THERMALLY BONDABLE FABRICS, PREPARATION AND USE

Abstract: Thermally bonded fabrics having high normalized tensile strength are disclosed. Blends of high molecular weight linear ethylene polymers and low molecular weight linear ethylene polymers provide improved staple fiber-forming capabilities over that found with either polymer taken alone. Staple fibers formed from the blends have Q values above 4.5 and/or I10/I2 values above 7. The staple fibers formed from the blends of high molecular weight linear ethylene polymers and low molecular weight linear ethylene polymers have a broader thermal bonding window than either linear ethylene polymer taken alone. At least one of the linear ethylene polymers useful for blending for forming staple fiber can be a higher alpha-olefin in the C3-C12 range, preferably in the C3-C8 range.

Description: THERMALLY BONDABLE FABRICS, PREPARATION AND USE Improvements are made in the making of staple fibers and fibrous products from linear ethylene polymer by melt spinning a blend comprising at least one high molecular weight linear ethylene polymer having a melt index less than 25 grams/10 minutes and at least one low molecular weight linear ethylene polymer having a melt index greater than 25 grams/10 minutes at blend ratios sufficient to form linear ethylene polymer staple fibers having a "Q" value above Α .5 and/or a melt index ratio I-]o / - r 2 °^ at l e s t 7.0. Linear low density ' olyethylene (LLDPE) is an ethylene polymer prepared using a coordination catalyst in the same manner used in preparing linear high density polyethylene (HDPE), and is actually a copolymer of ethylene and at least one higher alpha-olefin. The expression "linear ethylene polymers" includes those linear ethylene polymers which have from 0 percent to about 30 percent of at least one higher alpha-olefin of 3 to 12 carbon atoms copolymerized with the ethylene. According to Modern Plastics Encyclopedia, as defined today, linear high density polyethylene generally has a density in the range of about 0.941 gm/cir to about 0.965 gm/cπ . Skilled artisans realize that the density can vary in accordance with the reaction conditions and type of catalyst used. It is also known that densities a little above that range can be achieved by special techniques, such as by annealing the polymer. It is known that polymerization conditions which will produce a homopolymer having a density of about 0.965 gm/cπ will produce a copolymer of ethylene 10 and higher alpha-olefin having a density lower than the said 0.965 gm/cπ , the extent of the lowering of the density being directly related with the amount of the higher alpha-olefin used. 15 It is known from EPO 85 101380.5 (U.S. Patent 4,830,907) that linear low density polyethylene (LLDPE) can be made into fibers by melt-spinning and that even very fine fibers can be produced. 20 Whereas LLDPE has been introduced in the market place as a polymer suitable for making fibers, it is also known that not all versions and varieties of LLDPE are entirely adequate for commercial production of 2c staple fibers. In particular, the fabric strength of carded staple-based fabrics has generally been significantly less than fabrics made from carded staple- based polypropylene fibers. 30 It is recognized in the art of making LLDPE polymers that the density of the LLDPE is affected by the amount and kind of olefin comonomer which is copolymerized with the ethylene and, to some extent, by the process conditions and catalyst used. A given mole .5 percent of, e.g., propylene in the copolymer will reduce the density of the polyethylene less than the same mole percent of a higher olefin comonomer. 'The melt index or MI (sometimes called melt flow rate or MFR) as measured by ASTM D-1238 (E) conditions 190°C/2.16 kg, is also affected to some degree by the kind and amount of olefin comonomer in the copolymer, and is also affected to some extent by the coordination catalyst used, the polymerization conditions, and/or by any telogens or chain regulators or other reactants which may be present during polymerization. It is also recognized in the art that there are important distinctions between linear polyethylenes (which includes LLDPE polymers), and branched-chain ethylene polymers, which are made using a free-radical 5 catalyst and are generally referred to as LDPE (low density polyethylene), and were also known in the past as ICI-type polyethylene and as HPPE (high pressure polyethylene). Our invention deals with linear π polyethylenes. U.K. Patent Application GB 2,121,423A teaches away from our invention claimed hereinafter, because the U.K. patent application teaches away from the use of ,- "linear" polyethylene staple fibers having polymer "Q" values of more than 4 in order to prepare strong, thermally bonded fabrics, for the following reasons. In particular, the patent application relates to hot-melt adhesive binder fibers comprising specific polyethylene 0 resin compositions. Its Example 1 discloses cut short fibers of linear polyethylene homofilaments wherein the polyethylene has a density of 0.92; an MI of 25; and a "Q" value of "2.82". It also discloses the use of those homofilaments (having a Q value of 2.82) in preparing 5 hot-calendered non-woven fabrics from blends of such fibers with poly(ethylene terephthalate) staple fibers. Its Claim 1 is as follows: "1. Hot-melt ,- adhesive fibers comprising a polyethylene resin composition (C) alone, consisting of 50 to 100 percent by weight of a polyethylene (A) having a density of 0.910 to 0.940 g/cm 3 and a Q value (Q=Mw /Mn) of 4.0 or less and 50 to 0 percent by w ' eight of a polyethylene (B) 10 having a density of 0.910. to 0.930 g/cπ-3 and a Q value of 7.0 or more based on said composition, or composite fibers which contain said composition (C) as one of the composite components of said composite fibers and in which said composition (C) forms continuously at least a 15 part of the fiber surface of said composite fibers." Polyethylene B, however, is not a "linear" ethylene polymer. Polyethylene A is a linear ethylene polymer. However, when the polyethylene resin 20 composition (C) consists of 100 percent polyethylene (A), the