Methods for making items from recyclable fabrics

Abstract

The present invention relates to a method for making articles by recycling disperse dyed fabrics. The fabric is made from melt-spun thermoplastic polyurethane fibers containing a copolymer diol derived from caprolactone monomers and a polyether polyol. The fabric is shredded and then heat-treated to form granules that can be melted in an extruder to form articles.

Description

Background Art

[0001] In the apparel market, there is a growing interest in fabrics that are stretchable but can maintain their shape and fit. Thermoplastic polyurethane ("TPU") fibers show great potential for providing stretch and fit properties but have some drawbacks. Many polyurethane fibers are made by a dry spinning process that involves dissolving reactive components in a solvent. Such fibers generally have good heat resistance, but the dry spinning process is expensive, time-consuming, and involves the use of volatile solvents that raise environmental concerns. Melt spinning of fibers has manufacturing advantages, but not all TPUs are suitable for forming fibers under melt spinning conditions. In addition, prior art TPUs that can be melt spun into fibers do not have the heat resistance that would allow them to withstand specific dyeing conditions. This makes it difficult to combine melt-spun TPU fibers with other common synthetic or natural fibers. Because TPU fibers can lose their stretch and recovery properties after being exposed to dyeing conditions.

[0002] Therefore, it is desirable to have melt-spun TPU fibers that have good stretch and recovery properties and can be dyed under disperse dyeing conditions (e.g., at a temperature of about 130°C to 135°C). It is also desirable to have fabrics made from TPU fibers alone or in combination with other fiber materials to provide fabrics that can be dyed and have desirable properties.

[0003] In addition, recycling of scrap or used fabrics is an area of increasing interest. It is desirable to have a method for recycling fabric materials to make other articles.

Summary of the Invention

Means for Solving the Problems

[0004] In one embodiment, the present invention relates to a melt-spun fiber comprising a thermoplastic polyurethane composition and an isocyanate-functionalized crosslinking agent. The thermoplastic polyurethane composition used in the fiber comprises (i) a polyol component comprising or consisting of a copolymer diol derived from a caprolactone monomer and poly(tetramethylene ether glycol), (ii) a hydroxyl-terminate chain extender component, and (iii) a reaction product of a first diisocyanate component.

[0005] In another embodiment, the present invention provides a process for preparing a thermoplastic polyurethane having the following steps: (a) preparing a reactive thermoplastic polyurethane composition which is a reaction product of (a) a polyol component comprising a caprolactone monomer and a copolymer diol derived from poly(tetramethylene ether glycol), (b) a chain extender component comprising 1,4-bis(β-hydroxyethoxy)benzene, and (c) a diisocyanate; (2) drying the reactive thermoplastic polyurethane composition; (3) melting the reactive thermoplastic polyurethane composition in an extruder; (4) adding an isocyanate-functionalized prepolymer to the extruder; (5) mixing the reactive thermoplastic polyurethane composition and the isocyanate-functionalized prepolymer in the extruder to form a crosslinked thermoplastic polyurethane polymer; (6) supplying the crosslinked thermoplastic polyurethane polymer to at least one spinneret to produce melt-spun fibers; (7) cooling the melt-spun fibers; and (8) winding the melt-spun fibers onto a bobbin.

[0006] In yet another embodiment, the present invention provides a fabric comprising a first fiber component comprising a stiff yarn having an ultimate elongation of 10% to 75% as measured according to ASTM D2256, for example, polyester fiber, and a second fiber component comprising a melt-spun thermoplastic polyurethane filament having an ultimate elongation of at least 300% as measured according to ASTM D2731, wherein the first fiber component and the second fiber component are knitted together to form a fabric, and the fabric is dyed using dispersion dyeing conditions.

[0007] In another embodiment, the present invention provides a method for recycling fabrics produced herein to produce other articles.

[0008] These various embodiments will be described in more detail below. [Modes for carrying out the invention]

[0009] The characteristics and embodiments of the present invention will be described below by the following non-limiting examples.

[0010] The disclosed technology comprises a thermoplastic polyurethane ("TPU") composition and a melt-spun fiber comprising an isocyanate-functionalized crosslinking agent. A TPU composition useful for producing the melt-spun fiber of the present invention is a reaction product of a polyol component, a hydroxyl-terminal chain extender component, and a diisocyanate component. The isocyanate-functionalized crosslinking agent is a reaction product of a polyol and an excess isocyanate. Each of these components is described in more detail below.

[0011] Where used herein, weight-average molecular weight (Mw) is determined by gel permeation chromatography using a polystyrene standard, and number-average molecular weight (Mn) is determined by end-group analysis.

[0012] Thermoplastic polyurethane composition The TPU composition useful for producing melt-spun fibers of the present invention comprises a polyol component, which may also be described as a hydroxyl-terminated intermediate. In the present invention, the polyol component comprises or consists of a copolymer diol derived from a caprolactone monomer and a hydroxyl-functionalized polyether intermediate.

[0013] Caprolactone monomers useful for producing copolymer polyols used in the present invention include ε-caprolactone and 2-oxepanone. In one embodiment, the caprolactone monomer is reacted with a polyether diol to form a copolymer diol. In another embodiment, ε-caprolactone may be reacted with another bifunctional initiator (e.g., diethylene glycol, 1,4-butanediol, neopentyl glycol, or any other glycol and / or diol known to those skilled in the art).

[0014] In one embodiment in which ε-caprolactone reacts with a polyether polyol intermediate, suitable hydroxyl-functionalized polyether intermediates include polyether polyols derived from diols or polyols having a total of 2 to 15 carbon atoms, and in some embodiments, alkyldiols or glycols reacting with ethers containing alkylene oxides having 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide, or mixtures thereof. For example, hydroxyl-functionalized polyethers can be produced by first reacting propylene glycol with propylene oxide, and then with ethylene oxide. Primary hydroxyl groups obtained from ethylene oxide are more reactive than secondary hydroxyl groups and are therefore sometimes preferred. Useful commercially available polyether polyols include poly(ethylene glycol) containing ethylene oxide obtained by reacting with ethylene glycol, poly(propylene glycol) containing propylene oxide obtained by reacting with propylene glycol, and poly(tetramethylene ether glycol) containing water obtained by reacting with tetrahydrofuran (which can also be described as polymerized tetrahydrofuran and is generally referred to as PTMEG). In some embodiments, the hydroxyl-functionalized polyether intermediate used in the present invention includes or consists of PTMEG.

