor belt to form a nonwoven web. Before or after rolling, the material is stretched by the MDO (machine direction orientation) process or the ring rolling process. Bonding processes include heat calendering, adhesive bonding, and hot air bonding. The process includes the joining process, the needle punching process, the hydroentangling process, and combinations thereof. The nonwoven web may include, but is not limited to, at least 20% or at least 30%, or at least 40%, or at least 50%, or at least 75% The nonwoven web can be stretched to an elongation of 800% according to certain embodiments. or less, or 700% or less, or 600% or less, or 500% or less, or 400% or less, or 250% or less, or 200% or less, or 150% or less, or 100% The fibers can be drawn to an elongation of: do.

[0046] The nonwoven fabrics disclosed herein can be made by any known method. Such methods include the spunbond process, the meltblowing process, and carding. Web process, airlaid process, thermal calender process, adhesive bonding process, hot air Bonding process, needle punch process, hydroentanglement process, electrospinning pinning processes, and combinations thereof. The nonwoven fabrics disclosed herein are formed directly from constituent polymeric materials by a spunbond process. In the spunbond process, the production of nonwoven fabrics involves the following steps: (a) extruding one or more polymer compositions through a spinneret; (b) dissolving the molten spinneret in a solution; of one or more polymer compositions in a stream of air that is generally cooled to promote solidification of the strands. (c) pneumatically drawing the filaments in an air stream; or by winding over mechanical drawing rolls of the type commonly used in the textile fiber industry. The applied drawing tension thins the filaments by advancing them through a quenching zone. (d) passing the drawn strands through a foraminous surface, such as a moving screen or a porous (e) collecting the web of loose strands into a nonwoven fabric. Bonding step. The bonding may be performed by a thermal calendar process, an adhesive bonding process, a hot air bonding process, or the like. , needle punching process, hydroentangling process, and combinations thereof. This can be achieved by a variety of means, including but not limited to:

[0047] The staple fibers are blended and "opened" in a multi-step process and then passed through a conveyor belt. Distributed evenly over wet laid, air laid or carded / cross-lapped In a wet-laid operation, the fibers are typically spread into a uniform web of about 0.5 mm in length. Use 0.2-0.2cm fibers, but if the fibers are hard or thick, they may be longer. Airlaid processing typically uses fibers with lengths of about 1 to about 10 cm. Staple nonwovens are typically made with fibers 3-4 cm long. The bond is made by resin saturation or by total thermal bonding across the entire web. across the body or in separate patterns by resin printing or heat spot bonding Compatibility with staple fibers is typically found in high-end woven insulation. This refers to the combination with melt-blown, which is often used.

[0048] After the nonwoven fabric is formed, it is stretched in at least one direction. The web can be drawn using a roller or two rollers at different speeds. This can be used to stretch in the machine direction (MD) if the roller speed is adjusted to The web can be attached to a whole-web roll or mechanism for stretching in the cross direction. The stretching is preferably at least 5, or at least 10, or less. Temperature of at least 15°C and below 90, or below 80, or below 60, or below 50 The nonwoven fabric must have an elongation of at least 20% or less. At least 30%, or at least 50%, or at least 75% but not more than 800% stretched to 700%, 500%, 400%, or 300% or less It is.

[0049] Desirably, when the nonwoven fabric is stretched, at least a portion of the fibers are stretched by at least 20%. Or at least 30%, or at least 40%, or at least 50%, or less stretched to at least 75% elongation, but not more than 700%, or not more than 600%, or not more than 500% % or less, or 400% or less, or 300% or less, or 250% or less, or 200 % or less, or 150% or less, or 100% or less elongation.

[0050] According to certain embodiments, the fibers have a molecular weight of greater than 1, or greater than 1.5, or or greater than 2, or greater than 2.5, or 3 mm -1 Greater curl It is characterized by:

[0051] Spunbond nonwovens can be formed into multi-layer or laminate structures. The layer structure comprises at least two or more layers, wherein at least one or more layers is a material as defined herein. and one or more other layers are spunbonded nonwoven fabrics as disclosed in a blown nonwoven layer, one or more wet-laid nonwoven layers, one or more air-laid nonwoven layers, Any nonwoven fabric or one or more webs produced by a melt spinning process, 1 One or more film layers can be selected. Cast film, blown film, e.g. For example, extrusion coating, spray coating, gravure coating, printing, dipping, Derived from the coating composition via kiss-rolling or blade coating One or more coating layers. Laminated structures can be bonded using any number of bonding methods, thermal bonding, adhesive bonding, They can be bonded through layers, hydroentanglement, or needle punching. The structure can be S to SX or SX X, or SXXX, or SXXXX, or SXXXXX, where S is a nonwoven fabric as disclosed herein and X is a film, coating, or may be any combination of nonwoven materials, and one or more of X may be S The additional spunbond layer may be an ethylene / α-olefin copolymer, as described herein. from a terpolymer composition, and optionally one or more polymers and / or additives It can be made in combination with

[0052] Test Method density Density measurements of ethylene / α-olefin interpolymers were performed according to ASTM D792, Method This was done according to method B.

