CN1216191C - Drawable polymer fibers, spinnerets for forming 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

Drawable polymer fibers, spinnerets for forming fibers and articles produced therefrom

technical field

Background technique

The present invention relates to an extensible synthetic polymer fiber comprising: an axial core comprising a thermoplastic elastomeric polymer, and a plurality of radially spaced wings comprising a thermoplastic non-elastomeric polymer attached to the outer periphery of the core. At least one of the wing polymer or the core polymer protrudes into the other polymer to improve the attachment of the wings to the core. The invention also relates to methods of producing such fibers and spin packs that can be used to form such fibers. The invention also relates to articles formed from the fibers, including yarns, garments, and the like.

related technology

It is desirable to impart some extensibility to many products made from synthetic fibers, including various garments such as sportswear and hosiery. As disclosed in US Patent 4,861,660 to Ishii, various methods are known for imparting extensibility to synthetic filaments. In one approach, the fibers are crimped in two or three dimensions. In another such method, stretchable filaments are produced from elastic polymers, for example, natural or synthetic rubber, or synthetic elastomers such as polyurethane elastomers. A disadvantage of this type of stretchable filament is that the rubber or polyurethane elastomer filament itself exhibits very poor abrasion resistance and knitting processability and poor dyeability. Thus, the disadvantages of rubber or polyurethane filaments are overcome by covering rubber or elastomer filaments with another type of filament having satisfactory processability and dyeing properties.

However, such coated elastomeric filaments have disadvantages. Ishii attempted to overcome the disadvantages of such filaments by imparting asymmetry to the filaments formed from the two polymers. However, such fibers often suffer from the serious drawback that the two polymers frequently detach from each other (peeling) during processing. The resulting split fibers have low breaking strength, and the resulting fabrics are unsatisfactory in transparency and thinness, and have poor thermal conductivity. See also US Patent 3,017,686 to Breen et al., which discloses fibers formed from two different non-elastomeric polymers, which also suffer from this disadvantage.

In fact, U.S. Patent 3,418,200 to Tanner recognizes that, under certain conditions where the core polymer is extended to the wing polymer, it is in fact easier to form the wing portion and the protruding portion of the wing from a different polymer than the core Detach from the protrusion. In contrast, one may wish to improve the anchorage between two different polymers in the filament, as disclosed in US Patent No. 3,458,390, using mechanical interlocking to bond two high modulus, low elastic polymers together. However, such polymers, as well as those disclosed by Breen and Tanner, lack the elongation and recovery properties required for high elongation garments sought today due to their low elasticity.

Fibers containing both polymers can be spun with the spinnerettes disclosed in US Patent 3,418,200 and US Patent 5,344,297. However, with the spinnerettes disclosed in these two patents, polymer migration problems often arise when multiple polymer streams are combined in the feed channel prior to the spinneret. Such problems are described in Journal of Polymer Science [Physics Edition], Vol. 13(5), p. 863, 1975, and more specifically and recently in International Journal of Fibers ( International Fiber Journal) (1998), Vol. 13(5) p.48, on yet another prior art spinning method for trilobal shaped fibers with tips intended to split off from the core.

It can be seen that there remains a need for fibers and articles made therefrom which have excellent elongation and recovery and which retain their strength during processing and use, as well as convenient methods of making such fibers and articles. There is also a need for a spinnerette for the spinning of two polymers that overcomes the problems of polymer migration that often occur when multiple polymer streams are combined in the feed channel prior to the spinneret.

Summary of the invention

It has now been found that splitting (detachment or peeling) within the fibers of two stretchable polymers can be greatly reduced or eliminated as long as the two polymers are inserted into each other, that is, at least a portion of the wing polymers of one or more wings protrude. into the core polymer, or at least a portion of the core polymer protrudes into the wing polymer. This phenomenon was unexpected because it was originally thought that, under tension, the elastomeric polymer should easily deform and be pulled out of the joint with the non-elastomeric polymer, especially according to the above-mentioned Tanner the opinion of.

Based on the above findings, the present invention provides a stretchable synthetic polymer fiber comprising an axial core comprising a thermoplastic elastomeric polymer and a plurality of wings attached to the core comprising a thermoplastic non-elastomeric polymer, wherein the wing polymer Or at least one of the core polymers protrudes into the other polymer. In one embodiment, the axial core comprises an outer radius R ₁ and an inner radius R ₂ , and R ₁ /R ₂ is greater than about 1.2.

In another embodiment, the present invention provides a drawable synthetic polymer fiber comprising an axial core comprising a first polymer and a plurality of wings attached to the core comprising a second polymer, wherein the fiber has A peel rating of less than about 1 and an elongation after boil of at least about 20%.

Additionally, with the spin pack of the present invention, it is possible to meter a multicomponent polymer stream directly into a specific point at the rear entrance of the fiber forming holes in the spinneret. This eliminates the problem of polymer migration that often occurs when multiple polymer streams are combined in the feed channel at a considerable distance from the spin hole.

Accordingly, the present invention provides a spin pack for the melt extrusion of a plurality of synthetic polymers to produce fibers comprising: a metering plate comprising a first set of holes adapted to receive a first polymer melt and adapted for A second set of holes for receiving a second polymer melt; a spinneret, aligned with and in contact with a metering plate, having a spin through hole and having a conical hole less than about 60% of the length of the spin hole ( counterbore) length; and a spinneret bottom plate, which has holes larger than the spinneret holes, aligned with and in contact with the spinnerette; where the plates are aligned so that multiple polymers are fed into the metering plate, flow through the spinneret and The spinneret floor is thus formed into fibers.

Description of drawings

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

Figure 2 is a cross-sectional view of a fiber of the present invention with the core polymer protruding into the wings.

Figure 3 is a cross-sectional view of one embodiment of the fiber of the present invention in which the protruding polymer, eg, wing polymer protrudes like a tooth root into an inserted polymer, eg, core polymer.

Figure 4 is a cross-sectional view of one embodiment of the fiber of the present invention, wherein the protruding polymer, e.g., the core polymer, protrudes into the inserted polymer, e.g., the wing polymer, which is spline-like of.

Figure 5 is a cross-sectional view of one embodiment of the fiber of the present invention, wherein the core polymer protrudes into the wing polymer and includes an enlarged distal segment and a constricted segment connecting the distal segment to the remainder of the core polymer so that At least one necked portion is formed.

Figure 6 is a cross-sectional view of one embodiment of the fiber of the present invention in which the core surrounds a portion of one or more wing sides, thereby causing the wing to insert into the core.

Figure 7 is a schematic diagram of a process-equipment that can be used to make fibers of the present invention.

Figure 8 is a side view of an overlapping plate spinpack useful for making fibers of the present invention.

FIG. 8A is a plan view of the fine-well plate A viewed perpendicular to the stacked plate spinpack shown in FIG. 8 and taken along line 8A-8A of FIG. 8 .

Figure 8B is a plan view of the fine-well plate B viewed perpendicularly to the stacked plate spinpack shown in Figure 8 and taken along line 8B-8B of Figure 8 .

FIG. 8C is a plan view of the fine orifice plate C viewed perpendicular to the stacked plate spin pack shown in FIG. 8 and taken along line 8C-8C of FIG. 8 .

Figure 9 shows a partial cross-sectional representation of a prior art spinnerette section.

Figures 9A and 9B show partial cross-sectional representations of two spinnerettes of the present invention.

Figure 10 is a side view of an overlapping plate spinpack that may be used to make the fiber alternative of the present invention.

Figures 10A, 10B and 10C represent alternative plan views of the spinpack, distribution plate and metering plate, respectively, as seen perpendicular to the overlapping plate spinpack of Figure 10, each of which can be used in the spinpack of the present invention to make the present invention alternative fiber.

Figures 11A, 11B and 11C respectively represent alternative plan views of the spinpack, distribution plate and metering plate as seen perpendicular to the overlapping plate spinpack of Figure 10, each of which may be used in the spinpack of the present invention to manufacture Alternative Fibers of the Invention.

FIG. 12 is a sectional view of a fiber of the present invention as an example in Example 6. FIG.

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

Detailed description of the invention

The present invention provides a drawable synthetic polymer fiber generally as shown 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 elastomeric polymer; the wings comprise at least one thermoplastic non-elastomeric polymer attached to the core. Preferably, the thermoplastic non-elastomeric polymer is permanently drawable.

The term "fiber" is used herein interchangeably with the term "filament". The term "yarn (thread)" includes various yarns composed of monofilaments. The term "multifilament yarn" generally refers to a yarn composed of two or more monofilaments. The term "thermoplastic" refers to a polymer that can be repeatedly melt-processed (eg, melt-spun). By "elastomeric polymer" is meant a polymer in the form of a monocomponent fiber containing no diluent, having an elongation at break exceeding 100% and when stretched to twice its length, held for 1 min, then released When it is released, it will retract to less than 1.5 times its original length within 1 minute of loosening. The elastomeric polymers in the fibers of the present invention may have a flexural modulus of less than about 14,000 psi (96,500 kPa), more typically less than about 8500 psi (58,600 kPa), where spun into a single component The fibers are present and measured according to ASTM Standard D790 Flexural Properties at room temperature or 23°C and under conditions substantially as described therein. As used herein, the term "non-elastomeric polymer" refers to any polymer that is not an elastomeric polymer. Such polymers may also be referred to as "low elastic", "hard" and "high modulus". By "permanently extensible" is meant that the polymer has a certain yield point, and if the polymer is stretched beyond this point, it will not return to its original length.

Fibers of the present invention are referred to as "bicomponent" fibers when they consist of at least two polymers, each of a different class, such as polyamide, polyester or polyolefin, adhered to each other along the length of the fiber. If the elastic characteristics of the polymers vary sufficiently so that polymers of the same class can be used, the resulting fibers are "bicomponent" fibers. Such bicomponent fibers are also within the scope of the present invention.

According to the invention, at least one of the wing polymer and the core polymer protrudes into the other polymer. Figure 1 shows the wing polymer protruding into the core polymer; Figure 2 shows the core polymer protruding into the wing polymer. Insertion of the core and wing polymers can be accomplished by any method effective to reduce fiber splitting. For example, in one embodiment, the inserting polymer (eg, the wing polymer) can protrude into the inserted polymer (eg, the core polymer) like a tooth root to form a plurality of protrusions (see FIG. 3 ). In another embodiment, the insertion polymer (eg, core polymer) can protrude into the inserted polymer (eg, wing polymer), so that the insertion polymer acts like a spline (see Figure 4) . The splines have a substantially uniform diameter. In yet another embodiment, at least one polymer may have at least one protruding portion, i.e., a wing inserted into the core or a core inserted into the wing, comprising an enlarged distal segment and a constricted segment connecting the distal segment and the remainder of at least one polymer thereby forming at least one necked portion therein. FIG. 5 shows the core polymer protruding into each wing polymer with such an enlarged distal section 16 and a constricted section 18 . The wings and core are fixed to each other by means of such enlarged distal end sections and constricted neck sections, which are referred to as "mechanical interlocks". For ease of manufacture and more effective attachment between the wings and the core, the last-mentioned embodiment with a necked-in section is generally preferred. Other methods of protrusion are envisioned by those skilled in the art. For example, as seen in Figure 6, the core may surround a portion of one or more wing sides, so that the wing is inserted into the core.