claim expressly requires that the Q value be "4.0 or less". Further, the British patent application teaches that one advantage of the claimed invention r-,r- (when used as a binder fiber) is "superior strength" of the non-woven fabric. Accordingly, it clearly teaches away from the invention described hereinafter. European Patent Application No. 0 314 151 (A2) 30 published May 3 > 1989 relates to polymers used in making thermally bonded fabrics, but has no working examples directed to discontinuous staple fibers. All the working examples of invention of the European patent application are directed to the use of "continuous" 35 filaments prepared by melt-spinning at linear spinning velocities of at least 3,500 meters/minute. Its teachings are, therefore, much less relevant than the aforementioned U.K patent application. We have now found that blends, either discrete t - blends or in-situ polymerized blends, of linear ethylene polymers, especially LLDPE, having certain properties, are surprisingly well suited for making staple fibers and yield products having strengths more competitive with those attainable in carded, thermally bonded webs 10 of polypropylene. These blends have a broader molecular weight distribution than a sole linear ethylene polymer resin produced at the same MI (melt index). A first broad aspect of the invention is a 15 process for preparing a fabric, which fabric is either thermally bonded or bondable, from filaments including thermoplastic fine denier discontinuous staple fibers having an average denier per filament in a range of from 0.1 to 15 d.p.f., and having filament lengths up to 30 20 cm., and in which the staple fibers are prepared from a meltspun blend of linear ethylene polymers characterized in that the polymer blend in the staple fibers has a Q value above 4.5, wherein Q is defined as weight average rmr- molecular weight divided by number average molecular weight, as determined by gel permeation chromatography. A second broad aspect of the invention is a process for preparing a fabric, which fabric is either - 30 thermally bonded or bondable, from filaments including thermoplastic fine denier discontinuous staple fibers having an average denier per filament in a range of from 0.1 to 15 d.p.f., and having filament lengths up to 30 cm. , and in which the staple fibers are prepared from a 35 meltspun blend of linear ethylene polymers characterized in that the polymer blend in the staple fibers has an I10/I2 value of at least 7, wherein 110 is determined by ASTM D-1238(N) conditions, and I2 is determined by ASTM D-1238(E) conditions. A third broad aspect of the invention is a thermally bonded fabric wherein the thermally bonded fabric .has a normalized strip tensile strength of at least 3,000 grams. A fourth broad aspect of the invention is polymeric fibers including discontinuous staple fibers wherein the polymer has an I10/I2 value of at least 7 and the polymer is a blend of (A) at least one high molecular weight linear ethylene polymer having a MI value less than 25 grams/10 minutes and a density above 0.91 grams/cπ , and (B) at least one low molecular weight linear ethylene polymer having a MI above 25 grams/10 minutes and a density above 0.91 grams/cm^. A fifth broad aspect of the invention is a polymer blend characterized in that the polymer blend has an I10/I2 value of at least 7 as determined by ASTM D-1238(N) and (E) respectively and further wherein the blend is formed by blending (A) and (B) in appropriate weight ratios wherein (A) is at least one high molecular weight linear ethylene polymer having an MI measured in accordance with ASTM D-1238(E) (190°C/2.16 kg) less than 25 g/10 minutes and a density above 0.91 g/cπ ; and, (B) is at least one low molecular weight linear ethylene polymer having a MI measured in accordance with ASTM D- 1238(E) (190°C/2.16 kg) greater than 25 g/10 minutes and a density above 0.91 g/cπ . A sixth broad aspect of the invention is a process for preparing polymeric fibers characterized by the steps of (A) Melt-spinning the polymer into meltspun filaments; (B) Hauling off the meltspun filaments at a speed in a range of from 60 to 2,000 meters/minute; and, optionally, (C) drawing and/or crimping and/or cutting the'hauled-off meltspun filaments by conventional means. A seventh broad aspect of the invention a process wherein molten linear ethylene polymer fine denier staple fibers are spun at commercially feasible throughput rates, optionally followed by mechanical drawing to produce fiber sizes of from 0.1 to 15 denier/filament and used in making a web or fabric, characterized by spinning a blend comprising (A) at least one high molecular weight linear ethylene polymer having a MI measured in accordance with ASTM D-1238(E) (190°C/2.16 kg) less than 25 g/10 minutes and a density above 0.91 g/cπ , and (B) at least one low molecular weight linear ethylene polymer having a MI measured in accordance with ASTM D-1238(E) (190°C/2.16 kg) greater than 25 g/10.minutes and a density above 0.91 g/cπ , forming linear ethylene polymer staple fibers having a Q value above 4.5, wherein Q is defined as weight average molecular weight divided by number average molecular weight, as determined by gel permeation chromatography. An eighth broad aspect of the invention is a blend wherein the ratio of the high molecular weight linear ethylene polymer and low molecular weight linear ethylene polymer is sufficient to provide a blend having a MI value in the range of 0.1 to 40 grams/10 minutes and a density in the range of of 0.94 to 0.96 grams/cn . In still another aspect, the invention is a means for increasing the thermal bonding window of staple fibers made from linear polyethylene by blending high and low molecular weight linear pdlyethylenes, spinning into staple fiber and thermally bonding the fiber into fabric. Preferred aspects of the invention include the following. The average denier per_filament of the fiber is preferably in a range from 1 to 15 d.p.f., and more preferably in a range from 2 to 6 d.p.f. The use of d.p.f.'s below 1 makes silk-like products, but adversely affects productivity and tends to increase downstream problems such as poor