[0053] Melt index (I2) and (I10) The melt index (I2) value of the ethylene / α-olefin interpolymer is expressed as A Measured at 190°C and 2.16 kg according to STM D1238. The melt index (I10) values ​​of the α-olefin interpolymers were calculated according to ASTM D1 238 at 190°C and 10 kg. Values ​​are reported in g / 10 min, which is Corresponds to grams dissolved per minute.

[0054] Dynamic mechanical spectroscopy (DMS) The sample was heated at 177°C for 5 minutes under a pressure of 10 MPa in a 3 mm thick x 25 mm diameter circle. The sample is then removed from the press and placed on a counter. Under a nitrogen purge, the ARES strain-controlled rheometer with 25 mm parallel plates was used. A constant temperature was applied to the compression molded plaques using a thermostat (TA Instruments). For each measurement, the rheometer is turned on for a short time before the gap is zeroed. Place the sample disc on the plate and heat at 190°C for 5 minutes. The plates are then closed to a gap of 2 mm and the sample is trimmed before testing. The method may be delayed for an additional 5 minutes to allow for temperature equilibration. This experiment was carried out at 190°C, with 0.1 to 100 rad / s at 5 locations per 10-time interval. The strain amplitude is constant at 10%. The stress response is analyzed, and the storage modulus (G'), loss modulus (G''), and complex elastic modulus ( Rate (G * ), dynamic viscosity (η * ), and tan δ (or tan delta). You get tan delta in radians / second and tan delta in 100 radians / second.

[0055] Improved Comonomer Composition Distribution (ICCD) The improved Comonomer Composition Distribution (ICCD) test was performed using the IR-5 detector (Spanish PolymerChar) and a two-angle light scattering detector model 2040 (Precision Crystal detector (now Agilent Technologies) ization Elution Fractionation Equipment (CEF) (Pol The ICCD column is coated with gold. Nickel particles (Bright 7GNM8-NiS, Nippon Chemica) Industrial Co.) on a 15cm (length) x 1 / 4 inch (ID) strip Packing and conditioning of the column was performed according to the reference (Cong, R. ;Parrott,A.;Hollis,C.;Cheatham,M.WO20170 The slurry method using trichlorobenzene (TCB) slurry powder is used. The final pressure of the column is 150 bar. The column is then placed in the IR-5 detector oven. Orthodichlorobenzene (ODCB, 99% anhydrous grade or Silica gel (from EMD Chemicals) was used as the eluent. Obtain 40 (particle size 0.2 mm to 0.5 mm, catalog number 10181-3) and ODC It can be used to dry B solvent. The ICCD device is equipped with a nitrogen (N2) purge function. The ODCB was spat out with dry N2 for 1 hour before use. Sample preparation was performed by shaking at 160°C for 1 hour at 4 mg / ml (unless otherwise specified). The injection volume is 300 μl. The temperature profile was crystallization from 105°C to 30°C at 3°C / min, then at 30°C for 2 min. 30°C to 140°C. The flow rate during elution is 0.50 ml / min. Data points are collected per second. Column temperature calibration is performed using a linear homopolymer polyethylene standard. (Comonomer content: 0, Melt index (I2): 1.0 g / 10 min, Polydispersity: M w(GPC) / M n(GPC) is approximately 2.6 (1.0) by conventional gel permeation chromatography. A mixture of eicosane (2 mg / ml) in ODCB was used. The ICCD temperature calibration consists of four steps: (1) measurement The temperature offset was calculated by subtracting 30.00°C from the peak elution temperature of eicosane. (2) calculate the temperature offset of the elution temperature by the ICCD This temperature offset should be subtracted from the raw temperature data. (3) Linear homopolymer polyethylene reference 101 30.0°C, such that methylcellulose has a peak temperature at 30.0°C and eicosane has a peak temperature at 30.0°C. A linear calibration line was constructed to convert elution temperatures over the range 0.00°C to 140.00°C. and (4) an elution temperature of less than 30.0°C for the soluble fraction measured isothermally at 30°C. In the reference (Cerk and Cong et al., U.S. Patent No. 9,688,7 Linear extrapolation was performed using a dissolution heating rate of 3°C / min according to (No. 95). .

