KR20040005826A - Stretchable fibers of polymers, spinnerets useful to form the fibers, and articles produced therefrom - Google Patents

Abstract

A stretchable synthetic polymer fiber comprising an axial core formed from an elastomeric polymer, and two or more wings attached to the core and formed from a non-elastomeric polymer, wherein preferably at least one of the wings is mechanically locked with the axial core. The fibers can be used to form garments, such as hosiery. A spinneret pack for producing such fibers is also provided.

Description

Stretchable polymer fibers, spinnerets useful for making these fibers, and articles made therefrom {STRETCHABLE FIBERS OF POLYMERS, SPINNERETS USEFUL TO FORM THE FIBERS, AND ARTICLES PRODUCED THEREFROM}

It is desirable to impart elasticity to many products made from synthetic fibers, including various garments such as sportswear and socks. As described in Ishii, US Pat. No. 4,861,660, various methods of imparting flexibility to synthetic filaments are known. In one method, the fibers are crimped two- or three-dimensionally. In another method, elastic filaments are made from elastomers, such as natural or synthetic rubber, or synthetic elastomers, such as polyurethane elastomers. This type of stretch filament is inferior to wear of rubber or polyurethane elastomer filaments themselves or It is disadvantageous in that it exhibits knitting processability and inferior dyeing properties. Therefore, the disadvantages of rubber of polyurethane elastomeric filaments are avoided by coating the rubber or elastomeric filaments with other types of filaments having satisfactory workability and dyeing properties.

However, there are drawbacks associated with these coated elastic filaments. Ishii attempted to overcome these drawbacks by imparting asymmetry to filaments made from two polymers. Nevertheless, these fibers often have serious drawbacks in that the two polymers often easily delaminate from each other during processing. The resulting split fibers have low fracture toughness and can result in fabrics with thinness and thermal conductivity that are less than intended. See also US Pat. No. 3,017,686 to Breen et al., Which describes fibers made from two different inelastic polymers and has these drawbacks.

In fact, under certain conditions with the core polymer protruding into the wing polymer, it is noted that Tanner's can make that a wing portion made from a polymer substantially different from the core is produced and that the protrusion of the wing can be more easily separated from the protrusion portion. In US Patent No. 3,418,200. In contrast, it is sometimes desirable to improve the adhesion of two different polymers in a filament, as described in US Pat. No. 3,458,390, where two types of mechanical locking are used using one type of mechanical locking. Stiffness, low elastomers were bonded together. However, the polymers, as well as those published in Brin and Tanner, have stretch and recovery properties that are unsuitable for high stretch garments that are desirable today because of their low elasticity.

Fibers containing two polymers may be spun into spinnerets described in US Pat. No. 3,418,200 and US Pat. No. 5,344,297. However, spinnerets of these patents exhibit polymer migration when multiple polymer streams are substantially combined in a feed channel in front of spinneret. These problems are described in the Journal of Polymer Science [Physics Edition] Volume 13 (5) p.863, 1975 and are the most recent for spinning of different technical states of trilobal fibers with tips designed to be split from the core. See International Fiber Journal (1998), Volume 13 (5) p.48.

Thus, there remains a need for fibers and articles made from them that have good stretch and resilience and retain their toughness during processing and use, and convenient methods of making the fibers and articles. There is also a need for spinnerets to spin two polymers that substantially eliminate the problem of polymer migration when multiple polymer streams are combined in a feed channel in front of the spinneret orifice.

Summary of the Invention

Now, when one of the two polymers penetrates into the other polymer, that is, at least a portion of the wing polymer of one or more wings protrudes into the core polymer or at least a portion of the core polymer protrudes into the wing polymer It has been found that splitting in the polymer fibers (two layers) can be substantially reduced or eliminated. In particular, in view of the above Tanner literature, this behavior was unexpected because it was expected that the elastomer would readily deform under tension and be stretched in an interpenetrating relationship with the inelastic polymer.

In accordance with these findings, the present invention comprises a flexible core comprising a axial core comprising a thermoplastic elastomer and a plurality of wings comprising a thermoplastic inelastic polymer attached to the core, wherein at least one of the wing polymer or core polymer protrudes into another polymer. It provides a polymer fiber. In one embodiment, the shaft core contains an outer diameter R ₁ and an inner diameter R ₂ , and R ₁ / R ₂ is greater than about 1.2.

In another embodiment, the present invention comprises a axial core comprising a first polymer and a plurality of wings comprising a second polymer attached to the core, wherein the fibers are less than about one bilayer grade and at least about 20% boy-off Provided are stretchable synthetic polymer fibers having a (boil-off) stretch.

In addition, with the spinneret pack of the present invention, the multicomponent polymer stream can be metered directly into a specific point at the back entrance of the fiber forming orifice in the spinneret plate. This eliminates the problem of polymer migration when multiple polymer streams are mixed in the feed channel substantially in front of the spinneret orifice.

Thus, further according to the invention, there is provided a metering plate containing a first set of holes suitable for containing a first polymer melt and a second set of holes suitable for containing a second polymer melt; A spinneret plate having capillaries penetrating through the spinneret plate and aligned in contact with the metering plate having a counterbore length of less than about 60% of the length of the capillary tube; And a spinneret support plate aligned with the spinneret plate, the hole having a hole larger than the capillary, wherein the plates are provided such that a plurality of polymers fed to the metering plate pass through the spinneret plate and the spinneret support plate to form fibers; Provided are spinneret packs for melt extrusion of a plurality of synthetic polymers to produce aligned fibers.

The present invention relates to stretchable synthetic polymer fibers having a axial core comprising a thermoplastic elastomer and a plurality of radially spaced wings comprising a thermoplastic inelastic polymer attached around the outer periphery of the core. At least one of the wing polymer or core polymer protrudes into another polymer to improve the attachment of the wing to the core. The present invention also relates to a process for producing this fiber and to spinneret packs useful for making the fiber. The invention also relates to articles comprising yarns, garments, and the like, made from these fibers.

1 is a cross-sectional view of a fiber of the present invention with the wing polymer protruding into the core.

2 is a cross-sectional view of the fibers of the present invention with the core polymer protruding into the wing.

3 is a cross-sectional view of one embodiment of the fibers of the present invention in which protruding polymers, such as wing polymers, protrude into a penetrated polymer, such as a core polymer, such as the root.

4 is a cross-sectional view of one embodiment of the fibers of the present invention, wherein the protruding polymer, for example the core polymer, protrudes into the penetrating polymer, for example the wing polymer, and the penetrating polymer is a braking spline.

FIG. 5 shows one or more necked-downs in which the core polymer protrudes into the wing polymer and includes an enlarged far end region and a reduced neck region connecting the end region and the rest of the core polymer. A cross sectional view of one embodiment of a fiber of the present invention forming a portion.

6 is a cross-sectional view of one embodiment of a fiber of the present invention in which the core surrounds a portion of one or more wing sides such that the wings penetrate into the core.

7 is a process schematic of an apparatus useful for making the fibers of the present invention.

8 shows a side view of a stacked plate spinneret device that may be used to make the fibers of the present invention.

FIG. 8 shows a plan view of the orifice plate A viewed from 90 degrees with respect to the laminate spinneret device shown in FIG. 8, taken along line 8A-8A in FIG. 8.

FIG. 8B shows a plan view of the orifice plate B seen at 90 degrees with respect to the laminated plate spinneret device shown in FIG. 8, taken along line 8B-8B in FIG. 8.

FIG. 8C shows a plan view of the orifice plate C seen from 90 degrees with respect to the laminate spinneret device shown in FIG. 8, taken along line 8C-8C in FIG. 8.

9 shows a broken cross section showing a spinneret plate of the prior art.

9A and 9B show fracture cross-sectional views showing two spinneret plates of the present invention.

FIG. 10 shows a side view of a midplate spinneret device, which may be used to make the fibers of an alternative embodiment of the present invention.

Figures 10A, 10B and 10C show an alternative view from 90 degrees to the laminate spinneret device of Figure 10, which may be used in a device in the spinneret pack device of the present invention for producing fibers of an alternative embodiment of the present invention, respectively. The spinneret plate, distribution plate, and metering plate plan view of the embodiment are shown.

11A, 11B and 11C are alternative views seen at 90 degrees to the laminate spinneret device of FIG. 10, which may be used in the apparatus in the spinneret pack device of the present invention for producing fibers of an alternative embodiment of the present invention, respectively. A spinneret plate, a distribution plate, and a measurement plate plan view of an embodiment of FIG.

12 is a cross sectional view of the fiber of the invention as illustrated in Example 6. FIG.

FIG. 13 is a cross sectional view of the fiber of the present invention as illustrated in Example 7. FIG.

The present invention provides stretchable synthetic polymer fibers, shown generally at 10 in FIGS. 1, 2, 3, 4, 5, 6, 11 and 12. The fiber of the present invention comprises an axial core shown at 12 in FIGS. 1 and 2 and a plurality of wings shown at 14 in FIGS. 1 and 2. The axial core comprises a thermoplastic elastomer and the wing comprises at least one thermoplastic inelastic polymer attached to the core. Preferably, the thermoplastic nonelastic polymer is permanently stretchable.

The term "fiber" as used herein is interchangeable with the term "filament". The term "thread" includes a yarn of one filament. The term “multifilament yarn” generally relates to a yarn of two or more filaments. The term "thermoplastic" relates to a polymer that can be repeatedly melt processed (eg melt spun). 'Elastic polymer', in the form of a monocomponent fiber, is diluent free, has an elongation to break in excess of 100%, stretches to twice its length, maintained for 1 minute, and when released, within one minute of By a polymer shrinking to less than 1.5 times its length. The elastomers in the fibers of the present invention are substantially about 14,000 pounds per square inch (96,500 kPa) when provided as monocomponent fibers spun according to ASTM standard D790 flexural properties under conditions as described herein and at RT or 23 ° C. ), More typically less than about 8500 pounds per square inch (58,600 kPa). As used herein, "non-elastic polymer" means any polymer that is not an elastomeric polymer. This polymer may also be named "low elasticity", "hard" and "high stiffness". "Permanently stretchable" means that the polymer has a yield point, and if the polymer is stretched beyond this point it will not return to its original length.

The fibers of the invention are "bicomponent" when each polymer belongs to a different generic group, for example polyamide, polyester or polyolefin, and consists of two or more polymers attached to each other along the length of the fiber. It is named fiber. If the elastic properties of the polymers are sufficiently different, the same generic group of polymers can be used and the resulting fibers are "bicomponent" fibers. Such bicomponent fibers also fall within the scope of the present invention.

