TW201510070A - 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

Polyurethane urea fiber comprising a diol blend

The present invention solves the problem of using a PPG having a high concentration of non-reactive end groups (such as unsaturated or monol end groups) in the production of elastic rayon fibers to replace a portion of the polyether diol (such as PTMEG), thereby allowing for reduced manufacturing. The component cost and provides unique yarn characteristics (low hysteresis and high elongation) for the improved fabric.

In the past, attempts have been made to mix or blend diols of polytetramethylene ether glycol (hereinafter referred to as "PTMEG") with polypropylene glycol (hereinafter referred to as "PPG") for elastic rayon. PTMEG is a typical diol for elastic rayon, but considering its total content in elastic rayon, it has a high component cost. PPG is generally not desirable due to the large number of non-reactive end groups in the polymer, such as unsaturated or monol end groups. To overcome this problem, PPG having a lower monool concentration is often produced by a specific technique such as a double metal cyanide complex catalyst, but at a higher cost than PPG made with a conventional alkali metal hydroxide catalyst. Alternatively, a low level crosslinker having a functionality above 2.0 is used to counteract the negative effects of monol concentration in the PPG to achieve a polymer molecular weight that is sufficiently high in terms of the performance requirements of the elastomeric rayon product. The use of such crosslinkers often creates handling difficulties, such as the formation of polymer gels in the formation of fibers.

U.S. Patent No. 5,691,441 discloses a block polyurethane/urea elastic rayon elastomer made from an isocyanate terminated prepolymer derived from polytetramethylene ether glycol ( PTMEG) with ultra-low unsaturation, high molecular weight polyoxyalkylene a mixture of diols. In this case, a PPG having an average degree of unsaturation of less than about 10 meq/kg is used.

U.S. Patent No. 5,998,574 discloses a diol blend composition for use in cast elastomers, elastomeric rayon and thermoplastic polyurethanes comprising polytetramethylene ether glycol (PTMEG) and difunctional activity. A blend of hydrogen-initiated polyoxyalkylene ether polyols having a low degree of unsaturation of 40 meq/kg or less.

U.S. Patent 6,255,431 B1 discloses a diol blend comprising a polytetramethylene ether glycol (PTMEG) and a trifunctional active hydrogen compound for use in cast elastomers, elastomeric rayon and thermoplastic polyurethanes. The starting polyoxyalkylene ether polyol having an unsaturation of no more than 40 meq/kg.

Chinese Patent No. 101575406B discloses a process for preparing an elastic rayon polymer solution using a diol blend of PTMEG and PPG, wherein the PPG has an unsaturation of less than 30 meq/kg.

All of the patents discussed above for the use of diol blends of PTMEG and PPG in the preparation of elastomeric rayon polymers are limited to having ultra low unsaturation (<10 meq/kg) or low unsaturation (<40 meq/kg). PPG. The cost of preparing PPG with low/ultra-low unsaturation is high and the resulting fibers are not commercially competitive.

In general, PPG is a low cost diol compared to PTMEG. Replacing a portion of the more expensive polyether diol (such as PTMEG) with PPG not only reduces the cost of the elastomeric rayon component, but also changes the properties of the elastic rayon yarn, such as achieving reduced hysteresis in the draw cycle and achieving increased yarn breakage. Elongation or higher drawability is desirable. However, the use of conventional PPG in the manufacture of elastic rayon fibers is often hindered by the presence of excess non-reactive or unsaturated end groups or monols in the PPG, which act as polymer chain terminators and inhibit high molecular weight polymers. Formation. Need a solution to this problem, ie no It is desirable to use PPG having a lower monool concentration of typically no more than 40 meq/kg to achieve acceptable elastic rayon characteristics.

In one aspect, being an elastomeric fiber made from a novel polyurethaneurea composition, the novel polyurethaneurea composition is based on a polyglycol comprising PPG and a different polyether diol such as PTMEG. A combination of ether diols wherein PPG has a high concentration of non-reactive end groups, in other words, non-reactive or unsaturated or monool end groups. The diol blend is reacted with an excess of diisocyanate in a prepolymerization stage, chain extended with a diamine or diamine mixture in an aprotic polar solvent and optionally blocked with a dialkylamine, followed by a solution spinning method (specifically The dry spinning method or the wet spinning method) is spun into fibers. Overcoming the disadvantages of high concentration of unsaturated or monol end groups is overcome by maximizing the molecular weight of the polymer.

In some aspects, the problem of using a PPG having a high concentration of non-reactive end groups (such as non-reactive or unsaturated or monool end groups) is by using another polyether such as PTMEG in the production of elastic rayon. The alcohol is replaced by a portion of the amount of diol that allows for lowering the cost of the components in the manufacturing process and providing unique yarn characteristics such as low hysteresis and high elongation for improved fabric performance.

