JP6151233B2 - Fusion two-component spandex - Google Patents

Description

Includes multicomponent elastic fibers produced by solution spinning processes, such as spandex spinning, to contain polyurethaneurea and polyurethane compositions, the fibers comprising at least two distinct regions with definable boundaries The polyurethaneurea or polyurethane composition is contained in at least one region having a cross-section and defined by the boundary of the cross-section. One region of the fiber contains an additive for improving the fusion property, which improves the adhesion with itself or the substrate.

Polyurethane or polyurethaneurea (PU or PUU) elastic yarns have great elongation,
Products showing good recovery from tension and made from them, such as weft knitting, warp knitting, woven fabrics,
Good compatibility can be given to non-woven fabrics and other textile products. However, PU or P
In products containing UU elastic yarns, repeated drawing, scratching or cutting often causes wire, fraying and rolling problems. Such problems include wire-like cracks, which can create gaps, and the elastic yarn can slide out at the cutting edges, bare, and fray, resulting in fabric rollup. Can occur, thereby degrading the uniformity and appearance of the product. The phenomenon of the PU or PUU elastic yarn being pulled away from the seam under repeated stretching during the cutting and sewing process easily occurs, thereby losing the stretchability of the fabric, which is the so-called “
“Slip in” or slip of seam. Such effects also occur in elastic yarns other than PU or PUU yarns, which are particularly important for PU or PUU elastic yarns because they have a large stretch capacity. In addition, certain products,
Particularly in sock applications, high deformation efficiency by steam or heat is required.

Considerable efforts have been made to develop PU or PUU elastic yarns that can be fused with heat and deformed with steam. Certain highly fusible polyurethane elastic filaments are disclosed in US Pat. Nos. 5,047,036 and 5,200,086, which produce an isocyanate-terminated prepolymer formed by the reaction of a polyol and a diisocyanate by the reaction of a polyol, a diisocyanate and a low molecular weight diol. It was made by melt spinning a polymer synthesized by reacting with a hydroxyl-terminated prepolymer. The melting point of the fusible PU filament is 180 ° C.
It is as follows. The PU filaments were subjected to a dry heat treatment at 150 ° C. for 45 seconds in a stretched state of 100%, so that they could be fused with each other or with other elastic or inelastic filaments at the point of overlap. However, such PU filaments have a low melting point and, therefore, do not provide satisfactory heat resistance to creep under normal consumer use, thereby causing the garment to sag like a bag.

There is a need for an improved spandex yarn that has the ability to fuse during garment manufacturing, deform with steam, and exhibit superior stretch resilience to overcome one or more of the disadvantages of currently available fibers. ing.

US Patent Application Publication No. 2006 / 0030229A1 US Patent Application Publication No. 2008 / 0032580A1

The present invention relates to multicomponent spandex fiber products and methods of manufacture having improved functionality. Includes solvent-spun polyurethane or polyurethaneurea that can be manufactured in a two-component spinning process and that exhibits greater elongation / recovery performance and heat recovery capability, with the addition of a highly fusible additive, resulting in fusion Produces a fusible yarn that is suitable for use in applications, for example, showing that the wire and yarn are prevented from slipping and have high adhesion.

The fibers in some embodiments comprise a cross section, wherein at least a first region of the cross section includes elastic polyurethane or polyurethane urea or mixtures thereof and elastic polyurethane or polyurethane urea or mixtures thereof and at least It is an elastic multi-component solution spun fiber that also includes a second region containing one type of fusogenic additive.

The fiber may have one or more filaments, such as a single monofilament, a double (two filaments), three filaments, and the like. When the fiber has two or more filaments, each filament may include a multi-component cross section having two or more regions.

In another embodiment, the fabric includes a cross section, wherein at least a first region of the cross section includes at least one elastic polyurethane, polyurethaneurea composition, or a mixture thereof, and at least one elastic polyurethane. A fabric containing elastic multicomponent solution spun fibers that also includes a polyurethane urea composition or mixture thereof and a second region containing at least one fusogenic additive.

Also included is a method for producing a fusible elastic multicomponent solution spun fiber, which comprises:
(A) preparing first and second polymer solutions;
(B) bringing the solution together through a distributor plate and an orifice to produce a filament having a cross-section;
(C) extruding the filaments through a common capillary and (d) removing solvent from the filaments;
Including, where
The cross section includes a boundary between the polymer solutions;
Each of the first and second polymer solutions independently contains an elastic polyurethane, polyurethaneurea or a mixture thereof, and the second polymer solution contains an additive for improving fusion; And the fusible elastic multicomponent solution spun fiber includes a cross section having a plurality of regions, the first polymer solution corresponds to the first region of the cross section, and the second polymer solution comprises This corresponds to the second region of the transverse section.

The fibers in a further aspect comprise a cross section, wherein at least a first region of the cross section comprises an elastic polyurethane or polyurethaneurea or a mixture thereof and an elastic polyurethane or polyurethaneurea or a mixture thereof and a melting point of about 100 ° C
A second region containing at least one fusogenic additive comprising at least one low-melting polyurethane at from about 180 ° C. to about 180 ° C. and about 19 in the first region.
A fiber containing an elastic multicomponent solution spun fiber containing an elastic polyurethane having a high melting point from 0 ° C. to about 250 ° C.

FIG. 1 shows examples of fiber cross sections that can be achieved in some embodiments. FIG. 2 is a schematic view showing a cross section of a spinneret according to some embodiments. FIG. 3 is a schematic view showing a cross section of a spinneret according to some embodiments. FIG. 4 is a schematic view showing a cross section of a spinneret according to some embodiments. FIG. 5 is a diagram showing the results of differential scanning calorimetry shown by the fibers of Example 1. Scans were performed at 10 ° C / min from -100 ° C to 350 ° C. FIG. 6 is SEM micrographs taken of several embodiments of the fusion yarn.