[0015] In one embodiment, the polyol component comprises or consists of a copolymer diol which is a reaction product of caprolactone monomer and poly(tetramethylene ether glycol). In another embodiment, the polyol component comprises or consists of a reaction product of about 50% by weight of ε-caprolactone monomer and about 50% by weight of poly(tetramethylene ether glycol).

[0016] In one embodiment of the present invention, the reaction mixture for forming the TPU composition used herein comprises about 50% to about 80% by weight, for example, about 60% to about 75% by weight, or further about 65% to about 70% by weight of a polyol component.

[0017] Chain extender components The TPU compositions described herein are prepared using chain extender components. Suitable chain extenders include diols, diamines, and combinations thereof.

[0018] Suitable chain extenders include relatively small polyhydroxy compounds, such as lower aliphatic or short-chain glycols having 2 to 20, 2 to 12, or 2 to 10 carbon atoms. Suitable examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane (HEPP), 1,4-bis(β-hydroxyethoxy)benzene (HQEE), hexamethylenediol, heptanediol, nonanediol, dodecanediol, 3-methyl-1,5-pentanediol, ethylenediamine, butanediamine, hexamethylenediamine, and hydroxyethyl resorcinol (HER), as well as mixtures thereof. In one embodiment, the chain extender comprises or consists of 1,4-bis(β-hydroxyethoxy)benzene (HQEE).

[0019] In one embodiment of the present invention, the reaction mixture for forming the TPU composition used herein comprises about 5% to about 25% by weight, for example, about 5% to about 15% by weight, or further about 8% to 10% of a chain extender component.

[0020] Isocyanate components The TPU of the present invention is made using an isocyanate component. The isocyanate component may comprise one or more polyisocyanates, or more specifically, one or more diisocyanates. Suitable polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, or combinations thereof. In some embodiments, the polyisocyanate component comprises one or more aromatic diisocyanates. In some embodiments, the polyisocyanate component is essentially or completely free of aliphatic diisocyanates. In other embodiments, the polyisocyanate component comprises one or more aliphatic diisocyanates. In some embodiments, the polyisocyanate component is essentially or completely free of aromatic diisocyanates. In some embodiments, a mixture of aliphatic and aromatic diisocyanates may be useful.

[0021] Examples of useful polyisocyanates include aromatic diisocyanates such as 4,4'-methylenebis(phenylisocyanate) (MDI), 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), m-xylene diisocyanate (XDI), phenylene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, and toluene diisocyanate (TDI), as well as 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and 1,4-cyclohexyl diisocyanate (cyclohexyl Aliphatic diisocyanates include diisocyanate (CHDI), decane-1,10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), isophorone diisocyanate (PDI), and dicyclohexylmethane-4,4'-diisocyanate (H12MDI). Isomers of these diisocyanates may also be useful. A mixture of two or more polyisocyanates may be used. In some embodiments, the isocyanate component includes or consists of aromatic diisocyanates. In some embodiments, the isocyanate component includes or consists of MDI.

[0022] In one embodiment of the present invention, the reaction mixture for forming the TPU composition used herein comprises about 15% to about 30% by weight, for example, about 15% to about 25% by weight, or further about 18% to about 20% by weight of an isocyanate component.

[0023] Optionally, one or more polymerization catalysts may be present during the polymerization reaction of TPU. In general, any conventional catalyst can be used to react a diisocyanate with a polyol intermediate or a chain extender. In particular, examples of suitable catalysts that promote the reaction between the NCO group of the diisocyanate and the hydroxyl groups of the polyol and chain extender are conventional tertiary amines known from the prior art (e.g., triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane, etc.), and especially organometallic compounds (e.g., titanium esters, iron compounds (e.g., iron acetylacetonate), tin compounds (e.g., tin diacetate, tin octanoate, tin dilaurate), bismuth compounds (e.g., bismuth trineodecanoate), or dialkyltin salts of aliphatic carboxylic acids (e.g., dibutyltin diacetate, dibutyltin dilaurate, etc.)). The amount of catalyst typically used is 0.001 to 0.1 parts by weight per 100 parts by weight of the polyol component. In some embodiments, the reaction for forming the TPU of the present invention is substantially or completely catalyst-free.

[0024] The TPU composition used in the present invention may be produced via a "one-shot" process, in which all components are added together to a heated extruder simultaneously or substantially simultaneously and reacted to form a TPU. The equivalent ratio of diisocyanate to the total equivalents of the hydroxyl-terminated intermediate and chain extender is generally about 0.95 to about 1.10, for example, about 0.97 to about 1.03, or even more specifically, about 0.98 to about 1.0. In one embodiment, the equivalent ratio may be less than 1.0 so that the TPU has terminal hydroxyl groups to enhance the reaction with the crosslinking agent during the fiber spinning process. The weight-average molecular weight (MW) of the TPU is generally about 25,000 to about 300,000, for example, about 50,000 to about 200,000, or even more specifically, about 75,000 to about 150,000.

[0025] In another embodiment, the TPU can be prepared using a prepolymer process. In the prepolymer process, a hydroxyl-terminated intermediate is generally reacted with an equimolar excess of one or more diisocyanates to form a prepolymer solution having free or unreacted isocyanate therein. Subsequently, a chain extender as described herein is generally added in an amount equal to the isocyanate end groups and any free or unreacted diisocyanate compounds. Thus, the total equivalent ratio of the total diisocyanate to the total equivalents of the hydroxyl-terminated intermediate and the chain extender is from about 0.95 to about 1.10, such as from about 0.97 to about 1.03, or even from about 0.98 to about 1.0. In one embodiment, the equivalent ratio may be less than 1.0 such that the TPU has terminal hydroxyl groups to enhance the reaction with a crosslinking agent during the fiber spinning process. Typically, the prepolymer process can be carried out in any conventional device such as an extruder.