cardability. Q value is preferably in a range from 5.5 to 10. I-J Q /12 value (ratio) is preferably in a range from 10 to 20. The polymer blend is usually, prefer~bly formed by blending in-situ during polymerization of the polymer. However, it is sometimes preferred to blend discrete polymers. The thermally bonded fabric preferably has a normalized strip tensile strength of at least 3,000 grams; more preferably 3 > 600 grams; and most preferably 3,700 grams. The polymer blend preferably has a density in a range from 0.94 to 0.96 gm/cπ . It is preferred that at least one of the linear ethylene polymers comprise a copolymer of ethylene with at least one C3-C12 olefin (particularly octene, especially octene-1). It is preferred to use haul-off speeds in a range of 60 to 2,000 meters/minute during the melt spinning step. It is preferred and that at least one of the linear ethylene polymers by L'LDPE. Polymer blends of our invention wherein a high molecular weight linear polyethylene, especially LLDPE, and a low molecular weight linear polyethylene, especially LLDPE, are uniformly blended and used in making fibers, are found to exhibit not only the good hand, softness, and drape which one might expect of a linear polyethylene, especially the LLDPE variety, but a carded, thermally bonded web (fabric) of surprisingly high strength is produced at spinning rates which are very suitable for commercial operations. In the presently claimed invention, the important thing is to blend an appropriate amount of the low molecular weight linear polymer with the high molecular weight polymer to produce the improvement in making staple fibers from the high molecular weight polymers. We have found that in obtaining the desired improvement, the blends which are preferred will have a blend density of above 0.91 gm/cm^, especially above 0.94 gm/eπ and up to 0.96 gm/cm^. The types of "fabric" that may be prepared by our invention are essentially all types of fabric now made and new types of fabric that could be made in the future. Our invention is primarily directed towards textile fabrics. It does extend to industrial fabrics as industrial filter cloth. In this disclosure the expression "discrete m. blends" is in reference to the mixing of linear polymers which are made separate from each other, each under its own set. of reaction conditions, possibly at different times and/or places, the mixing taking place after the polymer has been collected from the respective reactors. 10 The expression "in-situ polymerized reactor blends" is in reference to blends of at least two linear polymers which have differing properties and which are prepared conjointly, but under differing reaction 15 conditions, whereby the properties of each are varied, one from another, and the so-prepared polymers are immediately and intimately mixed within the reaction system before removal therefrom. There are several ways known by skilled artisans for making in-situ polymerized 20 blends, such as in U. S. Patent 3,914,342, and the invention is not limited to any one of the methods. The linear ethylene polymer resin used for the "high molecular" weight portion of the blend of the 25 present invention can be any which may contain an amount of a C 3 to C 1 2 olefin comonomer, copolymerized with the ethylene, sufficient to yield a density in the range of 0.91 gm/cπ to 0.965 gm/cir , and has a MI of less than 30 25 gm/10 minutes, preferably less than 20 gm/10 minutes. Preferably, the comonomer is a C 3 to Cβ olefin, such as propylene, butene-1, hexene-1, 4-methyl pentene-1, octene-1, and the like, especially octene-1, and can be a mixture of olefins such as butene/octene or 35 hexene/octene. The above stated MI and density ranges include linear polyethylenes which contain no comonomer as well as those which contain at least one comonomer. The linear ethylene polymer resin used for the "low molecular" weight portion of the present blend can be any which contains an amount of C 3 to C 12 olefin comonomer, copolymerized with the ethylene, sufficient to yield a density in the range of 0.91 gm/cπ to 0.965 gm/cir , and has a MI of greater than 25 gm/10 minutes preferably greater than 40 gm/10 minutes. Preferably, the comonomer is a C 3 to Cg olefin, such as propylene, butene-1, hexene-1, 4-methyl pentene-1, octene-1 or the like, especially octene-1, and can be a mixture of olefins such as butene/octene or hexene/octene. The above stated MI and density ranges also apply to linear polyethylenes which contain no comonomer as well as those which contain at least one comonomer. The melt index (MI), also known as I 2 , of the polymers is measured in accordance with ASTM D-1238 using Condition E (also known as 190°C/2.16 kg) unless otherwise specified and is a measurement of the amount (grams) of melted polymer which is extruded from the orifice of the melt index barrel in 10 minutes. The melt index (MI) is an indication of relative molecular weight, with a given MI numerical value indicating a higher molecular weight than a greater MI numerical value. "Gel permeation chromatography" (herein called "GPC"), also known as "size exclusion chromatography", is a measurement made to characterize molecular weight distribution of a polymer and is well known in the industry. Data reported by this GPC technique includes weight average molecular weight (MWwa). number average molecular weight (MWna) . and weight average molecular weight divided by number average molecular weight (MW wa /MWna). Of these, the MW wa /MW na Is of the most interest, indicating broadness of molecular weight distribution. The higher the MW W a/ « na ratio, the broader the molecular weight distribution (sometimes called -polydispersity) of the resin. Molecular weight distribution, indicated by MW w /MWna» or "Q", or by the ratio of Iio (as measured by ASTM D-1238 (N) conditions 10 190°C/10.0 kg) divided by I2 has been found to influence thermal bonding of staple fiber. We find that resins having Q values above 4.5, or S ~ - ~\ Q/S ~ -2 va -l ues above 7 have shown extreme utility in broadening the thermal bonding window of staple fibers made from linear polyethylene. 