According to the invention, at least one wing polymer and core polymer protrude into the other polymer. 1 shows that the wing polymer protrudes into the core polymer, and FIG. 2 shows that the core polymer protrudes into the wing polymer. Penetration of the core and wing polymers can be achieved by any method effective to reduce splitting of the fibers. For example, in one embodiment, the penetrating polymer (e.g., winged polymer) may protrude into the penetrated polymer (e.g., core polymer), such as the root, to form a number of dubbers (see Figure 3). In other embodiments, the penetrating polymer (eg core polymer) may protrude into the penetrated polymer (eg wing polymer), the penetrating polymer being like a serving wedge (see FIG. 4). Braking wedges have a fairly uniform diameter. In another embodiment, the at least one polymer may have one or more protruding portions into the core of one wing or into the wing of the core, which is a distance between the enlarged end region and the end region and the one or more polymers. One or more neck down portions are formed therein, including a reduced neck region connecting the remaining portions. FIG. 5 shows the core polymer protruding into each wing polymer and having the distant enlarged end region 16 and reduced neck region 18. The wings and cores attached to each other by the enlarged end region and the reduced neck region are referred to as 'mechanically fixed'. For ease of manufacture and more effective adhesion between the wing and the core, embodiments with reduced neck zones, often mentioned at the end, are preferred. Other protrusion methods can be contemplated by one of ordinary skill in the art. For example, as shown in FIG. 6, the core may surround a portion on the face of one or more wings so that the wings penetrate the core.

The fibers of the present invention comprise a shaft core having an outer diameter and an inner diameter (eg, "R ₁ " and "R ₂ " in FIGS. 1 and 2, respectively). The outer diameter is the circle surrounding the outermost part of the core, and the inner diameter is the circle drawing the innermost part of the wing. In the fibers of the invention, R ₁ / R ₂ is generally greater than about 1.2. It is preferred that R ₁ / R ₂ range from about 1.3 to about 2.0. At lower ratios the resistance to the bilayer can be reduced, and at higher ratios the amount of high elastomer (or inelastic polymer in the core) in the wings can reduce the stretch and recovery of the fibers. When the core forms a braking wedge in the wing, R ₁ / R ₂ is close to two. In contrast, in fibers in which one of the wings or core polymer does not protrude into the other polymer, R ₁ is approximately R ₂ and neither the wing nor the core penetrates the other. Among the plurality of wings, when the polymer in some of the wings is penetrated into the core polymer, while the polymer in the other wings is penetrated by the core polymer, R ₁ and R ₂ correspond only to each wing, as illustrated in FIG. 2. And each R ₁ / R ₂ and R ' ₁ / R' ₂ is generally greater than about 1.2, preferably in the range of about 1.3 to 2.0. In other embodiments, some of the wings may be penetrated by the core polymer while the adjoining wings do not penetrate, and R ₁ and R ₂ are determined in relation to the penetrated wings; Similarly, R ₁ and R ₂ are determined in relation to the penetrating wing when only a portion of the core is penetrated by the wing polymer. Any combination of the core into the wing, the wing into the core, and no penetration can be used for the wing as long as one or more wings penetrate or are penetrated by the core.

The fibers of the invention are twisted around their longitudinal axis without significant two- or three-dimensional crimping properties (in higher dimension crimping, the longitudinal axis of the fiber itself takes a zigzag or spiral shape, Such fibers are not of the present invention). The fibers of the present invention may be characterized as having substantially helical twists and one-dimensional helical twists. Since it has been observed that a full 360 degree helical twist is not necessary to achieve the desired stretch properties in the fibers, “substantially helical twist” refers to both a spiral twist that passes completely around the elastic core and also only a spiral twist that only partially passes around the core. Include. The substantially helical twist may be almost completely circumferential, or may be almost completely non-circumferential. "One-dimensional" helical twist means that, unlike fibers with two- or three-dimensional crimps, the wings of the fiber may be substantially spiral, but the axis of the fiber is substantially straight even at low tensile forces. However, some wavy fibers are within the scope of the present invention.

The presence or absence of two- and three-dimensional crimps can be judged from the amount of stretch required to make the fiber substantially straight (by pulling any non-linear portion), and the radial symmetry of the fiber with a helical twist. It is a measure. The fibers of the present invention may require less than about 10% stretch, more typically less than about 7% stretch, such as from about 4% to about 6%, to make the fiber substantially straight.

The fibers of the present invention have a substantially radially symmetrical cross section, as can be seen in FIG. 1. "Substantially radial symmetrical cross section" means that the blade rotates 360 / n degrees (where "n" is an integer representing the "n-fold" symmetry) of the fiber around its longitudinal axis) before rotation By cross-section is meant to create substantially the same cross-section and have dimensions appropriate to it. The cross section is substantially symmetrical in terms of size, polymer and angular spacing around the core. This substantially radially symmetrical cross section gives an unexpected combination of high stretch and high uniformity, without a significant amount of two or three dimensional crimps. This uniformity is advantageous, for example, for the high speed processing of fibers through guides and knitting needles and for producing smooth, non-'picky 'fabrics, especially thin fabrics such as hosiery. Fibers having substantially radially symmetric cross sections have no self crimping potential, that is, they do not have significant two- or three-dimensional crimping properties (see generally Textile Research Journal , June 1967, p. 449).

For maximum cross-sectional radial symmetry, the core may have a substantially circular or regular polygonal cross section, for example, as shown in FIGS. 1 and 2. "Substantially circular" means that the length ratio of the two axes intersecting each other at 90 degrees from the center of the fiber cross section is about 1.2: 1 or less. In contrast to the core of US Pat. No. 4,861,660, the use of substantially circular or regular polygonal cores can protect the elastomer from contact with rolls, guides, and the like, as described later in connection with the number of wings. The plurality of wings is in any desired manner around the core, discontinuously, as shown for example in FIGS. 1 and 2, ie the wing polymer does not form a continuous mantle on the core, or is described, for example, in US Pat. Adjacent wing (s) may be arranged to meet at the core surface as illustrated in FIGS. 4 and 5 of 3,418,200. The wings may be of the same or different size as long as substantially radial symmetry is maintained. In addition, each wing may also have a different polymer from the other wing as long as substantially the radial geometry and polymer composition symmetry are maintained. However, in order to easily obtain radial symmetry and to prepare simply, it is preferred that the wings have approximately the same dimensions and are made of the same polymer or blend of polymers. It is also desirable for the wings to discontinuously surround the core for ease of manufacture.

Although the fiber cross section is substantially symmetrical in terms of size, polymer and angular spacing around the core, small changes from complete symmetry generally occur in any spinning method due to factors such as non-uniform quenching or incomplete polymer melt flow or incomplete spinning orifices. Should know. These changes are not far from sufficient for the purpose of the present invention, as long as they provide fibers with the desired stretch and recovery through, for example, one-dimensional spiral twist while minimizing two- and three-dimensional crimping. It should be appreciated that it is acceptable. That is, the fibers are not intentionally made asymmetric as in US Pat. No. 4,861,660.

The wings protrude outwards from the core to which they are attached to form a plurality of spirals at least partially around the core after particularly effective heating. The pitch of these spirals can be increased when the fibers are drawn. The fiber of the present invention has a plurality of wings, preferably 3-8, more preferably 5 or 6 wings. The number of wings used may depend on other characteristics of the fiber and the conditions under which the fiber is made and used. For example, when monofilaments are made, especially at higher draw ratios and fiber tensions, five or six wings can be used. In this case, the blade spacing may be sufficiently frequent around the core so that the elastomer is protected from contact with rolls, guides, and the like, so that fewer wings are easier to break, roll wrap, and wear than when fewer wings are used. The effect of higher draw ratios and fiber tensions is to compress the fibers more strongly against the rolls and guides, causing the wings to spread out at an angle so that the elastic core is in contact with the rolls or guides, so at higher draw ratios and fiber tensions Many wings are preferred. In monofilaments, five or six wings are often preferred for the optimal combination of ease of manufacture and core contact reduction. If multifiber yarns are desired, fewer wings can be used, such as two or three, because the tendency of contact between the elastic core and the roll or guide is reduced by the presence of other fibers.

Although it is desirable for the wings to discontinuously surround the core for ease of manufacture, the core may comprise an outer shell of inelastic polymer between the points where the wing contacts the core on its outer surface. The sheath thickness can range from about 0.5% to about 15% of the maximum radius of the fiber core. The sheath can provide more contact points between the core and the wing polymer, thereby aiding the attachment of the wing to the core, a particularly useful property when the polymers in the bicomponent fibers do not adhere well to each other. The sheath can also reduce the wear adhesion between the core and the rolls, guides and the like, especially when the fibers have a small number of wings.

The plurality of winged cross section cores and / or wings of the present invention may be solid or may comprise hollow or voids. Typically, both the core and the wings are substantial. In addition, the wings may have any shape, for example oval, T-, C- or S-shape (see, eg, FIG. 4). Examples of useful wing forms can be found in US Pat. No. 4,385,886. The T-, C- or S-form can help protect the elastomer core from contact with the guides and rolls as described above.

The weight ratio of the total wing polymer to the core polymer can be varied to impart the desired mix of properties such as elasticity from the preferred core and other properties from the wing polymer, such as low tack. For example, a weight ratio of wings to cores in the range of about 10/90 to about 70/30, preferably about 30/70 to about 40/60, can be used. Wing / core weight ratios in the range of about 35/65 to about 50/50 are preferred for high durability in combination with high stretch in applications where the fibers do not need to be used with a companion thread (eg socks). For the best adhesion between the core and the wing, typically from about 5% to about 30% by weight of the total fiber weight may be an inelastic polymer penetrating into the core or an elastic core polymer penetrating into the wing.

As mentioned above, the core of the fibers of the present invention can be made from any thermoplastic elastomer. Examples of useful elastomers include thermoplastic polyurethanes, thermoplastic polyester elastomers, thermoplastic polyolefins, thermoplastic polyesteramide elastomers and thermoplastic polyetheresteramide elastomers.