[0026] Optional additive components may be present during the polymerization reaction and / or may be incorporated into the above TPU elastomers to improve processing and other properties. These additives include antioxidants, organic phosphites, phosphines and phosphonites, hindered amines, organic amines, organic sulfur compounds, lactones and hydroxylamine compounds, biocides, bactericides, antibacterial agents, compatibilizers, electrical dissipative or antistatic additives, fillers and reinforcing agents (e.g., titanium dioxide, alumina, clay and carbon black), flame retardants (e.g., phosphates, halogenated materials, and metal salts of alkylbenzene sulfonates), impact modifiers (e.g., methacrylate-butadiene-styrene ("MBS") and methylmethacrylate butylacrylate ("MBA")), release agents (e.g., waxes, fats and oils, pigments and colorants, plasticizers, polymers), rheology modifiers (e.g., monoamines, polyamide waxes, silicones, and polysiloxanes), slip additives (e.g., paraffin wax, hydrocarbon polyolefins, and / or fluorinated polyolefins), and UV stabilizers (which may be of the hindered amine light stabilizer (HALS) and / or UV light absorber (UVA) type), but are not limited thereto. Other additives may be used to improve the performance of the TPU composition or blend product. All of the above additives can be used in customary effective amounts for these substances.

[0027] These additional additives can be incorporated into the components for the preparation of the TPU resin, or into the reaction mixture for the preparation of the TPU resin, or after the TPU resin has been made. In another process, all of the materials can be mixed with the TPU resin and then melted, or they can be incorporated directly into the melt of the TPU resin.

[0028] Isocyanate-functional crosslinking agent The above TPU composition is combined with an isocyanate-functionalized crosslinking agent. The crosslinking agent is a reaction product of a hydroxyl-terminated polyol selected from polyethers, polyesters, polycaprolactones, polycarbonates, and mixtures thereof, and an excess of diisocyanate. In one embodiment, the hydroxyl-terminated polyol used in the crosslinking agent is a polyether polyol. For example, the hydroxyl-terminated polyether may include or consist of poly(tetramethylene ether glycol). In another embodiment, the hydroxyl-terminated polyol used in the crosslinking agent is a polyester. For example, the hydroxyl-terminated polyester may include or consist of neopentyl glycol adipate. In one embodiment, the polyisocyanate component is an aromatic diisocyanate, e.g., MDI. In another embodiment, the polyisocyanate component is an aliphatic diisocyanate, e.g., H12MDI. The crosslinking agent has an isocyanate functional value greater than 1.0, e.g., about 1.5 to 2.5, and more specifically, about 1.8 to 2.2. Isocyanate-functionalized crosslinking agents can be prepared using the prepolymer process described herein, which involves reacting a hydroxyl-terminated intermediate with one or more diisocyanates in an equivalent excess to form a prepolymer solution having free or unreacted isocyanates.

[0029] The weight percentage of the crosslinking agent used with the TPU polymer is approximately 5.0% to 20% by weight, for example, approximately 8.0% to 15% by weight. The percentage of crosslinking agent used is a weight percentage based on the total weight of TPU and crosslinking agent.

[0030] Thermoplastic polyurethane fiber Melt-spun TPU fibers are produced by melting a TPU composition in an extruder and adding a crosslinking agent to the molten TPU. The molten TPU containing the crosslinking agent is fed into a spinneret. The molten material exits the spinneret to form fibers, which are then cooled and wound onto a bobbin. The method comprises the following steps: (1) preparing a reactive thermoplastic polyurethane composition which is a reaction product of (a) a polyol component comprising or comprising a copolymer diol derived from caprolactone monomer and poly(tetramethylene ether glycol), (b) a chain extender component comprising or comprising 1,4-bis(β-hydroxyethoxy)benzene, and (c) a diisocyanate; (2) drying the reactive thermoplastic polyurethane composition; (3) melting the reactive thermoplastic polyurethane composition in an extruder; (4) adding an isocyanate-functionalized prepolymer to the extruder; (5) mixing the reactive thermoplastic polyurethane composition and the isocyanate-functionalized prepolymer in the extruder to form a crosslinked thermoplastic polyurethane polymer; (6) supplying the crosslinked thermoplastic polyurethane polymer to at least one spinneret to produce melt-spun fibers; (7) cooling the melt-spun fibers; and (8) winding the melt-spun fibers onto a bobbin core. The steps of this process are explained in more detail below.

[0031] The melt spinning process begins with feeding a pre-formed TPU polymer into an extruder. The TPU is melted in the extruder, and the crosslinking agent is continuously added either downstream near the point where the TPU molten material exits the extruder, or after the TPU molten material has exited the extruder. If the crosslinking agent is added after the molten material has exited the extruder, it must be mixed with the TPU molten material using a static or dynamic mixer to ensure proper mixing of the crosslinking agent into the TPU polymer molten material. After exiting the extruder and mixer, the molten TPU polymer containing the crosslinking agent flows into a manifold. The manifold divides the molten stream into different streams, each of which supplies multiple spinnerets. Typically, there is a melt pump for each of the different streams flowing from the manifold, and each melt pump supplies several spinnerets. The spinnerets have small holes through which the molten material is extruded, exiting the spinneret in the form of fibers. The size of the holes in the spinneret depends on the desired fiber size (denier). The fibers are stretched or drawn as they exit the spindle and cooled before being wound onto the bobbin. The fibers are drawn by winding the bobbin at a speed faster than the speed at which the fibers exit the spindle. For melt-spun TPU fibers, the bobbin is typically wound at a speed greater than the speed at which the fibers exit the spindle, for example, 4 to 8 times the speed at which the fibers exit the spindle in some embodiments, but may be slower or faster depending on the specific equipment. Typical bobbin winding speeds can vary from 100 to 3000 meters / min, but a more typical speed for melt-spun TPU fibers is 300 to 1200 meters / min. Finishing oils, such as silicone oil, are typically added to the surface of the fibers after cooling, just before being wound onto the bobbin.