Fibers of the present invention include an axial core having an outer radius and an inner radius (eg, " _R1 " and " _R2 ", as shown in Figures 1 and 2, respectively). The outer radius is the radius of the circle circumscribing the outermost portion of the core; the inner radius is the radius of the circle inscribing the innermost portion of the wing. In the fibers of the present invention, R ₁ /R ₂ is generally greater than about 1.2. Preferably, R ₁ /R ₂ is between about 1.3 and about 2.0. Peel resistance decreases as this ratio decreases; while at higher ratios, high levels of elastomeric polymer in the wings (or non-elastomeric polymer in the core) reduce fiber elongation and recovery. R ₁ /R ₂ tends to 2 when the core forms the splines inside the wing. Conversely, in fibers where one of the wing or core polymers does not protrude into the other, _R1 is close to _R2 so that neither wing nor core inserts into the other. In the case of many wings, where the polymers of some wings protrude into the core polymer, and the polymers in other wings are inserted by the core polymer, _R1 and _R2 are only regarded as corresponding to each As shown in Fig. 2, each ratio of R ₁ /R ₂ and R ₁ '/R ₂ ' is generally greater than 1.2, preferably between about 1.3 and 2.0. In another embodiment where certain wings can be inserted by the core polymer while adjacent wings are not, then R _{and R} are determined according to the inserted wings; similarly, _R and R _are determined according to The wing is inserted to determine if only a portion of the core is inserted by the wing polymer. Each wing may take any combination of core-inserted wing, wing-inserted core, and not-inserted as long as at least one wing is inserted into or inserted by the core.

The fibers of the present invention are twisted (twist) along their own longitudinal axis without significant two- or three-dimensional crimping characteristics. (In such higher dimension crimps, the longitudinal axis of the fiber itself is in a meandering or helical configuration; such fibers are outside the scope of this invention). Fibers of the present invention can be characterized as having substantially helical turns and one-dimensional helical turns. "Substantially helical twist" includes both a helical twist that is completely coiled around an elastomeric core, and a helical twist that is only partially coiled around the core, since it has been observed that for the fiber to achieve the desired elongation The performance does not necessarily require a full 360° helical twist. The substantially helical twist can be a substantially helical turn that is almost entirely along the perimeter or a substantially helical turn that is almost not at all along the perimeter. "One-dimensional" helical twist means that although the wings of the fiber may be substantially helical, the axis of the fiber remains substantially straight even under low tension, as distinguished from coils having 2- or 3-dimensional crimps. of fiber. However, fibers with some corrugation are within the scope of the present invention.

The presence or absence of two- and three-dimensional crimps can be judged by the amount of stretch required to substantially straighten the fiber (to straighten any non-linear portions that exist), and is also a measure of the radial symmetry of fibers with helical twists . The fibers of the present invention may require less than about 10% elongation, more typically less than about 7% elongation, such as about 4% to about 6%, to substantially straighten the fiber.

The fibers according to the invention have a substantially radially symmetrical cross-section, as can be seen especially from FIGS. 1 and 2 . By "substantially radially symmetrical section" is meant a section in which the positions and dimensions of the individual wings satisfy the following conditions: when the fiber rotates 360/n degrees around its longitudinal axis, where n is the "n-weight" representing the fiber - Symmetrical integers produce substantially the same cross section as before rotation. The cross-section is substantially symmetrical about the core in terms of dimensions, polymers and spacing angles. This substantially radially symmetrical cross section provides the unexpected combination of high elongation with high uniformity and no significant degree of two- or three-dimensional curling. This uniformity is advantageous in high-speed processing of fibers, for example, as they pass through yarn guides and knitting needles, and in the manufacture of smooth, non-"picky" fabrics, especially sheer, lightweight fabrics such as hosiery classes etc. Fibers with substantially radially symmetrical cross-sections do not have a tendency to self-crimp, ie, they do not have appreciable two- or three-dimensional crimping properties. For a general description see Textile Research Journal 1967-06, p.449.

In order to achieve the highest cross-sectional radial symmetry, the core may have a substantially circular or regular polygonal cross-section, eg as seen in FIGS. 1 and 2 . By "substantially circular" is meant that the ratio of the lengths of the two axes intersecting each other at 90° through the center of the cross-section of the fiber is not greater than about 1.2:1. Using a substantially circular or regular polygonal core, unlike that of US Patent 4,861,660, protects the elastomer from contact with rollers, guides, etc., as described later when discussing the number of wings. The plurality of wings may be arranged in any desired manner around the core, e.g. discontinuously as in Figures 1 and 2, i.e. the wing polymer does not constitute a continuous mantel on the core nor is it separated from adjacent wings on the core. The surfaces are joined, for example as shown in Figures 4 and 5 of US Patent 3,418,200. The wings may be of the same or different dimensions as long as substantial radial symmetry is maintained. Again, each wing may have a different polymer than the other wings, again as long as the substantial radial geometry and symmetry of polymer composition is maintained. However, for simplicity of manufacture and ease of achieving radial symmetry, it is preferred that the individual wings are approximately the same size and made of the same polymer or polymer blend. It is also preferred that each wing discontinuously surrounds the core for ease of manufacture.

Although the fiber cross-section is substantially symmetrical with respect to size, polymer, and angular spacing around the core, be aware that small fluctuations from perfect symmetry, due to factors such as quench inhomogeneities or imperfections in polymer melt flow or spinning Imperfect holes are generally unavoidable in the spinning process. It should be understood that such undulations are permissible as long as they are not large enough to deviate from the purpose of the present invention, e.g., to provide fibers with the desired elongation and recovery through one-dimensional helical twists while minimizing two- and three-dimensional crimps . That is, the fibers are not intentionally asymmetric as in US Patent 4,861,660.

Wings projecting outwardly from the core are adhered to the core and form a plurality of helices at least partially surrounding the core, especially after effective heating. The pitch between these helices may increase when the fiber is stretched. The fiber of the present invention has a plurality of wings, preferably 3-8, more preferably 5 or 6 wings. The number of wings employed will depend on other characteristics of the fiber and the conditions under which the fiber is made and used. For example, when making monofilaments, 5 or 6 wings may be used, especially at higher draw ratios and fiber tensions. In this case, the wing spacing can be sufficiently close around the core to protect the elastomer so that it makes less contact with rollers, guides, etc. Filament, roll entanglement and wear. The effect of higher draft ratios and fiber tensions is to press the fiber more against the rollers and guides, causing the individual wings to spread out and cause the elastomeric core to contact the rollers or guides; thus, at More than 2 wings are preferred at high draw down ratios and fiber tensions. In a monofilament, 5 or 6 wings are often preferred for the best combination of ease of manufacture and less core contact. When multifilament yarn is required, as few as two or three wings can be used because the possibility of the elastomeric core coming into contact with the roller or guide is reduced by the presence of other fibers.

While it is preferred that the wings discontinuously surround the core for ease of manufacture, the core may also include a non-elastomeric polymer skin on its outer surface between the points of contact of the wings and the core. The thickness of the skin can range from about 0.5% to about 15% of the largest radius of the fiber core. The skin promotes wing-to-core adhesion by providing more points of contact between the core and wing polymers, which is especially useful when the polymers in bicomponent fibers do not adhere well to each other characteristics. The skin also reduces abrasive contact between the core and rollers, guides, etc., especially when the fiber has few wings.

The core and/or wings of the multi-wing section of the present invention may be solid or hollow or include voids. Typically, both the core and wings are solid. In addition, the wings may have any shape, such as elliptical, T-, C- or S-shaped (see eg Figure 4). Examples of useful wing shapes can be found in US Patent 4,385,886. A T-, C- or S-shape may help protect the elastomeric core from contact with the yarn guides and rollers, as described above.

The weight ratio between the total wing polymer and the core polymer can be varied to provide the desired combination of properties, for example, the core provides the desired elasticity and the wing polymer provides other properties such as low tack. For example, the weight ratio of the wings to the core may be from about 10/90 to about 70/30, preferably from about 30/70 to about 40/60. When the fiber does not need to be used with some accompanying yarn (for example, hosiery), it is generally preferred that the wing/core weight ratio be between about 35/65 and about 50/50. For optimum adhesion between the core and the wings, typically from about 5% to about 30% by weight of the total weight of the fibers can be either the non-elastomeric polymer inserted into the core or the elastic core polymer inserted into the wings.

As noted above, the core of the fibers of the present invention may be formed from any thermoplastic elastomeric polymer. 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 prepared from polymeric diols, diisocyanates, and at least one diol or diamine chain extender. A diol chain extender is preferred because polyurethanes made with it have a lower melting point than those made with diamine chain extenders. Polymeric diols useful in preparing elastomeric polyurethanes include polyether diols, polyester diols, polycarbonate diols, and copolymers thereof. Examples of such diols include poly(ethylene ether) glycol, poly(tetramethylene ether) glycol, poly(tetramethylene-co-2-methyl-tetramethylene ether) glycol , poly(ethylene glycol-co-1,4-butanediol adipate) diol, poly(ethylene glycol-co-1,2-propanediol adipate) diol, poly(1 , 6-hexanediol-co-2,2-dimethyl-1,3-propanediol adipate), poly(3-methyl-1,5-pentanediol adipate) di alcohol, poly(3-methyl-1,5-pentanediol nonanoate)diol, poly(2,2-dimethyl-1,3-propanediol dodecanoate)diol, poly (pentane-1,5-carbonate)diol and poly(hexane-1,6-carbonate)diol. Useful diisocyanates include 1-isocyanato-4-[(4-isocyanatophenyl)methyl]benzene, 1-isocyanato-2-[(4-isocyanato-phenyl )methyl]benzene, isophorone diisocyanate, 1,6-hexane diisocyanate, 2,2-bis(4-isocyanatophenyl)propane, 1,4-bis(p-isocyanate combined, α,α-dimethylbenzyl)benzene, 1,1'-methylenebis(4-isocyanatocyclohexane) and 2,4-toluene diisocyanate. Useful diol chain extenders include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, and mixtures thereof. Preferred polyglycols are poly(tetramethylene ether) glycol, poly(tetramethylene-co-2-methyl-tetramethylene ether) glycol, poly(ethylene glycol-co-1, 4-butanediol adipate) diol and poly(2,2-dimethyl-1,3-propanediol dodecanoate) diol. 1-Isocyanato-4-[(4-isocyanatophenyl)methyl]benzene is the preferred diisocyanate. Preferred diol chain extenders are 1,3-propanediol and 1,4-butanediol. Monofunctional chain terminators such as 1-butanol may be added to control the molecular weight of the polymer.

