WO2014210378A2 - Polyurethaneurea fiber including glycol blend - Google Patents

Abstract

Included is a polyurethane elastic fiber that includes a blended glycol. A polyether glycol, such as PTMEG is partially replaced with PPG. The ratio of total isocyanate (NCO) end groups from the prepolymer to total primary amine (NH₂) end groups from the diamine chain extender is about 0.99 to about 1.01; and the combined amount of non-reactive end groups from the PPG and dialkylurea end groups in the polyurethaneurea is less than about 50 meq/kg.

Description

POLYURETHANEUREA FIBER INCLUDING GLYCOL BLEND

Background of the Invention

Field of the Invention

The present invention solved the problem of using a PPG with high concentration of non- reactive end groups such as unsaturation or monol end groups to substitute a portion of a polyether glycol, such as PTMEG in spandex production, which allows reduction the ingredient cost in manufacturing and provides unique yarn properties (low hysteresis and high elongation) for improved fabrics.

Description of the Related Art

Attempts have been made in the past to use mixed or blended glycols of

polytetramethylene ether glycol, hereinafter "PTMEG" and polypropylene glycol, hereinafter "PPG" for spandex fibers. PTMEG has been the typical glycol for spandex fibers, however, it has high ingredient cost considering its total content in spandex fibers. PPG's are generally not desired due to the high amounts of non-reactive end groups such as unsaturation or monol end groups in the polymer. To overcome this problem, PPGs with lower monol concentrations are often produced by special technologies such as double metal cyanide complex catalyst, but cost more than those made with conventional alkali metal hydroxide catalyst. Alternatively, a low level crosslinking agent with functionality of higher than 2.0 is used to compensate the negative impact of monol concentration in PPG in order to achieve high enough polymer molecular weight for spandex product performance requirements. The use of such kind of crosslinking agents often introduces processing difficulties, such as polymer gel formation, in fiber formation.

U.S. Patent No. 5,691,441 discloses a segmented polyurethane/urea spandex elastomer made from an isocyanate-terminated prepolymer derived from mixtures of polytetramethylene ether glycols (PTMEG) and ultra-low unsaturation, high molecular weight polyoxyalkylene diols. In this case, the PPG with an average unsaturation of less than about 10 meq/kg is used.

U.S. Patent No. 5,998,574 discloses a glycol blend composition including blends of polytetramethylene ether glycols (PTMEG) and difunctional active hydrogen compound-initiated polyoxyalkylene ether polyols having a low degree of unsaturation of 40 meq/kg or less for applications in cast elastomers, spandex fibers and thermoplastic polyurethanes.

U.S. Patent 6,255,431 B1 discloses a glycol blend comprising polytetramethylene ether glycols (PTMEG) and a trifunctional active hydrogen compound-initiated polyoxyalkylene ether

l polyol having a degree of unsaturation of not greater than 40 meq/kg for applications of cast elastomers, spandex fibers and thermoplastic polyurethanes.

Chinese Patent 101575406B discloses a method of preparing a spandex polymer solution with the use of a glycol blend of PTMEG and a PPG where the unsaturation degree in the PPG is less than 30 meq/kg.

All patents, discussed above, using glycol blends of PTMEG and PPG in preparation of spandex polymers are limited to PPGs with ultra-low unsaturation level (<10 meq/kg) or low unsaturation level (<40 meq/kg). The preparation of PPGs with low/ultra-low unsaturation level is costly resulting in a fiber that is not commercially competitive.

Summary of the Invention

PPG in general is a low cost glycol compared to PTMEG. Substituting a portion of a more expensive polyether glycol, such as PTMEG with PPG is desired not only for reducing spandex ingredient cost, but also for modifying the spandex yarn properties such as for reduced hysteresis in stretch cycles and for increased yarn break elongation or higher draftability.

However, the use of conventional PPG in making spandex fibers is often prohibited by the presence of excessive non-reactive or unsaturation end groups or monols of the PPG which function as polymer chain terminators and inhibit the formation of high molecular weight polymers. There is a need for a solution to this problem that does not require the use of PPGs with lower monol concentrations, typically not more than 40 meq/kg, in order to achieve acceptable spandex properties.

In one aspect, is an elastomeric fiber which is made from a new polyurethaneurea composition based on a combination of polyether glycols including PPG and a different polyether glycol, such as PTMEG where the PPG has a high concentration of non-reactive end groups, in other words, non-reactive or unsaturation or monol end groups. The glycol blend is reacted with excess diisocyanate in prepolymerization stage, chain extended with a diamine or a diamine mixture and optionally terminated with a dialkylamine in an aprotic polar solvent, and then spun into fibers through a solution spinning process, specifically a dry-spinning process or a wet-spinning process. The deficiency of high concentration of unsaturation or monol end groups is overcome by maximizing the polymer molecular weight.

In some aspects, the concerns of using a PPG with high concentration of non-reactive end groups such as non-reactive or unsaturation or monol end groups are addressed by substituting with a portion of glycol amount with another polyether glycol such as PTMEG in spandex production, which allows reduction of the ingredient cost in manufacturing process and provides unique yarn properties such as low hyteresis and high elongation for improved fabric performance.

In some aspects is an article including a polyurethaneurea which is the reaction product of:

(a) a prepolymer comprising the reaction product of

(i) a polyol including PPG and another polyol such as PTMEG; and

(ii) a diisocyanate; and

(b) a diamine chain extender; and optionally a dialkyl amine terminator

wherein a ratio of total isocyanate (NCO) end groups from the prepolymer to total primary amine (NH₂) end groups from the diamine chain extender is about 0.99 to about 1.01 ; and the combined amount of non-reactive end groups from the PPG and dialkylurea end groups in the polyurethaneurea is less than about 50 meq/kg.

In another aspect is an article including at least one elastomeric fiber including a polyurethaneurea which is the reaction product of:

(a) a capped glycol comprising the reaction product of

(i) a polyol including PPG and another polyol such as PTMEG; and

(ii) a diisocyanate; and

(b) a diamine chain extender; and optionally a dialkyl amine terminator

wherein a ratio of the total isocyanate (NCO) end groups from the prepolymer to a total primary amine (NH2) end groups from the diamine chain extender is about 0.99 to about 1.01 ; and the amount of non-reactive end groups and dialkylurea end groups is less than about 50 meq/kg.

A further aspect provides a process for making spandex including of:

(a) providing a polyol including PPG and another polyol such as PTMEG;

(b) providing a diisocyanate;

(c) contacting the polyol and diisocyanate to form a capped glycol;

(d) providing a diamine chain extender in an amount to control a ratio of the total isocyanate (NCO) end groups from the prepolymer to a total primary amine (NH2) end groups from the diamine chain extender to about 0.99 to about 1.01 ;

(e) optionally providing a dialkylamine chain terminator in an amount to control the polymer molecular weight in a way that the combined amount of non-reactive end groups and dialkylurea end groups in said polyurethaneurea is less than about 50 meq/kg;

(f) contacting the capped glycol, the chain extender and the chain terminator composition in a solvent to form a polyurethaneurea in solution; and

(g) spinning the polyurethaneurea in solution to form the spandex fibers. Optionally, PTMEG can be replaced with polyester or polycarbonate glycols for blending with PPG in the present invention.

Detailed Description

Definitions

A fiber is defined herein as a shaped article in form of thread or filament with an aspect ratio, the ratio of length to diameter, of more than 200. A "fiber" can be single filament or multifilament, and can be used interchangeably with a "yarn".

Spandex fiber meets the definition of "a manufactured fiber in which the fiber-forming substance is a long chain synthetic polymer comprised of at least 85% of a segmented polyurethane". These are elastomeric fibers.