Detailed Description of the Invention
Definitions As used herein, the term “multicomponent fiber” exists continuously along at least two distinct distinct regions, ie, the length of the fiber, with distinct boundaries in addition to differing compositions. It means a fiber having two or more regions having different compositions. This is in contrast to polyurethanes or polyurethaneurea mixtures in which two or more compositions are combined to produce fibers that do not have distinct boundaries along the length of the fiber. The terms “multicomponent fiber” and “multicomponent fiber” are synonymous and are used interchangeably herein.

The term “different compositions” is defined as two or more compositions containing different polymers, copolymers or mixtures, or two or more compositions containing one or more different additives, The polymers contained in these compositions may be the same or different. If two comparable compositions contain different polymers and different additives, they are also “different in composition”.

The terms “boundary”, “two or more boundaries” and “boundary region” are terms used to describe the point of contact between different regions of the multicomponent fiber cross section. The point of contact is “well defined” so that the composition of the two regions does not overlap or is minimally overlapping. If an overlap exists between the two regions, the boundary region will contain a mixture of the two regions. Such a mixed region may be a uniformly mixed discrete portion with a separate boundary between the mixed boundary region and each of the other two regions. Alternatively, such a boundary region may have a composition of the second region that is adjacent to the second region from the high concentration portion of the composition of the first region that is adjacent to the first region. There may be a gradient leading to the high concentration part.

As used herein, a “solvent” is an organic solvent such as dimethylacetamide (DMAC
), Dimethylformamide (DMF), N-methylpyrrolidone and the like.

The term “solution spinning” as used herein includes the formation of fibers from solution in either a wet spinning or dry spinning process, both of which are common techniques for fiber production. It is.

Low melting point polyurethane (PU) with good steam deformability and excellent adhesive properties
The composition (T _m <180C) typically provides poor creep resistance, low strength and poor stretch recovery. Moreover, such low melting PU compositions are not well suited for fiber molding processes and high temperature fiber product processing requirements. In the present invention, excellent stretch and resilience based on solution spun polyurethane / polyurethane urea compositions and low melting point adhesive formulations are combined in a multicomponent fiber structure, such as a bicomponent fiber structure.

The properties of the polyurethane block copolymer depend on the phase separation of the urethane and polyol segments such that the hard urethane domain acts as a crosslink in the soft segment matrix. The urethane domain is governed by both the content and nature of the chain extender selected. Commercially important diol chain extenders include, but are not limited to:
Ethylene glycol, 1,3-propanediol (PDO), 1,4-butanediol (
1,4-BDO or BDO) and 1,6-hexanediol (HDO).
All of such diol-based chain extenders provide good phase separation resulting in polyurethanes that form well defined hard segment domains, and all but ethylene glycol are suitable for use in thermoplastic polyurethanes. Thereafter, the resulting urethane undergoes undesirable degradation when the hard segment concentration is high. Table 1 lists typical hard segment melting ranges exhibited by polyurethanes derived from several common chain extenders. Processing temperature 20
A temperature higher than 0 ° C. is not preferable for general TPU compositions because properties are lost accompanying thermal degradation during processing. In addition, PUs produced from compositions with high melting temperatures of the hard segments traditionally provide improved elasticity and heat recovery,
More preferred for textile processing. Polyurethane fibers having such a high hard segment melting point can only be produced by traditional solution spinning processes, which can provide excellent stretch / recovery properties.

In the present invention, a wide variety of polyurethane or polyurethaneurea compositions are useful for use in either or both of the first and second regions. It is also possible to include additional regions. Useful polyurethane / polyurethane urea compositions are detailed below.

In one aspect, a heat-fusible, steam-deformable spandex elastic yarn by solution spinning (dry spinning or wet spinning) is provided. Such fibers include monofilament structures or multifilament structures. Each filament of such a fiber (or the monofilament fiber itself) is a bicomponent fiber having an area that can be identified along the cross section of the fiber, such as a core-sheath configuration or a side-by-side configuration. The core is the first region and the sheath is the second region. It is also possible to include additional regions to provide different cross-sections, such as a side-by-side configuration combined with a core sheath or a core sheath with additional sheath regions.

Particularly useful compositions for the second region of the fusible fiber (which may be the sheath) may include:
A. The first component is at least one polyurethane with a high melting point, for example a melting point of about 190 ° C.
To a polymer mixture containing not only a polyurethane having a melting point of about 250 ° C. but also a polyurethane having a melting point of about 200 ° C. or more and an additive for improving fusion, such as a low-melting polyurethane. C. to about 150 ° C. polyurethanes, especially those having a melting point of less than 120 ° C.], or B. The first component is at least one polyurethane with a high melting point, for example a melting point of about 190 ° C.
To about 250 ° C. polyurethane as well as polyurethane having a melting point of about 200 ° C. or higher and at least one adhesive material or a fusion-improving additive for adhering the substrate later [the adhesive material improves the fusion property] Is an additive for use], or C.I. A mixture of at least one polyurethane and at least one adhesive coalescing additive.

Combinations and substitutions of A, B and C are also contemplated. It is also possible to include additional additives.