Useful thermoplastic polyester elastomers include polyether diols with low molecular weight diols, e.g., those with a molecular weight of less than about 250, and dicarboxylic acids or diesters thereof, e.g., terephthalic acid or dimethyl terephthalate , The reaction between the prepared polyether ester. Useful polyether diols include poly(ethylene ether) glycol, poly(tetramethylene ether) glycol, poly(tetramethylene ether-co-2-methyl-tetramethylene ether) diol Alcohol [derived from copolymerization between tetrahydrofuran and 3-methyltetrahydrofuran] and poly(ethylene-co-tetramethylene ether) glycol. Useful low molecular weight diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol and mixtures thereof; 1,3-propanediol and 1, 4-Butanediol is preferred. Useful dicarboxylic acids include terephthalic acid, optionally in combination with small amounts of isophthalic acid, and its diesters (eg, <20 mol%).

Useful thermoplastic polyester amide elastomers that can be used to make the core of the fibers of the present invention include those described in US Patent No. 3,468,975. For example, the polyester segments used in the preparation of such elastomers can be passed through ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3 - propylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,4-bis(hydroxymethyl)cyclohexane, diethylene glycol or triethylene glycol, with Malonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, 3-methyladipic acid, 3,4-dimethyladipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid or dodecanedioic acid or the reaction between their esters to prepare. Examples of polyamide segments in such polyesteramides include reaction between hexamethylenediamine or dodecamethylenediamine and terephthalic acid, oxalic acid, adipic acid or sebacic acid, and Those prepared by ring-opening polymerization of caprolactam.

Thermoplastic polyetheresteramide elastomers, such as those described in US Pat. No. 4,230,838, can also be used to make the fiber core. Such elastomers can be prepared, for example, by first preparing polyamide prepolymers with dicarboxylic acid chain ends from the following raw materials: low molecular weight (e.g., about 300 to about 15,000) polycaprolactam, polyenantholactam, polylaurolactam, Polyundecanoic acid, poly(11-aminoundecanoic acid), poly(12-aminododecanoic acid), poly(1,6-hexanediol adipate), poly(azelaic acid 1, 6-hexanediol ester), poly(1,6-hexanediol sebacate), poly(hexanediol undecanoate), poly(hexanediol dodecanoate), poly(hexanediol 1,9-nonanediol diacid) and the like, with succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, terephthalic acid, dodecanedioic acid wait. This prepolymer can then be combined with a hydroxyl chain-terminated polyether, for example, poly(tetramethylene ether) glycol, poly(tetramethylene-co-2-methyltetramethylene ether) glycol, poly(tetramethylene ether) glycol, Propylene ether) glycol, poly(ethylene ether) glycol and the like react.

As noted above, the wings may be formed from any non-elastomeric or rigid polymer. Examples of such polymers include non-elastomeric polyesters, polyamides and polyolefins.

Useful thermoplastic non-elastomeric wing polyesters include poly(ethylene terephthalate) (“2G-T”) and copolymers thereof, poly(1,3-trimethylene terephthalate) (“3G-T”) T"), polybutylene terephthalate ("4G-T") and poly(2,6-ethylene naphthalate), poly(1,4-cyclohexane di methyl ester), poly(lactide), poly(ethylene azelate), poly[2,7-ethylene naphthalate], poly(glycolic acid), poly(ethylene succinate) alcohol esters), poly(α,α-dimethylpropiolactone), poly(p-hydroxybenzoate), poly(ethylene glycol hydroxybenzoate), poly(ethylene isophthalate ester), poly(1,4-butylene terephthalate), poly(1,6-hexanediol terephthalate), poly(1,12-dodecanediol terephthalate ester), poly(1,4-cyclohexanedimethylene terephthalate) (trans), poly(1,5-ethylene naphthalate), poly(2,6-ethylene naphthalate glycol ester), poly(1,4-cyclohexanedimethylene terephthalate) (cis) and poly(1,4-cyclohexanedimethylene terephthalate) (cis), poly (1,5-ethylene naphthalate), poly(2,6-ethylene naphthalate), poly(1,4-cyclohexanedimethylene terephthalate) (cis) and poly(1,4-cyclohexanedimethylene terephthalate) (trans).

Preferred non-elastomeric polyesters include poly(ethylene terephthalate), poly(1,3-trimethylene terephthalate), and poly(1,4-butylene terephthalate) and their copolymers. When using higher melting point polyesters such as poly(ethylene terephthalate), comonomers can be added to the polyester to enable spinning at lower temperatures. Such comonomers may include linear, cyclic, and branched aliphatic dicarboxylic acids (eg, glutaric acid) of 4 to 12 carbon atoms; aromatic dicarboxylic acids of 8 to 12 carbon atoms other than terephthalic acid; Dicarboxylic acids (for example, isophthalic acid); linear, cyclic and branched aliphatic diols of 3 to 8 carbon atoms (for example, 1,3-propanediol, 1,2-propanediol, 1,4- butanediol and 2,2-dimethyl-1,3-propanediol); and aliphatic and araliphatic ether glycols of 4 to 10 carbon atoms (for example, hydroquinone bis(2-hydroxyethyl) ether) . Comonomers may be present in the copolyester in amounts of about 0.5 to 15 mole percent. Isophthalic acid, glutaric acid, adipic acid, 1,3-propanediol, and 1,4-butanediol are preferred comonomers for poly(ethylene terephthalate) because they are commercially Available and cheap.

The wing polyester may also contain small amounts of other comonomers as long as these do not have a negative impact on fiber properties. Such other comonomers include sodium 5-sulfoisophthalate used, for example, in amounts ranging from about 0.2 to 5 mole percent. Trifunctional comonomers, such as trimellitic acid, may be added in very small amounts, such as from about 0.1 to about 0.5% by weight, based on the total components, for viscosity control.

Useful thermoplastic non-elastomeric wing polyamides include poly(hexamethylene adipamide) (nylon 6,6); polycaprolactam (nylon 6); polyenantholactam (nylon 7); nylon 10; Dilactam) (nylon 12); polybutylene adipamide (nylon 4,6); polyhexamethylene sebacamide (nylon 6,10); poly(hexamethylene dodecanediamide) (nylon 6,12); polyamides of dodecanediamine and n-dodecanedioic acid (nylon 12,12), PACM-12 polyamides derived from bis(4-aminocyclohexyl)methane and dodecanedioic acid , Copolyamide of 30% isophthalic acid-hexamethylene diammonium salt and 70% hexamethylene diammonium adipate, up to 30% bis(p-amidocyclohexyl)methylene with terephthalic acid and caprolactam Amide, Poly(4-aminobutyric acid) (Nylon 4), Poly(8-Aminocaprylic acid) (Nylon 8), Poly(Heptamediamide) (Nylon 7,7), Poly(Suberoylsuberyl amine) (nylon 8,8), poly(nonanediamide azelayl)(nylon 9,9), poly(decanediamide azelayl)(nylon 10,9), poly(decanediamide azelayl) (Nylon 10,10), poly[1,10-decanediformylbis(4-amino-cyclohexyl)methane], poly(m-xylylene adipamide), poly(terephthalamide sebacyl methylamine), poly(2,2,2-trimethylhexamethylenediamine pimeloyl), poly(sebacylpiperazine), poly(11-aminoundecanoic acid) (nylon 11), polyisophenylene Hexamethylene diamide, polyhexamethylene terephthalamide and poly(9-aminononanoic acid) (nylon 9), polycaprolactam. Copolyamides may also be used, for example, poly(hexamethylene adipamide-co-2-methylpentamethylenediamine), in which the hexamethylene moieties may constitute about 75 to 90 mole percent of the diamine-derived moieties.

Useful polyolefins include polypropylene, polyethylene, polymethylpentene, and copolymers and terpolymers of one or more ethylene or propylene with other unsaturated monomers. For example, fibers comprising non-elastomeric polypropylene wings and an elastomeric polypropylene core are within the scope of the invention; such fibers are bicomponent fibers.

Combinations of elastomeric and non-elastomeric polymers may include polyetheramides, for example, polyetheresteramide elastomeric cores with polyamide wings, and polyetheresteramide elastomeric cores with polyester wings. For example, the wing polymer may comprise nylon 6-6 and its copolymers, e.g., poly(hexamethylene adipamide-co-2-methylpentamethylenediamine), wherein the hexamethylene moiety constitutes about 80 mole percent, From about 1% to about 15% by weight nylon-12 is optionally blended, and the core polymer may comprise polyetheresteramide with elastomeric blocks. "Blocked polyetheresteramide" means a polymer having soft segments (long-chain polyethers) covalently bonded (by ester groups) to hard segments (short-chain polyamides). Similar definitions correspond to segmented polyetheresters, segmented polyurethanes and the like. Nylon 12 improves the adhesion of the wings to the core, especially when the core consists primarily of PEBAX ^™ 3533SN (supplied by Atofina). Another preferred wing polymer may comprise a non-elastomeric polyester selected from the group consisting of poly(ethylene terephthalate) and copolymers thereof, poly(1,3-trimethylene terephthalate) and Poly(1,4-butylene terephthalate); Elastomeric cores suitable for use therewith may comprise polyether esters selected from the group consisting of poly(tetramethylene ether) glycol and poly(tetramethylene ether) Polyether diols of methylene-copoly-2-methyltetramethylene ether) diol with terephthalic acid or dimethyl terephthalate and selected from 1,3-propanediol and 1,4- Butanediol is the reaction product of a low molecular weight diol.

Elastomeric polyetherester cores can also be used with non-elastomeric polyamide wings, especially when tackifiers are used, as described elsewhere herein. For example, the wings of such fibers may be selected from: (a) poly(hexamethylene adipamide) and its copolymers with 2-methylpentamethylenediamine and (b) polycaprolactam; while the core of such fibers may be selected from: (a) polyether ester amides and (b) poly(tetramethylene ether) glycol or poly(tetramethylene-co-2-methyltetramethylene ether) glycol with terephthalate The reaction product of formic acid or dimethyl terephthalate and a diol selected from 1,3-propanediol and 1,4-butanediol.