Useful thermoplastic polyurethane core elastomers include those made from polymeric glycols, diisocyanates and one or more diol or diamine chain extenders. Diol chain extenders are preferred because the polyurethanes produced therewith have a lower melting point than when diamine chain extenders are used. Polymer glycols useful in the preparation of elastic polyurethanes include polyether glycols, polyester glycols, polycarbonate glycols, and copolymers thereof. Examples of the glycol include poly (ethylene ether) glycol, poly (tetramethylene ether) glycol, poly (tetramethylene-co-2-methyl-tetramethylene ether) glycol, and poly (ethylene-co-1,4-butylene adidiate. Pate) glycol, poly (ethylene-co-1,2-propylene adipate) glycol, poly (hexamethylene-co-2,2-dimethyl-1,3-propylene adipate), poly (3-methyl-1, 5-pentylene adipate) glycol, poly (3-methyl-1,5-pentylene nonanoate) glycol, poly (2,2-dimethyl-1,3-propylene dodecanoate) glycol, poly (pentane- 1,5-carbonate) glycol and poly (hexane-1,6-carbonate) glycol are mentioned. Useful diisocyanates include 1-isocyanato-4-[(4-isocyanatophenyl) methyl] benzene, 1-isocyanato-2-[(4-isocyanato-pentyl) methyl] benzene, isophorone Diisocyanate, 1,6-hexanediisocyanate, 2,2-bis (4-isocyanatophenyl) propane, 1,4-bis (p-isocyanato, alpha, alpha-dimethylbenzyl) benzene, 1,1 '-Methylenebis (4-isocyanatocyclohexane) and 2,4-tolylene diisocyanate are mentioned. Useful diol chain extenders include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propylene diol, diethylene glycol, and mixtures thereof. Preferred polymer glycols include poly (tetramethylene ether) glycol, poly (tetramethylene-co-2-methyl-tetramethylene ether) glycol, poly (ethylene-co-1,4-butylene adipate) glycol, and poly (2 , 2-dimethyl-1,3-propylene dodecanoate) glycol. 1-isocyanato-4-[(4-isocyanatophenyl) methyl] benzene is the preferred diisocyanate. Preferred diol chain extenders are 1,3-propane diol and 1,4-butanediol. A monofunctional chain stopper such as 1-butanol or the like may be added to control the molecular weight of the polymer.

Useful thermoplastic polyester elastomers include low molecular weight diols, for example polyethers prepared by the reaction of polyether glycols having a molecular weight of less than about 250 and dicarboxylic acids or diesters thereof such as terephthalic acid or dimethyl terephthalate. Ester is mentioned. Useful polyether glycols include poly (ethyleneether) glycol, poly (tetramethyleneether) glycol, poly (tetramethylene-co-2-methyltetramethyleneether) glycol [tetrahydrofuran and 3-methyltetrahydrofuran copolymerization] Derived from] and poly (ethylene-co-tetramethyleneether) glycol. Useful low molecular weight diols include ethylene glycol, 1,3-propane diol, 1,4-butanediol, 2,2-dimethyl-1,3-propylene diol and mixtures thereof; Preference is given to 1,3-propane diol and 1,4-butanediol. Useful dicarboxylic acids include terephthalic acid, optionally with a small amount of isophthalic acid, and diesters thereof (eg <20 mol%).

Useful thermoplastic polyesteramide elastomers that can be used to prepare the cores of the fibers of the present invention include those described in US Pat. No. 3,468,975. For example, the elastomer may be ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,4-di (methylol) cyclohexane, diethylene glycol, or triethylene glycol and malonic acid, succinic acid, glutaric acid, adipic acid, 2- Polyproduced by reaction with methyladipic acid, 3-methyladipic acid, 3,4-dimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or dodecanedioic acid or esters thereof It can be made of ester segments. Examples of polyamide segments in the polyesteramides include those prepared by the reaction of hexamethylene diamine or dodecamethylene diamine with terephthalic acid, oxalic acid, adipic acid or sebacic acid and by ring-opening polymerization of caprolactam. have.

Thermoplastic pulleyetheresteramide elastomers, such as those described in US Pat. No. 4,230,838, can also be used to make fiber cores. The elastomers are for example low molecular weight (e.g., about 300 to about 15,000) polycaprolactam, polyenantholactam, polydodecanolactam, polyundecanolactam, poly (11-aminoundecanoic acid), poly ( 12-aminododecanoic acid), poly (hexamethylene adipate), poly (hexamethylene azelate), poly (hexamethylene sebacate), poly (hexamethylene undecanoate), poly (hexamethylene dodecanoate), Poly (nonnamethylene adipate) and the like and dicarboxylic acid terminated polyamide prepolymers prepared from succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, terephthalic acid, dodecanedioic acid, and the like. Can be. The prepolymer is then hydroxy terminated polyethers such as poly (tetramethylene ether) glycol, poly (tetramethylene-co-2-methyltetramethylene ether) glycol, poly (propylene ether) glycol, poly (ethylene ether) glycol And the like.

As noted above, the wings can be made from any inelastic or hard polymer. Examples of such polymers include inelastic polyesters, polyamides and polyolefins.

Useful thermoplastic inelastic wing polyesters include poly (ethylene terephthalate) (“2G-T”) and copolymers thereof, poly (trimethylene terephthalate) (“3G-T”), polybutylene terephthalate (“4G -T ") and poly (ethylene 2,6-naphthalate), poly (1,4-cyclohexylenedimethylene terephthalate), poly (lactide), poly (ethylene azelate), poly [ethylene-2, 7-naphthalate], poly (glycolic acid), poly (ethylene succinate), poly (alpha, alpha-dimethylpropiolactone), poly (para-hydroxybenzoate), poly (ethylene oxybenzoate), poly (Ethylene isophthalate), poly (tetramethylene terephthalate), poly (hexamethylene terephthalate), poly (decamethylene terephthalate), poly (1,4-cyclohexanedimethylene terephthalate) (trans), poly (ethylene 1,5-naphthalate), poly (ethylene 2,6-naphthalate), poly (1,4- Cyclohexylidene dimethylene terephthalate) (cis) and poly (1,4-cyclohexylidene dimethylene terephthalate) (trans).

Preferred inelastic polyesters include poly (ethylene terephthalate), poly (trimethylene terephthalate), and poly (1,4-butylene terephthalate) and copolymers thereof. When relatively high melting point polyesters, such as poly (ethylene terephthalate), are used, comonomers can be incorporated into the polyester so that it can be spun at reduced temperatures. The comonomers include straight chain, cyclic and branched aliphatic dicarboxylic acids having 4-12 carbon atoms (eg pentanedionic acid); Aromatic dicarboxylic acids other than terephthalic acid (eg, isophthalic acid) having 8-12 carbon atoms; Straight, cyclic and branched aliphatic diols having 3-8 carbon atoms (e.g. 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, and 2,2-dimethyl-1, 3-propanediol); And aliphatic and cycloaliphatic ether glycols having 4-10 carbon atoms (eg hydroquinone bis (2-hydroxyethyl) ether). Comonomers may be present in the copolyester in an amount ranging from about 0.5 to 15 mole percent. Isophthalic acid, pentanedioic acid, hexanediionic acid, 1,3-propane diol and 1,4-butanediol are preferred comonomers for poly (ethylene terephthalate) because they are readily commercially available and inexpensive.

The wing polyesters may also comprise small amounts of other comonomers so long as they do not adversely affect fiber properties. Such other comonomers include, for example, 5-sodium-sulfoisophthalate in an amount ranging from about 0.2 to 5 mole%. Very small amounts, for example from about 0.1% to about 0.5% by weight of trifunctional comonomers such as trimellitic acid, based on the total ingredients, may be incorporated for viscosity control.

Useful thermoplastic inelastic wing polyamides include poly (hexamethylene adipamide) (nylon 6,6); Polycaprolactam (nylon 6); Polyenanthamide (nylon 7); Nylon 10; Poly (12-dodecanolactam) (nylon 12); Polytetramethyleneadipamide (nylon 4,6); Polyhexamethylene sebaamide (nylon 6,10); Poly (hexamethylenedodecaneamide) (nylon 6,12); PACM-12 polyamide, 30% hexamethylene diammonium isophthalate derived from polyamides (nylon 12,12), bis (4-aminocyclohexyl) methane and dodecanedioic acid of dodecamethylenediamine and n-dodecanedioic acid And copolyamide of 70% hexamethylene diammonium adipate, up to 30% of bis- (P-amidocyclohexyl) methylene and copolyamide of terephthalic acid and caprolactam, poly (4-aminobutyric acid) (nylon 4 ), Poly (8-aminooctanoic acid) (nylon 8), poly (hapta-methylene pimelamide) (nylon 7,7), poly (octamethylene subvertamide) (nylon 8,8), poly (nonmethylene azela) Mead) (nylon 9,9), poly (decamethylene azelamide) (nylon 10,9), poly (decamethylene sebaamide) (nylon 10,10), poly [bis (4-amino-cyclohexyl) methane -1,10-decanedicarboxamide], poly (m-xylene adipamide), poly (p-xylene sebaamide), Poly (2,2,2-trimethylhexamethylene pimelamide), poly (piperazin sebaamide), poly (11-amino-undecanoic acid) (nylon 11), polyhexamethylene isophthalamide, polyhexamethylene terephthal Amides and poly (9-aminononanoic acid) (nylon 9) polycaproamides. Copolyamides, for example poly (hexamethylene-co-2-methylpentamethylene adipamide), in which the hexamethylene component may be present in about 75-90 mole percent of the total diamine derived component may also be used.

Examples of useful polyolefins include copolymers and terpolymers of polypropylene, polyethylene, polymethylpentane and one or more of ethylene or propylene with other unsaturated monomers. For example, fibers comprising inelastic polypropylene wings and elastic polypropylene cores are within the scope of the present invention, which fibers are bicomponent fibers.

Mixtures of elastic and inelastic polymers can include polyetheramides such as polyetheresteramides, elastomeric cores and polyamide wings, and polyetherester elastomeric cores and polyester wings. For example, the wing polymer is mixed with nylon 6-6 and its copolymers, such as optionally from about 1% up to about 15% by weight of nylon-12, wherein the hexamethylene component is present at about 80 mole percent. And include poly (hexamethylene-co-2-methylpentamethylene adipamide), and the core polymer may comprise elastic segmented polyetheresteramide. "Segmented polyetheresteramide" means a polymer having a soft segment (long chain polyether) covalently bound (by ester group) to the hard segment (short chain polyamide). Similar definitions are made for segmented polyetheresters, segmented polyurethanes and the like. Nylon 12 can improve wing adhesion to the core, especially when the core is based on PEBAX ^™ 3533SN from Atofina. Other preferred wing polymers may include inelastic polyesters selected from the group of poly (ethylene terephthalate) and copolymers thereof, poly (trimethylene terephthalate), and poly (tetramethylene terephthalate), for use with them Suitable elastic cores below include polyether glycols selected from the group of poly (tetramethylene ether) glycol and poly (tetramethylene-co-2-methyl-tetramethylene ether) glycol and terephthalic acid or dimethyl terephthalate and 1,3-propane diol and Polyetheresters comprising reaction products with low molecular weight diols selected from the group of 1,4-butane diols.

Elastic polyetherester cores may also be used with inelastic polyamide wings, particularly when a fixative is used, as described elsewhere herein. For example, the wings of the fiber may be selected from the group of (a) a copolymer of poly (hexamethylene adipamide) and its 2-methylpentamethylene diamine and (b) polycaprolactam, The core comprises (a) polyetheresteramide and (b) poly (tetramethyleneether) glycol or poly (tetramethylene-co-2-methyltetramethylene ether) glycol and terephthalic acid or dimethyl terephthalate and 1,3-propane diol and It may be selected from the group of reaction products with diols selected from the group of 1,4-butanediol.