[0032] A key aspect of the melt spinning process is the mixing of the TPU polymer molten material with the crosslinking agent. Proper, uniform mixing is crucial for achieving uniform fiber properties and long run times without experiencing fiber breakage. The mixing of the TPU molten material with the crosslinking agent should be a plug-flow method, i.e., first-in, first-out. Proper mixing can be achieved using a dynamic or static mixer. For example, a dynamic mixer having a feed screw and a mixing pin can be used. U.S. Patent No. 6,709,147 describes such a mixer having a rotatable mixing pin.

[0033] TPU reacts with a crosslinking agent during the fiber spinning process to give the weight-average molecular weight (MW) of the TPU in fiber form about 200,000 to about 800,000, preferably about 250,000 to about 500,000, more preferably about 300,000 to about 450,000. The reaction between the TPU and the crosslinking agent in the fiber spinning process at the point where the TPU exits the spinneret should be greater than 20%, preferably about 30% to about 60%, more preferably about 40% to about 50%. A typical prior art TPU melt spinning reaction between the TPU polymer and the crosslinking agent is less than 20%, usually about 10-15%. The reaction is determined by the disappearance of NCO groups. A higher % reaction in the present invention improves the melt strength and therefore allows for a higher spinning temperature, which improves the spinnability of the TPU. The fibers are usually aged on the bobbin in an oven until the molecular weight stabilizes.

[0034] The spinning temperature (the temperature of the polymer molten in the spinneret) must be higher than the melting point of the polymer, preferably about 10°C to about 20°C higher. The higher the spinning temperature that can be used, the better the spinning. However, if the spinning temperature is too high, the polymer may decompose. Therefore, a temperature about 10°C to about 20°C higher than the melting point of the TPU polymer is optimal for achieving a good spinning balance without polymer decomposition. If the spinning temperature is too low, the polymer may solidify in the spinneret, causing fiber breakage. The spinning temperature of the fibers produced by the present invention is greater than 190°C, preferably about 190°C to about 220°C, or even more preferably about 190°C to about 200°C.

[0035] A key aspect of producing melt-spun TPU fibers is the time it can be carried out continuously without stopping the process. The need to stop the process is usually a result of fiber breakage. Fiber breakage occurs when the pressure at the spinneret increases to an unacceptable level. Fiber breakage typically occurs when the pressure reaches a force of approximately 140-200 kg per square centimeter. Pressure increases can occur for several reasons, including improper mixing. This results in the formation of products due to the self-reaction of the crosslinking agent, which can cause partial blockage of the small outlet holes at the spinneret for the fibers. The present invention allows for much longer run times before exceeding a harmful pressure increase leads to fiber breakage.

[0036] Melt-spun TPU fibers can be produced in various denier sizes. The term "denier" is defined as the mass in grams of a 9000-meter length of fiber, filament, or yarn. It describes the linear density, which is the mass per unit length of fiber, filament, or yarn, and is measured according to ASTM D1577, Option B. Typical melt-spun TPU fibers are produced in denier sizes of less than 240, more typically between 10 and less than 240 denier, with 20 and 40 denier being commonly used sizes.

[0037] Prior art melt-spun TPU fibers are not typically used in combination with polyester fibers due to the high temperatures required to dye them. Due to the lack of polarity and extremely high crystallinity of the polyester polymer and fibers, dispersible dyes are typically used for dyeing. Such fibers are usually dyed at 120°C to 135°C, for example, about 130°C for 60 minutes, at a rate of 1 to 1.5 kg / cm³. 2 The fabric is dyed under pressure. This pressure dyeing "opens" the polyester polymer, allowing dye molecules to penetrate. Once dyeing is complete and the fabric is removed from the pressure dyeing vessel (referred to as a dyeing machine), the polyester polymer system "closes" again, "trapping" the disperse dye molecules inside. No prior art melt-spun TPU fiber can withstand this type of temperature for 60 minutes without losing physical properties such as tenacity and strain rate, as measured according to ASTM D2731. In addition, prior art melt-spun TPU fibers also tend to fuse with adjacent fibers when exposed to the aforementioned high temperature and pressure, which is detrimental to the stretchability of the fabric.

[0038] The high heat resistance of the melt-spun TPU fibers of the present invention allows them to withstand dyeing operations of polyester fibers while maintaining sufficient physical properties to preserve elasticity.

[0039] Another property of the high heat-resistant melt-spun TPU fibers of the present invention is their ability to absorb dispersible dyes. The process for dispersible dyeing involves exposure to a temperature of about 130°C for about 60 minutes (dyeing conditions for polyester fibers). Many TPU fibers cannot exhibit dye pickup, color fastness (after washing), and bleach resistance after exposure to these temperatures.

[0040] Melt-spun fibers produced according to the present invention possess unique physical properties not exhibited by prior art TPU fibers. Firstly, the fibers exhibit unique elastic properties. For example, fibers produced according to the present invention exhibit hysteresis after the fifth loading and unloading cycle of less than 30% or further less than 20% at 100% elongation, less than 30% or further less than 18% at 150% elongation, and less than 30% or further less than 18% at 200% elongation. The term "hysteresis" is defined as a residual physical effect after the removal of an external stimulus, and in fibers, it is observed as a change in dimensions after stretching and recovery. It is expressed as a percentage of hysteresis at the corresponding elongation (or strain). Hysteresis is measured according to ASTM D2731. Hysteresis can be calculated using the following information and formulas. Modulus of elasticity at 100% elongation during a load cycle = m1 Modulus of elasticity at 100% elongation during the unloading cycle = m² Hysteresis at 100% elongation = (m1-m2) / m1 × 100. Hysteresis can be calculated similarly at 150% and 200% elongation.

[0041] Melt-spun TPU fibers produced according to the present invention also have an ultimate elongation of at least 300%, e.g., 300% to 650%, as measured by ASTM D2731. Typically, elastic materials are characterized by extensibility and elasticity, and when an external force is released, these materials return almost completely to their original dimensions. For an ideal elastic material, there is only one curve on the stress-strain plot that tracks the loading and unloading cycles. However, for most materials, due to the loss of energy (in the form of heat), most materials exhibit different curves for loading and unloading, also known as "hysteresis." A lower hysteresis % value indicates better elasticity. The use of elastic fibers with very low hysteresis % can be used to achieve fabrics with less deformation in clothing.