In some aspects, the article comprising polyurethaneurea, the polyurethaneurea is the reaction product of:

(a) a prepolymer comprising the reaction product of each of the following

(i) a polyol comprising PPG and another polyol such as PTMEG; and (ii) a diisocyanate;

(b) a diamine chain extender; and optionally a dialkylamine terminator

Wherein the ratio of total isocyanate (NCO) end groups from the prepolymer to total primary amine (NH ₂ ) end groups from the diamine chain extender is from about 0.99 to about 1.01; and non-reactive end groups and poly The combined amount of dialkyl urea end groups in the urethane urea is less than about 50 meq/kg.

In another aspect, an article comprising at least one elastomeric fiber comprising a polyurethane furanate that is a reaction product of:

(a) a capped diol comprising the reaction product of each of

(i) a polyol comprising PPG and another polyol such as PTMEG; and (ii) a diisocyanate;

(b) a diamine chain extender; and optionally a dialkylamine terminator

Wherein the ratio of total isocyanate (NCO) end groups from the prepolymer to total primary amine (NH ₂ ) end groups from the diamine chain extender is from about 0.99 to about 1.01; and non-reactive end groups and dialkyl ureas The amount of end groups is less than about 50 meq/kg.

Another aspect provides a method of making an elastic rayon fiber, the method comprising: (a) providing a polyol comprising PPG and another polyol such as PTMEG; (b) providing a diisocyanate; (c) providing a polyol with a diisocyanate Contacting to form a capped diol; (d) controlling the ratio of total isocyanate (NCO) end groups from the prepolymer to total primary amine (NH ₂ ) end groups from the diamine chain extender at from about 0.99 to about An amount of 1.01 provides a diamine chain extender; (e) optionally providing a dialkylamine chain terminator in an amount to control the molecular weight of the polymer, the control being a non-reactive end group in the polyurethane urea a combination with a dialkyl urea end group in an amount of less than about 50 meq/kg; (f) contacting the capped diol, chain extender, and chain terminator composition in a solvent to form a polyamine group in solution The acid ester urea; and (g) the polyurethane of the solution is spun to form an elastic rayon.

Optionally, PTMEG can be replaced with a polyester or polycarbonate diol for blending with PPG in the present invention.

definition

A fiber is defined herein as a shaped article in the form of a thin wire or filament having an aspect ratio (ratio of length to diameter) greater than 200. "Fiber" can be monofilament or multifilament and can be used interchangeably with "yarn".

Elastic rayon meets the definition of "a fiber-forming material in which the fiber-forming material is a long-chain synthetic polymer comprising at least 85% block polyurethane." These are elastomeric fibers.

The diol used herein is defined as a polymeric diol having a hydroxyl group at each chain end. This term can be used interchangeably with polyols.

Poly(tetramethylene ether) glycol (PTMEG) is defined as a diol made from 1,4-butanediol or tetrahydrofuran (THF) as the main monomer component (at least 50% by mole percentage), including Homopolymers and copolymers of tetramethylene ether repeating units.

Poly(propylene ether) glycol or polypropylene glycol (PPG) is defined as a diol produced by using 1,2-epoxypropane [CAS No. 75-56-9] as a main component (>50% by mole percentage). It includes homopolymers and copolymers containing repeating units of propylene ether.

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

The capping ratio (CR) is defined as the molar ratio of diisocyanate to diol used in the prepolymerization. In the case where a plurality of diisocyanates and/or diols are used in the reaction, the average molecular weight should be used in calculating the capping ratio. It is assumed that both the diisocyanate and the diol are difunctional, and the blocking ratio is the same as the ratio of the total number of isocyanate (-NCO) groups to the total number of hydroxyl groups (-OH) groups.

As used herein, "solvent" refers to organic solvents such as dimethylacetamide (DMAC), dimethylformamide (DMF) and N -methylpyrrolidone (NMP), in which elastic man-made The fibrous polymer can form a homogeneous solution.

Additives are defined herein as being added to the fibers in minor amounts for the production of fibers. A substance that improves appearance, efficacy and quality during manufacture, storage, handling and use. The additive itself may not form fibers.

In some aspects, it is an elastomeric rayon based on block polyurethane urethanes comprising mixed polyether diols for textile applications, such applications including knitwear , woven, non-woven and laminated. The elastic rayon fibers and the fabric containing the elastic rayon fibers may comprise a reaction of at least one mixture of polypropylene ether diol (PPG) and at least one other polyether diol such as polytetramethylene ether glycol (PTMEG). product. In the diol blend, the weight percentage of other polyether diols such as PTMEG can be used in any suitable amount, such as greater than about 50% by weight of the diol blend, and added to the PPG in the blend. There are from about 40 meq/kg to about 90 meq/kg of non-reactive end groups, such as unsaturated end groups or monoalcohols.