15 (The "bonding window" is the temperature range over which staple fiber can be satisfactorily thermally bonded.) For example, a single linear ethylene polymer having a melt index of 17 grams/10 minutes, a density of 20 0.950g/cc and a Q value of from 4 to 4.5 has a thermal bonding window of 5°C. A discrete polymer blend of the present invention having a melt index of 17 grams/10 minutes, a density of 0.950 g/cc and a Q value of 5.75 to 6 has a thermal bonding window of 10°C. Thus staple 25 fibers made from the polymer blends of the present invention have broader thermal bonding windows. The normalized fabric tensile strength (per 2.54 cm width) of a thermally bonded web (fabric) is 30 measured on 1-inch wide by 4-inch long (2.54 cm by 10.16 cm) samples by measuring conventionally the total •breaking load, and then normalizing it to 1-ounce/yard 2 (about 33.9 gm/m 2 ) and measured in grams. The tenacity -,-- of fibers is measured as "grams/denier". - ι3- Prior to our invention it has " been found to be difficult to make fine denier staple fibers of linear ethylene polymer for conversion into carded thermally bonded webs, especially at the high production rates and broad thermal bonding windows normally desired in commercial operations, which result in fabrics having typically more than about 50 percent of the normalized fabric tensile strength of fabrics obtained for carded, thermally bonded polypropylene staple fiber at 10 comparable Mi's. Greater strength of thermally bonded linear ethylene polymer staple fiber, including LLDPE, is desirable in various products, such as, for example, diaper cover stock, medical garments and feminine -r hygiene products. Since the formation of staple fibers includes such complex and varied operations as melt drawing, mechanical stretching, crimping, and cutting, the 20 requirements for the polymer are rigorous. The first requirement of the polymer is to withstand the melt drawing ' of the spinneret extrudate to a filament size ranging from approximately 0.1 to 15 denier at commercially feasible throughputs, especially 25 throughputs ranging from 0.1 to 0.67 grams/minute/hole (gm/min./hole) . These throughput variations are dependent not only upon desired production rates, but also equipment design limitations (such as compact melt spinning as compared to conventional melt spinning). 30 Subsequently, this resultant filament can be stretched at draw ratios ranging up to 6:1 to produce filament at the final desired fiber size, typically ranging from 0.5 to 6.0 denier. -* After stretching (or drawing) the fiber to the appropriate denier size the fiber is usually crimped, via a stuffer box, air texturizer or oEher device, and then cut to the desired length. Crimping imparts a thermo-mechanical deformation to the fiber, causing it to have numerous bends and greater entanglement. These bends, or crimps, are useful when carding fiber in order to create some degree of web cohesion prior to bonding. Staple ' fiber, especially for non-woven applications is usually carded into a web prior to being bonded. Typical bonding techniques include hydrodynamic entanglement (commonly referred to as spunlacing) , chemical bonding, and most frequently, thermal bonding. Thermal bonding is typically accomplished by passing carded web through heated calender rolls, infrared oven, ultrasonic bonding device, or through-air bonder. Most frequently, thermal bonding of these carded webs is achieved via heated calender bonding. The technique used to differentiate these various linear ethylene polymers will be described farther on in this disclosure, but it employs essentially all of these processing steps. We have found that the initial requirement of good melt draw-down of the filaments into small diameter fibers under the desired production conditions makes staple fiber spinning with a relatively high molecular weight linear ethylene polymer very difficult. While it is already realized that increasing molecular weight of a polymer results in an increased strength (tenacity) of articles formed from that polymer, the increased molecular weight also results in much greater staple spinning problems. That is, the higher molecular weight linear ethylene polymers (including LLDPE) are not well suited for spinning at commercially viable and economical rates. What has not been known is that there are unexpected benefits obtained by blending a low molecular weight linear ethylene polymer, especially LLDPE, with a high molecular weight linear ethylene polymer, especially LLDPE, especially in spinning, then carding and bonding staple fiber made from these polymers. For purposes of describing the present invention, a linear ethylene polymer, (including HDPE 10 and LLDPE) having a MI value of less than 25, preferably less than 20, especially less than 5, and, optionally, as low as 0.1, is considered to be in the high molecular weight range; the lower the MI value, the higher is the molecular weight. Linear ethylene polymer having a MI 15 value in the range of 25-40 may, in some aspects, be considered to be an "intermediate" molecular weight range, but in relating the present invention, it is considered as being on the "high" end of the low 0 molecular weight range. Linear ethylene polymer having a MI in the range above 40, especially above 45, is considered to be in the low molecular weight range and is not considered (in relating the present invention) to be in an "intermediate" molecular weight range. Whereas 5 MI values exceeding 300 can be used as the low molecular weight polymer, especially if the high molecular weight portion of the present blend has a MI value below 1 or 2, it is preferred that the MI values of the low molecular weight polymer be not more than 600, preferably not more than 500. Above 500-600 MI, one might encounter problems such as diminished melt strength properties. In a general sense, one should consider that the lower the MI value of the high -,,- molecular weight resin, the greater the need to blend it with an off-setting amount of a linear ethylene polymer -1fS- having a high MI value as the low molecular weight polymer. One can calculate the MI values and the density values of the polymers used in the