A glycol used herein is defined as a polymeric diol with a hydroxyl group at each chain end. This term can used be interchangeably with a polyol.

A poly(tetramethylene ether) glycol (PTMEG) is defined as a glycol made with 1 ,4- butanediol or tetrahydrofuran (THF) as the major monomer ingredient (at least 50% in mole percentage), including homopolymers and copolymers containing tetramethylene ether repeat units.

A poly(propylene ether) glycol or polypropylene glycol (PPG) is defined as a glycol made with 1 , 2-propylene oxide [CAS number 75-56-9] as the major ingredient (>50% in mole percentage), including the homopolymers and copolymers containing propylene ether repeat units.

The %NCO of the prepolymer or the capped glycol is defined as the weight percent of - NCO groups in the capped glycol prepolymer after completion of the capping reaction, which can be determined experimentally by a titration method.

The capping ratio (CR) is defined as the molar ratio of the diisocyanate to the glycol used in the prepolymerization. In case of multiple diisocyanates and/or glycols are used in the reaction, the average molecular weights should be used in calculating the capping ratio.

Assuming both diisocyanates and glycols are all bi-functional, the capping ratio is the same as the ratio of total number of isocyanate (-NCO) groups to the total number of hydroxyl (-OH) groups. As used herein, a "solvent" refers to an organic solvent such as dimethylacetamide (DMAC), dimethylformamide, (DMF) and -methylpyrrolidone (NMP) in which the spandex polymer can form a homogeneous solution.

An additive is defined herein as a substance added in the fiber in small amount to improve the appearance, performance and quality in manufacture, storage, processing and use of the fiber. An additive by itself may not be capable of fiber forming.

In some aspects are spandex fibers based on segmented polyurethaneureas including mixed polyether glycols for textile applications including fabrics with knitting, weaving, non- wovens and laminated articles. The spandex fibers, and fabrics containing such spandex fibers, may include the reaction product of a mixture of at least one polypropylene ether glycol (PPG) and at least one other polyether glycol such as polytetramethylene ether glycol (PTMEG). In the glycol blend the weight percent of the other polyether glycol, such as PTMEG may be used in any suitable amount such as more than about 50% by weight of the glycol blend and the PPG which is added to the blend has non-reactive end groups, such as unsaturation end groups or monol at about 40 to about 90 meq/kg.

The stress-strain properties of a polymeric material are greatly influenced by its molecular weight and molecular weight distributions. It is known that a certain weight average polymer molecular weight (Mw), so called "inflection molecular weight", exists for thermoplastic polyurethane elastomers, below which the properties continue to change and above which such trend levels off gradually with the increasing polymer molecular weight. Depending on the specific polyurethane compositions and specific properties, this inflection molecular weight by weight average is typically in the range of 100,000 to 200,000 g/mol. This phenomenon also exists for spandex polymers which are segmented polyurethanes including polyurethaneureas. In general, a minimum polymer molecular weight is required for the spandex fibers to develop adequate stretch and recovery properties and higher molecular weight is preferred to balance the tensile properties such as break elongation and tenacity. In addition, such polymer molecular weight should also be controlled in a reasonable range for processability

considerations in spandex fiber manufacturing as the polymer molecular weight can directly impact the viscosity in a solution.

The intrinsic viscosity of the polymer is an indicator of the molecular weight of the polymer. The polyurethaneurea including the glycol blend may have an intrinsic viscosity of 0.93 to about 1.02 dL/g.

A segmented polyurethaneurea can be made with mixed or blended glycols for spandex fibers for ingredient cost reductions or for property modifications. PPG in general is a low cost glycol compared to PTMEG or other polyether glycols. Substituting a portion of a spandex including PTMEG with PPG is desired not only for reducing spandex ingredient cost, but also for modifying the spandex yarn properties such as for reduced hysteresis in stretch cycles and for increased yarn break elongation or higher draftability.

Some aspects include of a segmented polyurethaneurea useful for the preparation of spandex with the use of mixed or blended glycols including a polyether glycol, such as poly(tetramethylene ether) glycol (PTMEG) and a polypropylene ether) glycol (PPG) for ingredient cost reduction and for product performance enhancement.

The PPG glycol useful for making the spandex fiber has relatively high concentration of non-reactive end groups, such as unsaturation or monol end groups, in a range of about 40 to about 90 meq/kg, such as about 45 to about 90 meq/kg or about 50 to about 90 meq/kg or about 50 to about 70 meq/kg or about 45 to about 70 meq/kg. The weight percent of the PPG in the mixed glycol is in a range of about 10% to about 50%, such as about 20% to about 40% or about 30% to about 50%. The spandex fiber with such mixed glycols has higher elongation at break and lower hysteresis in stretch-recovery cycles than the spandex fiber with PTMEG only. The PPG has a number average molecular weight about 1000 to about 5000, such as about 1000 to about 4000. When the polyether glycol is PTMEG it may have a number average molecular weight of about 600 to about 2900. Other suitable ranges include about 1600 to about 2200, and about 1800 to about 2000. The PTMEG and PPG are blended together may have a number average molecular weight about 1000 to about 4000, such as about 1800 to about 3600 or 1800 to 2500. .

Suitable polyether glycols, or polyether polyols, may include number average molecular weight of about 600 to about 7,000, including from about 1,000 to about 7,000 and about 2,000 to about 7,000. Mixtures of two or more polyols (in addition to the PPG) or copolymers can be included.

Examples of polyether polyols that can be used include those glycols with two or more hydroxy groups, from ring-opening polymerization and/or copolymerization of ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran, or from condensation polymerization of a polyhydric alcohol, such as a diol or diol mixtures, with less than 12 carbon atoms in each molecule, such as ethylene glycol, 1 ,3-propanediol, 1 ,4- butanediol, 1,5-pentanediol, 1 ,6-hexanediol, neopentyl glycol, 3-methyI-1 ,5-pentanediol, 1 ,7- heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10-decanediol and 1 ,12-dodecanediol. A linear, bifunctional polyether polyol is preferred, and a poly(tetramethylene ether) glycol of molecular weight of about 1 ,700 to about2900, such as Terathane® 1800 (INVISTA of Wichita, KS) with a functionality of 2, is one example of a specific suitable polyol. Copolymers can include poly(tetramethyleneether-co-ethyleneether) glycol and poly(tetramethylene ether-co-2- methyltetramethylene ether) glycol.

Examples of polyester glycols include those polyesters with two hydroxyl terminal groups such as polycaprolactone diol and those produced by condensation polymerization of aliphatic dicarboxylic acids and diols, or their mixtures, of low molecular weights with no-more than 12 carbon atoms in each molecule. 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. Example of suitable polyols for preparing the 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. A linear, bifunctional polyester polyol with a melting temperature or softening temperature below 55°C is preferred. Examples of polycarbonate glycols include those polycarbonates with two hydroxyl terminal groups, produced by condensation polymerization of aliphatic diols with phosgene,

dialkylcarbonates or diarylcarbonates. Example of suitable diols for preparing the polycarbonate glycols are 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, 1 ,12- dodecanediol or their mixtures, and oligomeric polyester or polyether diols. A linear, bifunctional polycarbonate polyol with a melting temperature or softening temperature below 55°C is preferred.