Methods of making such polymers are known in the art and may include the use of catalysts, cocatalysts and chain branching agents, as is known in the art.

The high elasticity of the core allows it to absorb compressive, torsional and stretching forces as the fiber is twisted by the wings to which the core is attached as it is stretched and relaxed. These forces can cause two layers of the two polymers if their adhesion is very weak. The present invention optionally utilizes mechanical fixation of the wing and core polymers to enhance adhesion in fiber processing and use and further to minimize bilayers. The bond between the core and the wing can be further enhanced by the choice of the wing and the core composition and / or by the use of a fixing agent added to one or both of the polymers. The fixer may be used in each wing or only some of the wings. Thus, individual wings may have different degrees of bilayer to the core, for example some of the wings may be manufactured to intentionally bilayer. One example of such an additive is 5% by weight of nylon 12 based on the total wing polymer, ie poly (also known as "12" or "N12", commercially available as Rilsan "AMNO" from Atopina) 12-dodecanolactam) blades and / or core polymers. In addition, maleic anhydride derivatives [eg. Byner® CXA or Rotader® ethylene / acrylic ester from registered trademarks of EI du Pont de Nemours and Company / Maleic anhydride terpolymer] can be used to modify the polyether-amide elastomer to improve its adhesion to the polyamide.

As another example, a thermoplastic novolac resin, such as HRJ12700 (Schenectady International) having a number average molecular weight in the range of about 400 to about 5000, is added to the (co) polyetherester core thereof to Adhesion to polyamide wings can be improved. The amount of novolak resin should be in the range of 1 to 20% by weight, more preferably in the range of 2 to 10% by weight. Examples of novolak resins useful in the present invention include phenol-formaldehyde, resorcinol-formaldehyde, p-butylphenol-formaldehyde, p-ethylphenol-formaldehyde, p-hexylphenol-formaldehyde, p-propylphenol -Formaldehyde, p-pentylphenol-formaldehyde, p-octylphenol-formaldehyde, p-heptylphenol-formaldehyde, p-nonylphenol-formaldehyde, bisphenol-A-formaldehyde, hydroxynaphthaleneformaldehyde and rosin Alkyl- (e.g. T-butyl) phenol modified esters (e.g. penterythritol esters), in particular but not limited to maleated rosin. See, for example, US Patent Application Serial No. 09 / 384,605, filed August 27, 1999, for examples of techniques for providing improved adhesion between copolyester elastomers and polyamides.

Polyesters functionalized with maleic anhydride (“MA”) may also be used as fixatives. For example, poly (butylene terephthalate) (“PBT”) is described by Battacharya, Polymer International (August, 2000), 49 : 8, pp. 860-866, which can be functionalized to MA by free radical grafting in a twin screw extruder, which also indicates that several percent by weight of the resulting PBT-g-MA is obtained from nylon 66 and poly (butylene terephthalate). And as a compatibilizer for binary blends of nylon 66 and poly (ethylene terephthalate). For example, the additive can be used to more firmly attach the (co) polyamide blade to the (co) polyetherester core of the fiber of the present invention.

The polymers used and the resulting fibers, yarns and articles used in the present invention may include conventional additives, which may be added during the polymerization process or added to the polymers or articles made, and that improve polymer or fiber properties. Can contribute towards. Examples of these additives include antistatic agents, antioxidants, antimicrobial agents, flame retardants, dyes, light stabilizers, polymerization catalysts and auxiliaries, fixatives, delustrants such as titanium dioxide, matting agents and organics. Phosphate.

For example, other additives that may be applied on the fibers during the spinning and / or stretching process include antistatic agents, slickening agents, fixatives, hydrophilic agents, antioxidants, antimicrobial agents, flame retardants, lubricants, and mixtures thereof. Can be mentioned. In addition, the additional additives may be added during various stages of the process as is known in the art.

While the above description focuses on the advantages of the fibers having a substantially radial symmetry cross section, this symmetry is often desirable, but not necessary in the following embodiments of the present invention:

(a) has a bilayer rating of less than 1 and a boy-off shrinkage of at least about 20%;

(b) the stretch synthetic polymer fiber has at least about 20% post-boil-off shrinkage and requires less than about 10% stretch to substantially straighten the fiber;

(c) the stretchable synthetic polymer fiber comprises an axial core comprising an elastomeric polymer and a plurality of wings comprising an inelastic polymer attached to the core, wherein the core is between its points of contact with the core on its outer surface Comprising an outer shell of inelastic polymer;

(d) the stretchable synthetic polymer fiber comprises an axial core comprising an elastomeric polymer and a plurality of wings comprising an inelastic polymer attached to the core, wherein the core has a substantially circular or regular polygonal cross section; or

(e) the stretchable synthetic polymer fiber comprises an axial core comprising an elastomer and a plurality of wings comprising an inelastic polymer attached to the core, wherein at least one of the wings has a T, S, or C shape .

The fibers of the invention may be in the form of continuous filaments (multifilament yarns or single filaments) or staples (including tow or spun yarn). Stretched fibers of the present invention may have a denier per fiber of about 1.5 to about 60 (about 1.7-67 dtex). Fully stretched fibers of the invention with polyamide wings typically have a toughness of about 1.5 to 3.0 g / dtex, and fibers with polyester wings have a toughness of about 1-2.5 g / dtex, depending on the wing / core ratio. Have The final fiber may have a stretch after the boil-off of about 20% or more. For greater stretch and recovery among fabrics made from the fibers of the present invention, the fibers may have a stretch after voiding off of at least about 45%.

When a yarn comprising a plurality of fibers is produced, the fibers may be of any desired number of fibers and of any desired dpf, and the ratio of elastomer to inelastic polymer may vary from fiber to fiber. Multifilament yarns may contain a number of different fibers, for example 2 to 100 fibers. In addition, the yarns comprising the fibers of the present invention may have a range of linear densities per fiber, and may also include fibers not of the present invention.

The synthetic polymer fibers of the present invention can be used to make fabrics by known means, including by weaving, warp knitting, weft (including circular) knitting or Maryas knitting. The fabric has excellent stretch and recovery. The fibers may be useful for fabrics and fabrics to form part or all of a garment including narrow sections, for example in upholstery and clothing (including lingerie and socks). Garments, such as socks and fabrics made using the fibers and yarns of the present invention, have been found to be smooth, light and very uniform (“non-picky”) with good stretch and recovery properties.

Further in accordance with the present invention, a melt spinning process for spinning continuous polymer fibers is provided. This method will be described with respect to FIG. 5, which is a schematic of one device that can be used to make the fibers of the present invention. However, it should be appreciated that other devices may be used. The process of the invention involves passing a melt comprising an elastomer through a spinneret to produce a plurality of stretchable synthetic polymer fibers comprising an axial core comprising an elastomer and a plurality of wings attached to the core and comprising an inelastic polymer. Include. Referring to FIG. 5, an unshown thermoplastic hard polymer feed is introduced into the laminate spinneret device 35 at 20, and an unshown thermoplastic elastomer feed is introduced into the spin pack device 35 at 22. Let's do it. Prefusion or postfusion spinneret packs may be used. Two polymers can be extruded from the laminated spinneret device 35 with the orifice designed to provide the desired cross section into the unstretched filaments 40. The method further comprises cooling the fibers by quenching the filaments in any known manner, for example by cooling air 50 in FIG. 7 after the filaments exit the capillary of the spinneret. Any suitable quench method can be used, for example cross-flow air or radial air.

The filaments are optionally treated with a finishing agent, such as silicone oil, optionally with magnesium stearate, using any known technique in the finishing agent applicator 60 as shown in FIG. These filaments are subsequently drawn after quenching so that they exhibit a stretch after boy-off of at least about 20%. The filaments are stretched and stretched in one or more stretching stages, for example, between the stretching roll 90 and the feed roll 80 (which can be operated at 150 to 1000 meters / minute) as schematically shown in FIG. 100) can be formed. The drawing step can be coupled with the yarn to produce a fully drawn yarn, or can be a split process with a delay between spinning and drawing if a partially oriented yarn is desired. Stretching may also be accomplished while winding the filaments as warp yarn of the yarn, referred to as "stretch warping" by one of ordinary skill in the art. Any desired draw ratio (without breaking the filament and disrupting the process) can be imparted to the filament, for example, a fully oriented yarn can be made with a draw ratio of about 3.0 to 4.5 times, and the partially oriented yarn It can be prepared by the draw ratio of about 1.2-3.0 times. In the present invention, the draw ratio is the speed around the draw roll 90 divided by the speed around the feed roll 80. Stretching can be performed at about 15-100 ° C., typically at about 15-40 ° C.

The stretched filament 100 may optionally be partially relaxed using steam, for example in 110 of FIG. 5. Any amount of thermal relaxation can be performed during spinning. The greater the relaxation, the more elastic the filament and the less shrinkage occurs in downstream operations. The elongated final filament after relaxation, as described below, may have a stretch after boy-off of at least about 20%. Before winding the filament just spun, it is desirable to thermally relax by about 1-35% based on the length of the stretched filament so that it can be treated as a representative hard yarn.

The quenched, stretched and optionally relaxed filaments may then be collected by winding up at a speed of 200 to about 3500 meters per minute and up to 4000 meters per minute in the winder 130 of FIG. 5. Or when a plurality of fibers are spun and quenched, the fibers converge, optionally blended, and then, for example, in the winder 130 up to 4000 meters per minute, for example in the range of about 200 to about 3500 meters per minute. Can be wound into. Single filament or multifilament yarns can be wound in the winder 130 in FIG. 5 in the same manner. If a plurality of filaments are spun and quenched, the filaments may converge and randomly mix before winding as is done in the art.

At any time after drawing, the bicomponent filaments can be dry or wet heat treated while they are fully relaxed to exhibit desirable stretch and recovery properties. Such relaxation can be carried out during filament production, for example during the above relaxation steps or after incorporating the filaments into yarns or fabrics, for example during refining, dyeing and the like. The heat treatment in the form of fibers or yarns can be carried out using hot rolls or hot chests or for example in a jet-screen bulking step. This relaxed heat treatment is carried out after the fibers are in a yarn or fabric, by which time the fibers can be processed like inelastic fibers, but in some cases heat treated and fully relaxed before being wound into high-stretch fibers. Can be. For greater uniformity in the final fabric, the fibers can be heat treated and relaxed evenly. The heat treatment / relaxation temperature ranges from about 80 ° C. to about 120 ° C. when the heating medium is dry air, about 75 ° C. to about 100 ° C. when the heating medium is hot water, and when the heating medium is pressurized steam (eg, auto In the clave) in the range from about 101 ° C to about 115 ° C. Lower temperatures may result in little or no heat treatment, and higher temperatures may melt the elastic core polymer. The heat treatment / relaxation step can generally be performed within a few seconds.