Particularly useful compositions for the first region of the fusible fiber (which may be the core) may include:
1) At least one polyurethane with a high melting point, for example a melting point of about 190 ° C. to about 250 ° C.
2) A mixture of a high melting point polyurethane in the range of 200 ° C. to 250 ° C. and a low melting point polyurethane of less than 180 ° C., or 3) at least one polyurethane And a mixture of at least one polyurethaneurea, or 4) polyurethaneurea including polyurethaneurea having a melting point higher than 240 ° C.

Some embodiments of the bicomponent fiber may contain a first region and a second region in a wide range of ratios. A second region (which may also be a sheath in the form of a core sheath) may be present in an amount of about 1% to about 60% based on the weight of the fiber, including from about 1 of the fiber About 50
% By weight, about 10 to about 35% by weight of the fiber and about 5 to about 30% by weight of the fiber.

Some embodiments of fusible fibers can have a steam deformation efficiency of 50% or more. The fiber may also exhibit a fusion strength higher than 0.15 cN / decitex.

Some embodiments are multicomponent or bicomponent fibers containing a solution spun polymer composition containing polyurethane, polyurethaneurea or mixtures thereof. The composition of the various regions imparted to the multicomponent fiber includes different polymer compositions in that the polymer is different, the additive is different, or both the polymer and the additive are different. Also included are multicomponent fibers having a solution spinning portion and a melt spinning portion.

Polyurethane urea and polyurethane composition Polyurethane urea compositions useful in the manufacture of fibers or long chain synthetic polymers contain at least 85% by weight of segmented polyurethane. They typically include high molecular weight glycols that react with diisocyanates to yield NCO-terminated prepolymers (“capped glycols”), which are then combined with a suitable solvent such as dimethylacetamide, dimethylacetate, and the like. It is dissolved in formamide or N-methylpyrrolidone or the like and reacted with a second bifunctional chain extender. If such a chain extender is a diol, a polyurethane is formed in the second stage (and its preparation can be carried out without solvent). When the chain extender is a diamine, polyurethane urea, a subclass of polyurethane, is produced. In making polyurethaneurea polymers that can be spun into spandex, the glycol's hydroxy end groups are sequentially reacted with a diisocyanate and one or more diamines to extend the glycol. In each case, the glycol must be chain extended to yield a polymer with the necessary properties (including viscosity). If necessary, dibutyltin dilaurate, stannous octoate, mineral acid, to assist the capping step,
Tertiary amines such as triethylamine, N, N′-dimethylpiperazine and the like and other known catalysts can also be used.

Suitable high molecular weight glycol components include polyether glycols, polycarbonate glycols and polyester glycols having a number average molecular weight of about 600 to about 3,500. Mixtures or copolymers of two or more high molecular weight glycols may also be included.

Examples of polyether glycols that can be used include ring-opening polymerization and / or copolymerization of ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran and 3-methyltetrahydrofuran, or polyvalent compounds having less than 12 carbon atoms in each molecule. Alcohols such as diols or mixtures of diols such as ethylene glycol, 1,3
-Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-
The number of hydroxy groups generated by condensation polymerization such as pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol is 2 or more. Glycol is included. Linear bifunctional polyether polyols are preferred, and poly (tetramethylene ether) glycol having a molecular weight of about 1,700 to about 2,100, such as Terathane ™ 1800 (functionality 2).
INVISTA (Wichita, KS)) and the like are examples of certain suitable glycols. The copolymer may include poly (tetramethylene-co-ethylene ether) glycol.

Examples of polyester polyols that can be used include ester glycols having two or more hydroxy groups generated by condensation polymerization of aliphatic polycarboxylic acids and low molecular weight polyols having no more than 12 carbon atoms in each molecule or mixtures thereof. Is included. Examples of suitable polycarboxylic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid. Examples of polyols suitable for use in the production of polyester polyols are ethylene glycol, 1
, 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6
-Hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1
, 10-decanediol and 1,12-dodecanediol. Linear bifunctional polyester polyols with a melting temperature of about 5 ° C. to about 50 ° C. are examples of specific polyester polyols.

Examples of polycarbonate polyols that can be used resulted from the condensation polymerization of phosgene, chloroformate, dialkyl carbonate or diallyl carbonate and low molecular weight aliphatic polyols or mixtures thereof having no more than 12 carbon atoms in each molecule. Carbonate glycol having 2 or more hydroxy groups is included. Examples of polyols suitable for use in the production of polycarbonate polyols include diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
With neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol is there. Linear bifunctional polycarbonate polyols with a melting temperature of about 5 ° C. to about 50 ° C. are examples of specific polycarbonate polyols.

The diisocyanate component can also include a single diisocyanate or a mixture of various diisocyanates, including 4,4'-methylenebis (phenylisocyanate).
And diphenylmethane diisocyanate (MDI) isomer mixtures containing 2,4'-methylenebis (phenylisocyanate). Any suitable aromatic or aliphatic diisocyanate can be included. Examples of diisocyanates that can be used include, but are not limited to, 4,4′-methylenebis (phenylisocyanate), 2,4′-methylenebis (phenylisocyanate), 4,4′-methylenebis (cyclohexylisocyanate), 1,3-diisocyanato-4-methyl-benzene, 2,2′-toluene diisocyanate, 2,4′-toluene diisocyanate and mixtures thereof are included.
Examples of specific polyisocyanate components include Mondur ™ ML (Bayer), L
upgrade (TM) MI (BASF) and Isonate (TM) 50 O, P
'(Dow Chemical) and combinations thereof are included.