[0056] Calibration curve of comonomer content (mol percent of ICCD vs. comonomer at elution temperature (T)) The mer content was measured using 12 reference materials (linear ethylene homopolymer and single-site metallopolymer). 11 ethylene-octene random copolymers prepared with Sen catalyst, 35000~12 8000) with a known comonomer content. All of these standards were analyzed at 4 mg / mL in the same manner as previously specified. The comonomer content in mole percent and the peak temperature on the elution curve are as follows: This is the case.

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[0057] Determination of peaks and full width at half maximum in ICCD elution profiles It begins with zero relative mass at the lowest and highest elution temperatures (typically 35°C to 119°C). A single baseline was used to generate a starting and ending relative mass elution profile plot. The IR signal is subtracted from the measured IR signal. For convenience, this is done by taking the normalized area for the total area equal to 1. The relative mass-elution profile plots from the ICCD are presented as the quantified amount. At each temperature (T), the weight fraction (w T (T)) can be obtained. T ( T) vs. T) ranges from 35.0°C to 119.0°C with a stepwise temperature increase of 0.200°C. It is from the ICCD and is as follows:

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[0058] w T In the (T) vs. T elution profile, a single peak has one maximum point in the center. It is defined as a curve with two minimum points on either side (low temperature side and high temperature side). The height of both lowest points must be at least 10% lower than the height of the highest point. If one or both of the following points are less than 10% lower than the height of the highest point, i.e., If one or both of the points has a height greater than 90% of the height of the highest point, such a curve is considered a shoulder associated with another peak, but is not the peak itself. The distinct peaks are represented by w T (T) vs. T Maximum height of the peak in the elution profile plot The width (°C) at 50% of the peak height is called the full width at half maximum of the peak. .

[0059] If there are multiple peaks in the ICCD elution profile, the separation point between the peaks (T分離 ) can be defined as the lowest point between two adjacent peaks. ピークn ) The weight fraction of can be calculated according to the following formula:

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[0060] Comonomer Distribution Constant (CDC) The comonomer distribution constant (CDC) was calculated according to the following steps, which are shown graphically in Figure 1: , by ICCD T (T) vs. T calculated from the elution profile. (1) In the range of 35.0°C to 119.0°C with a step temperature increase of 0.200°C From ICCD T (T) vs. T dissolution profile is obtained. The total weight fraction from 35°C to 119°C is It should be normalized to 1.0 and follow equation 2. (2) The median temperature (T median ) to calculate:

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[0061] Conventional Gel Permeation Chromatography (Conventional GPC) and MWCDI The chromatographic system was a Pol ion detector with a built-in IR5 infrared detector (IR5). ymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph The oven compartment of the autosampler was set to 160°C. The column compartment was set to 150 °C. The columns used were four Agilent "Mixed A" is a 30 cm, 20 micron linear mixed bed column. The chromatography solvent was 1,2,4-trichlorobenzene with 200 ppm butyl The solvent source is nitrogen-injected. The injection volume was 200 microliters and the flow rate was 1.0 milliliters / minute. be.

[0062] The GPC column set is calibrated for molecular weights ranging from 580 to 8,400,000 g / mol. At least 20 narrow molecular weight distribution polystyrene standards having The standards were placed in six "cocktail" mixtures with at least 10 molecular weight intervals between each standard. Standard materials are purchased from Agilent Technologies. The ethylene standard is 50 milliliters for molecular weights above 1,000,000 g / mol. at 0.025 grams in a solvent and at a molecular weight of less than 1,000,000 g / mol Prepare 0.05 grams in 50 milliliters of solvent. Dissolve at 5°C for 30 minutes with gentle stirring. Determine the peak molecular weight of the polystyrene standard. Convert to ethylene / α-olefin interpolymer molecular weight (W) using the following equation: illiams and Ward, J. Polym. Sci., Polym. Let. ,6,621(1968)).

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[0063] A fifth-order polynomial was used to calculate the respective ethylene / α-olefin interpolymer equivalents. The calibration points are matched to the NIST standard NBS1475, which is obtained with a molecular weight of 52,000 g / mol. To achieve this, a small adjustment to A (approximately 0.39-0.44) was made to the column resolution. and correct for band broadening effects.

[0064] The total plate count for the GPC column set was 0.0 in 50 ml TCB. Prepared with 4g of eicosane and dissolved for 20 minutes with gentle stirring. The speed count (Equation 8) and symmetry (Equation 9) are calculated for a 200 microliter output according to the following equations: Measured by injection of 1000 torr.