As noted above, the spinneret capillary has a design that matches the preferred cross-section of the fibers of the present invention, as described above, or produces other bicomponent or bicomponent fibers. Capillary or spinneret bore holes are drilled, electric discharge machines by any suitable method, for example by laser cutting as described in US Pat. No. 5,168,143, as is known in the art. It can be cut by machining (EDM) and punching. Capillary orifices can be cut using a laser beam to better control the cross-sectional symmetry of the fibers of the present invention. The orifice of the spinneret capillary can have any suitable dimension and can be cut to be continuous (prefusion) or discontinuous (postfusion). Discontinuous capillaries can be obtained by drilling small holes in a pattern such that the polymer fuses below the spinneret face to form the multi-wing cross section of the present invention.

For example, the filaments of the present invention can be made into prefused spinneret packs as illustrated in FIGS. 8, 8A, 8B and 8C. In FIG. 8, which is a side view of the laminate spinneret device as shown in FIG. 7, the polymer flow is in the direction of arrow F. FIG. The first plate in the spinneret device is plate D, which contains a polymer melt pool, and has a conventional design. Plate D is placed on weighing plate C (shown in cross section in FIG. 6C), which in turn is placed on an arbitrary distribution plate B (shown in cross section in FIG. 6B), which is spinneret plate A (cross section in FIG. 6A). ), Which is supported by the spinneret support plate E. The weighing plate C is aligned in contact with the distribution plate B below the weighing plate, and the distribution plate is arranged in contact with A on the spinneret plate A with a capillary tube through it but without significant counterbore, and the spinneret plate (S) is aligned in contact with the spinneret support plate E having a hole larger than the capillary. The polymer fed to the metering plate C is aligned to pass through distribution plate B, spinneret plate A and spinneret support plate E to form fibers. A conventional plate, molten pool plate D, is used to supply the weighing plate. The polymer melt pool plate D and spinneret device support plate E are thick and hard enough to prevent them from being tightly pressed against each other, preventing the polymer from leaking between the stacks of spinneret devices. The plates A, B, and C are thin enough so that the orifices can be cut by the laser light method. The hole in the spinneret support plate E is preferably opened at, for example, about 45 degrees to 60 degrees so that the fiber just spun does not come into contact with the edge of the hole. In addition, when the prefusion of the polymer is desired, the polymers are in contact with one another (pre-fusion) for less than about 0.30 cm, generally less than 0.15 cm, before the fibers are formed (measuring plate C, optional distribution plate D, and spinneret plate It is desirable for the cross-sectional shape intended by design E to be represented more accurately in the fiber. More accurate formation of fiber cross sections also results in spots of less than 100 microns in diameter where the multimode beam from the solid state laser is predominantly reduced to a single mode beam (eg TM ₀₀ mode) and is 0.2 to 0.3 mm above the metal sheet. Help may be aided by cutting holes through the plate as described in concentrated US Pat. No. 5,168,143. The resulting molten metal is discharged from the lower surface of the metal sheet by the laser beam and pressurized fluid flowing in the coaxial direction. The distance from the top of the top distribution plate to the spinneret face can be reduced to less than about 0.30 cm.

To produce a filament having any number of symmetrically placed wing polymer portions, the same number of symmetrically disposed orifices in each plate is used. For example, in FIG. 8A, spinneret plate A is shown in a plan view oriented at 90 degrees with respect to the laminated spinneret device of FIG. Plate A of FIG. 8A consists of six symmetrically disposed wing spinneret orifices 140 connected to a central round spinneret hole 142. Each wing orifice 140 may have a different width 144 and 146. Complementary distribution plate B is shown in FIG. 6B with tapered distribution orifices 150 that taper at an open end 152 to an optional slot 154 that connects the distribution orifices to a central round hole 156. 8C shows a metering plate C with metering capillary 160 for wing polymers and metering capillary 162 for core polymers in the center. The polymer melt pool plate D may be one having any conventional design in the art. The spinneret support plate E is provided with a through hole, which is large enough to extend away from the path of the filament just radiated (e.g. 45-60 degrees) so that the filament does not come into contact with the side of the hole, as shown in the side views of FIGS. Have The laminate spinneret device, plates A through D, has a core polymer from the polymer molten pool plate D, through the metering hole 162 in the middle of the metering plate C, through the six small capillaries 164, and in the center of the distribution plate B. Passed through the capillary 156, past the circular capillary 142 in the center of the spinneret plate A, and aligned to flow out through the large gaping hole in the spinneret support plate E. At the same time, the wing polymer passes from the polymer melt pool plate D, through the wing polymer metering capillary 160 of the metering plate C, and through the distribution orifice 150 of the distribution plate B (if any slot 154 is present, The polymer first comes into contact with each other), past the wing polymer orifice 140 of the spinneret plate A, and finally through the hole in the spinneret device support plate E.

The spinneret pack of the present invention can be used for melt extrusion of a plurality of synthetic polymers for making fibers. In the spinneret pack of the present invention, since the spinneret plate does not have a significant counterbore, the polymer can be fed directly into the spinneret capillary. The absence of significant counterbore means that the length of any counterbore present (any groove connecting the inlet of multiple capillaries) is less than about 60%, preferably less than about 40% of the length of the spinneret capillary. Reference may be made to FIG. 9A showing a cross section of the spinneret plate of the prior art and FIGS. 9B and C showing a cross section of the spinneret plate of the present invention. Direct metering of the multicomponent polymer stream into a specific point at the rear inlet of the fiber forming orifice in the spinneret plate results in polymer migration when multiple polymer streams are mixed in the feed channel substantially in front of the spinneret orifice, as in the standard case. Eliminate the problem

It may be useful to combine the functions of two plates into one through the use of recessed grooves on one or both sides of a single plate with suitable holes connecting the grooves through the plate. For example, the grooves, grooves and depressions can be cut upstream of the spinneret plate (eg by electrodischarge machining) and can act as distribution channels, or shallow and weak counterbore.

The spinneret pack of the present invention can produce a variety of fibers comprising two or more polymers. For example, other bicomponent fibers and bicomponent fibers disclosed and / or not claimed, including the cross sections described in US Pat. Nos. 4,861,660, 3,458,390, and 3,671,379, are thus Can be prepared. The resulting fiber cross sections can be, for example, side-by-side, shell-cores, concentric shell-cores, wings and cores, wings and shells and cores, and the like, which are side by side. In addition, the spinneret pack of the present invention can be used to spun splitable or non-splitable fibers.

The spinnerette packs of the present invention are desired for use with various synthetic polymers, for example, as needed to produce different denier or yarn modulus per filament by varying the number of capillary legs for different preferred wing numbers. It can be modified to achieve a fiber having a plurality of different wings by changing the slot dimensions to change the geometric parameters as will be. For example, in the embodiment of FIG. 10, a relatively thin spinneret pack is shown used to make three winged fibers, as illustrated in Example 7 below. In FIG. 10A, the spinneret plate was 0.015 inches (0.038 cm) thick, three widths each (having lengths 144 and 146, respectively) and three symmetrically arranged to be 120 degrees around the center of symmetry. In the form of a straight wing 140, having an orifice machined through the entire thickness of stainless steel by the laser light method described herein; There was no counterbore on the capillary orifice. Each wing 140 was 0.040 inches (0.102 cm) long from its tip to the circumference of the central round spinneret hole 142 having a diameter of 0.012 inches (0.030 cm) coinciding with the center of symmetry. Referring next to FIG. 10B, a 0.010 inch (0.025 cm) thick distribution plate B is placed on the spinneret plate A such that all other wing orifices 150 of the distribution plate B align with the wings 140 of the spinneret plate A. Aligned axially, each wing orifice 150 of distribution plate B was 0.1357 inches (0.349 cm) in length from its tip to the center of symmetry. Weighing plate C (FIG. 10C) was 0.010 (0.025 cm) inch thick, with holes 160 of 0.025 inch (0.064 cm) diameter, holes 162 of 0.015 inch (0.038 cm) diameter, and 0.010 inch (0.025) center cm) diameter of holes 164. Plate C is the wing polymer fed into hole 160 by molten pool plate D (see FIG. 10) during use and the core polymer fed into holes 162 and 164 of distribution plate C into plate A by plate B. The blades were aligned with the distribution plate B to form the fibers penetrating the core. Spinneret plate A had no counterbore and the combined thickness of plates A, B and C was only about 0.035 inches (0.089 cm).

In other spinneret pack assembly embodiments, spinneret support plate E (see FIG. 8) was not used. This is illustrated in Example 8 below. In FIG. 11A, spinneret plate A was 0.3125 inches (0.794 cm) thick and each spin orifice had a 0.100 inch (0.254 cm) diameter counterbore and 0.015 inch (0.038 cm) capillary at the bottom of the counterbore. As shown in FIG. 11A, each spinneret orifice in spinneret plate A had six straight wing orifices 170, each of which had a longitudinal axis centerline through the center of symmetry, a central round hole from its tip ( 172) to a length of 0.035 inches (0.089 cm). The length 174 from the tip of each wing to 0.015 inches (0.038 cm) was 0.004 inches (0.010 cm) wide and the length 176 was 0.020 inches (0.051 cm) long and 0.0028 inches (0.007 cm) wide. The tip of each wing was radius cut at half the width of the tip. Distribution plate B (see FIG. 11B) was 0.015 inch (0.038 cm) thick and had six wing orifices, each wing centered on the corresponding counterbore in spinneret plate A, with each wing orifice in plate B Oriented to align with the wing orifice of plate A. Each wing orifice 150 in plate B was 0.060 inches (0.152 cm) long and 0.020 inches (0.051 cm) wide, with its tip rounded to a radius of 0.0010 inches (0.025 cm). The center hole 152 in plate B was 0.100 inch (0.254 cm) in diameter. Weighing plate C (see FIG. 11C) was also 0.015 inches (0.038 cm). In plate C, hole 160 had a diameter of 0.008 inches (0.020 cm), 0.100 inch (0.254 cm) from the center of hole 162 in the center of plates B and A and formed the core of the fiber. The inelastic wing polymer is fed into the holes 160 in plate C, passing the wing orifices of plates B and A to form a wing of the fiber. The wing and core polymers were first contacted at the top of distribution plate B, 0.328 inches (0.833 cm) on the face of spinneret plate A from which the fibers were extruded, with a diameter of 0.080 inches (0.203 cm). Plate C was aligned with plate B such that the six holes 160 of plate C were above the centerline of the wing orifice 150 of plate B. The plates were aligned so that the elastic core polymer fed into the hole 162 of plate C passed through the center.

The invention is illustrated by the following non-limiting examples. In the examples, the following test methods were used.