Chain extenders for polyurethaneureas can be either water or diamine chain extenders.
Various chain extender combinations may be included depending on the desired properties of the polyurethaneurea and resulting fiber. Examples of suitable diamine chain extenders include hydrazine, 1,2-ethylenediamine, 1,4-butanediamine, 1,2-butanediamine, 1,3-butanediamine, 1,3-diamino-2,2 -Dimethylbutane, 1,6-hexamethylenediamine, 1,12-dodecanediamine, 1,2-propanediamine, 1,
3-propanediamine, 2-methyl-1,5-pentanediamine, 1-amino-3,3
5-trimethyl-5-aminomethylcyclohexane, 2,4-diamino-1-methylcyclohexane, N-methylamino-bis (3-propylamine), 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, 4, 4′-methylene-bis (cyclohexylamine), isophoronediamine, 2,2-dimethyl-1,3-propanediamine, meta-tetramethylxylenediamine, 1,3-diamino-4-methylcyclohexane, 1,
3-cyclohexane-diamine, 1,1-methylene-bis (4,4′-diaminohexane), 3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3-pentanediamine (1,3-diaminopentane) ), M-xylylenediamine and Jeffamine
(Trademark) (Texaco).

The chain extender when a polyurethane is desired is a diol. Examples of such diols that can be used include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,2-propylene glycol, 3-methyl-1,5-pentanediol, 2
, 2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 1,4-bis (hydroxyethoxy) ) Benzene and 1,4-butanediol and mixtures thereof.

Optionally, a monofunctional alcohol or a primary / secondary monofunctional amine can be included for the purpose of adjusting the molecular weight of the polymer. It is also possible to include a mixture of one or more monofunctional alcohols and one or more monofunctional amines.

Examples of monofunctional alcohols useful in the present invention include aliphatic and cycloaliphatic primary and secondary alcohols having 1 to 18 carbon atoms, phenols, substituted phenols, molecular weights less than about 750 (molecular weights less than 500 Ethoxylated alkylphenols and ethoxylated fatty alcohols, tertiary amines substituted with hydroxyamine, hydroxymethyl and hydroxyethyl, heterocyclic compounds substituted with hydroxymethyl and hydroxyethyl and combinations thereof At least one member selected from the group consisting of furfuryl alcohol, tetrahydrofurfuryl alcohol, N- (2-hydroxyethyl) succinimide, 4- (2-hydroxyethyl) morpholine, methanol,
Ethanol, butanol, neopentyl alcohol, hexanol, cyclohexanol, cyclohexane methanol, benzyl alcohol, octanol, octadecanol,
N, N-diethylhydroxylamine, 2- (diethylamino) ethanol, 2-dimethylaminoethanol and 4-piperidineethanol and combinations thereof are included.

Examples of suitable monofunctional dialkylamine blocking agents include N, N-diethylamine, N-ethyl-N-propylamine, N, N-diisopropylamine, Nt-butyl-N-methylamine, N- t-butyl-N-benzylamine, N, N-dicyclohexylamine, N-ethyl-N-isopropylamine, Nt-butyl-N-isopropylamine, N-isopropyl-N-cyclohexylamine, N-ethyl-N -Cyclohexylamine, N, N-diethanolamine and 2,2,6,6-tetramethylpiperidine.

Other Polymers Other polymers useful for use in the multicomponent and / or bicomponent fibers of the present invention include soluble or limited solubility or particulate morphology (eg, microparticles). Other polymers that can be included in are included. Such polymers may be dispersed or dissolved in the polyurethane or polyurethaneurea solution or coextruded with the solution spun polyurethane or polyurethaneurea composition. Such coextrusion can result in bicomponent or multicomponent fibers having a cross-section of side-by-side, concentric core sheath or eccentric core sheath, of which one
The component is a polyurethaneurea solution and the other component contains another polymer. Examples of other polymers include low melting point polyurethanes (as described above), polyamides, acrylic resins, polyaramids and polyolefins, among others. In some embodiments, the non-polyurethane polymer can be a fusogenic additive, particularly when the polymer has a melting temperature of about 150 ° C.
Can be less than.

Other polymers that can be included in the multicomponent fiber include nylon 6, nylon 6/6,
Nylon 10, nylon 12, nylon 6/10 and nylon 6/12 are included. The polyolefins include polyolefins produced to C ₂₀ monomers from C _2. It includes copolymers and terpolymers such as ethylene-propylene copolymers. Examples of useful polyolefin copolymers are disclosed in US Pat. No. 6,867,260 to Datta et al., Which is hereby incorporated by reference.

A wide variety of cross-sections are useful for the invention of some embodiments. They include two-component or multi-component concentric or eccentric core sheaths and two-component or multi-component parallels. Special cross-sections are also conceivable as long as there are at least two individual regions included in the cross-section.
An alternative cross-section may have a pie-slice configuration or an eccentric core-sheath analog where the sheath is only partially surrounding the core. In other words, the second region of the cross section may partially or completely surround the first region. Examples of various suitable cross sections are shown in FIG.

When the fusible polymer exhibits a desired melting point, the fusible polymer may be contained as a main component or a single component in a sheath or side-by-side form or in an alternative form without using a separate fusogenic additive.

The fiber cross section shown in FIG. 1 has a first region and a second region, all having different compositions. 4
A 4 dtex / 3 filament yarn is shown in FIGS. 1A and 1B, while a 44 dtex / 4 filament yarn is shown in FIGS. 1C and 1D. The first region in each contains the pigment and the second region does not. 1A and 1B include a 50/50 core-sheath cross-section, FIG. 1C includes a 17/83 sheath-core cross-section, and FIG. 1D includes a 50/50 parallel cross-section.