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[0065] The samples were analyzed using PolymerChar's "Instrument Control" software. The sample is prepared semi-automatically using software. The target weight of the sample is 2 mg / ml. via a ymerChar high-temperature autosampler with pre-nitrogen-filled septa caps Add solvent (containing 200 ppm BHT) to the vial. Shake at "low speed" at 160°C. Dissolve the sample at RT for 3 hours.

[0066] M n(GPC) , M w(GPC) , and M z(GPC) The calculation is Polymer Char GPCOne™ software, each equally spaced data collection point i(IR i )in The baseline-subtracted IR chromatogram and the narrow standard calibration curve for point i from Eq. The ethylene / α-olefin interpolymer equivalent molecular weight (g / mol) obtained from the M ポリエチレン、i ) to obtain PolymerChar G according to Equations 11a-c. The results of GPC using the built-in IR5 detector (measurement channel) of the PC-IR chromatograph Next, the GPC molecular weight distribution (GPC-MWD) plot (wt GPC (lg MW) vs. lgMW plot, where wt GPC (lgMW) has a molecular weight of lgMW The molecular weight is in g / mol. Ri, wt GPC (lgMW) follows Equation 10.

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[0067] Number average molecular weight M n(GPC) , weight average molecular weight M w(GPC) and z-average molecular weight M z(GPC) can be calculated as follows:

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[0068] To monitor deviations over time, a PolymerChar GPC-IR system was used. Introduce a flow marker (decane) into each sample via a stem-controlled micropump This flow marker (FM) is used to determine the flow rate of each decahydrate in the sample (RV (FM sample)). The RV of the decane peak is aligned with the RV of the decane peak in the narrow standard calibration (RV(FM calibration)). The pump flow rate (nominal flow rate) for each sample is then linearly corrected by Any change in the time of the camcar peak will affect the flow rate (effective flow rate) throughout the experiment. This is assumed to be related to a linear shift in the flow marker peak, facilitating the highest accuracy of RV measurements. To advance the flow marker concentration chromatogram, a least-squares fitting routine is used. Then, use the first derivative of the quadratic equation to find the true After calibrating the system based on the flow marker peak, For semi-calibration, the effective flow rate is calculated as in Equation 12. The processing of the flow marker peak is performed by P via the PolymerChar GPCOne™ software. Volume correction is made so that the effective flow rate is within 0.5% of the nominal flow rate.

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[0069] The IR5 detector ratio calibration ranges from homopolymer (0 SCB / 1000 total C) to approximately Range up to 50SCB / 1000 total C (where total C = carbons in main chain + carbons in branches) The known short-chain branching (SCB) frequency of 13 At least eight of these (measured by C NMR) Ethylene / α-olefin interpolymer standard (one polyethylene homopolymer) and seven ethylene / octene copolymers). The weight average molecular weight of the polymer is 36,000 g / mol to 126,000 g / mol when measured by GPC. / mol. The molecular weight distribution (M w(GPC) / M n(GPC )) is GPC The baseline value of the IR5 methyl channel sensor is 2.0-2.5. Baseline-subtracted area response vs. baseline-subtracted area response for the IR5 measurement channel sensor "IR5 area ratio" (or "IR5 methyl channel area / IR5 measurement channel area") of "area response" Standard filters and filters supplied by PolymerCharge Wheel: Part Number IR5_FWM01 is part of the GPC-IR instrument. The SCB frequency vs. "IR5" is calculated for each of the "SCB" standards. A linear approximation of the "area ratio" is constructed in the form of the following equation:

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[0070] A study on the chromatogram generated by the "IR5 methyl channel sensor" The "linear baseline-subtracted chromatographic height" of each run was calculated as the column elution volume. Generate baseline-corrected chromatograms (methyl channels) as a function of A series of "linear" measurements for the chromatograms generated by the "IR5 measurement channel" The "baseline-subtracted chromatographic height" as a function of column elution volume Establish and generate a baseline-corrected chromatogram (measurement channel).

[0071] "Baseline corrected chromatogram (methyl channel)" vs. "Baseline corrected chromatogram The "IR5 height ratio" of the "IR5 chromatogram (measurement channel)" is the ratio of each column across the sample integration boundary. Dissolution volume index (each index spaced equally, at 1 ml / min dissolution) Calculate the "IR5 height ratio" using the coefficient A1 and add the coefficient A0 to this result to get the predicted SCB frequency for the sample, as shown in Equation 14 below. Convert the results to mole percent comonomer as follows: Mole percent comonomer = {SCBf / [SCBf + ((1000-SCBf*comonomer)}} (monomer length) / 2)]}*100 (Eq. 14), During the ceremony, “SCB f " is "SCB per 1000 total C" and "comonomer The "length" is the number of carbon atoms in the comonomer, e.g., 8 for octene, 6 for hexene, etc. That is it.