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

Because the core is highly elastic, it is able to absorb the compressive and tensile forces that occur during twisting caused by the attached wings as the fiber elongates and relaxes. These forces have the potential to cause the wings to detach from the core polymer if their adhesion is too weak. The present invention optionally employs mechanical interlocking of the wings with the core polymer to enhance anchorage and further greatly reduce delamination after fiber processing and use. The bond between the wing and core can even be enhanced by choice of wing and core composition and/or the use of additives that enhance the adhesion of either or both polymers. Tackifiers may be added to each or some of the wings. Each wing may then have a different degree of lamination relative to the core. For example, some of the wings can be made intentionally layered. An example of such an additive is Nylon 12, e.g., 5 wt%, based on the total wing polymer, i.e., poly(12-laurolactam), also known as "12" or "N12", sold by Atofina under the tradename Rilsan "AMNO" is commercially available. Also, maleic anhydride derivatives (e.g., ^Bynel® CXA, a registered trademark of DuPont, or Lotader® ^ethylene /acrylate/maleic anhydride terpolymer, supplied by Atofina) can also be used to modify polyether Amide elastomers to improve their adhesion to polyamides.

As another example, a thermoplastic novolac resin, such as HRJ12700 (Schenectady International), with a number average molecular weight in the range of about 400 to about 5000, can be added to the elastomeric (co)polyetherester core to improve its compatibility with the (co)polyetherester. Adhesion of polyamide wings. The amount of novolac resin should be 1-20 wt%, more preferably 2-10 wt%. Examples of novolac resins useful in the present invention include, but are not limited to, phenol-formaldehyde, resorcinol-formaldehyde, p-butylphenol-formaldehyde, p-ethylphenol-formaldehyde, p-hexylphenol-formaldehyde, p-propylphenol - formaldehyde, p-amylphenol-formaldehyde, p-octylphenol-formaldehyde, p-heptylphenol-formaldehyde, p-nonylphenol-formaldehyde, bisphenol-A-formaldehyde, naphthol-formaldehyde and rosin (especially partially maleated Alkyl-(eg, tert-butyl-)phenol-modified esters (eg, pentaerythritol esters) of rosin). See issued US Patent Application Serial No. 09/384,605, filed 1999-08-27, for examples of techniques for improving adhesion between copolyester elastomers and polyamides.

Polyesters functionalized with maleic anhydride ("MA") can also be used as tackifying additives. For example, poly(butylene terephthalate) ("PBT") can be functionalized with MA by free radical grafting in a twin-screw extruder, see J.M. Bhattacharya, "(Polymer International (2000- 08), 49:8, pp.860～866, it is also reported in the paper that a few weight percent of PBT-graft-MA is produced as poly(butylene terephthalate) and nylon 66 and poly(terephthalate) respectively. The use of compatibilizers for binary blends of ethylene glycol diformate) and nylon 66. For example, such additives can be used to more firmly adhere the (co)polyamide wings of the fibers of the present invention to the (co)polyamide wings. ) on a polyetherester core.

The polymers used in the present invention and the resulting fibers, yarns and articles may contain conventional additives, which may be added during the polymerization process, or added to the resulting polymer or article, and may contribute to improving the properties of the polymer or fiber. Contribute to performance. Examples of these additives include antistatic agents, antioxidants, antimicrobial agents, flame retardants, dyes, light stabilizers, polymerization catalysts and various auxiliary agents, tackifiers, delusterants (delustrants) such as titanium dioxide, delusterants ( matting agents) and organophosphates.

Other additives that can be applied to the fibers, for example during spinning and/or drawing, include antistatic agents, slip agents, tackifiers, hydrophilic agents, antioxidants, antimicrobial agents, flame retardants, Lubricants and their combinations. In addition, these additional additives may be added during various steps of the process, as is known in the art.

While the above description has focused on the advantages when the fibers have a substantially radially symmetrical cross-section, such symmetry, although often desirable, is not required by embodiments of the present invention in the following situations:

(a) the stretchable synthetic polymer fiber has a peel rating of less than about 1 and a boil shrinkage of at least about 20%;

(b) a stretchable synthetic polymer fiber having at least about 20% boil shrinkage and requiring less than about 10% elongation to substantially straighten the fiber;

(c) a stretchable synthetic polymer fiber comprising an axial core comprising an elastomeric polymer and a plurality of wings comprising a non-elastomeric polymer attached to the core, wherein the core includes on its outer surface at points of contact between the wings and the core a skin of non-elastomeric polymer in between;

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

(e) A stretchable synthetic polymer fiber comprising an axial core comprising an elastomeric polymer and a plurality of wings comprising a non-elastomeric polymer attached to the core, wherein at least one wing has a T, C or S shape.

The fibers of the present invention can be in the form of continuous filaments (multifilament yarns or monofilaments) or staple fibers (including, for example, tows or staple spun yarns). The drawn fibers of the present invention may have a denier per filament of about 1.5 to about 60 (about 1.7 to 67 dtex). Typical fully drawn fibers of the present invention with polyamide wings have a strength of about 1.5 to 3.0 g/dtex (grams per dtex); fibers with polyester wings have about 1 to 2.5 g/dtex, depending on Depending on the wing/core ratio. Fibers of the present invention are produced having an elongation after boil of at least about 20%. To achieve greater elongation and recovery in fabrics made from the fibers of the present invention, the fibers may have an elongation after boil of at least about 45%.

When making yarns comprising multiple fibers, the fibers can have any desired fiber count and any desired denier per filament (dpf), and the ratio of elastomeric to non-elastomeric polymers can vary from one fiber to another One root is different from each other. Multifilament yarns may contain many different fibers, for example, 2-100 fibers. Additionally, yarns comprising fibers of the present invention may have a range of linear filament densities and may also contain fibers not of the present invention.

The synthetic polymeric fibers of the present invention can be formed into fabrics in known manner, including by weaving, warp knitting, weft knitting (including circular knitting), or hosiery knitting. Such fabrics have excellent elongation and recovery capabilities. The fiber can be used in textiles and fabrics, for example, upholstery fabrics, and garments (including lingerie and hosiery) to make all or part of garments, including narrow weaves (lace). Garments, such as hosiery and fabrics made from the fibers and yarns of the present invention, were found to be smooth, lightweight and very uniform ("spotless") with excellent elongation and recovery properties.

Additionally, in accordance with the present invention, there is provided a melt spinning process for spinning continuous polymeric fibers. The method will be described with reference to Figure 7, which is a schematic diagram of an apparatus that can be used to make fibers of the present invention. However, it is to be understood that other devices may also be used. The method of the present invention comprises passing a melt comprising an elastomeric polymer through a spinnerette to form a plurality of drawable synthetic polymer fibers comprising an axial core comprising an elastomeric polymer and a plurality of fibers attached to the core and comprising Non-elastomeric polymer wings. Referring to Figure 7, a hard thermoplastic polymer feed (not shown) is introduced at 20 into the overlapping plate spin pack 35 while a thermoplastic elastomeric polymer feed (not shown) is introduced at 22 into the spin pack 30. Both pre-bonded and post-bonded spinneret packs are available. The two polymers are extruded as undrawn filaments 40 from an overlapping plate spin pack 35 having spin holes designed to produce the desired cross-section. The method of the invention also includes quenching the tows after they leave the spinneret to cool the fibers, in any known manner, for example by means of cold air 50 in FIG. 7 . Any suitable quenching method can be used, such as side blowing or radial flow air.

The tow is optionally treated with a finish such as silicone oil, optionally supplemented with magnesium stearate, at soil oil roller 60 shown in FIG. 7 using known techniques. After quenching, the tows are then drawn such that they exhibit at least about 20% post-boil elongation. The tow can be drawn in at least one drawing step, for example between a feed roll 80 (which can run at 150-1000 m/min) and a draw roll 90, as schematically shown in Figure 7, resulting in a draft Silk 100. The drawing step can be coupled with spinning to produce a fully drawn yarn, or, if partially oriented yarn is desired, in a separate process with a time delay between spinning and drawing. Drafting can also be done at the same time as the filaments are wound into a warp; this is known to those skilled in the art as "draw warping". Any desired draft ratio can be given to the tow (as long as the processing is not affected by broken filaments); for example, fully oriented yarns can be made by a draft ratio of about 3.0 to 4.5 times; partially oriented yarns can be made by about 1.2 to 3.0 times times the draft ratio made. Here, the draft ratio is the peripheral speed of the draft roll 90 divided by the peripheral speed of the feed roll 80 . Drawing may be performed at about 15-100°C, typically about 15-40°C.

The drawn filament 100 optionally can be partially relaxed, such as with steam at 110 in FIG. 7 . Any degree of thermal relaxation can be performed during spinning. The more it relaxes, the more elastic the filament is and the less it shrinks in downstream operations. The final drawn filament after relaxation as described below may have an elongation after boil of at least about 20%. The as-spun tow is preferably thermally relaxed from about 1 to 35 percent, based on drawn filament length, before it is wound up so that it can be handled as a typical hard yarn.

The quenched, drawn and optionally relaxed filaments can then be collected by winding at a speed of 200 to about 3500 m/min, up to 4000 m/min at the winder 130 of FIG. 7 . Alternatively, if multifilaments are spun and quenched, the fibers may be bundled and optionally subjected to interlacing before being passed on winder 130 at, for example, up to 4000 m/min, for example at about 200 to about 3500 m/min speed range winding. Monofilament and multifilament yarns can be wound in the same manner on the winder 130 of FIG. 7 . After the multifilaments are spun and quenched, the tows can be bundled and optionally interlaced before being wound as is common practice in the art.

At any point after drawing, the bicomponent filaments can be dry- or wet-heat treated in a fully relaxed state to develop the desired elongation and recovery properties. Such relaxation can be accomplished during filament production, eg during the relaxation step described above, or after the filaments have been incorporated into a yarn or fabric, eg during scouring, dyeing or like treatments. Heat treatment in fiber or yarn form can be carried out using, for example, heated rolls or ovens or a jet-screen bulking step. Preferably, this relaxing heat treatment can be performed after the fiber is in the yarn or fabric so that it can be processed like a non-elastomeric fiber before then; however, if desired, it can also be heat treated and fully relaxed before Wound in high elongation fiber form. To achieve greater uniformity in the final fabric, the fibers can be uniformly heat treated and relaxed. The heat treatment/relaxation temperature may range from about 80°C to about 120°C if the heating medium is dry air; from about 75°C to about 100°C when the heating medium is hot water; and from about 101°C to about 115°C when heated When the medium is water vapor at superatmospheric pressure (eg, in an autoclave). Insufficient temperature may result in little or no heat treatment effect, while excessive temperature will melt the elastomeric core polymer. The heat treatment/relaxation step can usually be completed within seconds.