[0042] In addition, melt-spun TPU fibers produced according to the present invention may also have a melting initiation temperature of 140°C to 170°C, for example 150°C to 170°C, and even more specifically, about 155°C to 166°C, as measured according to ASTM D3418, and an elastic modulus of 3.5E+05 to 12E+05 Pa at 130°C, as measured by DMA (Dynamic Mechanical Analysis). DMA measurement is performed using a parallel plate configuration at a heating rate of 2°C / min with a strain of 0.1% and a frequency of 1 Hz, from -100°C to 250°C.

[0043] fabric The TPU fibers of the present invention can be used alone or combined with other natural or synthetic fibers by knitting or weaving to produce fabrics that can be used in various articles. It is desirable to dye such fabrics in various colors.

[0044] In one embodiment, the melt-spun TPU fibers of the present invention can be woven to produce a fabric. In another embodiment, the melt-spun TPU fibers of the present invention can be combined with one or more different TPU fibers to produce a fabric. In yet another embodiment, the melt-spun TPU fibers of the present invention can be combined with other fibers such as cotton, nylon, or polyester to produce a variety of end-use articles, including clothing.

[0045] For example, the fabric according to the present invention can be made by combining the melt-spun TPU fibers of the present invention with yarns that have lower elasticity than the TPU fibers of the present invention, which are also referred to herein as "rigid yarns". Examples of rigid yarns include polyester, nylon, cotton, wool, acrylic, polypropylene, or viscose rayon. Other examples of rigid yarns include other TPU fibers (not of the present invention) that have lower elasticity than the TPU fibers of the present invention. In one embodiment, the rigid yarn has an ultimate elongation of 10% to 200%, for example, 10% to 75%, or 10% to 60%, or further 10% to 50%, or further 10% to 30%, and the melt-spun TPU fibers of the present invention have an ultimate elongation of at least 300%, for example, 300% to 650%. Each of the fiber components may be included in the composition in an amount of 1 to 99% by weight. The weight percentage of melt-spun TPU fibers in the final use can vary depending on the desired elasticity. For example, woven fabrics may contain 1-8% by weight of melt-spun TPU fibers, underwear 2-5% by weight, swimwear and sportswear 8-30% by weight, foundations 10-45% by weight, and medical hoses 35-60% by weight, with the remaining amount being rigid, non-elastic fibers. Fabrics made from these two fiber materials can be constructed by various processes, including but not limited to circular knitting, warp knitting, weaving, braiding, nonwoven fabrics, or combinations thereof. In one embodiment, a fabric made from the fibers of the present invention has a draw of more than 100% as measured according to ASTM D4964. The fibers may be dyed at a high temperature of at least 130°C.

[0046] Recycled fabric The present invention also includes a method for producing articles through the recycling of fabrics disclosed herein. In this method, a dispersion-dyed fabric made from thermoplastic polyurethane fibers as described herein can be shredded and then heat-treated to form granules. The heat-treatment process for forming the granules will be understood by those skilled in the art. The granules can then be melted and sheared in an extruder to form articles, as is commonly understood in the art.

[0047] The recyclable fabrics in this invention include those made from melt-spun thermoplastic polyurethane fibers produced herein. Such fabrics may also contain other fibers, including polyester, nylon, acrylic, polypropylene, or mixtures thereof. In one embodiment, the fabric contains up to 70% polyester fibers in addition to the melt-spun thermoplastic polyurethane fibers.

[0048] In another embodiment, the second polymer material may be added to the extruder together with granules made from recycled fabric. Examples of second polymers that can be used include polyester or other thermoplastic polyurethanes, or mixtures thereof.

[0049] In this application and the following embodiments, the following characteristics are referred to along with methods for measuring such characteristics. Denier is a measure of linear density and was measured according to ASTM D1577, Option B. The tenacity of the elastic filament, which is the tensile strength normalized by denier, was also measured and reported according to ASTM D2731. The ultimate elongation of the elastic filament, which is the elongation at the break point, was also measured and reported according to ASTM D2731. • Hysteresis of the elastic filament, defined, calculated, and reported in each elongation according to ASTM D2731. For rigid yarns such as polyester, which are inelastic, tenacity and elongation were measured using the ASTM D2256 standard. • The content of individual components in the fabric was measured according to ASTM D629. • Fabric stretch and fabric modulus were measured according to ASTM D4964. The fabric was washed using Test Method 135 of the American Association of Textile Chemists and Colorists (AATCC). ·

[0050] The present invention will be better understood by referring to the following embodiments. [Examples]

[0051] Table 1 lists the prepared TPU compositions used to produce fibers in the present invention. The TPU hard segment is the total amount of isocyanate and chain extender in the TPU composition.

[0052] [Table 1]

[0053] The TPU polymers of Examples A to G were dried in a vacuum batch dryer for 80°C. o The TPU polymer was pre-dried at C for 12 hours. After drying, the TPU polymer was melted in a 1.25-inch single-screw extruder with an L / D ratio of 24. The extruder had four heating zones maintained at 180°C to 225°C throughout the process. Upon exiting the extruder, the melted TPU polymer was mixed with 10% by weight of a prepolymer crosslinking agent (90% by weight of melted TPU polymer / 10% by weight of crosslinking agent). The TPU and crosslinking agent combinations are summarized in Table 2.

[0054] [Table 2]

[0055] The crosslinking agent was mixed with the TPU polymer molten material in a dynamic mixer and then pumped through a manifold to the spinneret. Each spinneret had an orifice size of 0.65 mm. The polymer stream exiting the spinneret was cooled with air, a silicone finishing oil was applied, and the formed fibers were wound onto bobbins. Before testing the physical properties of the fibers, the fibers on the bobbins were heat-aged at 80°C for 24 hours. Table 3 summarizes the key properties of the fibers.