[0072] Using the method of Williams and Ward (Equation 7 above), each elution volume The mole percent comonomer is calculated by converting the index to a molecular weight value (Mwi). The plot is made as a function of wi, and the slope is Calculated in moles of Mwi (end-group corrections for chain ends are omitted for this calculation) ) Linear regression was used to determine the Mwi between 20,000 and 200,000 g / mol and beyond. Calculate the slope of the concentration chromatogram (wt GPC (lgMW) vs. l The slope of the gMW plot is at least 10% of the peak height in the chromatogram. is defined as the molecular weight comonomer distribution index (MWCDI).

[0073] Zero Shear Viscosity Ratio (ZSVR) The zero shear viscosity ratio is calculated by the equivalent weight average molecular weight (M w(GPC) ) Zero shear viscosity (ZSV) of branched polyethylene materials versus that of linear polyethylene materials (See ANTEC minutes below).

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[0074] Interpolymer

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[0075] Creep Test Interpolymer

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[0076] 1 H NMR method The stock solution (3.26 g) was added to 0.133 g of polymer sample in a 10 mm NMR tube. The stock solution is a mixture of tetrachloroethane-d2 (TCE) and perchloroethylene (50:5 0 wt.) and 0.001M Cr 3+ The solution in the tube was purged with N2 for 5 min. The capped sample tubes were left at room temperature overnight to allow the polymer samples to swell. The sample was dissolved at 110°C with periodic vortex mixing. It does not contain additives that can contribute to slippage, such as erucamide. 1 HNM R analysis was performed on a Bruker AVANCE 400MHz spectrometer at 120°C for 10 min. Perform with a cryoprobe.

[0077] Two experiments were performed to measure the degree of unsaturation, one as a control experiment and the other as a duplicate. In the control experiment, the data were processed with an exponential window function with a line broadening of 1 Hz. The baseline is corrected to approximately 7 to -2 ppm. 1 Set the signal from H to 100 In the control experiment, the integral value ( I 合計 The total number of carbon atoms in the polymer, NC, is calculated using Equation 16 as follows: NC=Itotal / 2 (Formula 16)

[0078] For double presaturation experiments, data were processed with an exponential window function with 1 Hz line broadening and based Correct the line to approximately 6.6 to 4.5 ppm. TCE residue 1 Set the signal from H to 100 and the corresponding integral for unsaturation (I ビニレン , I トリ置換 , I ビニル , and I ビ ニリデン ) is integrated. NMR spectroscopy can be used to determine polyethylene unsaturation. is well known and is described, for example, in Busico, V., et al., Macromolecules, 2 See US Pat. No. 5,386,6988. Vinylene, trisubstituted, vinyl, and vinylidene The number of unsaturated units in the amine is calculated as follows:

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[0079] 13 C NMR method The sample was prepared in tetrachloroethane-d2 / containing 0.025M Cr(AcAc)3. Approximately 3g of a 50 / 50 mixture of orthodichlorobenzene and Norell 1001- 7 Prepare by adding 0.25 g of polymer sample in a 10 mm NMR tube. Oxygen is removed from the sample by purging the tube headspace with nitrogen. Using a heating block and heat gun, heat the tube and its contents to 150 °C. Dissolve and homogenize the samples by visually inspecting each sample to ensure homogeneity. The sample must be thoroughly mixed immediately before analysis and allowed to cool before being inserted into the heated NMR probe. This is necessary to ensure that the sample is homogeneous and representative of the whole. All data was obtained using a Bruker 400 MHz spectrometer equipped with a Bruker cryolobe. Data was collected using a 6-second pulse repetition delay, a 90-degree flip angle, and All measurements were collected using inverse gated decoupling with a sample temperature of 120 °C. Measurements are performed on non-rotating samples in locked mode. The samples are allowed to thermally equilibrate for 7 minutes before data acquisition. 13C NMR chemical shifts are internally referenced to the EEE triad at 30 ppm. .

[0080] C13 NMR Comonomer Content: NMR spectroscopy to determine polymer composition It is well known that ASTM D 5017-96, JCRanda ll et al., in “NMR and Macromolecules” ACS Symposium series 247;JCRandall,Ed.,Am Chem. Soc., Washington, DC, 1984, Ch. 9; and JCRandall in “Polymer Sequence Determinition” "The Nation," Academic Press, New York (1977) A general method for polymer analysis by MR spectroscopy is presented.

[0081] Denier Measurement Fiber size is measured using an optical microscope. Denier (the number of denier per 9000 meters of such fiber) The fiber density (defined as the weight of the polymer) is calculated based on the density and fiber size of each polymer component.