As noted above, the spinholes have a pattern corresponding to the desired cross-section of the fibers of the present invention, as described above, or are suitable for producing other bicomponent or bicomponent fibers. The spin holes may be cut by any suitable method, for example, by laser drilling, as described in US Pat. No. 5,168,143, drilling, electrical discharge machining (EDM) and punching, as known in the art. Spinning holes can be cut with a laser beam to achieve good control over the cross-sectional symmetry of the fibers of the present invention. The spin holes can be of any suitable size and can be cut to be continuous (pre-bonded) or discontinuous (post-bonded). Discontinuous spin holes can be obtained by drilling a number of small holes in a pattern that will allow the polymers to coalesce below the face of the spinneret and form the multi-winged sections of the present invention.

For example, filaments of the present invention can be made using prebonded spin packs as shown in Figures 8, 8A, 8B and 8C. In Figure 8, a side view of the stacked plate spinpack as shown in Figure 7 is given, with polymer flow in the direction of arrow F. The first plate in the spin pack was plate D of conventional design containing the pool of polymer melt. Plate D sits on metering plate C (shown in cross section in Figure 8C), which in turn sits on optional distribution plate B (shown in cross section in Figure 8B), which in turn sits on spinneret A (shown in cross section). The cross-sectional view is shown in Figure 8A), the latter is supported by the bottom plate E of the spinning pack. The metering plate C is aligned and in contact with the distribution plate B under the metering plate; the distribution plate is on the top of the spinning plate A and is aligned and in contact with it; although the spinning plate A has small through holes but lacks substantial cone holes; spinning The plate is in turn aligned and in contact with the spinneret base plate (E), which has larger holes than the spinneret holes. The alignment is such that the polymer fed into metering plate C can pass through distributor plate B, spinneret A and spinneret floor E to form fibers. Melt collection plate D, is a conventional plate used to feed the metering plate. The polymer melt collecting plate D and the spin pack bottom plate E are of sufficient thickness and rigidity that they can be securely compressed against each other to prevent polymer leakage from between overlapping plates of the spin pack. Plates A, B and C are thin enough so that the holes can be laser cut. Preferably, the holes in the spin pack floor (E) are flared, for example at a taper angle of about 45° to 60°, so that the nascent fibers do not touch the edges of the holes. It is also preferred that when polymer prebonding is desired, the different polymers may contact each other (prebond) less than about 0.30 cm, typically less than 0.15 cm, prior to fiber formation, so that metering plate C, optional distribution plate D, and The expected cross-sectional shape of the spinneret pattern E can be more accurately represented in the fiber. More precise specification of fiber cross-sections can also be achieved by means of hole-in-slab methods as described in U.S. Patent 5,168,143, wherein a multi-mode beam from a solid-state laser is reduced to a substantially single-mode beam (e.g., TM ₀₀ mode) and Focus on points with a diameter of less than 100 μm and 0.2 to 0.3 mm above the metal plate. The resulting molten metal is expelled from the lower surface of the metal plate by the pressurized fluid flowing coaxially with the laser beam. The distance from the top surface of the uppermost distribution plate to the face of the spin plate can be reduced to less than about 0.30 cm.

To produce filaments with any number of symmetrically distributed wing polymer segments, the same number of symmetrically arranged pores will be used in each plate. For example, in FIG. 8A , spinneret A is shown as a view in a plane perpendicular to the overlapping plate spinpack of FIG. 7 . Plate A in FIG. 8A consists of six wing spinning holes 140 connected to a central circular spinning hole 142 arranged symmetrically. Each wing spin hole 140 may have a different width 144 and 146 . FIG. 8B shows a complementary distribution plate B having a distribution hole 150 that tapers from a hole end 152 to an optional slot 154 connecting the distribution hole to a central circular hole 156 . Figure 8C shows a metering plate C including a metering hole 160 for wing polymer and a center metering hole 162 for core polymer. The polymer melt collecting plate D may be of any conventional design known in the art. The spin pack floor E has through holes that are large enough and taper outwards (for example, along 45-60°) so as to stay away from the path of the nascent filaments so that the filaments do not touch the walls of the holes, as shown in side views in Figures 7 and 8 shown. Overlapping plate spin packs, spin plates A-D are aligned with each other so that core polymer flows from polymer melt onto plate D, through central metering hole 162 of metering plate C and through six small spin holes 164, through Pass through the central circular spinning hole 156 of the distribution plate B, pass through the central circular spinning hole 142 of the spinning plate A and flow out through the large trumpet hole of the bottom plate E of the spinning assembly. At the same time, the wing polymer passes from the polymer melt collecting plate D through the wing polymer metering hole 160 of the metering plate C and through the distribution hole 150 of the distribution plate B (wherein if there is an optional slit 154, then this Here the two polymers come into contact with each other for the first time), pass through the wing polymer spin holes 140 of the spinneret A, and finally exit through the holes in the spin pack bottom plate E.

The spin pack of the present invention can be used in the melt extrusion of a variety of synthetic polymers to produce fibers. In the spin pack of the present invention, the polymer can be fed directly into the spinholes because the spinneret does not have a substantial counterbort. By devoid of substantial counterbores, it is meant that the length of any counterbores present (including any depressions connecting a plurality of spinholes) is less than about 60%, preferably less than about 40%, of the length of the spinholes. See Figure 9A, which shows a cross-section of a prior art spinneret; and Figures 9B and C, which show a cross-section of a spinneret according to the present invention. The multi-component polymer stream is directly metered into a specific point from the back inlet of the fiber-forming spin hole of the spinneret, eliminating the need for multiple polymer streams to be fed at a considerable time (or distance) away from entering the spin hole. When merging within channels, as is generally the case, the problem of polymer migration arises.

It may be useful to combine the functions of the two boards into one single board by making grooves on one or both sides of a single board and connecting the grooves by means of suitable through holes. For example, depressions, grooves, and dips can be cut (eg, by EDM) on the upstream side of the spinnerette and made to function as distribution channels, shallow grooves, insubstantial counter bores, and the like.

A wide variety of fibers comprising two or more polymers can be made using the spin packs of the present invention. For example, other bicomponent fibers and bicomponent fibers not disclosed and/or claimed herein may also be so made, including the cross-sections disclosed in US Pat. The resulting fiber sections can be, for example, side-by-side, eccentric sheath-core, concentric sheath-core, wing-and-core, wing-and-sheath-and-core, and the like. Additionally, the spin packs of the present invention can also be used to spin splittable or non-splittable fibers.

The spin pack of the present invention can be modified to obtain different multi-lobe fibers, for example, changing the number of orifice legs to obtain a different number of wings required, changing the slit size as needed to change the geometric parameters to produce different deniers per filament or yarns Thread count, or change according to the use requirements of various synthetic polymers. For example, in the embodiment of Figure 10 a thinner spin pack for making three-winged fibers is shown, as exemplified in Example 7 below. In FIG. 10A, the spinnerette is 0.015 inches (0.038 cm) thick and has pores machined through the full thickness of the stainless steel plate using laser methods disclosed herein in the form of three straight wings 140, each of two widths ( have lengths 144 and 146 respectively) and are arranged symmetrically about a center of symmetry 120° apart; there is no conical orifice above the spinning hole. Each wing 140 has a circumference of 0.040 inches (0.102 cm) from its tip to a central circular spinhole 142 with a diameter of 0.012 inches (0.030 cm) and a center coincident with the center of symmetry. Referring now to Figure 10B, a 0.010 inch (0.025 cm) thick distribution plate B is aligned coaxially from above the spinneret A such that every other distribution plate B wing spinner hole 150 is aligned with the spinneret A wing 140 ; Each wing spin hole 150 of distribution plate B is 0.1375 inches (0.349 cm) long from its tip to the center of symmetry. Metering plate C (FIG. 10C) is 0.010 (0.025 cm) inches thick and has a 0.025 inch (0.064 cm) diameter hole 160, a 0.015 inch (0.038 cm) diameter hole 162, and a 0.010 inch (0.025 cm) diameter center Hole 164. Plate C is aligned with distribution plate B so that, in use, wing polymer is fed from melt collecting plate D (see Figure 10) to hole 160, while core polymer is fed into holes 162 and 164 of distribution plate C, and then Fibers are formed from plate B assigned to plate A with the wings inserted into the core. There were no counterbores in spinneret A, and the total thickness of plates A, B, and C was only about 0.035 inches (0.089 cm).

In another spin pack embodiment, the spin pack floor E is not used (see Figure 8). This is an example in Example 8 below. In Figure 11A, spinneret A is 0.3125 inches (0.794 cm) thick and each spinhole has a 0.100 inch (0.254 cm) diameter cone and a 0.015 inch (0.038 cm) long capillary at the bottom of the cone. hole. As shown in FIG. 11A, each spinning hole in the spinneret A has six linear wing spinning holes 170, and the major axis centerline of each wing hole passes through the center of symmetry and extends from its tip to the central circular hole 172. The length of the circumference is 0.035 inches (0.089 cm). Length 174 from each wing tip to 0.015 inches (0.038 cm) is 0.004 inches (0.010 inches) wide; length 176 is 0.020 inches (0.051 cm) long and 0.0028 inches (0.007 cm) wide. The tip of each wing is cut into a rounded head with a radius half the width of the tip. Distributor plate B (see FIG. 11B ) was 0.015 inches (0.038 cm) thick and had six wing holes, each wing hole being centered over a corresponding counterbore in spinneret A and oriented so that Each of the wing holes in A aligns with the wing holes in plate A. Each wing hole 150 in plate B is 0.060 inches (0.152 cm) long and 0.020 inches (0.051 cm) wide, and its tip is a rounded tip with a radius of 0.010 inches (0.025 cm). The central hole 152 in plate B is 0.100 inches (0.254 cm) in diameter. Metering plate C (see FIG. 11C ) was also 0.015 inches (0.038 cm) thick. In plate C, hole 160 has a diameter of 0.008 inches (0.020 cm) and is 0.100 inches (0.254 cm) from the center of center hole 162, which connects the center holes of plates B and A and forms the fiber core. The non-elastomeric airfoil polymer is fed into holes 160 in plate C and flows through the airfoil holes of plates B and A to form the airfoils of fibers. The first contact of the wings with the core polymer is at the top of distribution plate B, 0.328 inches (0.833 cm) above the face of spinneret A where the fibers are extruded, and is 0.080 inches (0.203 cm) in diameter. Plate C is aligned with plate B such that plate C's six holes 160 are above the centerline of plate B's wing holes 150 . The plates are aligned so that the elastomeric core polymer fed into the holes 162 of plate C flows through the centre.