Another aspect is a method to produce the spandex fiber including a polyurethaneurea with the use of mixed or blended glycols including a polyether polyol and a PPG of relatively high concentration of non-reactive end groups or unsaturation or monol end groups. The mixed glycol is reacted with an excess diisocyanate to form an isocyanate-terminated prepolymer, the prepolymer is diluted with an aprotic polar solvent and further reacted with an aliphatic diamine or a diamine mixture chain extender and a dialkylamine terminator in the solvent, and the formed polyurethaneurea solution is then spun into fibers through a solution spinning process such as a dry-spinning process or a wet-spinning process. The polymer molecular weights of the spandex polymer are controlled, before and after the fiber formation, in a way to overcome the deficiency of high non-reactive end group/monol concentration in the glycol and to balance the needs for manufacturing processability and for product performance. Specifically, the polymer molecular weight is controlled by keeping the relative ratio of individual components participating in the chain extension and chain termination reactions such that: (a) the concentration ratio of the isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to the primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures is in a range of 0.99 to 1.01 , such as at about 1.00, and

(b) the sum of the dialkylamine from the terminator and monol end groups from PPG

is less than about 50 milliequivalent per kilogram (meq/kg) of the polymer,

including about 20 to 40 meq/kg of the polymer.

In other words, the polyurethaneurea polymer has total non-reactive end groups in an amount of less than about 50 meq/kg, including about 10 meq/kg to about 45 meq/kg or about 20to 40 meq/kg.

A further aspect is a fabric. Several methods of preparing fabrics are known in the art. Examples include knitting or weaving or laminating. These articles may include about 1% to about 30% by weight of the inventive spandex fiber. Such fabrics have soft stretch without sacrificing recovery power.

An article of some aspects may be a yarn, a covered yarn, a woven fabric, a nonwoven fabric, a knit or a laminated article. A knit may be a warp knit or a circular knit. Suitable laminated articles may include one more layers of a fabric, film, etc. between which spandex fibers are placed and adhered or bonded.

The polyurethaneurea for the spandex fibers may be prepared by a two-step process.

In the first step, an isocyanate-terminated urethane prepolymer or capped glycol is formed by reacting a blend of two or more glycols with a diisocyanate. In the glycol blend, at least one of the components is polyether polyol such as a poly(tetramethylene ether) glycol (PTMEG) or a copolyether glycol containing at least 50 mole percent of tetramethylene ether repeat units, and at least another component in the glycol blend is a poly(propylene ether) glycol (PPG) including copolyethers with at least 50 more percent of propylene ether repeat units. The PTMEG or its copolyether glycol has at least 50% by weight in the blended glycol and has the number average molecular weight in a range of 1000 to 4000, including 1000 to 3000. The PPG or its copolyether glycol has at least 10% by weight of the blended glycol and has the number average molecular weight in a range of 1000 to 5000. Furthermore, the PPG glycol used for such glycol blend is with relatively high concentration of unsaturation or monol end groups, in a range of 40 to 90 milliequivalent, preferably 40 to 70 milliequivalent per kilogram (meq/kg) of the PPG glycol. The capping ratio for making the prepolymer, that is the molar ratio of the diisocyanate to the blended glycol, or the ratio of total number of isocyanate groups (-NCO) to the total number of hydroxyl groups (-OH), is controlled in a range of about 1.50 to about 2.50. Optionally, catalyst can be used to assist the reaction in this prepolymerization step.

In the second step, the urethane prepolymer or the capped glycol is dissolved in a solvent such as A/,A/-dimethylacetamide (DMAc) to form a solution from 30 to 50% solids content. This diluted capped glycol solution is then chain extended with a low molecular weight aliphatic primary diamine or a mixture of diamines and optionally terminated with a small amount of dialkylamine at the same time to form the polyurethaneurea solution. The amount of the diamine chain extender or extenders used should be controlled in such a way that the ratio of the total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures is in a range of 0.99 to 1.01 , such as at about 1.00. The terminator amount is controlled in a way that the sum of the dialkylamine from the terminator and monol end groups from PPG is less than 50 milliequivalent per kilogram (meq/kg) of the polymer solids, preferably in a range of 20 to 40 meq/kg of the polymer solids.

Additional solvent can be added, during or after the chain extension step, to the polymer solution to adjust the polymer solids in the solution and the solution viscosity. Typically, the solids content in the solution is controlled in a range of 30 to 50% by weight of the solution, and the solution viscosity after the chain extension step is controlled in a range of 2000 to 3500 poises measured at 40°C by falling ball method.

The additives can be mixed into the polymer solution at any stage after the

polyurethaneurea is formed but before the solution is spun into the fibers. The solid content including the additives in the polymer solution prior to spinning is typically controlled in a range of 30.0% to 50.0% by weight of the solution. The viscosity of the solution kept in the storage tank prior to spinning is typically controlled in a range from 3000 to 5000 poise by adjusting the ageing time, agitation speed and tank temperature for optimum spinning performance.

Examples of PTMEG and copolyether glycols include, but are not limited to, Terathane® glycol from INVISTA (Wichita, Kansas, U.S.A.), POLYMEG polyols from LyondellBasell (Houston, Texas, U.S.A), PolyTHF® glycols from BASF (Geismer, Louisiana, U.S.A.), PTG polyols from Dairen Chemical Corp. (DCC) (Taipei, Taiwan), PTMG glycols from Mitsubishi Chemical Corp (MCC) (Tokyo, Japan), PTMEG glycols from Tianhua Fubang Chemical Industry Ltd Co (Luzhou, Sichuan, China), and PTG & PTG-L glycols from Hodogaya Chemical Co. (Tokyo, Japan).

Examples of PPG glycol and copolyether glycols include, but are not limited to,

Pluracol® polyether polyols from BASF (Wyandotte, Michigan, U.S.A.), Multranol® and Arcol® polyether polyols from Bayer MaterialScience (Leverkusen, Germany), VORANOL polyether polyols from Dow Chemical (Midland, Michigan, U.S.A.), Poly-L® polyether polyols from Lonza Group Ltd (Basel, Switzerland), and polyether polyols from SINOPEC Gaoqiao Petrochemical Co. (Shanghai, China).

Examples of diisocyanates that can be used include, but are not limited to 4,4'- methylene bis(phenyl isocyanate) (also referred to as 4,4'diphenylmethane diisocyanate (MDI), 2,4'- methylene bis(phenyl isocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1 ,4- xylenediisocyanate, 2,6-toluenediisocyanate, 2,4-toluenediisocyanate, and mixtures thereof. Examples of specific polyisocyanate components include Takenate® 500 (Mitsui Chemicals), Mondur® MB (Bayer), Lupranate® M (BASF), and Isonate® 125 MDR (Dow Chemical), and combinations thereof.

Examples of suitable diamine chain extenders include one or more diamines selected from 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-l,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); isophorone diamine; 2,2-dimethyl-l,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-xylylene diamine; and Jeffamine® (Texaco).

Examples of suitable monofunctional dialkylamine chain terminators include N,N- diethylamine, A/-ethyl-N-propylamine, A/,A/-diisopropylamine, A/-tert-butyl-A/-methylamine, /V-tert- butyl-W-benzylamine, A/,A/-dicyclohexylamine, W-ethyl-N-isopropylamine, W-tertbutyl-N- isopropylamine, A/-isopropyl-A/-cyclohexylamine, A/-ethyl-W-cyclohexylamine, N,N- diethanolamine, and 2,2,6, 6-tetramethylpiperidine.

Exemplary and non-limiting list additives that may be optionally included are antioxidants, UV stabilizers/screeners, colorants, pigments, cross-linking agents, antimicrobials, microencapsulated additives, flame retardants, anti-tack additives (metal stearates), chlorine degradation resistant additives, dyeability and/or dye-assist agents, delustrant such as titanium dioxide, stabilizers such as hydrotalcite, a mixture of huntite and hydromagnesite, and combinations thereof. Other additives which may be included in the spandex compositions such as adhesion promoters, anti-static agents, optical brighteners, electro-conductive additives, luminescent additives, lubricants, organic and inorganic fillers, preservatives, texturizing agents, wetting agents, stabilizers (hindered phenols, zinc oxide, hindered amine), slip agents(silicone oil) and combinations thereof.