blends of the present invention and obtain values which are reasonably close to the .actual values obtained by actual measurement of the blend. The following formula may be used to calculate the melt index of polymer blends: In blend = (fraction A)ln A + (fraction B) In B The following formula may be used to calculate the density of polymer blends: pblend = (fraction A)pA + (fraction B)pB The present invention employs, in a blend, an amount of low molecular weight linear ethylene polymer which is effective in overcoming the deficiencies of high molecular weight linear ethylene polymer in the making of staple fiber based webs or fabrics and enables one to utilize the high molecular weight linear ethylene polymer in the demanding processing conditions of staple fiber spinning, carding and bonding, while substantially maintaining the inherent strength of the high molecular weight linear ethylene polymer. This strength, when evaluated in bonded fabric form, improves by as much as 165 percent or more at a comparable MI r s. The strengths of thermally bonded fabric made from ; ;hese higher molecular weight blended polymers, approach the strength of typical commercial polypropylene-based fabrics by as much as 75 percent or more. The thermally bonded webs or fabrics prepared using the blends of the present invention can be made wettable by incorporating into one or both of the polymers certain additives such as in U.S. 4,578,414. Furthermore, the addition of minor amounts of additives, such as colorants and pigments is within the purview of the present invention. The webs or fabrics made using the present blends exhibit excellent softness, good gamma irradiation stability, high strength, and good thermal bondability to itself and to other thermoplastic films or webs, such as other polyolefins. The ratio of high molecular weight linear ethylene polymer to low molecular weight linear ethylene polymer in the blend is largely dependent on the MI of each. Generally, the amount of low molecular weight polymer used in modifying the high molecular weight polymer is desirably about the minimum amount needed to render the high molecular weight polymer processable at the desired spinning rate and denier size and to improve thermal bonding strength of fabrics made therefrom. Conversely, the amount of high molecular weight polymer added to the low molecular weight polymer is desirably an amount needed to render the low molecular polymer processable at the desired spinning rate and denier size and to improve thermal bonding strength of fabrics made therefrom. It is obvious that "trial and error" and "successive approximation" techniques can be used to determine the particular "weight ratios of the unblended components" that are needed in order to make a blended polymer having a Q value of at least 4.5 and/or an I-J Q /12 value of at least 7. Further, it is obvious that, if so desired, the polymer may be formed from more than two unblended components. ,- The examples hereinafter illustrate some embodiments of the present invention, but the invention is not .limited to these specific embodiments. It should be noted that in all the following 10 examples the molecular weights were determined on a Water's Associates Model No. 150C GPC. The measurements were made by dissolving polymer samples in hot, filtered, 1, 2, 4 trichlorobenzene (TCB). The GPC (Gel Permeation Chromatography) runs were made at 140°C in 15 TCB. A flow rate of 1.0 ml/min was used and the columns used were 3 Polymer Laboratories 10 micron linear columns. Column performance was typically around 30,000 plates/meter (see Yau, W. W., J. J. Kirkland, D. D. Bly and H. J. Stoklosa, Journal of Liquid Chromatography, 20 125, 219 (1976)) as determined using 0.02 grams eicosane in 50 milliliters of TCB. Columns were disposed of if the plate count was below 20,000 plates per meter. Column performance was also monitored using the c multiplied product of the spreading factor "σ" and the slope of the calibration curve "D" (see Yau, W. W., J. J. Kirkland, D. D. Bly and H. J. Stoklosa, Journal of Liquid Chromatography, 125, 219 (1976)). This value was typically around 0.081. Columns with values above 0.09 30 for Dσ were not employed. The antioxidant butylated hydroxytoluene was added at a concentration of 250 parts per million to the TCB. The system was calibrated using narrow molecular weight polystyrene standards. The following formula (see Williams, T. and I. M. Ward, J. • * Polymer Sci, Polymer Letters, 6, 621 (1968)) was used to transform polystyrene molecular weights to polyethylene molecular weights: Mw polyethylene = 0.4316 (Mw polystyrene) The polyethylene samples were prepared at a concentration of 0.25 grams of polyethylene in 50 milliliters of TCB. The volume, injected was 100 microliters. Example I A discrete polymer blend comprising 40 by weight high molecular weight linear ethylene polymer (ethylene/octene, 2.3 MI, 0.917 g/cιr-3) and 60% low molecular weight linear polyethylene (ethylene/octene, 105 MI, 0.953 g/cm 3 ), a blended density of 0.939 g/cm 3 , a blended MI of 23, and a Q-value of about 6.82 is formed into fiber at about 0.4 g/min./hole and 1,200 meters/minute haul-off speed and collected on spool. These filaments had average d.p.f of about 3.0. The spooled yarn was then unwound and conventionally cut into 1.5 inch (3.81 cm) staple fibers. Fabric made from the resulting fiber has a maximum 1" (2.54 cm) normalized fabric strip tensile strength at 2686 grams, which is more than 55 of commercially available fiber- grade polypropylene and over 140 of a single commercially available polyethylene at a comparable MI. Data are shown in Table I (shown after Example III). A test on the above polymer blend is performed as follows: A one inch diameter extruder, 24 inches in length, t-ontaining a high shear type screw was used to melt and convey polymer to a positive displacement gear pump, which accurately metered polymer to the spin pack. Many different screw designs may be used, including one commonly used in the extrusion industry for polyethylene, i.e., the low shear or barrier type screw. Spin pick configuration may vary considerably, but that used in