Each such core sheath and parallel cross-section contains a boundary region between at least two polyurethaneurea compositions having different compositions. Such regions appear to have well-defined boundaries in each of the figures, but the boundaries may include mixed regions. If the boundary contains a mixed area, the boundary itself is the first and second (
Or a third, fourth, etc.) region that is a distinguishable region that is a mixture of compositions. Such a mixture may be a homogeneous mixture or may contain a concentration gradient from the first region to the second region.

Additives The types of additives that may optionally be included in the polyurethaneurea composition are shown below. Examples of non-limiting lists are included below. However, additional additives are well known in the art. Examples include antioxidants, UV stabilizers, colorants, pigments, crosslinkers, phase change materials (paraffin wax), antibacterial agents, minerals (ie copper), microencapsulated additives (ie
Aloe, vitamin E gel, aloe, kelp, nicotine, caffeine, perfume or fragrance)
Nanoparticles (ie silica or carbon), calcium carbonate, flame retardants, anti-stick additives, additives that resist degradation by chlorine, vitamins, chemicals, fragrances, conductive additives, dyeing and / or dyeing aids (eg first Quaternary ammonium salts). Other additives that can be added to the polyurethaneurea composition include adhesion promoters and additives for improving fusion, antistatic agents, anti-creep agents, optical brighteners, coalescing agents, conductive additives, and luminescent additives. Agents, lubricants, organic and inorganic fillers,
Preservatives, texturing agents, thermochromic additives, insect repellents and wetting agents, stabilizers (hindered phenols, zinc oxide, hindered amines), slip agents (silicone oil) and combinations thereof are included.

Such additives may provide one or more beneficial properties, such properties include: dyeability, hydrophobicity [ie polytetrafluoroethylene (PTFE)], hydrophilicity ( Ie cellulose), friction control, chlorine resistance, degradation resistance (ie antioxidants), adhesion and / or fusion (ie adhesives and adhesion promoters), flame retardant, antibacterial (silver, copper, ammonium) Salt), barrier, conductivity (carbon black), tensile properties, color, light emission, reusability,
Biodegradable, aroma, adhesion control (ie, metal stearate), tactile properties, deformability, heat regulation (ie, phase change material), nutritional supplements, matting agents, eg titanium dioxide, stabilizers, eg hydro UV screening agents and combinations of these, such as talcite, a mixture of hunt and waterstones.

  Additives may be included in any amount suitable to achieve the desired effect.

Several types of additives are useful for use as low melt temperature additives for inclusion in some embodiments. They include reactive hot melt grade linear aromatic thermoplastic polyurethanes or mixtures thereof that deform with moisture and heat bond based on polyethers, polyesters, polycarbonates and polycaprolactones. Examples of specific commercial products include, among others, Mor-Melt (R-5022) (Rohm and Haa
s), Pellathane ™ 2103C (Dow), Desmopan ™
5377, Desmopan 9375A, Texin DP7-1197 (Bayer
Material Science), Pearlbond 104, 106, 122
, 123 (Merquinsa Mercados Quimicos, SL) and TPUA-252A (TPUCO, Taiwan). Such a fusogenic additive may be included in any amount suitable to achieve the desired fusogenicity of the fiber. The fusogenic additive may be included in the sheath or second region of the fiber in an amount of about 10 to about 90% by weight of the sheath or second region, including the sheath or second region. About 30 to about 60% by weight is included. The weight percent of the fusion enhancing additive based on the total weight of the multicomponent or bicomponent fiber is the core of the fiber or the second region or 1
It will depend on the weight ratio of the second region. In some cases, the second sheath region itself may be a polymer that exhibits fusibility with or without additional fusibility enhancing additives.

The production of device bicomponent fibers is typically carried out in a melt spinning process. The apparatus used in the process can be made suitable for use in the solution spinning process. Dry spinning and wet spinning are well known solution spinning processes.

Useful references (incorporated herein by reference) for fibers and filaments, including those of artificial bicomponent fibers, are for example:
a. Fundamentals of Fiber Formation-The Sc
ience of Fiber Spinning and Drawing, Adre
zij Ziabicki, John Wiley and Sons, London /
New York, 1976;
b. Bicomponent Fibers, R Jeffries, Merrow P
publishing Co. Ltd, 1971;
c. Handbook of Fiber Science and Technology
gy, T .; F. Cooke, CRC Press, 1993;

Similar references describe U.S. Pat. No. 5, which describes a method and apparatus for producing bicomponent fibers.
, 162,074 and 5,256,050 (incorporated herein by reference).

Extrusion that produces fibers by extruding the polymer through a die is performed using conventional equipment such as an extruder, gear pump, and the like. It is preferred to use a separate gear pump when feeding the polymer solution to the die. When mixing functional additives, preferably
For the purpose of obtaining a more uniform dispersion of the components, the polymer mixture is mixed using, for example, a fixed mixing device positioned upstream of the gear pump. In preparation for the extrusion process, for the purpose of improving the spinning yield, each spandex solution may be individually heated in a container with a temperature control jacket and then filtered.

In an exemplary embodiment of the invention, two different polymer solutions are introduced into a segmented jacketed heat exchanger, which is operated at 40-90 ° C. The extrusion dies and plates are arranged according to the desired fiber morphology, which are shown in FIG. 2 for the core sheath, in FIG. 3 for the eccentric core sheath and in FIG. 4 for the parallel. In any case, the component streams are brought together just above the capillaries. The previously heated solution is fed into the supply ports (2) and (
5) through the screen (7) through the distribution plate (4) and the spinneret (9) [this is the shim (8
) And support it with a nut (6).