[0082] 2% secant modulus (E) and yield stress (σ y ) The yield stress and 2% secant modulus are measured as follows: Using Toyo Si-90 Plastar injection molding machine, ASTM D36 41. This is done with a 1.1 inch (i.e., 28 mm) diameter screw. The temperature profile is from the throat to the nozzle. The melting temperature was set at 48°C / 121°C / 175°C / 204°C / 204°C. The injection pressure was 2000 bar and the injection time was 1.43 seconds. The holding pressure was set at 300 bar and the holding time was 25 seconds. The cooldown time was 20 seconds, and the recovery time was 12.49 seconds for PE and 9.84 seconds for PP. The screw speed was 90 rpm.

[0083] For injection molded Type I ASTM bars according to ASTM D638 test procedure The tensile test is carried out at a tension rate of 2 inches / min at room temperature. y ) and 2 The % secant modulus (E) is obtained from the tensile stress-strain curve. The 2% secant modulus is E = The yield stress is defined as the stress at 2% strain / 2%. The yield stress is the stress at 0% strain to 5% strain on the stress-strain curve. The highest stress in the 0% strain range. Five specimens were measured and the average value was reported.

[0084] Curl property Curl is measured under an optical microscope. Curl (defined as the curvature of the fiber) is the amount of curl caused by the fiber. The radius of the spiral is calculated as the reciprocal of the radius of the approximate spiral formed by the fiber. formed by projecting the approximate spiral formed by the fiber onto a surface perpendicular to it The average value of at least five samples is reported. Example Materials used ASPUN™ 6835 is manufactured by The Dow Chemical Company Unimodal (i.e., unimodal or monomodal, showing only one peak in the ICCD elution) It is an ethylene / octene copolymer of ethylene / octene (Dal). ASPUN™ 6000 is manufactured by The Dow Chemical Company It is an ethylene / octene copolymer. Sample 1 is a bimodal ethylene / α-olefin copolymer, synthesized as follows: do. Sample 2 is a bimodal ethylene / α-olefin copolymer, synthesized as follows: do. Exxon 3854 polypropylene is manufactured by Exxon Mobil. The yield stress and 2% secant modulus of these samples are summarized in Table 1. [Table 1]

[0085] Example 1 - Synthesis and Properties of Ethylene / α-Olefin Interpolymer Compositions All raw materials (ethylene monomer, 1-octene comonomer) and and process solvents (Isopar E (trade name) from ExxonMobil Chemical) High-purity isoparaffin solvent with a narrow boiling point range (product name) is purified with molecular sieves. Hydrogen is supplied under pressure as a high purity grade and is not further purified. The feed stream is compressed via a mechanical compressor to a pressure higher than the reaction pressure. The catalyst feed is pressurized via a pump to a pressure higher than the reaction pressure. , manually dilute the batch to the appropriate component concentration using purified solvents, and then perform the dilution at a pressure higher than the reaction pressure. All reaction feed streams were measured by mass flow meters and controlled by a computerized automatic valve control system. independently controlled by the system.

[0086] Two reactor systems are used in a series configuration. Each continuous solution polymerization reactor is A liquid-filled, non-adiabatic, isothermal circulating tank is used to simulate a continuous stirred tank reactor (CSTR). The loop reactor consists of a separate reactor for all fresh solvent, ethylene, hydrogen and catalyst component feeds. The total fresh feed to each reactor (solvent, ethylene, 1-octene, and hydrogen) is controlled. The fresh feed stream is heated to maintain a single solution phase by passing the feed stream through a heat exchanger. The total unused feed to each polymerization reactor is controlled to a roughly equal reactor volume between each injection location. The fresh feed is injected into the reactor at two locations, with each injector providing a total fresh feed mass flow rate. The catalyst components are pumped through specially designed injection stringers. The main catalyst component feed (precatalyst) is injected into the polymerization reactor at a specific target. The reactor is computer controlled to maintain ethylene conversion. The cocatalyst components are calculated and specified. The feed is based on the molar ratio of the main catalyst (pre-catalyst) component to the reactor. Immediately after the injection point, the feed stream is mixed with the contents of the circulation polymerization reactor using a static mixing element. The contents of each reactor are passed through a heat exchanger which serves to remove most of the heat of reaction, and in particular The coolant side temperature is continuously circulated to maintain an isothermal reaction environment at a constant temperature. Circulation around the reactor loop is provided by a pump.

[0087] In the dual series reactor configuration, the (solvent, ethylene, 1-octene) from the first polymerization reactor an effluent (containing hydrogen, catalyst components, and polymer) exiting the first reactor loop; Add to the second reactor loop.