tests described herein had, as its major components, a 40 micron sintered metal filter media and a spinneret which had hole size of 600 microns, with length-to-diameter ratio of 4:1. Fibers are collected continuously onto spools using godet speeds necessary to achieve the desired denier per filament (dpf), relative to the throughput. For example, a throughput of about 0.4 gms/min./hole requires a corresponding 6 inch (15.24 cm) diameter godet speed of about 2600 revolutions per minute to achieve about 3.0 dpf. at 1,200 meters/minute. For all the tests herein, fibers were melt spun with no additional drawing. After collection of sufficient sample size, the fibers are cut off of the collection spool and cut into 1.5-inch (3.81 cm) staple fibers. Samples of these staple fibers (each 1.25 gm) are weighed out and formed into slivers using a Roto Ring (manufactured by Spinlab, Inc.); a sliver is an ordered collection of fibers such that the fiber ends are randomized while the fibers themselves are all paralleled. The structure is about 10 cm wide by about 25.4 cm long after gently opening the sliver tow. This opened sliver tow (simulating a carded web) is then fed into a Beloit Wheeler calender bonder for thermal tie down of the filaments where pressure and temperature are adjusted for optimal bonding conditions and fabric strength. The fibers produced from the blend described above are found to have optimum bonding conditions at a top roll (or embossed roll with about 20 percent land area) temperature of about 115°C and a bottom roll (smooth roll) temperature of about llδ^C. The bonding pressure is typically found to be optimal at about 700 psig (4927.9 kPa) or about 199 pli (pounds per linear inch) (90.3 kgs/linear 2.54 cm or 35.6 kgs/linear cm). After forming a sufficient number of thermally bonded fabrics under the same bonding conditions, a single sample " is cut out of each bonded strip which measures one inch by four inches (2.54. by 10.16 cm), with the four inch dimension cut such that it is in the machine direction. These samples are individually weighed and then tensiled by use of an Instron tensile tester affixed with a data systems adapter for measuring and recording load and displacement. The fabric samples are loaded into the Instron such that the one inch section of each sample is held by the Instron jaws during the test, thus pulling the fabric in the machine direction. The mean value of the force required to break this fabric strip, normalized to one ounce per square yard weight for every test described herein, is then recorded. For this particular example, the normalized fabric tensile strength (or bonded fabric tenacity) is about 2686 grams. The above procedure is also carried out for Examples II-XIII. Example II (for comparison; not example of invention) A commercially available LLDPE, ethylene/octene copolymer, having a MI of 26, a density of 0.940 g/cn , and a Q-value of 3.74 is formed into fiber at about 0.4 g/min./hole. Fabric made from the fibers has a maximum 1" (2.54 cm) normalized fabric tensile strength of 1855 g-to-break which is less than 40% of commercially available fiber-grade polypropylene. Data are shown in Table I. Example III A blend comprising 50 percent by weight of low molecular weight linear ethylene polymer (ethylene/octene, 52 MI, 0.953 density) and 50 percent by weig ' ht of high molecular weight linear ethylene polymer (ethylene/octene, 12 MI, 0.936 density) is found to have a peak normalized fabric tensile strength of about 2400 gms. Blend MI is 25 and blend density is 0.945 g/cm 3 . See Table I below. Example IV (for comparison; not example of invention) A commercially available LLDPE, ethylene/octene copolymer, having a MI of 12, a density of 0.935 g/cm 3 , and a Q-value of 4.36 is formed into fiber at about 0.4 g/min./hole. Fabric made from the resulting fiber has a maximum 1" (2.54 cm) normalized fabric tensile strength of about 2700 grams-to-break which is less than 60% of commercially available fiber grade polypropylene. Data are shown in Table II. Example V An in-situ polymerized reactor blend (ethylene/octene copolymer) having a blended MI of 11, a blended density of 0.934 g/cm 3 , and a Q-value of 13.6 is formed into a fiber at about 0.4 g/min./hole. Fabric made from the resulting fiber has a maximum 1" (2.54 cm) normalized fabric tensile stren-gth of about 3700 grams which is about 80% of commercially available fiber-grade polypropylene and about 140% of commercially available single linear ethylene polymer at a comparable MI. Data are shown in Table II. TABLE II Normalized Fabric Tensile Strength (grams) DensityQ-value 0.935 4.36 2700 0.934 13.6 3700 An in-situ polymerized reactor blend (ethylene/octene copolymer)having a blended MI of 10, a blended density of 0.955 gm/cπ-3 and a Q-value of 8.87 is formed into a fiber at a throughput of about 0.4 gm/min. /hole. Fabric samples of 1" (2.54 cm) made from the resulting fiber has a maximum normalized fabric tensile strength of about 3614 grams which is about 78% of that of commercially available fiber grade polypropylene and 129% of commercially available single linear ethylene polymer at a comparable MI (see Example VII for comparison). The following data indicates tenacity and bonding temperature for 6 tests. Also, some data are shown in Table III. Example VII (for comparison: not example of Invention) A commercially available high density single linear, ethylene/propylene copolymer, having a MI of 12, a density of 0.95 gm/cm 3 , and a Q value of 3.92 is formed into fiber at about 0.4 gm/min./hole. Fabric made from the resulting fiber has a maximum 1" (2.54 cm) normalized fabric tensile strength of about 2794 grams- to-break which is less than 60% of commercially available fiber grade polypropylene. The following chart of data indicates normalized fabric tensile strength and bonding temperature for 4 tests. Also see Table III. 