The extrusion dies and plates described in FIGS. 2, 3 and 4 are combined with that shown in a conventional spandex spinning cell, eg, US Pat. No. 6,248,273 (incorporated herein by reference). Use together.

The production of such bicomponent spandex fibers can also be carried out by using individual capillaries to produce individual filaments and then fusing to produce a single fiber.

The features and advantages of the present invention are shown in greater detail in the following examples, which are presented for purposes of illustration and are not to be construed as limiting the invention in any way.

Fiber Production Method Fibers of some embodiments are produced by solution spinning of polyurethane or polyurethaneurea polymer (either wet spinning or dry spinning). In this production, a common urethane polymer solvent (eg DMAc) Use the solution formed together. Any of the above-described compositions or additives may be added to the polyurethane or polyurethaneurea polymer solution. In the production of polyurethaneurea, an organic diisocyanate and a suitable glycol are reacted so that the molar ratio of diisocyanate to glycol is in the range of 1.6 to 2.3, preferably 1.8 to 2.0. Manufacture is carried out through the generation of "glycol". The capped glycol is then reacted with a mixture of diamine chain extenders. The soft segment in the resulting polymer is the polyether / urethane portion of the polymer chain. Such soft segments exhibit a melting temperature of less than 60 ° C. The hard segment is the polyurethane / urea portion of the polymer chain, and the melting temperature they exhibit is 20
Higher than 0 ° C. The amount of hard segment is 5.5 to 12%, preferably 6 to 10% of the total polymer weight. In the production of polyurethane polymers, the molar ratio of organic diisocyanate and appropriate glycol to diisocyanate to glycol is 2.2 to 3.3, preferably 2.
Manufacture is carried out by reacting to be in the range of 5 to 2.95 to produce “capped glycol”. The capped glycol is then reacted with a mixture of diol chain extenders. The hard segment is a polyurethane segment of a polymer chain, and their melting temperature is in the range of 150-240 ° C. The hard segment may constitute 10 to 20%, preferably 13 to 7.5% of the total weight of the polymer.

In one embodiment of fiber production, filaments are produced by metering a polymer solution with a polymer solids content of 30-40% through the desired arrangement of distributor plates and orifices. The distributor plate is positioned such that the polymer streams are extruded through a common capillary after being brought together in one of a concentric core sheath, an eccentric core sheath and a side-by-side configuration. Extruded filaments are dried by introducing a hot inert gas of 300 ° C.-400 ° C. to a gas: polymer mass ratio of at least 10: 1 and stretching is at least 400 meters per minute ( Wake up at a speed of preferably at least 600 m / min) and then wind up at a speed of at least 500 meters per minute (preferably at least 750 m / min). All of the following examples are 8
It was carried out by using an extrusion temperature of 0 ° C. and entering a hot inert gas atmosphere at a winding speed of 762 m / min. Standard process conditions are well known in the art.

Yarns produced using elastic fibers produced according to the present invention generally exhibit a tensile strength at break of at least 0.6 cN / dtex, an elongation at break of at least 400%, and an unloaded tensile at 300% elongation. The stress is at least 27 mg / dtex.

Yarns and fabrics can be made by any conventional means using the elastic multicomponent fibers described herein. Such an elastic yarn can be coated with a second yarn, such as a hard yarn. Suitable hard yarns include nylon, acrylic resin, among others
Cotton, polyester and mixtures thereof are included. Coated yarns include single coated, double coated, air coated, corespun yarn and core twisted (core)
twisted) yarns may be included.

Some embodiments of elastic yarns can be included in a variety of structures, such as knitted (longitudinal and transverse), woven and non-woven. They are useful for use in socks, legwear, shirting, women's underwear, swimwear, clothing worn on the lower body, and sanitary nonwoven structures.

If the yarns need to be fused or glued, this can be achieved by subjecting them to heat and / or a static pressure of 3.5 bar or less depending on the composition of the fusogenic additive. Heat may be applied as steam or dry heat. Suitable fusing conditions for socks include applying a temperature of about 105 ° C. to about 135 ° C. for about 3 seconds to about 60 seconds when using steam heat, and a temperature of 165 ° C. to about 195 ° C. for using dry heat. It can include from about 3 seconds to about 60 seconds. Appropriate fusing conditions can vary depending on a number of factors including, among other things, the selected fusing enhancement additive, polymer chemistry, yarn linear density and fabric structure (ie, Knitting, weaving, etc.).

In the case of socks, the fabric is subjected to various process conditions, including the application of heat and / or pressure. Thus, a separate thermal deformation / fusion process is not necessary because the thermal deformation of the fabric also results in the fusion of yarns containing a fusogenic additive or other adhesive. is there.

In this example, the measurement of strength and elastic properties exhibited by the spandex fiber is performed according to ASTM D2.
Performed according to the general method of 731-72. The gauge length is 2 inches (5 cm) for each measurement.
3) and a 0-300% elongation cycle. 1 sample
Stretching at a constant elongation rate of 50 centimeters per minute was repeated 5 times. The load force (M200), which is the stress applied to the spandex when it is first stretched, is measured at 200% stretch during the first cycle and reported as gram force per given denier. Unloaded force (U200) is the stress at 200% stretch during the fifth unloaded cycle, which is also reported in gram forces. The percent elongation at break and tensile strength measurements were taken during the sixth tensile cycle. The set percentage was also measured after the sample was subjected to 5 0-300% elongation / relaxation cycles. The set percentage (% S) was then calculated as follows:
% S = 100 (Lf−Lo) / Lo
Here, Lo and Lf are the lengths of the filaments (yarns) when held straight without tension before and after 5 stretch / relaxation cycles, respectively.