[0088] The second reactor effluent is inactivated by the addition and reaction of water. Following catalyst deactivation and additive addition, the reactor effluent is The polymer melt is then pelletized. The non-polymer stream separates the majority of the ethylene that is removed from the system. The solvent and most of the unreacted 1-octene are removed through a purification system. After filtering, the solvent and 1-octene are recycled to the reactor. Do it.

[0089] To generate the examples, use the reactor stream feed data flow corresponding to the values ​​in Table 2. The data are based on the complexity of the solvent recycle system and the reaction system is run on a once-through flow diagram. The catalyst components used are shown in Table 3. Each polymer produced was tested for various properties according to the methods described above. The results are shown in Table 4. [Table 2] [Table 3] [Table 4]

[0090] Example 2 - Spun and drawn eccentric fibers Exxon3854PP one of the ethylene copolymers as core and sheath Bicomponent fibers with a highly eccentric core-sheath configuration were fabricated using the following: The extruder profile was set to a melt temperature of 240°C and a Hills line temperature of 100°C. Adjust to achieve a throughput rate of 0.6 ghm (grams per hole per minute). A Hills bicomponent die was operated with a 40 / 60 core / sheath weight ratio and one extruder. One extruder uses Exxon 3854 PP, and another extruder uses ethylene copolymer. The die configuration had a hole diameter of 0.6 mm and a length / diameter (L / D) of 4 / 1, resulting in a 14 The quench air temperature and flow rate were set at 23°C and 520 cfm (300 sq ft). After the quenching section, the filament is evacuated in the slot unit by an air flow. A drawing tension is applied to the 144 filaments by air drawing the air flow velocity. , controlled by the pressure of the slot aspirator, and the pressure of the slot aspirator was set to 20 ps Set it to i.

[0091] The resulting fibers were stretched at room temperature using an Instron tensile machine at a stretch rate of 100% / min for 5 min. The stretched fiber was then removed from the Instron and the curvature was measured. The results are shown in Table 5. [Table 5]

[0092] Example 3 - Spun and drawn concentric fibers used as staple fibers It has a polypropylene core and sheath (having a concentric core-sheath configuration). The bicomponent fibers were fabricated using ASPUN™ 6835 or Sample 1. , sample 2. On a Hills bicomponent continuous filament fiber spinning line, 0. Fiber is spun at a throughput rate of 5 ghm (grams per hole per minute). The extruder was operated at a 40 / 60 core / sheath ratio by weight and was fed with Exxon 3854 Use PP and ethylene / α-olefin intercopolymer in a separate extruder The diameter of the hole used was 0.5 mm, and the length / diameter L / D ratio was 4 / 1. Set the air temperature and flow rate to 25°C and 520 cfm (cubic feet per minute). The machine profile is adjusted to achieve a melt temperature of 240°C. After the quenching section, The 44 fibers are collected by a denier roll and then guided to two drawing rolls. The two draw rolls rotate at different speeds and draw the fiber between them. The fibers are then removed from the bobbin before being examined under a microscope for curl. The fiber spinning conditions are shown in Table 6. The curvature results are shown in Table 7. [Table 6] [Table 7] Examples of the invention of this application include the following. [1] A method for manufacturing a fiber comprising forming a fiber having at least a first region and a second region. The first region is a process including: 3 Density in the range , ethylene / α characterized by a melt index (I2) in the range of 10 to 60 g / 10 min olefin interpolymer composition, wherein I2 is a copolymer of olefin interpolymers as defined by ASTM D1238 , 190°C, 2.16 kg, and the weight average molecular weight and number average molecular weight measured by GPC Molecular weight ratio (M w(GPC) / M n(GPC) ) molecular weight distribution is 1.5 to 2 0.6 range, with a tan delta at 1 radian / sec of at least 45, and improved The low-temperature peak and high-temperature peak on the elution profile by the integrated comonomer composition distribution (ICCD) method The high-temperature peak and the full width at half maximum of the high-temperature peak are less than 6.0°C, and the fiber is Stretching to 0% elongation, thereby increasing the curl of said fiber. [2] The ethylene / α-olefin interpolymer composition has the following: a density of 0.930 ~0.940g / cm 3 The ethylene / α-olefin interpolymer The composition has a peak temperature of the low-temperature peak in the range of 60 to 80°C, a weight of the low-temperature peak of 25 to 65%, The amount fraction, the peak temperature of the high-temperature peak above 90°C, and the weight of the high-temperature peak between 35 and 75% The process according to [1] above, characterized in that it has one or more of the following amount fractions. [3] The first region has a first 2% secant modulus E 1 and the first yield stress σ y1 With The second region has a second 2% secant modulus E 2 and the second yield stress σ y2 have , the first 2% secant modulus E 1 is the second 2% secant modulus E 2 Is it different from or the first yield strength σ y1 is the second yield strength σ y2 different from, or both The process according to any one of the above [1] to [2], [4] The difference in the yield stress of the materials of the first and second regions is the yield stress of the second region. The process according to [3] above, wherein the divided value is at least 0.4. [5] The difference between the 2% secant modulus of the material of the first and second regions is The process according to [3] above, wherein the secant modulus is at least 0.4. [6] |σ y1 / E 1 -σ y2 / E 2 | / (σ y2 / E 2 ) is at least 0.01 The process described in [3] above. [7] The second region is the ethylene / α-olefin interpolymer of the first region. Any of the above [1] to [6] containing a polyolefin or polyester different from the composition. 3. The process according to claim 1. [8] The process of [7] above, wherein the second region comprises polypropylene. [9] The first region is a sheath around the core of the second region, or The second region is a sheath around the core of the first region, The process described in paragraph .