Test Methods

The terms post-off stretch is used interchangeably with the following terms in the art: "% stretch", "recoverable stretch", "recoverable shrinkage" and "crimp potential". The term "unrecoverable shrinkage" is used interchangeably with the following terms: "% shrinkage", "apparent shrinkage" and "absolute shrinkage".

Example 1 The stretch properties (stretch after boy-off, shrink after boy-off and stretch recovery after boy-off) of the fibers produced in A, B, C and D were measured as follows. 5000 denier (5550 dtex) thread was wound on a 54 inch (137 cm) reel. The entire denier contained both sides of the looped thread. Initial thread length was measured in 2 gram weights (length CB) and 1000 gram weights (0.2 g / denier) (length LB). The thread was placed in 95 ° C. water for 30 minutes (“boiled off”) and the initial (after boil-off) length with 2 gram weight (length CA _initial ) and 1000 gram weight (length LA _initial ) was measured. After measuring with 1000 gram weights, additional lengths were measured after 2 seconds (length CA _{30 seconds} ) and after 2 hours (length CA _{2 hours} ) with 2 gram weights. Shrinkage after boy-off was calculated as 100 × (LB-LA) / LB. Stretch% after boyle-off was calculated as 100 × (LA-CA @ 30 sec) / CA @ 30 sec. Stretch recovery after boy-off was calculated as 100 × (LA-CA _{2 hours} ) / (LA-CA _initial ).

Tests for unload forces at 20% and 35% stretch, which are readily available, were performed as follows. A bicomponent fiber skein having 5000 mm denier (5550 dtex) after boy-off was prepared. The entire denier contained both sides of the looped thread. An Instron tensile tester (Canton, Massachusetts, USA) was used at 21 ° C. and 65% relative humidity. The thread was placed in tester jaws with a 3 inch (76 mm) gap in between. The tester was cycled through three stretch-and-relax (load-and-unload) cycles, each load cycle having a force of up to 500 grams (0.2 grams per denier), and then the force on the third unloading cycle Measured. Effective denier (ie, actual line density at test elongation) was measured for 20% and 35% stretch readily obtainable on the third unload cycle. "Easily obtainable 20% and 35% stretch" means that 20% and 35% of the thread loosened from the 500 gram force on the third cycle, respectively. Unloading forces at 20% and 35% stretch, which are readily available, were recorded in milligrams per effective denier (mg / denier).

The bilayers of the wings from the core of the fiber were first measured by winding 5000 denier (5550 dtex) thread (thread size includes both sides of the resulting loops) on a 1.25 meter reel. The thread was steamed at 102 ° C. for 30 minutes in an autoclave. 20 cm long individual fibers were selected from the skein and folded in half. The open ends of the resulting loops were taped together at the bottom and the taped loops were hung vertically on the hooks. One gram per denier (50 grams for 25 denier loops) was attached to the bottom (taped) end of the loop. The weight was raised until the loop was limp and then gently reduced to stretch the loop and apply the entire weight. After these ten cycles, the loops were magnified to observe and grade for the double layer. Three samples were graded as follows:

0 = no visible wing / core bilayer along the fiber

1 = slight double layer observed at one or more knot conduction points

2 = a double layer is observed in which the fibers rubbed against the hanging hooks on which they hang

3 = edge bunk (with small loops, and only a few spots)

4 = small loop, representing a double layer along the entire fiber

5 = total bilayer (large loops along all fibers)

Results from three samples were averaged.

By superimposing two circles on a cross-sectional micrograph of the fiber such that the perimeter of one circle (R ₁ ) is approximately the outermost part of the core polymer and the perimeter of the other circle (R ₂ ) is approximately the innermost part of the wing polymer. R ₁ and R ₂ were measured.

Example 1

Each elongated fiber had a linear density of 26 denier (28.6 dtex) and was substantially radial symmetry. The properties after boy-off are reported in Table 1.

Example 1.A (Comparative)

The bicomponent fibers were spun using the apparatus illustrated in FIG. 7 and the laminate spinneret apparatus illustrated in FIG. 8. The first polymer forming the core of the fiber was introduced into spin filter pack 30 in FIG. The core polymer was polyetheresteramide (Pebox ^™ 3533SN from Atopina) and was volume metered to yield a core that was 51% by weight of each fiber. In (22) of FIG. 7, the molten nylon copolymer was introduced into the spin filter pack 30. The nylon copolymer forming six wings was poly (hexamethylene-co-2-methylpentamethylene adipamide) in which the hexamethylene component was present at 80 mol% of the diamine derived component. There was no significant penetration of the wing by the core or vice versa (R ₁ / R ₂ = 1.09).

The pre-fusion spinneret pack device 30 consists of laminates labeled A through E, shown in side view in FIG. 8. Orifices were drilled through a stainless steel spinneret plate A of 0.015 inch (0.038 cm) thickness such that six wings are symmetrically disposed about 60 degrees around the center of symmetry using a method as described in US Pat. No. 5,168,143. Cut. As illustrated in FIG. 8A, each wing orifice 140 is straight with a longitudinal axis centerline penetrating the center of symmetry, and the central round spinneret hole from the tip when the origin of the center and radius of symmetry are shifted. It had a length of 0.049 inches (0.124 cm) to the perimeter of 142. There was no counterbore at the entrance of the spinneret capillary. Wing length 144 from the tip to 0.027 inches (0.069 cm) was 0.0042 inches (0.0107 cm) wide and the remaining length 146 of 0.022 inches (0.056 cm) was 0.0032 inches (0.0081 cm) wide. The tip of each wing was radially cut at half the width of the tip. Distribution plate B (FIG. 8B) with a thickness of 0.015 inch (0.038 cm) was aligned with spinneret plate A (FIG. 8A) such that the distribution orifice coincided with the spinneret orifice of spinneret plate A. FIG. The six wing orifices of plate B were 0.094 inches (0.239 cm) long and 0.020 inches (0.051 cm) wide, with their wing tips rounded to a width of half the radius. As illustrated in FIG. 8B, each of the six wing orifices 150 of distribution plate B is tapered to a rounded (0.006 inch [0.015 cm] diameter) open end 156 and then 0.013 inch (0.033 cm) long and It continues to the central hole 156 with a slot 154 of 0.0018 inches (0.0046 cm) in length. The central hole 156 in this plate had a diameter of 0.0125 inches (0.032 cm). Slot 154 was connected to the central hole with the end of each wing distribution orifice. Weighing plate C was one having a thickness of 0.010 inches (0.025 cm) (see Figure 8C). Each metering hole was centered on the wing longitudinal centerline or on the center of symmetry of distribution plate B. The central metering hole 162 and one hole 160 per wing were 0.010 inches (0.025 cm) in diameter and the center of the hole 160 was 0.120 inches (0.305 cm) from the center of the hole 162. The molten elastomer filtered from the conventional molten pool plate D was fed to the central metering hole (see FIG. 7) to form a core element in the final fiber. The outer six metering holes 160 of plate C were fed with inelastic polymer from the molten pool plate D to form a polymer wing. A large hole (typically 0.1875 inches (0.4763 cm) in diameter) in the spinneret support plate E (also see FIG. 8) is aligned with the spinneret orifice in the spinneret plate A and is open at 45 degrees. As shown in FIG. 8, spinneret plate A, distribution plate B and metering plate C were sandwiched by molten pool plate D and spinneret support plate E. FIG. Typically, plate E was 0.2-0.5 inches (0.4-1.3 cm) thick and plate D was 0.02-0.03 inches (0.05-0.08 cm) thick.

Thus, there was no counterbore in spinneret plate A, and the combined thickness of plates A, B and C was only about 0.040 inch (0.102 cm). The wing and core polymers were brought into contact with each other directly above distribution plate B, and were prefused to each other for about 0.076 cm (0.038 cm distribution plate + 0.038 cm spinneret plate) before the fibers were formed.

The just spun fiber 40 (see FIG. 7) is cooled by the flow of air 50 to solidify and a finish (approximately 5% by weight based on fiber) comprising silicone oil and metal stearate (60) ). The fibers were sent to the draw zone between the feed roll 80 and the draw roll 90 and several wraps were taken around each roll. The speed of the draw roll 90 was four times the speed of the feed roll 80 for a draw ratio of 4.0, and the speed of the feed roll was 350 meters per minute. The fibers are then treated with 6 pounds per square inch (0.87 kilopascals) of steam in the chamber 110, and the winder 130 is operated at a rate 20% lower than the speed of the draw roll pair 90, resulting in The fiber was partially relaxed (20%) to reduce shrinkage in the fiber. The stretched and partially relaxed fibers 120 were wound in the winder 130 and had a line density of 26 deniers (29 dtex).

Example 1.B (comparative)

5% by weight of nylon 12 (poly (12-dodecanolactam), "N12") (Rilsan® AMNO from Atopina) based on the total wing polymer to support wing-to-core flocculation Except for addition to the polymer, substantially 6 poly (hexamethylene-co-2-methylpentamethylene adipamide) having 80% by mole of hexamethylene component as in Example 1.A. Fibers with two wings and a core of Pebox ^™ 3533SA were spun. The wing / core weight ratio was 48/52 and R ₁ / R ₂ was 1.05.

Example 1.C (invention)

Weighing plate C has an additional set of holes (shown in FIG. 8C), one hole per wing on the centerline of the wing, each hole was 0.005 inch (0.013 cm) in diameter, 0.0475 inch from the center of symmetry of the hole Except for (0,121 cm), substantially the same as in Example 1.A, poly (hexamethylene-co-2-methylpentamethylene adipamide) (20 mol% of 2 based on the diamine derived component Fibers with six wings and a Pebox ^™ 3533SA core (flexural modulus 2800 psi (19,300 kPa)) of -methylpentamethylene component) were prepared. Molten polymer was fed from these common melt pools to these additional holes and the central hole to form core elements that protrude within the core and the wing. As a result, there was wing penetration by the core polymer (R ₁ / R ₂ = 1.6, estimated from the ratio of similarly manufactured fibers) to better attach the wing to the core. The fiber cross section was substantially as illustrated by FIG. 2.

Example 1.D (Invention)

Except for 5% by weight of nylon 12 [poly (12-dodecanolactam)] (rylic acid® AMNO) flocculant additive from atopina, the fibers were substantially as in Example 1.C. Spun. The fibers had wing penetration (R ₁ / R ₂ = 1.5) by the core polymer to better adhere the wing to the core. The fiber cross section was substantially as illustrated by FIG. 2.