'stic point A commercially available fiber-grade polypropylene (PP) is spun into fibers and made into a heat-bonded fabric. The PP had a 15.6 MI (@190°C) and 0.91 density. The following data indicates normalized fabric tensile strength and temperature for 5 tests: A discrete blend comprising 50 percent by weight of high molecular weight linear ethylene polymer (ethylene/octene, 12 MI, 0.935 density) and 50 percent by weight of low molecular weight linear ethylene polymer (ethylene/octene, 105 MI, 0.953 density) is spun into fibers and a bonded web (fabric) is obtained. The blend has a calculated MI of 35.5 and density of 0.944. Bonding temperature and normalized fabric tensile strength is shown below at different bonding pressures. Also see Table IV. Example X A discrete blend comprising 70 percent by weight of high molecular weight linear ethylene polymer (ethylene/octene, 18 MI, 0.93 density) and 30 percent by weight of low molecular weight linear ethylene polymer (ethylene/octene, 105 MI, 0.953 density) and having a calculated MI of 30.5 and densirty of 0.937, is spun into fibers and bonded as a fabric in 3 tests; data are shown below. Also see Table IV. Example XI (for comparison; not claimed invention) A single linear ethylene polymer (ethylene/octene) having a MI of 30 and a density of 0.94 g/cir is found to have a maximum normalized fabric tensile strength of about 1531 gms. See Table IV below. TABLE IV Example Type MI IX discrete blend 35.5 X discrete blend 30.5 XI LLDPE, single 30. Example XII A discrete blend comprising 71% by weight of a high molecular weight linear ethylene polymer (ethylene/propylene, 8 MI, 0.952 density) and 29% by weight of low molecular weight linear ethylene polymer (ethylene/octene, 105 MI, 0.954 density) and having a calculated MI of 17 and density of 0.953 g/cπ is spun into staple fibers and bonded into fabric at 200 PLI (35.7 kg/linear cm). Data are shown below. Also see Table V below. Example XIII (for comparison; not claimed invention) A single linear ethylene polymer (ethylene/propylene copolymer) having a MI of 17 and a density of 0.95 g/cirπ is spun into fibers and bonded as a fabric at 200 PLI (35.7 kg/linear cm). Data are shown below. Also see Table V below. Bonding Temp. °C 116 117 118 119 120 (embossed/smooth) 118 119 120 121 122* 2016 2213 2202 2749 2837* Normalized Fabric TensileStrength (grams) *stick point Finally, the following is a hindsight partial explanation as to how our claimed invention results in superior products, notwithstanding the strongly negative teachings of the prior art. Continuous fiber (and subsequently the thermally bonded fabric) made using the spunbonded process differs dramatically from staple fiber spinning, optionally drawing the fiber, crimping the fiber, cutting the fiber making it discontinuous, carding the fiber into fabric and thermally bonding the fiber. The spunbonded process can effectively use polyethylene having lower densities (such as about 0.94 g/cc and lower) and the continuous filaments are thermally bonded into fabric. Spunbonding of polymer results in fiber which simulates the shrinkage properties of low draw ratio staple fiber. The thermal bonding " window of lower density polyethylene is broader than for higher density polyethylene at equivalent melt indices and molecular weight distributions and the thermal calenders are operated such that the fabric can be bonded. There is no carding step and thus no need to modify the polymer for forming the fiber into fabric. In the staple process, the discontinuous or cut fiber has to be carded into fabric. Carding can be accomplished with polyethylene fiber by using a high draw ratio during the spinning step. But, this high draw ratio results in fiber having high shrinkage and resultant low thermally bonded fabric strength. The heat shrinks the fiber instead of bonding it together. However, the density of the polyethylene can be increased to enable it to card, but then the melting point range of the fiber is too narrow to effectively thermally bond it into fabric. Trying to control a thermal calender within a narrow range either results in an unbonded fabric or fiber/fabric sticking to the calender rolls resulting in equipment shutdown. The present invention solves these staple fiber and fabric forming deficiencies by broadening the thermal bonding' indow of the polyethylene staple fiber making it useful in forming high strength thermally bonded fabric while maintaining the cardability of the fiber, especially when higher density polyethylene is used, such as densities between 0.94 and 0.965 g/cc.

Claims: 1. A process for preparing a fabric, which fabric is either thermally bonded or bondable, from filaments including thermoplastic fine denier discontinuous staple fibers having an average denier per filament in a range of from 0.1 to 15 d.p.f., and having filament lengths up to 30 cm. , and in which the staple fibers are prepared from a meltspun blend of linear ethylene polymers: characterized in that the polymer blend in the staple fibers has a Q value above 4.5, wherein Q is defined as weight average molecular weight divided by number average molecular weight, as determined by gel permeation chromatography. 2. A process for preparing a fabric, which fabric is either thermally bonded or bondable, from filaments including thermoplastic fine denier discontinuous staple fibers having an average denier per filament in a range of from 0.1 to 15 d.p.f., and having filament lengths up to 30 cm. , and in which the staple fibers are prepared from a meltspun blend of linear ethylene polymers: characterized in that the polymer blend in the staple fibers has an I10/I2 value of at least 7, wherein 110 is determined by ASTM D-1238(N) conditions, and 12 is determined by ASTM D-1238(E) conditions. 3. The process of Claims 1 or 2 wherein an c - unbonded fabric prepared thereby is capable of being thermally bonded to give a stronger fabric, as determined by normalized strip tensile strength, over a broader range of thermal bondirrg temperatures, than an otherwise identical process used to prepare a 10 comparative product wherein the polymer blend in the staple fibers in the comparative product has either a Q value in a range of from 3.5 to 4.0 or an I10/I2 value in a range from 6.0 to 6.5. 15 4. The process of Claim 1 wherein the polymeric blend in the staple fibers has a Q value in a range from 5.5 to 10. 