In the measurement of steam set, which simulates sock processing and boarding operations, a sample of length Yo (conveniently 10 cm) selected from a straight, untensioned state is originally taken. After stretching to 3 times the length of about 2 minutes, relax. This simulated a coating operation in which spandex was coated with normal yarn and drafted. The spandex test sample so relaxed after being stretched was then placed in a boiling water bath for 30 minutes. Such contact with boiling water simulated the dyeing operation. The sample was then removed from the bath, dried, and stretched to twice the length that was relaxed after being placed in the bath. The stretched sample was exposed to a steam atmosphere at 121 ° C. for 30 seconds. This steam treatment simulates sock boarding. The sample was removed from the steam atmosphere, dried, and the length Yf in a straight state without tension was measured. Next, deformation due to steam (
SS,%) was calculated according to the following formula:
% SS = 100 (Yf−Yo) / Yo
For the measurement of the fusion exhibited by the yarn, a 15 cm long sample is placed on an adjustable triangular frame (the vertex is located in the center of the frame and the length of two equal sides is 7.5 cm) Measurements were made through. A second filament of the same length is placed on the frame from the opposite side so that the two yarns intersect at a single point of contact.

After the fibers have been relaxed to 5 cm, they are brought into contact with a washing bath solution for 1 hour, rinsed and dried with air, then brought into contact with a dyeing bath for 30 minutes, rinsed and then dried with air.

The length of the frame is adjusted from 5 cm to 30 cm with fibers attached thereto, 121 ° C.
For 30 seconds, cool for 3 minutes, and then relax. After the yarn was removed from the frame, it was transferred to a tensile tester and one end of each yarn was clamped so that the contact point remained between the clamps. The yarn is stretched at 100% / min and the force at which the contact point breaks (gram force) is recorded as the fusion strength.

The features and advantages of the present invention are shown in greater detail in the following examples, which are presented for purposes of illustration and are not to be construed as limiting the invention in any way.

In Examples 1-3 below, the fiber is produced by dry spinning a solution produced by placing a high melting polyurethane elastic polymer in N, N-dimethylacetamide (DMAc) CAS No. 127-19-50. It was carried out. A high melting point polyurethane polymer was prepared as follows and used as the basis for the core and sheath composition for the purpose of ensuring that the final fibers had adequate stability. MD production of polyurethane prepolymer with capping ratio 2.70
I ((benzene, 1,1-methylenebis [isocyanato-] CAS number [26447-4
0-5]) and a mixture of PTMEG (poly (oxy-1,4-butanediyl), α-hydro-ω-hydroxy, CAS number 25190-06-1) having a number average molecular weight of 2000 is 75.
This was carried out by heating to ° C for 2 hours. The prepolymer was then dissolved in DMAc to a solids concentration of about 39%. The solution was stretched at 75 ° C. by adding ethylene glycol (CAS No. 107-21-1) to the prepolymer solution in an amount sufficient to increase the falling ball solution viscosity at 40 ° C. to 4000 poise. After the solution reached the target viscosity, the monofunctional alcohol (1-butanol (CAS No. 71-36-3)) was added to stop the polymerization.

Filaments were produced by metering a polymer solution with a polymer solids content of 35-40% through the desired array of distributor plates and orifices. The distributor plate was positioned so that the polymer streams were combined into a concentric core-sheath array and then extruded through a common capillary. The extruded filament is subjected to drying by introducing a hot inert gas of 320-440 C in a gas: polymer mass ratio of at least 10: 1 and stretching is at least 400 meters per minute (preferably Was taken at a speed of at least 600 m / min) and then winding was carried out at a speed of at least 500 meters per minute (preferably at least 750 m / min). Yarns produced from the elastic fibers generally have a tensile strength at break of at least 1 cN / dtex, an elongation at break of at least 400%, and an M20 of at least 0.2 cN / dtex.
0 is shown.

Linear polyurethane based on polycaprolactone [Merquinsa Merc
35% DMAc solution by dissolving and mixing Pearlbond 122] supplied by ados Quimicos, SL together with the above prepared high melting point PU polymer (described above) to a weight ratio of 30% Then, it was extruded as a sheath component.
The core solution was composed of high temperature PU polymer in DMAc and combined with the sheath solution in a 4: 1 ratio to produce a 22 dtex double filament yarn. 700m of product
After taking out at / min and coating with silicone oil, the package was wound up at 850 m / min. Table 2 shows the product properties including fusibility, steam set efficiency and tensile properties. The differential scanning calorimetry trajectory (FIG. 5) shows a low melting transition due to the fusible additive, about 56
It shows that it is ° C.

Thermoplastic polyurethane elastic polymer (ester / ether) [Bayer Materi
Desmopan 5377A supplied by al Science (USA) and the above prepared high temperature PU polymer (described above) were dissolved in a weight ratio of 60% and mixed to obtain a 36% DMAc solution. After being produced, it was extruded as a sheath component. The core solution was composed of a high melting point PU polymer in DMAc and combined with the sheath solution in a 4: 1 ratio to produce a 22 dtex double filament yarn. The product was drawn at 700 m / min and wound on the package at 850 m / min after coating with silicone oil. Table 2 shows the product properties including fusibility, steam set efficiency and tensile properties.

(Comparison)
By using the prepared high temperature PU polymer (described above) as a 39% DMAc solution and extruding without modification to a ratio of 4: 1 sheath to core, 2 decitex 2 This filament yarn was produced. The product was drawn at 700 m / min and wound on the package at 850 m / min after coating with a silicone based finishing oil. Table 2 shows the product properties including fusibility, steam set efficiency and tensile properties.