The invention will be illustrated by the following non-limiting examples. The following test methods were used in the Examples.

experiment method

The term post-boil elongation is technically synonymous with the following terms: "% elongation (percent elongation)", "recoverable elongation", "recoverable shrinkage" and "latent crimp". The term "irrecoverable shrinkage" is used generically with the following terms: "% shrinkage", "apparent shrinkage" and "absolute shrinkage".

The elongation properties (elongation after boiling, shrinkage after boiling and recovery from elongation after boiling) of the fibers prepared in Examples 1A, B, C and D were determined as follows. A skein of 5000 denier (5550 dtex) was wound on a 54 inch (137 cm) bobbin. Both sides of the looped skein are included in the total denier. The initial skein lengths at 2 g weight (length CB) and 1000 g weight (0.2 g/denier) (length LB) were measured respectively. The skeins were placed in water at 95°C for 30 minutes ("boiling") and the initial (after boiling) lengths were measured with a 2 g weight ( _initial length CA) and a 1000 g weight ( _initial length LA). After measuring the length under a weight of 1000 g, the length under a weight of 2 g was measured after 30 seconds (length CA _30s ) and after 2 hours (length CA _2h ). The shrinkage after boiling is calculated as 100x(LB-LA)/LB. The elongation percentage after boiling is calculated according to 100x(LA-CA@30s)/CA@30s. The recovery after boiling is calculated according to 100x(LA-CA _2h )/(LA-CA _initial ).

The unloading force test at 20% and 35% of available stretch is carried out according to the following procedure. A boiled 5000 (5550 dtex) total denier bicomponent fiber skein was prepared. Both sides of the looped skein are included in the total denier. An Instron tensile tester (Canton, MA) was used at 21°C and 65% relative humidity. The skein is placed in the grips of the testing machine with a spacing of 3 inches (76 mm) between the grips. The testing machine completes 3 "stretch-and-relax (load-and-unload)" cycles, each with a maximum force of 500 g (0.2 g/denier), and then measures the force of the third unload cycle. The effective denier (ie, the actual linear density at the test stretched state) was determined at 20% and 35% available elongation for the third unloading cycle. "20% and 35% usable elongation"means that the skein has relaxed 20% and 35%, respectively, from a force of 500 g in the third cycle. The unload force at 20% and 35% available elongation is reported in "mg/(effective) denier".

Flap-to-core detachment (detachment) of the fiber is measured by first winding a 5000 denier (5550 dtex) skein on a 1.25 m frame (the skein size includes both sides of the loop being formed). The skein was treated in an autoclave under steam conditions of 102°C for 30 minutes. Select a 20cm length single fiber from the skein and fold it in half once. The silk head of the formed loop is pasted together below with an adhesive tape, and the pasted silk loop is hung vertically on the hook. A weight of 1 gram per denier (50 g hanging from a 25 denier loop) was secured to the lower (taped) end of the loop. Lift the weight until the loop becomes loose, then lower it slowly to stretch the loop until full weight is applied. After 10 such cycles, the detachment of the loops was viewed under magnification and rated. The 3 samples were rated as follows:

0 = No wings/Visible core peeling along fiber

1 = Slight peeling observed at the bend of one or more knots

2 = Peeling is observed where the fiber rubs against the suspension hook

3 = Peeling started to occur (in small circles and only at a few spots)

4 = Small loops, indicating peeling along the entire fiber

5 = Extensive peeling (large circles along the entire length of the fiber)

The results of the 3 samples were averaged.

Determination of R ₁ and R ₂ : Two circles are drawn on the photomicrograph of the fiber cross section, one circle (R ₁ ) is the circumcircle around the approximate outermost extent of the core polymer and the other circle (R ₂ ) is the wing The approximate innermost degree inscribed circle of a polymer portion.

Example

Example 1

Each drawn fiber had a linear density of 26 denier (28.6 decitex) and was substantially radially symmetric. The properties after boiling are shown in Table 1.

Example 1A (comparative example)

Biconstituent fibers were spun using the apparatus shown in Figure 7 and the overlapping plate spin pack shown in Figure 8. The first polymer to be formed into the fiber core is introduced from 20 in FIG. 7 to the spin filter assembly 30 . The core polymer was polyetheresteramide (PEBAX ^™ 3533SN supplied by Atofina) and was metered in by volume to form a core of 51 wt% per fiber. From 22 in FIG. 7 , molten nylon copolymer is introduced into the spin filter pack 30 . The nylon copolymer forming the six wings is poly(1,6-hexanediamine-co-2-methyl-1,5-pentanediamine) in which the hexamethylene moiety is derivatized with 80 mol% diamine Partial form exists. There was no apparent core insertion into the wing or wing insertion into the core (R ₁ /R ₂ =1.09).

The pre-bonded spin pack consisted of overlapping plates A-E, a side view of which is shown in Figure 8. The spinning holes are cut through the 0.015 inch (0.038cm) thick stainless steel spinning plate A, and become 6 wings arranged symmetrically at 60° around the center of symmetry, according to the method described in US Patent No. 5,168,143. As shown in FIG. 8A, each wing spin hole 140 is a linear hole with its major axis centerline passing through the center of symmetry and having a circular spin hole 142 (0.012 inch [0.030 cm] in diameter) circumference of 0.049 inches ( 0.124cm), the origin of the radius of the central circular spinning hole is the same point as the center of symmetry. The inlet of the spinning hole does not have a cone hole. The wing length 144 from the tip to 0.027 inches (0.069 cm) has a width of 0.0042 inches (0.0107 cm); the remaining 0.022 inches (0.056 cm) of length 146 has a width of 0.0032 inches (0.0081 cm). Each wing is cut at the tip into a circle with a radius of half the width. 0.015 inch (0.038 cm) thick distribution plate B (FIG. 8B) was aligned with spinneret A (FIG. 8A) such that its distribution orifices matched the spinneret holes in spinneret A. The six wing spinning holes 150 of Plate B were 0.094 inches (0.239 cm) long and 0.020 inches (0.051 cm) wide, and their wing tips were rounded with a radius half their width. As shown in Figure 8B, each of the six wing spinning holes 150 of distribution plate B tapers to a circular (0.006 inch [0.015 cm] cm) long in the form of a slit 154 extending to a central hole 156. The diameter of the central hole 156 in the plate is 0.0125 inches (0.032 cm). A slot 154 connects the central hole to one end of each wing distribution hole. Metering plate C was 0.010 inches (0.025 cm) thick (see Figure 8C). Each metering hole is centrally arranged above the centerline of the long axis of the distribution plate B wing or above the center of symmetry. The center metering hole 162 and one hole 160 in each wing are both 0.010 inches (0.025 cm) in diameter; the center of hole 160 is 0.120 inches (0.305 cm) from the center of hole 162 . Feed to the central metering orifice is filtered molten elastomeric polymer from a conventional melt collecting plate D (see Figure 7) and forming the core element in the final fiber. The outer six metering holes 160 of plate C are fed non-elastomeric polymer from melt collecting plate D which will become the polymer wings. The large holes (typically, 0.1875 inch (0.4763 cm) diameter) in the spin pack floor E (see Figure 8) were aligned with the spin holes in spin pack A and diverged at a 45° cone angle. Spinning plate A, distribution plate B and metering plate C are sandwiched between melt collecting plate D and spinning assembly bottom plate E, as shown in FIG. 8 . Typically, Panel E is 0.2-0.5 inches (0.4-1.3 cm) thick; Panel D is 0.02-0.03 inches (0.05-0.08 cm) thick.

There were no counter holes in spinneret A, and the combined thickness of plates A, B, and C was only about 0.040 inches (0.102 cm). The wings and core polymer first contact each other just above distribution plate B so that they are prebonded to each other approximately 0.076 cm (0.038 cm distribution plate + 0.038 cm spinneret) prior to fiber formation.

The nascent monofilaments 40 (see FIG. 7 ) are cooled to solidify under the action of flowing air 50 and about 5 wt % (based on the fiber) of a finish comprising silicone oil and metal stearate is applied at 60 . The fiber proceeds to the drafting zone between feed roll 80 and draft roll 90, with several turns on each roll. The speed of drafting roll 90 is 4 times that of feeding roll 80 (the speed of the latter is 350 m/min), so as to achieve a draft ratio of 4 times. Subsequently, the fiber is subjected to 6psi (0.87kPa) water vapor treatment in the chamber 110; the winder 130 is operated at a speed 20% lower than that of the draft roller 90, so that the fiber is partially (20%) relaxed, thereby reducing Final fiber shrinkage. The drawn and partially relaxed fiber 120 was wound on a winder 130 and had a linear density of 26 denier (29 dtex).

Example 1B (comparative example)

A fiber with 6 wings consisting of poly(1,6-hexanediamine-co-2-methylpentamethylenediamine) was spun substantially as in Example 1A, wherein the hexamethylene moiety was present in an amount of 80 mol % is present, the core is made of PEBAX ^TM 3533SN, the difference is that 5 wt% is added to the wing polymer, based on the total wing polymer, nylon 12 [poly(laurolactam) "N12"] ( Rilsan ^(R) AMNO, supplied by Atofina) to aid attachment of the wings to the core. The wing/core weight ratio is 48/52; R ₁ /R ₂ is 1.05.

Example 1C (invention)

According to a method similar to Example 1A, a compound having 6 poly(1,6-hexanediamine-co-2-methylpentamethylenediamine) (20mol% 2-methylpentamethylene moieties, Fibers based on diamine derived moieties) wings and PEBAX ^™ 3533SN core (flexural modulus 2800 psi (19,300 kPa)), except that metering plate C has another set of holes 164 (as shown in Figure 8C) , one per wing, on wing centerline, 0.005 inch (0.013 cm) diameter per hole, 0.0475 inch (0.121 cm) from the center of symmetry of the hole. These additional holes and the central hole are fed molten polymer from the same melt pool to form the core and the "protruding core" elements within the wings. As a result, the wings are inserted by the core polymer (R ₁ /R ₂ =1.6, estimated from the ratio of similarly prepared fibers), improving the attachment of the wings to the core. The cross-section of the fiber is basically shown in Figure 2.

Example 1D (invention)

The fibers were spun essentially as in Example 1C, but with the addition of 5 wt% nylon 12 [poly(laurolactam)] (Rilsan ^(R) AMNO) cohesive additive in the wings. The wing portion of the fiber is inserted by the core polymer (R ₁ /R ₂ =1.5), improving the attachment of the wing to the core. The cross-section of the fiber is basically as shown in FIG. 2 .