[0056] [Table 3]

[0057] The fibers from Example 1 were used to produce a single jersey knit fabric on a Vanguard circular knitting machine. A 70D (68 filament) multifilament textured polyester yarn (as a stiff yarn) was combined with the examples in Table 3. The knitting tension on the machine was adjusted to knit a balanced ratio throughout the fabric to contain 25% elastomer yarn and 75% polyester yarn as shown in Table 3 (this was confirmed by mechanical separation of elastomer yarn and stiff yarn by weight in a small piece of fabric according to ASTM D629-15). Fiber Example 1 in Table 2 was successfully converted into fabric. Fiber Examples 2-7 were too sticky and consistently broke during the knitting process, and could not be converted into fabric.

[0058] The knitted fabric was dyed using the fibers from Example 1 as follows. Scouring, dyeing, and reduction to clear solution: 1000 ml of scouring solution contained 2 grams of Na2CO3, 6 grams of NaOH, and the remainder was deionized water. 1000 ml of dye solution contained 2 grams of Archroma US Foron Navy S-2GRL 200, 6 grams of Na2CO3, and the remainder was deionized water. The pH of the dye bath was adjusted to 4.5 using acetic acid. 1000 ml of reduction to clear solution contained 6 grams of NaOH, and the remainder was deionized water.

[0059] A 10-meter-long, 1kg piece of fabric was placed in a Thies miniMaster® dyeing machine. The dyeing machine was programmed for scouring, dyeing, and reduction / transparency temperature cycles.

[0060] Scouring was performed for 30 minutes at 65°C using 1 liter of the scouring solution prepared above, followed by rinsing with warm tap water. Next, the dyeing process was started at 50°C with the dye container filled with 1 liter of dye solution. Then, the bath temperature was slowly increased at a rate of 2°C / min to 130°C and held at that temperature for 60 minutes. Then, the temperature was lowered to 80°C, the dye solution was drained from the dye container, followed by rinsing with tap water in two cycles.

[0061] After rinsing, 1 liter of the reducing clear solution prepared above was introduced into the dyeing container at 75° to 80°C for 30 minutes. The fabric sample was then rinsed with warm tap water until no further dye bleeding occurred. Finally, the fabric was immersed in a 1% acetic acid neutralizing solution for 30 seconds.

[0062] The damp fabric sample was air-dried overnight. Once dry, the fabric was heat-cured in a tenter frame, pre-stretching it to 20% greater than its original width. This fabric was then passed through the tenter frame twice.

[0063] Next, the fabric samples were washed using the American Association of Textile Chemists and Color Technicians (AATCC) Test Method 135-2018. Following washing, the fabric samples were evaluated for their stretch properties according to Table 4 below.

[0064] [Table 4] * The test was performed in accordance with ASTM D4964, with a constant load of 10 lb-f in both the warp (fabric length) and weft (fabric width) directions.

[0065] Fabrics made using the fibers of the present invention can also be recycled. In one embodiment, fabrics made according to the present invention are recycled to produce extruded or molded articles. Accordingly, the present invention provides a dispersion dyed fabric prepared according to the present invention, and a method for producing an article comprising shredding such fabric, heat-treating such shredded fabric to form granules, and then melting and shearing the granules in an extruder to form an article.

[0066] Each of the documents mentioned above, including any prior application claiming priority, whether or not they are specifically listed above, is incorporated herein by reference. Reference to any document does not constitute an endorsement that such document is eligible as prior art or constitutes the general knowledge of a person skilled in the art in any jurisdiction. Except as provided in the examples, or otherwise expressly indicated, all quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, etc., should be understood to be modified by the word “about.” The upper and lower limits of quantities, ranges, and ratios described herein can be combined independently. Similarly, the ranges and quantities for each element of the present invention can be used together with the ranges or quantities for any of the other elements.

[0067] As used herein, the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is comprehensive or open-ended and does not exclude additional unlisted elements or method steps. However, in each use of “comprising” herein, the term is also intended to encompass the phrases “essentially from” and “consisting of,” where “consisting of” excludes any unspecified elements or steps, and “essentially from” allows for the inclusion of additional unlisted elements or steps that do not substantially affect the basic and novel characteristics of the composition or method under consideration.