[10] Any of the above [1] to [9], further comprising heating the fiber before or after drawing. 10. The process according to any one of claims 1 to 9.

[11] Any of the above [1] to

[10] , wherein the stretching is carried out at a temperature in the range of 5 to 90°C. 10. The process of claim 1.

[12] The fiber according to any one of the above [1] to

[11] , wherein the fiber is formed into a nonwoven web. process.

[13] The process according to

[12] above, wherein the stretching is carried out after the nonwoven fabric web is formed. Process.

[14] The loft of the nonwoven fabric increases after stretching by at least 10%. 3].

Claims

1. A process for forming fibers each having at least a first region and a second region, wherein the first region comprises: 0.930~0.965g / cm ３ Density in the range of a melt index (I2) in the range of 10 to 60 g / 10 min (said I2 being measured according to ASTM D1238 at 190°C and 2.16 kg); a molecular weight distribution (expressed as the ratio of weight average molecular weight to number average molecular weight measured by GPC (M w(GPC) / M n(GPC) )) ranging from 1.5 to 2.6; tan delta at 1 radian / sec that is at least 45; an improved comonomer composition distribution (ICCD) elution profile with a low temperature peak and a high temperature peak; and a full width at half maximum of the high-temperature peak that is less than 6.0°C and a process comprising the ethylene / α-olefin interpolymer composition, drawing the fiber to an elongation of at least 20%, thereby increasing the curl of the fiber; The process includes:

2. The ethylene / α-olefin interpolymer composition has the following properties: a density of 0.930 to 1.000; 0.940 g / cm ３ The ethylene / α-olefin interpolymer composition The composition has a low-temperature peak temperature in the range of 60 to 80°C, and a low-temperature peak weight of 25 to 65%. fraction, peak temperature of the high temperature peak above 90°C, and weight of the high temperature peak between 35 and 75% 10. The process of claim 1 further characterized by one or more of:

3. The first region has a first 2% secant modulus E １ and the first yield stress σ ｙ１ have , the second region has a second 2% secant modulus E ２ and the second yield stress σ ｙ２ and The first 2% secant modulus E １ is the second 2% secant modulus E ２ Is it different from or the first yield stress σ ｙ１ is the second yield stress σ ｙ２ 3. The process of claim 1, wherein the .alpha.-methyl- ...

4. Dividing the difference in the yield stress of the materials of the first and second regions by the yield stress of the second region 4. The process of claim 3, wherein the value obtained is at least 0.

4.

5. The difference between the 2% secant modulus of the materials of the first and second regions is the 2% secant modulus of the second region.

4. The process of claim 3, wherein the value divided by the linear modulus is at least 0.

4.

6. |σ ｙ１ / E １ -σ ｙ２ / E ２ | / (σ ｙ２ / E ２ ) is at least 0.01 The process of claim 3.

7. The second region comprises the ethylene / α-olefin interpolymer of the first region.

7. The composition according to claim 1, wherein the composition comprises a different polyolefin or polyester. The process described in paragraph .

8. The process of claim 7 , wherein the second region comprises polypropylene.

9. The first region is a sheath around the core of the second region, or The second region is a sheath around the core of the first region. The process described.

10. 10. Any of claims 1 to 9, further comprising heating the fiber before or after drawing.

10. The process of claim 1.

11. 11. The method according to claim 1, wherein the stretching is carried out at a temperature in the range of 5 to 90° C. The process described.

12. The process of any one of claims 1 to 11, wherein the fibers are formed into a nonwoven web. Seth.

13. The process of claim 12, wherein the stretching occurs after forming the nonwoven web. vinegar.

14. 14. Any of claims 12 to 13, wherein the loft of the nonwoven increases after stretching by at least 10%.

10. The process according to any one of claims 1 to 9.

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