The polyurethaneurea polymer solution prepared as described above is then spinning into spandex fibers through a dry-spinning process as is known in the art.

The features and advantages of the present invention are more fully shown by the following examples which are provided for purposes of illustration, and are not to be construed as limiting the invention in any way.

TEST METHODS

The viscosity of the polymer solutions was determined in accordance with the method of ASTM D1343-69 with a Model DV-8 Falling Ball Viscometer (Duratech Corp., Waynesboro, VA), operated at 40°C and reported as poises.

The solid content in the polymer solutions was measured by a microwave heated moisture/solids analyzer, Smart System 5 (CEM Corp. (Matthews, NC).

Percent isocyanate (%NCO) of the capped glycol prepolymer was determined according to the method of S. Siggia."Quantitative Organic Analysis via Functional Group", 3rd Edition, Wiley & Sons, New York, pages 559-561 (1963) using a potentiometric titration.

The strength and elastic properties of the spandex and films were measured in accordance with the general method of ASTM D 2731-72. Three filaments, a 2-inch (5-cm) gauge length and a 0-300% elongation cycle were used for each of the measurements. The samples were cycled five times at a constant elongation rate of 50 centimeters per minute. Load power (TP2), the stress on the spandex during initial extension, was measured on the first cycle at 200% extension and is reported as gram-force for a given denier. Unload power (TM2) is the stress at an extension of 200% for the fifth unload cycle and is also reported in gram-force. Percent elongation at break (ELO) and tenacity (TEN) were measured on a sixth extension cycle. Stress decay (%SD) was measured as the percentage of the stress reduction in the fifth cycle after a 30 second delay at 300%

%SD = (5LP - 5UP) x 100 / 5LP

Where 5LP and 5UP in gram-force are respectively the load power and unload power at 300% extension of the sample.

Percent set was also measured on samples that had been subjected to five 0 -300% elongation/relaxation cycles. The percent set, %SET, was then calculated as

%SET = 100 x (Lf - Lo)/Lo where Lo and Lf are respectively the filament (yarn) length when held straight without tension before and after the five elongation/relaxation cycles.

EXAMPLES

Terathane® 1800 is a linear poly(tetramethylene ether) glycol (PTMEG), with a number average molecular weight of 1 ,800 g/mol (commercially available from Invista, S. a. r. L, of Wichita, KS);

Pluracol® 1062 is a linear polypropylene polyol with primary hydroxyl end groups which includes an ethylene oxide cap of 18% by weight based on the total weight of the polyol and has a number average molecular weight of 4000 g/mol, commercially available from BASF

Corporation of Wyandotte, Mich.. This glycol has a maximum unsaturation level of 65 milliequivalent per kg according to its specifications and the unsaturation level for the specific lot used for the inventive spandex fiber was 59 milliequivalent per kg as determined by the supplier.

Isonate® 125MDR is a pure mixture of diphenylmethane diisocyanate (MDI) containing 98% 4,4'-MDI isomer and 2% 2,4'-MDI isomer (commercially available from the Dow Company, Midland, Michigan);

Dytek® A is 2-methyl-1 ,5-pentamethylenediamine (MPMD) (commercially available from Invista, S. a. r. L, of Wichita, KS) ;

Terathane® 2900 is a linear poly(tetramethylene ether) glycol (PTMEG), with a number average molecular weight of 2,900 g/mol (commercially available from Invista, S. a. r. L, of Wichita, KS and Wilmington, DE);

Terathane® E 2049 is a linear copolyether glycol of tetrahydrofuran and ethyleneoxide, with a number average molecular weight of 2,000 g/mol and about 49 mole percent of ethylene ether repeat units, from Invista, S. a. r. L, of Wichita, KS and Wilmington, DE;

Terathane® E 2549 is a linear copolyether glycol of tetrahydrofuran and ethyleneoxide, with a number average molecular weight of 2,500 g/mol and about 49 mole percent of ethylene ether repeat units, from Invista, S. a. r. L, of Wichita, KS and Wilmington, DE;

Terathane® E 2538 is a linear copolyether glycol of tetrahydrofuran and ethyleneoxide, with a number average molecular weight of 2,500 g/mol and about 38 mole percent of ethylene ether repeat units, from Invista, S. a. r. L, of Wichita, KS and Wilmington, DE;

PTG-L2200 is a linear copolyether glycol of tetrahydrofuran and 3-methyl- tetrahydrofuran, with a number average molecular weight of 2,200 g/mol and about 8 mole percent of 2-methyl-tetramethylene ether repeat units, from Hodogaya Chemical Co., Ltd., Tokyo, Japan; PTG-L3500 is a linear copolyether glycol of tetrahydrofuran and 3-methyl- tetrahydrofuran, with a number average molecular weight of 3,500 g/mol and about 13 mole percent of 2-methyl-tetramethylene ether repeat units, from Hodogaya Chemical Co., Ltd., Tokyo, Japan;

Desmophen® C 2200 is a linear aliphatic polycarbonate diol (CAS# 101325-00-2), with a number average molecular weight of 2,000 g/mol, commercially available from Bayer

MaterialScience, Pittsburgh, PA;

Polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone glycol is a tri-block copolymer with a number average molecular weight at about 2000 g/mol, from Sigma-Aldrich Co., St. Louis, MO;

VORANOL™ 222-056 polyol is a linear polyether diol based on propylene oxide with ethylene oxide capping at the ends and has a number average molecular weight of 2000 g/mol, commercially available from the Dow Company, Midland, Michigan. The unsaturation level for the specific lot used for the inventive spandex fiber was 50 milliequivalent per kg as provided by the supplier;

EDA stands for ethylenediamine;

DETA stands for diethylenetriamine;

DEA stands for Ν,Ν-diethylamine as the chain terminator

Fiber Example 1 (Comparative)

Terathane® 1800 glycol of 100.00 parts by weight was mixed and reacted with Isonate® 125MDR MDI of 23.47 parts, with the capping ratio (NCO/OH) at 1.69, to form an isocyanate- terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.60% of the prepolymer. This prepolymer was then dissolved in Ν,Ν-dimethylacetamide (DMAc) of 165.52 parts. This diluted prepolymer solution was allowed to react with a mixture of amines in DMAc solution, containing 1.94 parts of EDA, 0.42 parts of Dytek*A, 0.03 parts of DETA, 0.42 parts of DEA and 71.05 parts of DMAc using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 34.8% and a viscosity of 2600 poises measured at 40°C. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivelents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.05 and the end group concentration from

diethylamine terminator was about 45 meq per kg of the polymer solids.

This polymer solution was mixed with a slurry of additives including 4.0% bleach resistant agent, 0.17% delustrant, 1.35% antioxidant, 0.5% dye-assist agent, 0.3% spinning aid and 0.4% anti-tack additive based on the solid weight. This mixture was spun into 40 denier spandex yarn with 4 filaments twisted together at a wound-up speed of 930 meters per minute. The as-spun yam properties of this test item were measured and listed in Table 1.