Table 1 Example 1A (comparative example) Example 1B (comparative example) Example 1C (invention) Example 1D (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+5wt%N12 6/MPMD(80/20)-6 6/MPMD(80/20)-6+5wt%N12 core polymer PEBAX ^™ 3533SN PEBAX ^™ 3533SN PEBAX ^™ 3533SN PEBAX ^™ 3533SN Elongation percentage after boiling 67 92 103 70 Shrinkage percentage after boiling 31 19 twenty two twenty one Stripping grade 3.8 1.2 0.2 0.0

These data show that the fiber is well suited for hosiery and apparel applications. The fiber's superior performance in wing-to-core adhesion is reflected in the peel data. Fibers of the present invention may have a peel rating of less than about 1.0. Additionally, the data also show that the use of tackifiers such as N12 in the wing polymer is beneficial.

Example 2A

A bicomponent yarn of the present invention consisting of three filaments was spun essentially as in Example 1D. The difference is that each plate has 5 holes for wing polymer arranged symmetrically every 72°, so each fiber has 5 wings. The polymer in the 5 wings is 95 wt% polycaprolactam (3.14 IV, manufactured and supplied by DuPont (Brazil)) with 5 wt% nylon 12 additive. The wing/core ratios were changed as shown in Table 2A. The finishing agent is a mixture of coconut oil, quaternary ammonium, water and non-ionic surfactant, applied in an amount of 2 wt%, based on fiber. The feed roll speed was 420 m/min; the drawn fibers received 15% relaxation before winding. The cross section was substantially as shown in Figure 2; R ₁ /R ₂ was about 1.4 and the drawn fiber was 23 denier (25 dtex).

The wing/core ratio was varied and the percent elongation after boiling was determined as described above.

Table 2A Wing/Core Weight Ratio Elongation percentage after boiling 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 2A show that, in the fibers of this example, higher post-boil elongations are obtained at wing/core weight ratios of less than about 50/50, which is preferred when the inventive fibers are not used with companion fibers. Lower wing/core ratios (eg, from about 20/80 to about 40/60) are generally preferred when used with the fibers of the present invention with companion fibers to increase recovery in the combined yarn.

Example 2B

The sock durability, sheer thinness and elongation were evaluated as a function of the overall density (denier, dtex) of the wings. Fibers from Example 2A were knitted into socks. No other fibers are used. The overall denier and airfoil-to-core volume ratio of the fibers were varied. A panel of judges rated the socks for: a) fastness based on abrasion life, b) sheer lightness aesthetic quality (using 5 strands of 10 denier LYCRA ^™ spandex for a total of 7 denier (8 decitex) ) nylon 6-6 fiber-coated partial yarn knitted in a similar way as a reference standard), and c) percent elongation after boiling. If it is more than 7 days, the fastness is rated as acceptable; if it is equal to the reference standard, then the transparency and thinness are acceptable; if it is between 40% and 120%, and the local swelling and bloomer shape of the socks are eliminated ("ride-down") ”), the percent elongation is considered acceptable. In Table 2B, the asterisked (*) and bold numbers indicate the preferred denier (dtex) and wing/core ratio according to these three criteria. The numbers given in the table are the total decitex of the wings of each fiber.

Table 2B Wing/Core Weight Ratio Wing/Core Weight Ratio Wing/Core Weight Ratio Wing/Core Weight Ratio Wing/Core Weight Ratio Wing/Core Weight Ratio total score 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 twenty two 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

As the total dtex exceeds about 33, the sheer lightness of the sock decreases. Fastness begins to decline as the total decitex drops below about 22 and the wing total decitex drops below about 11. As the airfoil/core weight ratio exceeds about 50/50, the percent elongation begins to decrease (as previously shown in Example 2A).

According to the results of the test, it can be concluded that the preferred bicomponent fibers of the present invention may have a total density between about 22 and 33 decitex, a total decitex of the wing portion of at least about 11, and between 35/65 and 50/ Wing to core weight ratio of 50.

Example 3A

A bicomponent fiber of the present invention was spun essentially as described in Example 2A, except that 4 wt% (based on fiber) of a polysiloxane-based finish (as described in U.S. Patent No. 4,999,120) was applied instead of Example 2A. For finish 2A, the fibers were relaxed 20% prior to winding, and 3 psi (20.7 kPa) of water vapor was used during the relaxation step. The airfoil/core/bulge core weight ratio is 38/53/9 and R ₁ /R ₂ is about 1.4. Figure 5 is a micrograph of a cross section of a fiber which is 32 denier (36 dtex, freshly spun) and has 108% boil elongation, 24% boil shrinkage and 92% boil recovery.

Example 3B

The fibers of Example 3A were knitted into sock blanks on a commercial knitting machine using a mechanical double-covered spandex leg weave in a typical configuration per course. The machine is a MATEC HSE 4.5, weaves at about 700rpm in the thigh area and 800rpm in the ankle and is configured in size F. Knit each leg blank for about 2 minutes. The leg yarn is fed into the machine in the same way as hard yarns are normally: no electronic tensioner is used. The tubular blank is post-processed by drum steaming under atmospheric pressure for 30 min. The garments were then heat set at 102°C for 4 s using standard industrial automated autoclave sock plate heatsetting equipment, followed by drying at 95°C for 30 s. The heat-set fabric length is chosen to be as small as possible while keeping the fabric wrinkle-free. Garments are dyed with standard acid dyes at 98°C for 45 minutes, and then heat-set using the same size sock plate and conditions.

The obtained fabric has an unexpectedly high thermal conductivity of 3.38×10 ⁻⁴ w/cm-°C.

Example 4

A three-filament bicomponent yarn of the present invention was prepared on the apparatus shown in FIG. 7 with polyester wings and a polyetherester core. The core polymer of Fiber 4A was ^HYTREL® 3078 polyetherester elastomer (trade name of DuPont; flexural modulus 4000 psi (27,600 kPa). The core polymer of the fibers of Example 4B and Example 4C was a polyetherester elastomer body, with poly(tetramethylene-co-2-methyltetramethylene ether) glycol soft block and 1,4-butylene terephthalate (4G-T) hard block, basically Prepared as described in U.S. Patent 4,906,721. The addition of 3-methyltetrahydrofuran in the copolyether diol is 9 mol%, the number average molecular weight of the diol is 2750, and the molar ratio of 4G-T to copolyether diol is 4.6 : 1. In Table 4, this polymer is labeled as "2MePO4G:4G-T". The wing polymer in the fibers of Examples 4A and 4B is poly(1,4-butylene terephthalate) ( 4G-T, Crastin® ⁶¹²⁹ ; trade name of DuPont; flexural modulus 350,000 psi (2.4 million kPa)), in fiber 4C, it is poly(1,3-trimethylene terephthalate) (3G -T). 3G-T is made of 1,3-propanediol and dimethyl terephthalate in a two-vessel process with 60 ppm (based on the polymer) tetraisopropyltitanium, ^Tyzor® TPT (commercial product of DuPont) name) was prepared as a catalyst. In the transesterification vessel, at 185° C., molten DMT was added to 3G and the catalyst, and then the temperature was raised to 210° C. while continuously removing methanol. The intermediate product obtained was transferred to the polycondensation vessel, Here, the pressure is reduced to 1mbar (10.2kg/cm ² ), and the temperature is raised to 255°C. When the required melt viscosity is reached, the pressure is increased, and then the polymer is extruded, cooled and cut into slices. The slices are in operation In a drum dryer at 212°C, further polymerize to an intrinsic viscosity of 1.04dl/g in a solid state.The spinning assembly and spinning conditions used by each fiber of this example are basically the same as those of Example 2A. The difference is that in No polymer additive was added to the wings, the wings were 40% by weight of the entire fiber, 4% by weight (based on the fiber) of the finish described in Example 3A was applied, and the fibers were relaxed with steam at 3 psi pressure (20.7 kPa) prior to winding 20%.Fiber properties are shown in Table 4.

Table 4 Example 4A Example 4B Example 4C Denier (dtex) 25(27.5dtex) 24(26dtex) 27(30dtex) wing polymer 4G-T 4G-T 3G-T core polymer HYTREL ^™ 3078 2MePO4G: 4G-T 2MePO4G: 4G-T R ₁ /R ₂ 1.6 1.6 1.6 Elongation percentage after boiling 60 100 76 Shrinkage percentage after boiling 10 12 12 percent recovery after boiling 85 94 89 Unloading force @ 20% available elongation 15 18 17 Unloading force @ 35% available elongation 3 5 1

The fiber of Example 4B had a peel rating of 0.0. The sheer skimpy sock blanks woven from the fibers of Examples 4A, 4B and 4C had a uniform appearance and good elongation and recovery after steam heatsetting, dyeing and finishing.

Example 5A

A kind of bicomponent fiber of the present invention is spun by the polymer of Example 1D and finishing agent and adopts the equipment shown in Figure 7 and the spinning assembly and spinning conditions of Example 3A, and the difference is that 13wt% finishing agent is used, and the fiber weight is benchmark. The wing and core polymers first contact each other about 0.076 cm before spinning into fibers.

The core was inserted into the wing to obtain a wing/core/protruding core weight ratio of 39/51/10 (R ₁ /R ₂ was about 1.5). The linear density of the fibers is 20 denier (22 dtex); the percent elongation after boiling, 100%; the percent shrinkage after boiling, 23%; and the recovery after boiling, 94%.

Example 5B

Four fibers from Example 5A were formed into bicomponent yarns by air jet interlacing. A 3/1 weave was woven on a SULZER RUTI 5100 (air-jet loom) with the air-jet interlaced bicomponent yarn used as the weft at a weft density of 38 yarns/cm (96 wefts/inch) and 44 denier (48 dtex)/34 filaments TACTEL ^™ (DuPont trade name) model 6342 nylon as the warp yarn, with a warp density of 48 per centimeter (121 per inch). The woven fabric was subjected to the following post-processing: steam relaxation at 115 °C; MCF jet scouring at 70 °C; MCF jet dyeing at 100 °C for 60 min using standard acid dyes for nylon; and heat setting at 190 °C for 30 s. The fabrics were not bulky after air drying, but were smooth and wrinkle-free, and they exhibited good elongation and recovery as well as excellent stiff fiber hand and visual aesthetics. Relaxed finished woven fabrics have the following properties:

Basis weight = 3.29 ounces per square yard (112g/m ² )

Thickness = 0.079 inches (2mm)

Weft density = 160 per inch (63/cm)

Warp density = 208 per inch (82/cm)

A piece of fabric 5 cm wide by 10 cm long can be stretched 40% by hand, after which it can recover more than 95%.