[0068] For illustrative purposes, certain representative embodiments and details have been provided, but it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention. In this regard, the scope of the invention should be limited only by the following claims. The present invention provides, for example, the following items: (Item 1) A method for manufacturing an article, (1) To provide a dispersion-dyed fabric containing melt-spun thermoplastic polyurethane fibers, wherein the fibers contain a reaction product of (a)(i) a polyol component comprising a copolymer diol derived from a caprolactone monomer and a polyether polyol, (ii) a hydroxyl terminal chain extender component, and (iii) a first diisocyanate component, and (b) an isocyanate-functionalized prepolymer crosslinking agent. (2) Shredding the fabric, (3) Heat-treating the shredded fabric to form granules, (4) A method comprising melting and shearing the granules in an extruder to form an article. (Item 2) The method according to item 1, wherein the fabric further comprises a second fiber selected from thermoplastic polyurethane fibers, polyester fibers, nylon fibers, acrylic fibers, polypropylene fibers, or mixtures thereof. (Item 3) The method according to item 1 or 2, wherein the fabric contains up to 99% or up to 70% polyester fibers. (Item 4) The method according to any one of items 1 to 3, wherein the copolymer comprises a reaction product of a caprolactone monomer polyol and poly(tetramethylene ether glycol). (Item 5) The method according to item 4, wherein the copolymer comprises a reaction product of 50% by weight of caprolactone monomer polyol and 50% by weight of poly(tetramethylene ether glycol). (Item 6) The method according to any one of items 1 to 5, wherein the copolymer has a number average of about 2000 Daltons. (Item 7) The method according to any one of items 1 to 5, wherein the chain extender component consists of 1,4-bis(β-hydroxyethoxy)benzene. (Item 8) The method according to item 7, wherein the chain extender component further comprises a co-chain extender. (Item 9) The method according to item 8, wherein the co-chain extender is selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, hexamethylenediol, heptanediol, nonanediol, dodecanediol, 3-methyl-1,5-pentanediol, ethylenediamine, butanediamine, hexamethylenediamine, hydroxyethyl resorcinol, and mixtures thereof. (Item 10) The method according to any one of items 1 to 9, wherein the first diisocyanate component comprises or consists of an aromatic diisocyanate. (Item 11) The method according to item 10, wherein the first diisocyanate component comprises or consists of 4,4'-diphenylmethane diisocyanate. (Item 12) The method according to any one of items 1 to 10, wherein the reactive thermoplastic polyurethane composition contains 50% to 80% by weight, 60% to 80% by weight, or 70% to 80% by weight of the polyol component. (Item 13) The method according to any one of items 1 to 12, wherein the reactive thermoplastic polyurethane composition contains 5% to 25% by weight, 5% to 15% by weight, or 5% to 10% by weight of the chain extender component. (Item 14) The method according to any one of items 1 to 13, wherein the reactive thermoplastic polyurethane composition contains 15% to 30% by weight, 15% to 25% by weight, or 15% to 20% by weight of the first diisocyanate. (Item 15) The method according to any one of items 1 to 13, wherein the isocyanate-functionalized prepolymer crosslinking agent comprises or consists of a reaction product of poly(tetramethylene ether glycol) and a second diisocyanate component. (Item 16) The method according to any one of items 1 to 13, wherein the isocyanate-functionalized prepolymer crosslinking agent comprises or consists of a reaction product of neopentyl glycol adipate and a second diisocyanate component. (Item 17) The method according to item 15 or 16, wherein the second diisocyanate component comprises an aromatic diisocyanate. (Item 18) The method according to item 17, wherein the second diisocyanate component comprises or consists of 4,4'-methylenebis(phenylisocyanate). (Item 19) The method according to item 15 or 16, wherein the second diisocyanate component comprises an aliphatic diisocyanate. (Item 20) The method according to item 19, wherein the second diisocyanate component comprises or consists of dicyclohexylmethane-4,4'-diisocyanate. (Item 21) The method according to any one of items 1 to 20, further comprising the steps of providing a second polymer material and adding the second polymer together with the granules to the extruder. (Item 22) The method according to item 21, wherein the second polymer is selected from polyester or thermoplastic polyurethane. (Item 23) A method for manufacturing an article, (1) A step of providing a dispersion-dyed fabric comprising: (i) a first fiber component which is a thermoplastic rigid yarn having an ultimate elongation of 10% to 200%, 10% to 75%, or 10% to 60% as measured according to ASTM D2256; and (ii) a second fiber component which comprises a melt-spun thermoplastic polyurethane fiber having an ultimate elongation of at least 300% as measured according to ASTM D2731, wherein the first fiber component and the second fiber component are knitted together to form the fabric, and the fabric is dyed at a temperature of at least 130°C. (2) The step of shredding the fabric, (3) The step of heat-treating the shredded fabric to form granules, (4) A method comprising the step of melting and shearing the granules in an extruder to form an article. (Item 24) The melt-spun thermoplastic polyurethane fiber exhibits the following hysteresis after the fifth loading and unloading cycle: (a) Having less than 30% hysteresis at 100% elongation (b) Having less than 30% hysteresis at 150% elongation (c) Has less than 30% hysteresis when elongated to 200%. The method described in item 23, wherein hysteresis is measured according to ASTM D2731. (Item 25) The method according to item 23 or 24, wherein the second fiber component is a melt-spun thermoplastic fiber comprising a polyol component containing a copolymer diol derived from caprolactone monomer and poly(tetramethylene ether glycol), a hydroxyl terminal chain extender component, a reaction product of a first diisocyanate component, and an isocyanate-functionalized prepolymer crosslinking agent. (Item 26) The method according to item 25, wherein the copolymer diol comprises a reaction product of 50% by weight of a caprolactone monomer polyol and 50% by weight of poly(tetramethylene ether glycol). (Item 27) The method according to item 25 or 26, wherein the melt-spun thermoplastic polyurethane fiber has a weight-average molecular weight of 300,000 to 450,000 as measured by gel permeation chromatography. (Item 28) The method according to any one of items 25 to 27, wherein the first diisocyanate component comprises or consists of an aromatic diisocyanate. (Item 29) The method according to item 28, wherein the first diisocyanate component comprises or consists of 4,4'-diphenylmethane diisocyanate. (Item 30) The method according to any one of items 25 to 29, wherein the isocyanate-functionalized prepolymer crosslinking agent comprises or consists of a reaction product of poly(tetramethylene ether glycol) and a second diisocyanate component. (Item 31) The method according to any one of items 27 to 29, wherein the isocyanate-functionalized prepolymer crosslinking agent comprises or consists of a reaction product of neopentyl glycol adipate and a second diisocyanate component. (Item 32) The method according to item 30 or 31, wherein the second diisocyanate component comprises an aromatic diisocyanate. (Item 33) The method according to item 32, wherein the second diisocyanate component comprises or consists of 4,4'-methylenebis(phenylisocyanate). (Item 34) The method according to item 30 or 31, wherein the second diisocyanate component comprises an aliphatic diisocyanate. (Item 35) The fabric according to item 34, wherein the second diisocyanate component comprises or consists of dicyclohexylmethane-4,4'-diisocyanate. (Item 36) The fabric according to any one of items 23 to 35, wherein the first fiber is selected from thermoplastic polyurethane fiber, polyester fiber, nylon fiber, cotton fiber, wool fiber, acrylic fiber, polypropylene fiber, viscose rayon fiber, or a mixture thereof.

Claims

1. A method for manufacturing an article, (1) To provide a dispersion dyed fabric, wherein the dispersion dyed fabric comprises (a) a reaction product of a reactive thermoplastic polyurethane composition comprising (i) a polyol component comprising a copolymer diol derived from a caprolactone monomer and a polyether polyol, (ii) a hydroxyl terminal chain extender component, and (iii) a first diisocyanate component, and (b) an isocyanate-functional prepolymer crosslinking agent, and a second fiber selected from thermoplastic polyurethane fibers, polyester fibers, nylon fibers, acrylic fibers, polypropylene fibers, or mixtures thereof. (2) Shredding the fabric, (3) Heat-treating the shredded fabric to form granules, (4) A method comprising melting and shearing the granules in an extruder to form an article.

2. The method according to claim 1, wherein the fabric comprises up to 99% or up to 70% polyester fibers.

3. The method according to claim 1 or 2, wherein the copolymer comprises a reaction product of a caprolactone monomer polyol and poly(tetramethylene ether glycol).