Fiber Example 2:

Terathane® 1800 glycol of 44.49 parts by weight was blended with Pluracol® 1062 polyol of 22.25 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 13.26 parts, with the capping ratio (NCO/OH) at 1.75, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.38% of the prepolymer. This prepolymer was then dissolved in Ν,Ν-dimethylacetamide (DMAc) of 99.60 parts. This diluted prepolymer solution was allowed to react with 11.41 parts of a mixture of diamine extender in DMAc solution (containing 1.22 parts of EDA, 0.26 parts of Dytek®A, 0.01 parts of DETA and

9.92 parts of DMAc) and 8.00 parts of DEA in DMAc solution (containing 0.07 parts of DEA and

7.93 parts of DMAc) with additional 34.01 parts DMAc using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 35.0% and a viscosity of 2600 poises measured at 40°C. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivelents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.00, and the end group concentration from diethylamine terminator was about 12 milliequivalent per kg of the polymer solids and the monol end groups from PPG was about 16 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was mixed with a slurry of additives including 4.0% bleach resistant agent, 0.17% delustrant, 1.35% antioxidant, 0.5% dye-assist agent, 0.3% spinning aid and 0.4% anti-tack additive based on the solid weight. This mixed solution was spun into 40 denier spandex yarn with 4 filaments twisted together at a wound-up speed of 930 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 1.

Fiber Example 3 (comparative)

Terathane® 1800 glycol of 200.00 parts by weight was blended with Pluracol® 1062 polyol of 100.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 59.84 parts, with the capping ratio (NCO/OH) at 1.75, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.40% of the prepolymer. This prepolymer was then dissolved in Ν,Ν-dimethylacetamide (DMAc) of 578.22 parts. This diluted prepolymer solution was allowed to react with 201.86 parts of a mixture of diamine extender in DMAc solution (containing 5.46 parts of EDA, 1.17 parts of Dytek®A, and 195.23 parts of DMAc) and 8.00 parts of DEA in DMAc solution (containing 0.70 parts of DEA and 7.30 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0% and a viscosity of 301 1 poises measured at 40°C. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivelents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.02, and the end group concentration from diethylamine terminator was about 20 milliequivalent per kg of the polymer solids and the monol end groups from PPG was about 18 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was not able to spin into 40 denier fibers with 4 filaments due to frequent breaks in the spinning cell.

Fiber Example 4: (comparative)

Terathane® 2000 glycol of 200.00 parts by weight was blended with Pluracol® 1062 polyol of 100.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 56.78 parts, with the capping ratio (NCO/OH) at 1.82, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.46% of the prepolymer. This prepolymer was then dissolved in Ν,Ν-dimethylacetamide (DMAc) of 575.30 parts. This diluted prepolymer solution was allowed to react with 203.78 parts of a mixture of diamine extender in DMAc solution (containing 5.51 parts of EDA, 1.18 parts of Dytek®A, and 97.08 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0%. The solution viscosity was too high to be measured by falling ball method at 40°C. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivelents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.03, and the end group concentration was only the monol end groups from PPG at about 18 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was not able to spin into 40 denier fibers with 4 filaments due to frequent breaks in the spinning cell.

Fiber Example 5:

Terathane® 2000 glycol of 200.00 parts by weight was blended with Pluracol® 1062 polyol of 100.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 56.74 parts, with the capping ratio (NCO/OH) at 1.75, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.45% of the prepolymer. This prepolymer was then dissolved in Ν,Ν-dimethylacetamide (DMAc) of 513.65 parts. This diluted prepolymer solution was allowed to react with 203.78 parts of a mixture of diamine extender in DMAc solution (containing 5.51 parts of EDA, 1.18 parts of Dytek®A, and 197.08 parts of DMAc) and 1.82 parts of DEA in DMAc solution (containing 0.16 parts of DEA and 1.66 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0% and a viscosity of 2541 poises measured at 40°C by falling ball method. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivelents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.02, and the end group concentration from diethylamine terminator was about 6 milliequivalent per kg of the polymer solids and the monol end groups from PPG was about 18 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was spun into 40 denier spandex yarn with 4 filaments twisted together at a wound-up speed of 930 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 1.

Fiber Example 6:

Terathane® 1800 glycol of 200.00 parts by weight was blended with Pluracol® 1062 polyol of 100.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 62. 7 parts, with the capping ratio (NCO/OH) at 1.82, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.60% of the prepolymer. This prepolymer was then dissolved in Ν,Ν-dimethylacetamide (DMAc) of 566.84 parts. This diluted prepolymer solution was allowed to react with 224.08 parts of a mixture of diamine extender in DMAc solution (containing 6.06 parts of EDA, 1.30 parts of Dytek®A, and 2 6.72 parts of DMAc) and 1.86 parts of DEA in DMAc solution (containing 0.16 parts of DEA and 1.70 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0% and a viscosity of 4795 poises measured at 40°C by falling ball method. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivelents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.00, and the end group concentration from diethylamine terminator was about 6 milliequivalent per kg of the polymer solids and the monol end groups from PPG was about 18 milliequivalent per kilogram (meq/kg) of the polymer solids. This polymer solution was spun into 40 denier spandex yarn with 4 filaments twisted together at a wound-up speed of 930 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 1.

Table 1. As-spun yarn properties of 40 denier 4 filament fibers for Fiber Examples

The above Fiber Examples 2, 5 and 6 illustrate that a spandex fiber can be made with a glycol blend of a PTMEG glycol and a PPG glycol with high concentration of unsaturation end groups or monol level. These spandex fibers offers unique properties, such as lower load power, high unload power and high elongation to break compared to the spandex fiber made with PTMEG only. However, the relative ratios of the components in making the spandex polymer with blended PTMEG and PPG must be strictly controlled, as the current invention describes and exemplifies, in order to achieve the necessary polymer structure and molecular weights to produce such spandex fibers.

Fiber Example 7:

PTG-L2200 glycol (Hodogaya Chemical Co., Ltd.) of 200.00 parts by weight was blended with Pluracol® 1062 polyol of 100.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 51.05 parts, with the capping ratio

(NCO/OH) at 1.70, to form an isocyanate-terminated prepolymer with a percent of

isocyanate groups (-NCO) at 2.06% of the prepolymer. This prepolymer was then

dissolved in Ν,Ν-dimethylacetamide (DMAc) of 595.23 parts. This diluted prepolymer solution was allowed to react with 168.01 parts of a mixture of diamine extender in

DMAc solution (containing 4.54 parts of EDA, 0.98 parts of Dytek®A, and 162.49 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea

solution with a polymer solids about 32.0%. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to the total primary amine (NH₂) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.00, and the mono] end groups from PPG was about 16,5 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was spun into 40 denier spandex yarn with 3 filaments twisted together at a wound-up speed of 850 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 2.

Fiber Example 8:

Terathane® 2900 glycol of 134.00 parts by weight was blended with Pluracol® 1062 polyol of 66.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 28.25 parts, with the capping ratio (NCO/OH) at 1.80, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 1.84% of the prepolymer. This prepolymer was then dissolved in N,N-dimethylacetamide (DMAc) of 395.00 parts. This diluted prepolymer solution was allowed to react with 100.33 parts of a mixture of diamine extender in DMAc solution (containing 2.71 parts of EDA, 0.58 parts of Dytek®A, and 97.03 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0%. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.00, and the monol end groups from PPG was about 16.8 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was spun into 40 denier spandex yarn with 3 filaments twisted together at a wound-up speed of 850 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 2.

Fiber Example 9:

PTG-L3500 glycol (Hodogaya Chemical Co., Ltd.) 150.00 parts by weight was blended with Pluracol® 1062 polyol of 50.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 23.55 parts, with the capping ratio

(NCO/OH) at 1.70, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 1.50% of the prepolymer. This prepolymer was then dissolved in Ν,Ν-dimethylacetamide (DMAc) of 404.47 parts. This diluted prepolymer solution was allowed to react with 77.50 parts of a mixture of diamine extender in DMAc solution (containing 2.10 parts of EDA, 0.45 parts of Dytek®A, and 74.95 parts of DMAc) and 1.13 parts of DEA in DMAc solution (containing 0.10 parts of DEA and 1.03 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0%. in this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.00, and the end group concentration from diethylamine terminator was about 6 milliequivalent per kg of the polymer solids and the monol end groups from PPG was about 13 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was spun into 40 denier spandex yarn with 3 filaments twisted together at a wound-up speed of 850 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 2.