The yarn of this example (of Example 1-3) was coated with a flat 11 dtex / 7 filament flat polyamide 66 yarn using a commercial Menetatto or ICBT coater. The draft ratio of the elastic yarn is 2.8x and the coverage is 1500 tpm
I made it. The sock sample was knitted on a commercial knitting machine, such as a Lonati 400 circular sock knitting machine. The coated yarn is knitted so that it has a tricot structure in all directions, but this structure allows the elastic yarn to fuse at each contact point of the knitted structure. is there. Appropriate fusion could also be achieved if the fusible yarn was included in alternating directions.

After the garment is subjected to standard operations of autoclaving and assembly, it is subjected to the set for 10-60 seconds in a 110 ° C. and 130 ° C. steam chamber using standard boarding equipment. The suitability of the fusion is tested through placing the garment on an open board, which will result in typical tension during wearing. A hole is created by creating a tear in the elastic yarn using a knife or scissors. If the force of the elastic yarn caused by the tension on the structure is lower than the force created by the fusion of the elastic yarns, the hole size will not increase. If the force of the elastic yarn is higher, the fusion point will not remain intact and the knitted structure will unravel (so-called loosening or wire). The wire performance exhibited by the clothing was visually observed and shown in Table 2.
FIG. 6 shows the SEM analysis results of adhesion formation and fusion quality exhibited by the knitted socks (Example 1). The 22 dtex yarn 10 which is a two-filament component in this figure is the fusion point 1.
1 and surrounded by a nylon covering yarn 12, which is a smaller filament.

Fusion sheath Crystalline thermoplastic polyurethane hot melt adhesive (Merquinsa Merca
dos Quimicos' Pearlbond 122) is prepared as a 50/50 mixture with conventional segmented polyurethane urea (as a 35% solution in DMAC) and with a conventional spandex core that is segmented polyurethane urea as a sheath Was spun into a 44 dtex / 3 filament yarn. By making the content of the entire sheath 20% based on the fiber weight, a yarn capable of fusing when heated to 80 ° C. or higher was produced.

Fibers that exhibit excellent stretch / recovery performance in addition to exhibiting excellent coalescence properties are advantageous. Table 3 shows the results of physical property tests including steam setting and fusion strength.

Having described what is presently considered to be a preferred embodiment of the present invention, those skilled in the art will recognize that variations and modifications can be made therein without departing from the spirit of the invention. It is envisioned that the present invention is intended to encompass all such variations and modifications as fall within the true scope of the present invention.

Claims (18)

Solution-spun fibers,
An elastic polyurethane or polyurethaneurea or a mixture thereof, and at least one fusogenicity comprising an elastic polyurethane or polyurethaneurea or a mixture thereof at least in the first region of the cross section A fiber that also includes a second region containing an additive for enhancement,
The first region and the second region, Ri region der having different compositions with boundaries, continuously exist along the length of the fibers,
The fusion-improving additive contains at least one low-melting polyurethane having a melting point of less than 180 ° C.,
A fiber characterized in that the set efficiency by steam is 50% or more .   The fiber of claim 1 comprising a monofilament structure or a multifilament structure.   The fiber according to claim 2, wherein the first region and the second region exist in parallel in each filament. The fiber according to any one of claims 1 to 3, wherein the low-melting polyurethane has a melting point of 50 ° C to 150 ° C. The fiber according to claim 4 , wherein the low-melting polyurethane has a melting point of less than 120 ° C. The fiber according to any of claims 1 to 5 , wherein the second region is located adjacent to the first region or at least partially surrounds it. The fiber according to any one of claims 1 to 6 , wherein the first region is made of an elastic polyurethane having a high melting point of 190 ° C to 250 ° C. The fiber according to any one of claims 1 to 6 , wherein polyurethane urea having a melting point higher than 240 ° C is contained in the first region. The fiber according to any one of claims 6 to 8 , wherein the second region constitutes 11 to 60% by weight of the fiber. The fiber according to any of claims 6 to 8 , wherein the second region constitutes 5 to 30% by weight of the fiber. The fiber according to any one of claims 1 to 10 , wherein the first region is a core and the second region is a sheath. The fiber according to any one of claims 1 to 11 , wherein the fusion strength of the fiber is higher than 0.15 cN / dtex. A fabric containing the fiber according to any one of claims 1 to 12 . The fabric according to claim 13, wherein the fibers are coated. The fabric of claim 14 , wherein the fibers are coated with polyamide, cotton, polyester, or a combination thereof. The fabric according to any of claims 13 to 15 , comprising a knitted, woven or non-woven structure. The cloth according to any one of claims 13 to 16 , constituting socks, leg wear, shirting, women's underwear, swimwear, clothes worn on the lower body, and a non-woven structure for hygiene. A method of manufacturing a fiber,
(A) preparing first and second polymer solutions;
(B) bringing the solution together through a distributor plate and an orifice to produce a filament having a cross-section;
(C) extruding the filament through a common capillary,
(D) removing the solvent from the filament;
Including
Each of the first and second polymer solutions independently contains elastic polyurethane, polyurethaneurea or a mixture thereof;
The second polymer solution contains an additive for improving fusibility,
The first polymer solution corresponds to a first region of the cross section, the second polymer solution corresponds to a second region of the cross section;
The cross section includes a boundary between the first region and the second region;
The first region and the second region are continuously present along the length direction of the fiber,
The fusion-improving additive contains at least one low-melting polyurethane having a melting point of less than 180 ° C.,
A method in which the setting efficiency by steam is 50% or more .