4. The method according to claim 3, wherein the copolymer comprises a reaction product of 50% by weight of caprolactone monomer polyol and 50% by weight of poly(tetramethylene ether glycol).

5. The method according to any one of claims 1 to 4, wherein the copolymer has a number average of about 2,000 daltons.

6. The method according to any one of claims 1 to 4, wherein the chain extender component comprises 1,4-bis(β-hydroxyethoxy)benzene.

7. The method according to claim 6, wherein the chain extender component further comprises a co-chain extender.

8. The method according to claim 7, wherein the co-chain extender is selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, hexamethylenediol, heptanediol, nonanediol, dodecanediol, 3-methyl-1,5-pentanediol, ethylenediamine, butanediamine, hexamethylenediamine, hydroxyethyl resorcinol, and mixtures thereof.

9. The method according to any one of claims 1 to 8, wherein the first diisocyanate component includes or consists of an aromatic diisocyanate.

10. The method according to claim 9, wherein the first diisocyanate component includes or consists of 4,4'-diphenylmethanediisocyanate.

11. The method according to any one of claims 1 to 9, wherein the reactive thermoplastic polyurethane composition contains 50% to 80% by weight, 60% to 80% by weight, or 70% to 80% by weight of the polyol component.

12. The method according to any one of claims 1 to 11, wherein the reactive thermoplastic polyurethane composition contains 5% to 25% by weight, 5% to 15% by weight, or 5% to 10% by weight of the chain extender component.

13. The method according to any one of claims 1 to 12, wherein the reactive thermoplastic polyurethane composition contains 15% to 30% by weight, 15% to 25% by weight, or 15% to 20% by weight of the first diisocyanate.

14. The method according to any one of claims 1 to 13, wherein the isocyanate-functionalized prepolymer crosslinking agent includes or consists of a reaction product of poly(tetramethylene ether glycol) and a second diisocyanate component.

15. The method according to any one of claims 1 to 13, wherein the isocyanate-functionalized prepolymer crosslinking agent includes or consists of a reaction product of neopentyl glycol adipate and a second diisocyanate component.

16. The method according to claim 14 or 15, wherein the second diisocyanate component comprises an aromatic diisocyanate.

17. The method according to claim 16, wherein the second diisocyanate component includes or consists of 4,4'-methylenebis(phenylisocyanate).

18. The method according to claim 14 or 15, wherein the second diisocyanate component comprises an aliphatic diisocyanate.

19. The method according to claim 18, wherein the second diisocyanate component includes or consists of dicyclohexylmethane-4,4'-diisocyanate.

20. The method according to any one of claims 1 to 19, further comprising the steps of providing a second polymer material and adding the second polymer together with the granules to the extruder.

21. The method according to claim 20, wherein the second polymer is selected from polyester or thermoplastic polyurethane.

22. A method for manufacturing an article, (1) A step of providing a dispersion-dyed fabric comprising: (i) a first fiber component which is a thermoplastic rigid yarn having an ultimate elongation of 10% to 200%, 10% to 75%, or 10% to 60% as measured according to ASTM D2256; and (ii) a second fiber component which comprises a melt-spun thermoplastic polyurethane fiber having an ultimate elongation of at least 300% as measured according to ASTM D2731, wherein the first fiber component and the second fiber component are knitted together to form the fabric, and the fabric is dyed at a temperature of at least 130°C. (2) The step of shredding the fabric, (3) The step of heat-treating the shredded fabric to form granules, (4) A method comprising the step of melting and shearing the granules in an extruder to form an article.

23. The melt-spun thermoplastic polyurethane fiber exhibits the following hysteresis after the fifth loading and unloading cycle: (a) Having a hysteresis of less than 30% at 100% elongation (b) Having less than 30% hysteresis at 150% elongation (c) Having less than 30% hysteresis at 200% elongation The method according to claim 22, wherein the hysteresis is measured according to ASTM D2731.

24. The method according to claim 22 or 23, wherein the second fiber component is a melt-spun thermoplastic fiber comprising a polyol component containing a copolymer diol derived from caprolactone monomer and poly(tetramethylene ether glycol), a hydroxyl terminal chain extender component, a reaction product of a first diisocyanate component, and an isocyanate-functionalized prepolymer crosslinking agent.

25. The method according to claim 24, wherein the copolymer diol comprises a reaction product of 50% by weight of a caprolactone monomer polyol and 50% by weight of poly(tetramethylene ether glycol).

26. The method according to claim 24 or 25, wherein the melt-spun thermoplastic polyurethane fiber has a weight-average molecular weight of 300,000 to 450,000 as measured by gel permeation chromatography.

27. The method according to any one of claims 24 to 26, wherein the first diisocyanate component includes or consists of an aromatic diisocyanate.

28. The method according to claim 27, wherein the first diisocyanate component comprises or consists of 4,4'-diphenylmethanediisocyanate.

29. The method according to any one of claims 24 to 28, wherein the isocyanate-functionalized prepolymer crosslinking agent includes or consists of a reaction product of poly(tetramethylene ether glycol) and a second diisocyanate component.

30. The method according to any one of claims 24 to 28, wherein the isocyanate-functionalized prepolymer crosslinking agent includes or consists of a reaction product of neopentyl glycol adipate and a second diisocyanate component.

31. The method according to claim 29 or 30, wherein the second diisocyanate component comprises an aromatic diisocyanate.

32. The method according to claim 31, wherein the second diisocyanate component includes or consists of 4,4'-methylenebis(phenylisocyanate).

33. The method according to claim 29 or 30, wherein the second diisocyanate component comprises an aliphatic diisocyanate.

34. The method according to claim 33, wherein the second diisocyanate component includes or consists of dicyclohexylmethane-4,4'-diisocyanate.

35. The method according to any one of claims 22 to 24, wherein the first fiber component is selected from thermoplastic polyurethane fibers, polyester fibers, nylon fibers, cotton fibers, wool fibers, acrylic fibers, polypropylene fibers, viscose rayon fibers, or mixtures thereof.

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