Fiber Example 10:

Desmophen® C 2200 glycol (Bayer MaterialScience LLC) 150.00 parts by weight was blended with Pluracol® 1062 polyol of 50.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 40.46 parts, with the capping ratio (NCO/OH) at 1.80, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.50% of the prepolymer. This prepolymer was then dissolved in Ν,Ν-dimethylacetamide (DMAc) of 382.60 parts. This diluted prepolymer solution was allowed to react with 143.06 parts of a mixture of diamine extender in DMAc solution (containing 3.87 parts of EDA, 0.83 parts of Dytek®A, and 138.36 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0%. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.00, and the monol end groups from PPG was about 12 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was spun into 40 denier spandex yam with 3 filaments twisted together at a wound-up speed of 850 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 2. Fiber Example 11 :

Terathane® E 2049 glycol (Invista) 225.00 parts by weight was blended with Pluracol® 1062 polyol of 75.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR DI of 61.87 parts, with the capping ratio (NCO/OH) at 2.00, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.49% of the prepolymer. This prepolymer was then dissolved in N,N-dimethylacetamide (DMAc) of 547.14 parts. This diluted prepolymer solution was allowed to react with 247.22 parts of a mixture of diamine extender in DMAc solution (containing 6.69 parts of EDA, 1.44 parts of Dytek®A, and 239.10 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0%. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.00, and the monol end groups from PPG was about 12 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was spun into 40 denier spandex yarn with 3 filaments twisted together at a wound-up speed of 850 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 2.

Fiber Example 12:

Terathane® E 2538 glycol (Invista) 225.00 parts by weight was blended with Pluracol® 1062 polyol of 75.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 52.97 parts, with the capping ratio (NCO/OH) at 1.95, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.45% of the prepolymer. This prepolymer was then dissolved in N,N-dimethylacetamide (DMAc) of 565.39 parts. This diluted prepolymer solution was allowed to react with 205.80 parts of a mixture of diamine extender in DMAc solution (containing 5.57 parts of EDA, 1.20 parts of Dytek®A, and 199.04 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0%. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about .00, and the monol end groups from PPG was about 12 milliequivalent per kilogram (meq/kg) of the polymer solids. This polymer solution was spun into 40 denier spandex yarn with 3 filaments twisted together at a wound-up speed of 850 meters per minute. The as-spun yam properties of this test item were measured and listed in Table 2.

Fiber Example 13:

Terathane® E 2549 glycol (Invista) 225.00 parts by weight was blended with Pluracol® 1062 polyol of 75.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 51.71 parts, with the capping ratio (NCO/OH) at 1.90, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.26% of the prepolymer. This prepolymer was then dissolved in N,N-dimethylacetamide (DMAc) of 571.73 parts. This diluted prepolymer solution was allowed to react with 195.76 parts of a mixture of diamine extender in DMAc solution (containing 5.29 parts of EDA, 1.14 parts of Dytek®A, and 189.33 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0%. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to the total primary amine (NH2) end groups (in milliequivalents) from the chain extender or extender mixtures was about 1.00, and the monol end groups from PPG was about 12 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was spun into 40 denier spandex yarn with 3 filaments twisted together at a wound-up speed of 850 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 2.

Fiber Example 14:

Terathane® 1800 glycol (Invista) 200.00 parts by weight was blended with Voranol™ 222-056 polyol of 100.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 68.57 parts, with the capping ratio (NCO/OH) at 1.70, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.55% of the prepolymer. This prepolymer was then dissolved in N,N- dimethylacetamide (DMAc) of 580.73 parts. This diluted prepolymer solution was allowed to react with 225.65 parts of a mixture of diamine extender in DMAc solution (containing 6.10 parts of EDA, 1.31 parts of Dytek®A, and 218.24 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0%. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivelents) from the prepolymer to the total primary amine (NH2) end groups (in miliiequivalents) from the chain extender or extender mixtures was about 1.00, and the monol end groups from PPG was about 13 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was spun into 40 denier spandex yarn with 3 filaments twisted together at a wound-up speed of 850 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 2.

Fiber Example 15:

Polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone glycol with average Mn about 2000 (Sigma-Aldrich) 150.00 parts by weight was blended with Pluracol® 1062 polyol of 50.00 parts by weight, and this blended glycol was reacted with Isonate® 125MDR MDI of 41.25 parts, with the capping ratio (NCO/OH) at 1.85, to form an isocyanate-terminated prepolymer with a percent of isocyanate groups (-NCO) at 2.62% of the prepolymer. This prepolymer was then dissolved in N,N-dimethylacetamide (DMAc) of 376.73 parts. This diluted prepolymer solution was allowed to react with 151.48 parts of a mixture of diamine extender in DMAc solution (containing 4.10 parts of EDA, 0.88 parts of Dytek®A, and 146.50 parts of DMAc) using a high speed disperser to form a homogenous polyurethaneurea solution with a polymer solids about 32.0%. In this polymer, the ratio of the total isocyanate (NCO) end groups (in milliequivelents) from the prepolymer to the total primary amine (NH2) end groups (in miliiequivalents) from the chain extender or extender mixtures was about 1.00, and the monol end groups from PPG was about 12 milliequivalent per kilogram (meq/kg) of the polymer solids.

This polymer solution was spun into 40 denier spandex yarn with 3 filaments twisted together at a wound-up speed of 850 meters per minute. The as-spun yarn properties of this test item were measured and listed in Table 2.

Table 2. As-spun yarn properties of 40 denier 3 filament fibers

Fabric Examples with Fiber of Fiber Example 2:

The following examples demonstrate the present invention and its capability for use in manufacturing a variety of weight fabrics. Accordingly, the examples are to be regarded as illustrative in nature and not as restrictive. Fabrics from Example 1 to Example 9 are woven fabrics. Fabrics from Example 10 to Example 20 are circular knit fabrics. In each of the examples, D48 elastic fiber refers to the fiber of Example 2.

For each of the following woven fabrics, 100 % cotton staple spun yarn is used as warp yarn. They included two count yarns: 7.0 Ne OE yarn and 8.5 Ne OE yarn with irregular arrangement pattern. The yarns were indigo dyed in rope form before beaming. Then, they were sized and were made the weaving beam.

D48 elastic fiber /cotton core spun yarns (CSY) and D48 elastic fiber/Polyester textured air jet covered yarns (AJY) were used as weft yarn. Table 3 lists the materials and process conditions that were used to manufacture the core spun yarns and air covered yarn for each example. Elastic yarn is available from Invista, s. a. r. L, of Wichita, KS. For example, in the column headed elastic fiber 40d means 40 denier; and 3.3X means the draft of the elastic imposed by the core spinning machine (machine draft). In the column headed 'Hard Yarn', 16's is the linear density of the spun yarn as measured by the English Cotton Count System. The rest of the items in Table 3 are clearly labeled.

Stretch woven fabrics were subsequently made, using the core spun yarn and air covered yarn of each example in Table 3. The core spun yarns and air covered yarns were used as weft yarns. Table 4 summarizes the yarns used in the fabrics, the weave pattern, and the quality characteristics of the fabrics. Some additional comments for each of the examples are given below. Unless otherwise noted, the fabrics were woven on a Donier air-jet loom. Loom speed was 500 picks/minute. The widths of the fabric were about 76 and about 72 inches in the loom and greige state respectively.