Example 6

This example illustrates the use of a full thickness spinneret for making fibers of the invention. Using the same prebonded spin pack as in Example 1C, the difference is that the bottom plate E is replaced by a 0.3125 inch (0.794 cm) thick spinneret (Fig. Long) had the same arrangement pattern, size, axial alignment and radial orientation as the spinholes in spinnerette A (FIG. 8A) and had a conical orifice of 0.1406 inch (0.357 cm) diameter. The wings and core polymer first contact each other at about 0.87 cm (0.794 cm spinneret + 0.038 cm plate A + 0.038 cm plate B) before fiber formation. A 25 denier (28 dtex) bicomponent fiber is spun with six poly(adipyl 1,6-hexamethylenediamine-copoly-2-methylpentamethylenediamine) in which hexamethylene The part exists with 80mol% diamine derivatization part (prepared by conventional method, relative viscosity 90), the wings of composition, and the core of PEBAX 3533SN polyether ester amide, adopt equipment as shown in Figure 7, and 4 times of drafting ratio, And coiled at 1400m/min. The airfoil/core/bulge core weight ratio was 45/48/7 and R ₁ /R ₂ was about 1.4. In fibers so spun, the core is inserted into the wings but without the generally preferred necked section, as shown in FIG. 3 .

Example 7

This example illustrates a biconstituent fiber with three wings inserted into the core, and also illustrates the application of a thin spin pack for making fibers. The wing polymer was poly(hexamethylene lauramide) (intrinsic viscosity 1.18, Zytel ^(R) 158, a DuPont trade name); the core polymer was PEBAX 3533SA polyetheresteramide. A yarn of 70 denier (78 dtex) was spun from 10 filaments at a spinneret temperature of 265°C, with a wing/core volume ratio of 40/60. A prebonded spin pack roughly as shown in Figure 10 was used, but the individual plates were different from those of the previous examples. Stainless steel spinnerette A as shown in Figure 10A was 0.015 inches (0.038 cm) thick, wherein the through-holes were cut using the method of Example 1A, in the form of 3 straight wings, each wing having two widths and spaced along the center of symmetry. 120° symmetrical arrangement; there is no taper hole above the spinneret. Each wing 140 is 0.040 inches (0.102 cm) long (in FIG. length 146). Referring now to Figure 10B, a 0.010 inch (0.025 cm) thick distribution plate B is aligned coaxially from above the spinneret A such that every other distribution plate B wing spinner hole 150 is aligned with the spinneret A wing 140 ; Each wing spin hole 150 of distribution plate B is 0.1375 inches (0.349 cm) long from its tip to the center of symmetry. Metering plate C (FIG. 10C) is 0.010 (0.025 cm) inches thick and has a 0.025 inch (0.064 cm) diameter hole 160, a 0.015 inch (0.03 cm) diameter hole 162, and a 0.010 inch (0.025 cm) diameter center Hole 164. Plate C is aligned with distributor plate B so that, in use, wing polymer is fed from melt collecting plate D (see Figure 10) to hole 160, while core polymer is fed into holes 162 and 164 of distributor plate C, which in turn is supplied by Sheet B is assigned to sheet A to form filaments with the wings inserted into the core. There were no counterbores in spinneret A, and the total thickness of plates A, B, and C was only about 0.035 inches (0.089 cm). The yarn was drawn 3.5 times under the condition of drafting roller speed 1225m/min, then relaxed in the steam jet at atmospheric pressure, and finally wound up at a speed of 1045m/min. When steamed in a relaxed state, the yarn develops helical twists with high elongation and recovery. A photomicrograph of the cross-section of the fiber produced in this example is shown in FIG. 13 .

Example 8

This example illustrates the use of a conventional thickness spinnerette in the manufacture of fibers of the present invention.

Example 1A was repeated but with the difference that spin pack bottom plate E (see Figure 8) was not used. Spinneret A was 0.3125 inches (0.794 cm) thick with each spinhole having a 0.100 inch (0.254 cm) diameter cone and a 0.015 inch (0.038 cm) long capillary at the bottom of the cone. As shown in FIG. 11A, each spinning hole in the spinneret A has six linear wing spinning holes 170, and the major axis centerline of each wing hole passes through the center of symmetry and extends from its tip to the central circular hole 172. The length of the circumference is 0.035 inches (0.089 cm). Length 174 from each wing tip to 0.015 inches (0.038 cm) is 0.004 inches (0.010 inches) wide; length 176 is 0.020 inches (0.051 cm) long and 0.0028 inches (0.007 cm) wide. The tip of each wing is cut into a rounded head with a radius half the width of the tip. Distributor plate B (see FIG. 11B ) was 0.015 inches (0.038 cm) thick and had six wing holes 150 each centered over a corresponding counterbore in spinneret A and oriented to ensure the Each wing hole 150 is aligned with a wing hole 170 in plate A. As shown in FIG. Each wing hole 150 in plate B is 0.060 inches (0.152 cm) long and 0.020 inches (0.051 cm) wide, and its tip is a rounded tip with a radius of 0.010 inches (0.025 cm). The central hole 152 in plate B is 0.100 inches (0.254 cm) in diameter. Metering plate C (see FIG. 11C ) was also 0.015 inches (0.038 cm) thick. In plate C, holes 160 are 0.008 inches (0.020 cm) in diameter and 0.100 inches (0.254 cm) from the center of central hole 162, which is 0.080 inches (0.203 cm) in diameter. Plate C is aligned with plate B such that plate C's six holes 160 are above the centerline of plate B's wing holes 150 . The plates are aligned so that the elastomeric core polymer fed into the holes 162 of plate C flows through the center of plates B and A and forms the core of the fiber. The non-elastomeric airfoil polymer is fed into the holes 160 of plate C and passed through the airfoil holes of plates B and A to form the airfoils of the fibers. The first contact of the wings with the core polymer occurs at the top surface of distributor plate B, which is 0.328 inches (0.833 cm) above the face of spinnerette A where the fibers are extruded.

The spinneret temperature was 247°C. A 14-filament yarn was spun and a 5 wt% polyether ester-based finishing agent was applied to replace the previously used finishing agent. The yarn was then relaxed by 15% (based on the drawn yarn length) before winding. ). The drawn and partially relaxed yarn had a linear density of 75 denier (83 dtex) and R ₁ /R ₂ was 1.20. A photomicrograph of the cross-section of this fiber is shown in FIG. 6 .

While the present invention has been described in detail, it is to be understood that the foregoing description is by way of example only and is intended to illustrate the invention and its preferred embodiments. Through routine experimentation, it will be apparent to those skilled in the art that various modifications and changes can be made without departing from the spirit of the invention.

Claims (20)

1. An extensible synthetic polymer fiber comprising: an axial core comprising a thermoplastic elastomeric polymer, and a plurality of wings attached to the core comprising a thermoplastic non-elastomeric polymer, wherein the wing polymer or the core is polymerized At least one of the objects protrudes into another polymer. 2. The fiber of claim 1, wherein the core comprises an outer radius _R1 and an inner radius _R2 , and _R1 / _R2 is greater than about 1.2. 3. The fiber of claim 2, wherein R ₁ /R ₂ is in the range of about 1.3 to about 2.0, the weight ratio of the non-elastomeric wing polymer to the elastomeric core polymer is in the range of about 10/90 to about 70/30, and The elongation after boiling is at least about 20%. 4. The fiber of claim 1, wherein the protruding polymer includes an enlarged distal segment and a constricted segment, the latter connecting the distal segment to the remainder of the protruding polymer, thereby forming at least one constriction therein. 5. The fiber of claim 1, wherein each wing is of substantially the same size and is arranged substantially symmetrically about the axial core. 6. The fiber of claim 1, wherein the non-elastomeric polymer is selected from the group consisting of polyamides, non-elastomeric polyolefins and polyesters, and the elastomeric polymer is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyester elastomers, thermoplastic polyolefins, thermoplastic Polyesteramide elastomers and thermoplastic polyetheresteramide elastomers. 7. The fiber of claim 1, further comprising an additive added to the wing polymer for improving the adhesion of the wing to the core, wherein the fiber has a peel rating of less than about 2.5. 8. The fiber of claim 7, wherein the non-elastomeric polymer is selected from the group consisting of a) poly(hexamethylene adipamide) and its copolymers with 2-methylpentamethylenediamine, and b) polycaprolactam, and the elastomer The polymer is polyetheresteramide. 9. A garment comprising the fiber of claim 1. 10. An extensible synthetic polymer fiber comprising: an axial core comprising a thermoplastic elastomeric polymer, and a plurality of wings attached to the core comprising at least one thermoplastic non-elastomeric polymer, wherein the fiber has a low At a peel rating of about 1 and an elongation after boil of at least about 20%. 11. A melt spinning process for spinning continuous polymer fibers comprising: passing a melt comprising a non-elastomeric polymer and a melt comprising an elastomeric polymer through a spinnerette to form a drawable synthetic polymer fiber having a plurality of wings attached to a core, wherein the wing polymer or the core At least one of the polymers protrudes into the other polymer; the fibers are quenched after exiting the spin hole to cool the fibers, and the fibers are collected. 12. The method of claim 11, including the additional step after quenching: thermally relaxing the fiber so that it exhibits at least about 20% post-boil elongation. 13. The method of claim 12, wherein the thermal relaxation step is carried out under the following conditions: with dry air, hot water or superatmospheric pressure steam as the heating medium; temperature: at about 80° C. when the heating medium is the dry air ~120°C range, when the heating medium is the hot water, it is about 75°C to about 100°C, or when the heating medium is the superatmospheric pressure steam, it is about 101°C to about 115°C. 14. The method of claim 11 including the additional step of relaxing the fibers after quenching from about 1 to about 35 percent, based on the fiber length before relaxation. 15. A spin pack for melt extrusion of first and second synthetic polymers to produce fibers, comprising: a metering plate comprising a first set of holes adapted to receive a first polymer melt and a second set of holes adapted to receive a second polymer melt; a spinneret aligned with and in contact with the distribution plate, the spinnerette having a spin hole and having a cone length less than about 60% of the spin hole length; and a spinneret floor having holes larger than the spinneret holes aligned with and in contact with the spinneret; The plates are aligned such that the first and second polymers are fed to the metering plate, flow through the distribution plate, the spinneret and the spinneret floor to form fibers. 16. The spin pack of claim 15, wherein the spinneret cone length is less than about 40% of the spinhole length. 17. The spin pack of claim 15, wherein the spinneret floor opening is a bell mouth. 18. The spin pack of claim 15, wherein the holes and the spinholes are laser cut. 19. The spin pack of claim 15, further comprising a distribution plate. 20. The spin pack of claim 19, wherein the maximum combined thickness of both the distribution plate and the spinneret is less than about 0.3 cm.

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