Example 1.A (1 l) Example 1.B (comparative) Example 1.C (invention) Example 1.D (Invention) R ₁ / R ₂ 1.1 1.1 1.6 1.5 Wing polymer 6 / MPMD (80/20) -6 6 / MPMD (80/20) -6 + 5% N12 6 / MPMD (80/20) -6 6 / MPMD (80/20) -6 + 5% N12 Core polymer Pebox ^TM 3533SN Pebox ^TM 3533SN Pebox ^TM 3533SN Pebox ^TM 3533SN Stretch after Boyle-off 67 92 103 70 % After shrink 31 19 22 21 Double story 3.8 1.2 0.2 0.0

These data show that the fibers are very good for the socks and apparel sector. The good performance of the fiber with the wings attached to the core is revealed by the bilayer data. The fibers of the present invention may have a bilayer rating of less than about 1.0. The data also shows that the use of a fixer such as N12 in the wing polymer is advantageous.

Example 2.A

The three-filament bicomponent yarns of the present invention were spun substantially as in Example 1.D, with the following differences: Each plate was symmetrically 72 degrees apart so that the fiber had five wings. It had five holes for the arranged wing polymer. The polymer in the five wings was 95% by weight polycaprolactam (3.14 IV, conventionally made and obtained from DuPont, Brazil) with 5% by weight of nylon 12 additive. Wing / core ratios were varied as shown in Table 2. The finish was a mixture of coconut oil, quaternary amine, water and nonionic surfactants, applied at 2% by weight based on the fibers. The feed roll speed was 420 meters per minute and was 15% relaxed before winding the drawn fibers. The cross section was substantially as shown in FIG. 2, R ₁ / R ₂ was about 1.4, and the drawn fibers were 23 deniers (25 dtex).

The percent stretch after boy-off for yarns with various wing core ratios was measured as before.

Wing-to-core ratio (weight ratio) Stretch after Boyle-off 35.5 / 67.5 127 35.0 / 65.0 148 40.0 / 60.0 100 42.5 / 57.5 91 45.0 / 55.0 85 47.5 / 52.5 80 50.0 / 50.0 79 52.5 / 47.5 69 55.0 / 45.0 58

The results in Table 2. A show that a higher post-boile-off stretch is obtained when the wing / core weight ratio in the fibers of the examples is less than about 50/50, which is preferred when the fibers of the invention are used without accompanying fibers. Even lower wing / core ratios are often preferred when companion fibers are used with the fibers of the present invention to increase resilience in the mixing yarn (eg about 20/80 to about 40/60).

Example 2.B

Hosiery durability, thinness, and stretch were evaluated as a function of the overall linear density (denier, dtex) of the wing. The fiber from Example 2.A was knitted into a sock. No other fibers were used. The total denier and the wing to core volume ratios of the fibers were varied. The observer panels are similarly knitted socks from 10 denier lycra (LYCRA ^™ spandex) coated with a) abrasion based on wear life, b) thin aesthetic (seven denier (8 dtex) nylon 6-6 of five fibers) for socks. For subjects)) and c)% stretch after boy-off. Durability was rated as acceptable over 7 days; Thinning is rated as acceptable when the same as the reference; And% stretch was rated to be acceptable when between 40 and 120%, to prevent looseness and "ride-down" of the socks. Asterisk (*) and bold numbers in Table 2.B indicate that the desitex and wing-to-core ratio are qualitatively desirable based on three grade regions. The numbers in the table are the decitex of the sum of the wings of each fiber.

Wing / core weight ratio Wing / core weight ratio Wing / core weight ratio Wing / core weight ratio Wing / core weight ratio Wing / core weight ratio Full Dtex 35/65 40/60 45/55 50/50 55/45 60/40 17 5.8 6.7 7.5 8.3 9.2 10.0 22 7.8 8.9 10.0 11.0 ^* 12.2 13.3 28 9.7 11 ^* 12.5 ^* 13.9 ^* 15.3 16.6 33 11.7 ^* 13.3 ^* 15.0 ^* 16.6 ^* 18.3 20.0

When the total decitex was increased above about 33, the thinness of the hosiery decreased. When the total desiccant was reduced to less than about 22 and the total wing decitex fell below about 11, durability began to decline. As the wing / core weight ratio rose above about 50/50, the% stretch began to fall (as shown in Example 2.A above).

As a result of this test, preferred bicomponent fibers of the present invention have a total line density in the range of about 22 to 33 dtex, a summed wing dtex of at least about 11, and a wing to core weight ratio between 35/65 to 50/50. Can be concluded.

Example 3A

Instead of the finish of Example 2A, 4% by weight (based on the weight of the fiber) of the polysiloxane based finisher (as described in US Pat. No. 4,999,120) was applied, 20% relaxed before winding the fiber, and relaxed The bicomponent seal of the present invention was spun substantially as in Example 2.A, except that the steam used during the step was 3 psi (20.7 kilopascals). The wing / core / projected core weight ratio was 38/53/9 and R ₁ / R ₂ was about 1.4. 5 is a cross-sectional micrograph of this fiber, 32 denier (36 dtex when stretched), and stretch after 108% boy-off, shrink after 24% boy-off and recovery after boy-off of 92% Had

Example 3.B

The hosiery blanks were knitted from the fibers prepared in Example 3.A on a commercial machine, typically set up with every-course double coated spandex leg constructions. The machine was MATEC HSE 4.5, and knitting was set to size F at about 700 rpm in the thigh area and 800 rpm in the ankle. One leg blank was knitted within about 2 minutes. The leg thread was fed to the machine in the usual manner for the hard thread, and no electronic tensioner was used. Pantyhose blanks, neither bleached nor stained, were finished with tumble heating for 30 minutes at atmospheric pressure. The garment was then boarded at 102 ° C. for 4 seconds using a standard industrial automated autoclave boarding device and then dried at 95 ° C. for 30 seconds. The boarding fabric length was chosen as small as possible while keeping the fabric free of wrinkles. Clothing was dyed for 45 minutes at 98 ° C. using standard acid dyes and candidates were used using boards and conditions of the same dimensions.

The resulting fabric had an unexpectedly high thermal conductivity of 3.38 × 10 ⁻⁴ watts / cm- ° C.

Example 4

Three-filament bicomponent yarns according to the present invention were made of polyester blades and polyetherester cores using the apparatus shown in FIG. The core polymer of Fiber 4.A was HYTREL® 3078 polyetherester elastomer (registered trademark of E. Dupont di Nemoas and Campanile; flexural modulus 4000 psi (27,600 kPa)). The core polymers for the fibers of Examples 4.B and 4.C are substantially poly (tetramethylene-co-2-methyltetramethylene ether) glycol, prepared as described in US Pat. No. 4,906,721. Polyetherester elastomer with segments and butylene terephthalate (4G-T) hard segments. The amount of 3-methyltetrahydrofuran incorporated into the copolyether glycol was 9 mol%, the glycol number average MW was 2750 and the molar ratio of 4G-T to copolyether glycol was 4.6: 1. In Table 4, this polymer is designated as "2MePO4G: 4G-T". Wing polymers in the fibers of Examples 4A and 4B include poly (butylene terephthalate) [4G-T, Crastin® 6129; this child. Registered trademarks of Dupont di Nemoas and Campanie; Flexural modulus was 350,000 psi (2.4 million kPa), and in fiber 4.C, it was poly (trimethylene terephthalate) (3G-T). 3G-T is based on 60 ppm tetraisopropyl titanate catalyst, Tyzor® TPT (registered trademark of I. Dupont Di Nemoas and Campanile). Prepared from 1,3-propanediol and dimethylterephthalate by a two vessel method. Molten DMT was added to 3G and catalyst at 185 ° C. in a transesterification vessel and methanol was removed while the temperature was increased to 210 ° C. The resulting intermediate was transferred to a polycondensation vessel, in which the pressure was reduced to 1 millibar (10.2 kg / cm ² ) and the temperature was increased to 255 ° C. Once the desired melt viscosity was reached, the pressure was increased, the polymer was extruded, cooled and cut into pellets. The pellets were further polymerized to an inherent viscosity of 1.04 dl / g in a tumble dryer operating at 212 ° C. in the solid state. The spinneret pack and spinning conditions for each fiber of this example were 40% by weight of the total fibers without the use of a polymer additive on the blades, and 4% by weight of the finishing agent described in Example 3A (fiber based) was applied. The fibers were 20% relaxed with the aid of 3 pounds of pressure (20.7 kilopascals) of steam per square inch before winding up. The fiber had the properties reported in Table 4.

Example 4A Example 4B Example 4C Denier 25 (27.5 dtex) 24 (26 dtex) 27 (30 dtex) Wing polymer 4G-T 4G-T 3G-T Core polymer Hytrel ^TM 3078 2MePO4G: 4G-T 2MePO4G: 4G-T R ₁ / R ₂ 1.6 1.6 1.6 Stretch after Boyle-off 60 100 76 % After shrink 10 12 12 % Recovery after Boyle-Off 85 94 89 Unloading Force @ 20% Stretch Easily Available 15 18 17 Unloading Force @ 35% Stretch Easily Available 3 5 One

The bilayer rating for the fibers of Example 4B was 0.0. Thin sock blanks knitted from the fibers of Examples 4A, 4B and 4C had a uniform appearance and good stretch and recovery after steam boarding, dyeing and finishing.

Example 5.A

The spinneret pack and spinning conditions of Example 3A and the finishing agents and polymers of Example 1D using the apparatus of FIG. 7 were used, except that 13% by weight of the finishing agent was used based on the fibers. The bicomponent fibers were spun. The wing and core polymers first contacted each other for about 0.076 cm before being spun into fibers.

The core was penetrated into the wing so that the wing / core / projected core weight ratio was 39/51/10 (R ₁ / R ₂ was about 1.4). The fibers had 20 denier (22 dtex), stretch after 100% boyle-off, shrink after 23% boyle-off and recovery after 94% boyle-off.

Example 5.B

The four components of the fiber of Example 5.A were air-jet interconnected to make a bicomponent yarn. 38 denier (48 dtex) / 34 of 38 warp ends (121 / inch) per cm as warp and 38 warps per cm (96 pick / inch) as weft and warp Weaved on a SULZER RUTI 5100 (air jet loom) in 3/1 construction using filament TACTEL ^™ (registered trademark of E.I. DuPont di Nemoas and Company) type 6342 nylon. The fabric was steam relaxed at 115 ° C. and MCF jet refined at 70 ° C .; MCF jet dye at 100 ° C. for 60 minutes using standard acid dyes for nylon; And heat cured at 190 ° C. for 30 seconds to finish. These fabrics are smooth without wrinkles and bulky when air dried, and they exhibit good stretch and recovery and good hard fiber hand feel and a visible appearance. The relaxed and finished fabric had the following properties:

Basis weight = 3.29 oz / yard ² (112 grams / m ² );

Thickness = 0.079 inches (2 mm);

Fill number = 160 (63 / cm) per inch;

Number of warps = 208 (82 / cm) per inch.

The 5 cm width x 10 cm length of this fabric could be stretched by 40% hand, and then recovered more than 95%.