Each greige fabric in the examples was finished by: scouring, desizing, relaxation and adding softener.

"Table 3 Weft Yarn Specification," "Table 4 Fabric Example List," and "Table 5 CK Fabric Example List" refer to Fabric Examples, which are described below.

Table 3: Weft Yarn S ecification

Table 4: Fabric Example List

In Table 4 AJY is air covered yarn and CSY is corespun yarn having a spandex core. Fabric Example 1C: Stretch denim with normal elastic AJY

This is a comparison example, not according to the invention. The warp yarn was 7.0 Ne count and 8.4 Ne count mixed open end yarn. The warp yarn was indigo dyed before beaming. The weft yarn is 300d/192filamanets polyester air covered yarn with 40D T162B Lycra® spandex. The Lycra® fiber was drafted 3.3X during covering process. Table 4 lists the fabric properties. This fabric had weight (10.1 OZ/Y²), stretch (32.4 %), growth (4.1 %) and fabric recovery is 84.18%.

Fabric Example 2: Stretch denim containing 40D D48 elastic AJY

This sample had the same fabric structure as example 1. The difference was the air covered yarn in weft direction, which containing 40D D48 LYCRA® fiber. This fabric used the same warp and structure as Example 1. Also, the weaving and finishing process were the same as Example 1. Table 4 summarizes the test results. We can see that this sample had low fabric growth (3.3 %) and high fabric recovery (86.30%) than fabrics in example 1.

Fabric Example 3: Stretch denim containing 70D D48 elastic AJY

This sample had the same fabric structure as example 1 and example 2. The difference was the air covered yarn in weft direction, which containing 70D D48 LYCRA® fiber. Table 4 summarizes the test results. Because the higher denier D48 is used, this sample had high stretch (39.3%), low fabric growth (3.1 %) and high fabric recovery (90.14%) than fabrics in example 1 and 2.

Fabric Example 4: Stretch denim containing 40D D48 elastic AJY with heatset

This sample had the same fabric structure and processes as example 2. The difference was that this fabric has been heatset at 380 OF for 45 seconds. The fabric performance listed in Table 4 shown that D48 elastic fiber could stand heatset process. After heatset, the fabric has low shrinkage and better dimensional stability. Fabric weft shrinkage reduces from -5.85% in no- heatset fabric in Example 2 to -2.73% in heatset fabric in this example.

Fabric Example 5C: Stretch denim with normal elastic CSY

This is a comparison example, not according to the invention. The warp yarn was 7.0 Ne count and 8.4 Ne count mixed open end yarn. The warp yarn was indigo dyed before beaming. The weft yarn is 16Ne core spun yarn with 70D T 62B Lycra® spandex. The Lycra® fiber was drafted 3.8X during covering process. Table 4 lists the fabric properties. This fabric had weight (1 1.60/m2), stretch ( 44.4 %), growth (5.6%) and fabric recovery (84.23%).

Fabric Example 6: Stretch denim containing 70D D48 CSY

This sample had the same fabric structure as example 5C. The difference was the core spun yarn in weft direction, which containing 70D D48 LYCRA® fiber. This fabric used the same warp and structure as Example 5C. Also, the weaving and finishing process were the same as Example 5C. Table 4 summarizes the test results. We can see that this sample had similar performance as Sample 5C: fabric stretch (43%), fabric growth (5.7 %) and fabric recovery (83.4%).

Fabric Example 7: Stretch denim containing 70D D48 elastic CSY

This sample had the same fabric structure as example 5C and example 6. The difference was the draft of elastic fiber in core spun yarn. The draft of 70D D48 LYCRA® fiber is 4.6X in this example vs. 3.8X in above two examples. Table 4 summarizes the fabric results. This sample had similar fabric stretch (45.4%), fabric growth (5.6 %) and fabric recovery (84.59%) with fabric in example 5. This demonstrates that D48 fiber could be stretched out more than conventional spandex during yarn covering process. High draft provides the ability for textile mills to use less content spandex and reduce the raw materials cost.

Fabric Example 8: Stretch denim containing 40D D48 elastic CSY

This sample had the same fabric structure and processes as example 6. The difference was the core spun yarn in weft direction, which containing 40D D48 LYCRA® fiber. The fabric performance listed in Table 4 shown that 40D D48 elastic fiber could be used to make good fabric with acceptable performance.

Fabric Example 9: Stretch denim containing 70D D48 elastic CSY with heatset

This sample had the same fabric structure and processes as example 6. The difference was that this fabric has been heatset at 380 OF for 45 seconds. The fabric performance listed in Table 4 shown that D48 elastic fiber could stand heatset process. After heatset, the fabric has low shrinkage and better dimensional stability. Fabric weft shrinkage reduces from -9.75% in no- heatset fabric in Example 6 to -3.65% in heatset fabric in this example. Table 5 lists the circular fabric examples. Fabrics from Example 10 to Example 15 are low content spandex cotton CK fabrics. Fabrics from Example 16 to Example 20 are high spandex content CK fabrics with nylon and polyester filaments. All fabrics are single jersey structure made with 28 gauge machine.

Table 5: CK Fabric Example List

Fabric Example 10C: Cotton stretch CK

This is a comparison example, not according to the invention. The hard yarn was 32 Ne count cotton ring spun yarn. The elastic fiber is 40D T162B Lycra® spandex. The Lycra® fiber was drafted at 3.5X during knitting at 28 gauge machine. After the fabric is dyed and finished, the heatset is conducted under 380o F for 45 seconds. Table 5 lists the fabric properties. This fabric had weight (314 g/m2), stretch (129.8%X124.6%) and Shrinkage (-4.25%X-0.71 %).

Fabric Example 11 : Cotton Stretch CK with D48 fiber

This sample had the same fabric structure as example 10C. The difference was the elastic fiber: 40D D48 LYCRA® fiber spun under 950 meters per minute is used. Table 5 summarizes the fabric results. We can see that this sample had light fabric weight (282 g/m2), similar stretch level (128.4%X129.4%) and lower shrinkage (-3.65X-0.36%) than fabrics in example 10C. D48 fiber can be used to make good CK fabrics with lighter weight, soft stretch and less shrinkage.

Fabric Example 12: Cotton Stretch CK with D48 fiber spun in high speed

The elastic fiber is 40D/4f D48 spun under 10% higher speed than the fiber in Example 1 1. Fiber spinning speed is 1 140 meters per minute. The fabric results listed in Table 5 indicate that this high speed D48 has high elastic power, which results in slight heavier weight, higher stretch level and higher shrinkage. Fabric performance is acceptable.

Fabric Example 13C: Cotton stretch CK (Pre-heatset)

This is a comparison example, not according to the invention. The hard yarn was 32 Ne count cotton ring spun yarn. The elastic fiber is 40D T162B Lycra® spandex. The Lycra® fiber was drafted at 3.5X during knitting at 28 gauge machine. After pre-heatset in greige stage the fabric is dyed and finished. The pre-heatset is conducted under 380° F for 30 seconds. Table 5 lists the fabric properties. This fabric had weight (189 g/m2), stretch (75.7%X113.6%) and Shrinkage (-5.2%X 0.0%).

Fabric Example 14: Cotton Stretch CK with D48 fiber (Pre-heatset)

This sample had the same fabric structure as example 13C. The difference was the elastic fiber: 40D D48 LYCRA® fiber spun under 950 meters per minute. From Table 5, we can see that this sample had similar fabric weight (194 g/m2), similar stretch level (76.3%X113.9%) and lower shrinkage (-3.64%X-1.43%) as fabrics in example 13C. This result confirmed that D48 fiber could be used in pre-heatset stretch CK fabrics.