5. The process of Claim 2 wherein the 20 polymeric blend in the staple fibers has an I10/I2 value in the range from 10 to 20. 6. Thermally bonded fabric prepared by the process of Claims 1 or 2, wherein the thermally bonded 25 fabric has a normalized strip tensile strength of at least 3,000 grams. 7. The thermally bonded fabric of Claim 6 wherein the polymeric staple fibers comprise a polymeric 30 blend is an in-situ blend formed during polymerization of the polymer; and the thermally bonded fabric has a normalized strip tensile strength of at least 3,600 grams. 35 8. The thermally bonded fabric of Claim 7 having a normalized strip strength of at least 3,700 grams. -. 9. Polymeric fibers including discontinuous staple fibers suitable for use in the process of Claims 1 or 2.wherein the polymer has an I10/I2 value of at least 7 and the polymer is a btend of 10 (A) at least one high molecular weight linear ethylene polymer having a MI value less than 25 grams/10 minutes and a density above 0.91 grams/cm^, and (B) at least one low molecular weight 1C - linear ethylene polymer having a MI above 25 grams/10 minutes and a density above 0.91 grams/cπ . 10. The staple fibers of Claim 9, having an average denier per filament in a range of from 0.1 to 15 20 d.p.f., and being homofilaments. 11. A polymer blend suitable for use in preparing the polymeric fibers of Claim 9 characterized in that the polymer blend has an I-|o /l2 value of at 25 least 7 as determined by ASTM D-1238(N) and (E) respectively and further wherein the blend is formed by blending (A) and (B) in appropriate weight ratios wherein 30 (A) is at least one high molecular weight linear ethylene polymer having an MI measured in accordance with ASTM D-1238(E) (190°C/2.16 kg) less than 25 g/10 minutes and a density above 0.91 g/cπ ; and, (B) is at least one low molecular weight 35 linear ethylene polymer having a MI measured in accordance with ASTM D-1238(E) (190°C/2\16 kg) greater than 25 g/10 minutes and a density above 0.91 g/cπ . 12. The blend of Claim 11 wherein the ratio of the high molecular weight linear ethylene polymer and low molecular weight linear ethylene polymer is sufficient to provide a blend having an MI value in the range of 0.1 to 40 grams/10.minutes and a density in the range of 0.94 to 0.96 grams/cπ . 13. The blend of Claim 11 wherein at least one of the linear ethylene polymers comprises a copolymer of ethylene with at least one C3~Ci2 olefin. 14. The blend of Claim 13 wherein at least one of the linear ethylene polymers is a copolymer of ethylene and propylene or octene. 15. The blend of Claim 11 wherein the blend is a blend of discrete polymers. 16. The blend of Claim 11 wherein the blend is an in-situ blend formed during polymerization. 17. The blend of Claim 15 or 16 wherein the high molecular weight linear ethylene polymer is HDPE, having an MI value within the range between 0.1 and 25 grams/10 minutes and the low molecular weight linear ethylene polymer is HDPE having an MI value within the range between 25 and 300 grams/10 minutes. 18. The polymeric staple fibers of Claim 9 wherein the polymer is the blend of any of Claims 11 to 17. 19. A process for preparing t e polymeric staple fibers of Claim 9 characterized by the steps of (A) Melt-spinning the polymer of any of r. Claims 11 to 17 into meltspun filaments; (B) Hauling off the meltspun filaments at a speed in a range of from 60 to 2,000 meters/minute; and, optionally, 10 (C) drawing and/or crimping and/or cutting the hauled-off meltspun filaments by conventional means. 20. A process wherein molten linear ethylene 15 polymer fine denier staple fibers are spun at commercially feasible throughput rates, optionally followed by mechanical drawing to produce fiber sizes of from 0.1 to 15 denier/filament and used in making a web 20 or fabric, characterized by: spinning a blend comprising (A) at least one high molecular weight linear ethylene polymer having a MI measured in accordance with 25 ASTM D-1238(E) (190°C/2.16 kg) less than 25 g/10 minutes and a density above 0.91 g/cm^, and (B) at least one low molecular weight linear ethylene polymer having a MI measured in accordance with 30 ASTM D-1238(E) (190°C/2.16 kg) greater than 25 g/10 minutes and a density above 0.91 g/cirH, forming linear ethylene polymer staple fibers having a Q value above 4.5,- wherein Q is defined as weight average.molecular rmr- weight divided by number average molecular weight, as determined by gel permeation chromatography. 21. The blend of Claim 20 wherein the ratio of the high molecular weight linear ethylene polymer and low molecular weight linear ethylene polymer is sufficient to provide a blend having a MI value in the ran^e of 0.1 to 40 grams/10 minutes and a density in the range of of 0.94 to 0.96 grams/cm^. 22. The blend of Claim 20 wherein at least one of the linear ethylene polymers comprises a copolymer of 10 ethylene with at least one C3-C12 olefin. 23. The blend of Claim 22 wherein at least one of the linear ethylene polymers is a copolymer of ethylene and propylene or octene. 15 24. The blend of Claim 23 wherein at least one of the linear ethylene polymers is LLDPE. 25. The blend of Claim 20 wherein the blend is 0 a blend of discrete polymers. 26. The blend of Claim 20 wherein the blend is an in-situ reactor blend formed during polymerization. 27. The blend of Claim 25 or 26 wherein the 25 high molecular weight linear ethylene polymer is HDPE, having a MI value within the range between 0.1 and 25 grams/10 minutes and the low molecular weight linear ethylene polymer is HDPE having a MI value within the 30 range between 25 and 300 grams/10 minutes. 28. The blend of Claim 25 or 26 wherein the high molecular weight linear ethylene polymer is HDPE, having a MI value within the range between 0.1 and 25 - jj - grams/10 minutes and the low molecular weight linear ethylene polymer is HDPE having a MI v&lue within the range between 25 and 300 grams/10 minutes.

Inventors: BIESER JOHN O, KNICKERBOCKER EDWARD N, KRUPP STEPHEN P, BIESER, JOHN, O., KNICKERBOCKER, EDWARD, N., KRUPP, STEPHEN, P.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1990
Main classification: D04H3
IPC codes: B01F13, C08L23, D01F6, D03D15, D04H1, D04H3