Example 6

This example illustrates the use of spinnerets of full thickness to make the fibrous fabric of the present invention. Support plate E is a spinneret capillary (0.015 inch (0.038 cm) long) and 0.1406 inch (0.357 cm) diameter round counter with the same pattern, size, axial and radial orientation as the orifice of spinneret plate A (FIG. 8A) The same pre-fusion spinneret pack as used in Example 1C was used, except that it was replaced with a spinneret having a thickness of 0.3125 inches (0.794 cm) with a bore (FIG. 11A). The wing and core polymers were first contacted with each other for about 0.87 cm (0.794 cm spinneret + 0.038 cm plate A + 0.038 cm plate B) before the fibers were formed. 6 wings of poly (hexamethylene-co-2-methylpentamethylene adipamide) in which the hexamethylene component is present at 80 mol% of the diamine derived component (conventionally produced; relative viscosity of 90) and 25 denier (28 dtex) bicomponent fibers having a core of Pebox 3533SA polyetheresteramide were spun using the apparatus of FIG. 7 with a draw ratio of 4 × and wound up to 1400 meters per minute. The wing / core / projected core weight ratio was 45/48/7 and R ₁ / R ₂ was about 1.4. Among the fibers thus spun, the core penetrated into the wings, often without the desired reduced neck area, as shown in FIG. 3.

Example 7

This example illustrates a bicomponent fiber having three wings with the wings penetrated into the core, and also illustrates the use of a thin spinneret pack to make this fiber. The wing polymer was poly (hexamethylene dodecanamide) (intrinsic viscosity 1.18, Zytel® 158, registered trademark of E. Dupont di Nemoas and Campanie) and the core polymer was Pebox 3533SA polyetheresteramide. Ten filament yarns with 70 denier (78 dtex) were spun at a 40/60 volume ratio of wing to core at a spinneret temperature of 265 ° C. Although pre-fusion spinneret packs as shown generally in FIG. 10 were used, the individual plates differed from those used in the previous examples. The stainless steel spinneret plate A shown in FIG. 10A was 0.0015 inches (0.038 cm) thick and was implemented in the form of three straight vanes 1 each having two widths and symmetrically arranged at intervals of 120 degrees around the center of symmetry. It had an orifice cut by the method of Example 1A, with no counterbore on the capillary orifice. Each wing 140 was 0.040 inches (0.102 cm) long from its tip to the circumference of the central round spinneret hole 142 having a diameter of 0.012 inches (0.030 cm) coinciding with the center of symmetry. Referring next to FIG. 10B, a 0.010 inch (0.025 cm) thick distribution plate B is placed on the spinneret plate A such that all other wing orifices 150 of the distribution plate B align with the wings 140 of the spinneret plate A. Aligned axially, each wing orifice 150 of distribution plate B was 0.1357 inches (0.349 cm) in length from its tip to the center of symmetry. Weighing plate C (FIG. 10C) was 0.010 (0.025 cm) inch thick, with holes 160 of 0.025 inch (0.064 cm) diameter, holes 162 of 0.015 inch (0.038 cm) diameter, and 0.010 inch (0.025) center cm) diameter of holes 164. Plate C is the wing polymer fed into hole 160 by molten pool plate D (see FIG. 10) during use and the core polymer fed into holes 162 and 164 of distribution plate C into plate A by plate B. The blades were aligned with the distribution plate B to form the fibers penetrating the core. Spinneret plate A had no counterbore and the combined thickness of plates A, B and C was only about 0.035 inches (0.089 cm). The yarn was stretched to 3.5X at a draw roll speed of 1225 meters / minute and relaxed in an atmospheric steam jet at a winding speed of 1045 meters / minute. The thread, which showed a spun twist when relaxed in the relaxed state, had high stretch and recovery. A micrograph of the cross section of the fiber produced according to this example is shown in FIG. 13.

Example 8

This example illustrates the use of spinnerette plates having conventional thickness in making the fibers of the present invention.

Example 1.A was repeated with the following differences: No spinneret support plate E (see FIG. 8) was used. Spinneret plate A was 0.3125 inches (0.794 cm) thick and each spin orifice had a 0.100 inch (0.254 cm) diameter counterbore and 0.015 inch (0.038 cm) capillary at the bottom of the counterbore. As shown in FIG. 11A, each spinneret orifice in spinneret plate A had six straight wing orifices 170, each of which had a longitudinal axis centerline through the center of symmetry, a central round hole from its tip ( 172) to a length of 0.035 inches (0.089 cm). The length 174 from the tip of each wing to 0.015 inches (0.038 cm) was 0.004 inches (0.010 cm) wide and the length 176 was 0.020 inches (0.051 cm) long and 0.0028 inches (0.007 cm) wide. The tip of each wing was radius cut at half the width of the tip. Distribution plate B (see FIG. 11B) was 0.015 inch (0.038 cm) thick and had six wing orifices, each wing centered on the corresponding counterbore in spinneret plate A, and each wing orifice in plate B ( 150 is oriented to align with the wing orifice 170 of plate A. Each wing orifice 150 in plate B was 0.060 inches (0.152 cm) long and 0.020 inches (0.051 cm) wide, with its tip rounded to a radius of 0.0010 inches (0.025 cm). The center hole 152 in plate B was 0.100 inch (0.254 cm) in diameter. Weighing plate C (see FIG. 11C) was also 0.015 inch (0.038 cm) thick. In plate C, the hole 160 had a diameter of 0.008 inches (0.020 cm) and 0.100 inches (0.254 cm) from the center of the central hole 162 with a diameter of 0.080 inches (0.203 cm). Plate C was aligned with plate B such that the six holes 160 of plate C were above the centerline of the wing orifice 150 of plate B. The plates were aligned so that the elastic core polymer fed into the holes 162 of plate C passed through the center of plates B and A to form the core of the fiber. The inelastic wing polymer was fed into holes 160 in plate C, passing the wing orifices of plates B and A to form a wing of the fiber. The wing and core polymers were first contacted at the top of distribution plate B, 0.328 inches (0.833 cm) above the face of spinneret plate A from which the fibers were extruded.

The spinneret temperature was 247 ° C. Fourteen filament yarns were spun and 5% by weight of a polyetherester based finisher was applied in place of the finishing agent used previously, and 15% relaxed prior to winding (based on elongated yarn length). The drawn and partially relaxed yarn had a line density of 75 deniers (83 dtex) and R ₁ / R ₂ was 1.20. The micrograph of the cross section of this fiber is shown in FIG.

While the invention has been described in conjunction with the description thereof, it is to be understood that the foregoing description is intended to be illustrative and explanatory, and to illustrate the invention and its preferred embodiments. Routine experimentation will enable those skilled in the art to recognize obvious variations and changes that can be made without departing from the spirit of the invention.

Claims (20)

A stretchable synthetic polymer fiber comprising an axial core comprising a thermoplastic elastomer and a plurality of wings comprising a thermoplastic inelastic polymer attached to the core, wherein at least one of the wing polymer or the core polymer protrudes into another polymer. The fiber of claim 1, wherein the core comprises an outer diameter R ₁ , an inner diameter R ₂ , and wherein R ₁ / R ₂ is greater than about 1.2. 3. The stretch of claim 2 wherein the R ₁ / R ₂ is in the range of about 1.3 to about 2.0 and the weight ratio of the inelastic wing polymer to the elastic core polymer is in the range of about 10/90 to about 70/30, and stretch after the boy-off Fiber at least about 20%. 2. The apparatus of claim 1, wherein the protruding polymer comprises at least one necked-down therein including a distant enlarged end region and a reduced neck region connecting the end region and the remaining portion of the protruding polymer. Fiber forming part. The fiber of claim 1 wherein the vanes have substantially the same dimensions and are disposed substantially symmetrically about an axial core. The method of claim 1, wherein the inelastic polymer is selected from the group consisting of polyamides, inelastic polyolefins and polyesters, and the elastomeric polymer is thermoplastic polyurethane, thermoplastic polyester elastomers, thermoplastic polyolefins, thermoplastic polyesteramide elastomers and thermoplastic polyethers. A fiber selected from the group consisting of esteramide elastomers. The fiber of claim 1 further comprising an additive added to the wing polymer to improve adhesion to the core of the wing, wherein the fiber has a bilayer rating of about 2.5 or less. 8. The elastomer of claim 7, wherein the inelastic polymer is selected from the group consisting of (a) poly (hexamethylene adipamide) and copolymers thereof with 2-methylpentamethylene diamine and (b) polycaprolactam, The fiber is a polyetheresteramide. Clothing comprising the fiber of claim 1. An elastic composite comprising an axial core comprising a thermoplastic elastomer and a plurality of wings comprising one or more thermoplastic inelastic polymers attached to the core and having a less than about two layer grade and at least about 20% post-off-off stretch Polymer fibers. The melt comprising the inelastic polymer and the melt comprising the elastomer are passed through a spinneret to form a stretchable synthetic polymer fiber having a plurality of wings attached to the core, wherein at least one of the wing polymer or the core polymer protrudes into another polymer. Making a step; Cooling the fiber by quenching the fiber after the fiber exits the spinneret; And collecting the fibers. 12. The method of claim 11, further comprising thermally relaxing the fibers after said quenching such that the fibers exhibit a stretch after at least about 20% boy-off. The method of claim 12, wherein the thermal relaxation step comprises: a range of about 80 ° C. to about 120 ° C. when the heating medium is dry air, about 75 ° C. to about 100 ° C. when the heating medium is hot water, and the heating medium is pressurized steam. And at a temperature in the range from about 101 ° C. to about 115 ° C., with a heating medium which is dry air, hot water or pressurized steam. The method of claim 11, further comprising, after the quenching, relaxing the fibers in the range of about 1% to about 35% based on the fiber length prior to relaxation. A metering plate containing a first set of holes suitable for containing a first polymer melt and a second set of holes suitable for containing a second polymer melt; A spinneret plate aligned with the distribution plate having a capillary tube passing through the spinneret plate and having a counterbore length of less than about 60% of the length of the capillary tube; And Spinneret support plate aligned with the spinneret plate with holes larger than the capillary Wherein the first and second synthetic polymers fed to the metering plate are aligned so that the first and second synthetic polymers are passed through the distribution plate, spinneret plate and spinneret support plate to form the fiber. Spinneret pack for melt extrusion of synthetic polymers. 16. The spinneret pack of claim 15 wherein the spinneret plate counterbore is less than about 40% of the length of the spinneret capillary. The spinneret pack according to claim 15, wherein the spinneret support plate hole is opened. 16. The spinnerette pack of claim 15, wherein said holes and capillaries are cut by a laser. The spinnerette pack of claim 15 further comprising a distribution plate. 20. The spinneret pack of claim 19 wherein the maximum combined thickness of the distribution plate and spinneret plate is less than about 0.3 cm.