Fabric Example 15: Cotton Stretch CK with D48 fiber spun in high speed (Pre-heatset)

The elastic fiber is 40D/4f D48 spun under 10% higher speed than the fiber in Example 14. Fiber spinning speed is 1 140 meters per minute. The fabric results listed in Table 5 indicate that this high speed D48 fiber can be used in pre-heatset CK fabric. Fabric performance is acceptable. Fabric Example 16: High Content Stretch CK with 70D D48 fiber

The hard yarn was 150D/200f T935 COOLMAX® polyester filaments. The elastic fiber is 70D/5f D48 Lycra® spandex. The Lycra® fiber was drafted at 2.8X during knitting at 28 gauge machine. The LYCRA® fiber content within the fabric is 13.9% by weight. After pre-heatset at 190 Oc for 40 seconds, the fabric is dyed and finished. Table 5 lists the fabric properties. This fabric had weight (232 g/m2), stretch (85%X123%) and Shrinkage (-0.3%X -0.3%).

Fabric Example 17: High Content Stretch CK with 70 D D48 fiber

The hard yarn was 71 D/68f Tactel® nylon filaments. The elastic fiber is 70D/5f D48 Lycra® spandex. The Lycra® fiber was drafted at 2.8X during knitting at 28 gauge machine. The LYCRA® fiber content within the fabric is 25.9% by weight. After pre-heatset at 190 0c for 40 seconds, the fabric is dyed and finished. Table 5 lists the fabric properties. This fabric had weight (354 g/m2), stretch (209%X183%) and Shrinkage (-1.3%X -0.2%). Fabric has soft hand and high recovery power.

Fabric Example 18: High Content Stretch CK with 40D D48 fiber

70D/72f 564DT polyester filaments were used as hard yarn. 40D/4f D48 Lycra® spandex was used as elastic yarn. The Lycra® fiber was drafted at 2.8X during knitting at 28 gauge machine. The LYCRA® fiber content within the fabric is 17.3% by weight. After pre-heatset at 190 0c for 40 seconds, the fabric is dyed and finished. The fabric properties listed in Table 5 shown that 40D D48 fiber was able to provide good stretch and recovery for polyester based CK fabrics.

Fabric Example 19: High Content Stretch CK with 40D D48 fiber

The difference of this fabric from Example 18 is the hard yarn. 80D/68f Supplex® nylon filaments were used. The elastic fiber is 40D/4f D48 Lycra® spandex. The Lycra® fiber was drafted at 2.8X during knitting.. After pre-heatset at 190 0c for 40 seconds, the fabric is dyed and finished. The LYCRA® fiber content within the fabric is 16.1 % by weight. Table 5 lists the fabric properties as: weight (207 g/m2), stretch (192%X189%) and Shrinkage (-1.4%X -0.7%). Fabric also has soft hand and high recovery power.

Fabric Example 20: High Content Stretch CK with 140D D48 fiber

The hard yarn was 162D/136f nylon filaments. The elastic fiber is 140D/10f D48 Lycra® spandex. The Lycra® fiber was drafted at 2. OX during knitting at 28 gauge machine. The LYCRA® fiber content within the fabric is 29% by weight. After pre-heatset at 190 Oc for 40 seconds, the fabric is dyed and finished. This fabric had weight (309 g/m2), stretch

(99%X163%) and shrinkage (-0.6%X -0.9%). The fabric recovery force at 30% extension is 550 X 444 grams, which is almost 3 times bigger than normal cotton stretch CK fabric. This fabric is an idea material for making high power shaping garments.

While there have been described what are presently believed to be the preferred embodiments of the invention, those skilled in the art will realize that changes and modifications may be made thereto without departing from the spirit of the invention, and it is intended to include all such changes and modifications as fall within the true scope of the invention.

Claims

Claims:

1. An article comprising a polyurethaneurea which is the reaction product of:

(a) a prepolymer comprising the reaction product of

(i) a polyol including PPG and at least one other polyol; and

(ii) a diisocyanate; and

(b) a diamine chain extender, and optionally a dialkyl amine chain terminator;

wherein a ratio of total isocyanate (NCO) end groups from the prepolymer to total primary amine (NH₂) end groups from the diamine chain extender is about 0.99 to about 1.01 ; and the combined amount of non-reactive end groups from the PPG and dialkylurea end groups in said polyurethaneurea is less than about 50 meq/kg.

2. The article of claim 1 , wherein said at least one other polyol includes PTMEG.

3. The article of claim 1 , further comprising (c) a chain terminator.

4. The article of claim 3, wherein said chain terminator comprises a dialkylamine chain terminator.

5. The article of claim 1 , wherein said polyol has a number average molecular weight about 600 to about3500.

6. The article of claim 1 , wherein said PPG has a number average molecular weight about 1000 to about 5000.

7. The article of claim 1 , wherein said polyol including PPG and at least one other polyol are blended together have a number average molecular weight about 1000 to about 4000.

8. The article of claim 1 , wherein said prepolymer has a capping ratio of about 1.50 to about 2.50.

9. The article of claim 1, wherein said PPG has non-reactive end groups in an amount of about 40 to about 90 meq/kg, such as about 45 to about 90 meq/kg or about

50 to about 90 meq/kg or about 50 to about 70 meq/kg or about 45 to about 70 meq/kg.

10. The article of claim 1 , wherein said polyurethaneurea has an intrinsic viscosity of about 0.93 to about 1.02 dL/g.

11. The article of claim 1 , wherein said polyurethaneurea has total non-reactive end groups in an amount of about 10 meq/kg to about 45 meq/kg such as about 20 to 40 meq/kg.

12. The article of claim 1 , wherein said diisocyanate comprises a diphenylmethane diisocyanate (MDI).

13. The article of claim 1, wherein said diamine chain extender includes a blend of diamine chain extenders.

14. The article of claim 1 , wherein said article is an elastomeric fiber.

15. An article comprising at least one elastomeric fiber comprising a polyurethaneurea which is the reaction product of:

(a) a capped glycol comprising the reaction product of

(i) a polyol including PPG and at least one other polyol; and

(ii) a diisocyanate; and

(b) a diamine chain extender, and optionally a dialkyl amine chain terminator;

wherein a ratio of the total isocyanate (NCO) end groups from the prepolymer to a total primary amine (NH₂) end groups from the diamine chain extender is about 0.99 to about 1.01 ; and the amount of non-reactive end groups and dialkylurea end groups is less than about 50 meq/kg.

16. The article of claim 15, further comprising (c) a chain terminator.

17. The article of claim 16, wherein said chain terminator comprises a dialkylamine chain terminator.

18. The article of claim 15, wherein said article is a covered yarn, woven fabric, a nonwoven fabric, a knit or a laminated article.

19. The article of claim 15, wherein said knit is selected from warp knit and circular knit. a process for making spandex including of:

(a) providing a polyol including PTMEG and PPG;

(b) providing a diisocyanate;

(c) contacting the polyol and diisocyanate to form a capped glycol;

(d) providing a diamine chain extender in an amount to control a ratio of the total isocyanate (NCO) end groups from the prepolymer to a total primary amine (NH₂) end groups from the diamine chain extender to about 0.99 to about 1.01 ;

(e) providing a dialkylamine chain terminator in an amount to control the polymer molecular weight in a way that the combined amount of non-reactive end groups and dialkylurea end groups in said polyurethaneurea is less than about 50 meq/kg;

(f) contacting the capped glycol, the chain extender and the chain terminator composition in a solvent to form a polyurethaneurea in solution; and

(g) spinning the polyurethaneurea in solution to form the spandex.