The stress-strain properties of polymeric materials are greatly affected by their molecular weight and molecular weight distribution. It is known that in the case of thermoplastic polyurethane elastomers, there is a certain weight average polymer molecular weight ((Mw), the so-called "folded molecular weight"), in which the following characteristics continue to change and above this trend The increased molecular weight of the polymer gradually stabilizes. Depending on the particular polyurethane composition and the particular characteristics, the molecular weight of the folded back is on a weight average, typically in the range of from 100,000 g/mol to 200,000 g/mol. This phenomenon also exists with respect to elastic rayon polymers which are block polyurethanes comprising polyurethane urethane. In general, in the case of elastic rayon fibers, a minimum polymer molecular weight is required to form sufficient tensile and recovery characteristics, and a higher molecular weight is preferred to balance tensile properties such as elongation at break and tensile strength. In addition, due to the treatability of the elastic rayon, the molecular weight of the polymer should also be controlled within a reasonable range, because the molecular weight of the polymer can directly affect the viscosity in the solution.

The inherent viscosity of the polymer is an indication of the molecular weight of the polymer. The polyurethane urethane comprising a diol blend can have an intrinsic viscosity of from 0.93 dL/g to about 1.02 dL/g.

In order to reduce the cost of the component or to modify the properties, the block polyurethane can be used Used in the mixing or blending of diols made of elastic rayon. In general, PPG is a low cost diol compared to PTMEG or other polyether diols. Not only to reduce the cost of elastic rayon components, but also to modify the properties of elastic rayon yarns, such as to reduce the hysteresis in the stretching cycle and to increase the elongation at break or higher drafting ability of the yarn, replacing part of it with PPG Elastic rayon fibers including PTMEG are desirable.

Some aspects include block polyurethane urethanes which are suitable for use including polyether diols such as poly(tetramethylene ether) diol (PTMEG) and poly(propylene ether) diol (PPG). Elastomeric fibers are prepared by blending or blending diols to reduce component cost and enhance product performance.

PPG diols suitable for use in the manufacture of elastic rayon fibers have relatively high concentrations of non-reactive end groups, such as unsaturated or monool end groups, which are from about 40 meq/kg to about 90 meq/kg, such as about 45 meq/ From kg to about 90 meq/kg or from about 50 meq/kg to about 90 meq/kg or from about 50 meq/kg to about 70 meq/kg or from about 45 meq/kg to about 70 meq/kg. The weight percent of PPG in the mixed diol ranges from about 10% to about 50%, such as from about 20% to about 40% or from about 30% to about 50%. The elastic rayon fibers using the mixed diols have higher elongation at break and lower hysteresis in the stretch recovery cycle than the elastic rayon fibers using only PTMEG. PPG has a number average molecular weight of from about 1000 to about 5,000, such as from about 1000 to about 4,000. When the polyether diol is PTMEG, it can have a number average molecular weight of from about 600 to about 2900. Other suitable ranges include from about 1600 to about 2200 and from about 1800 to about 2000. The PTMEG and PPG blended together may have a number average molecular weight of from about 1000 to about 4000, such as from about 1800 to about 3600 or from 1800 to 2500.

Suitable polyether diols or polyether polyols can comprise a number average molecular weight of from about 600 to about 7,000, including from about 1,000 to about 7,000 and from about 2,000 to about 7,000. Mixtures of two or more polyols (other than PPG) or copolymers may be included.

Examples of the polyether polyol which can be used include diols having two or more hydroxyl groups derived from ring-opening polymerization of ethylene oxide, propylene oxide, propylene oxide, tetrahydrofuran and 3-methyltetrahydrofuran, and / or copolymerization or from polyols, such as molecules a diol or mixture of diols having less than 12 carbon atoms, such as 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 condensation polymerization of 1,12-dodecanediol. Linear, difunctional polyether polyols are preferred, and poly(tetramethylene ether) glycols having a molecular weight of from about 1,700 to about 2,900 and a functionality of 2, such as Terathane® 1800 (INVISTA, Wichita, KS) It is an example of a particular suitable polyol. The copolymer may include poly(tetramethylene ether-co-extended ethyl ether) glycol and poly(tetramethylene ether-co-2-methyltetramethylene ether) glycol.

Examples of the polyester diol include a polyester having two hydroxyl end groups such as polycaprolactone diol and a low molecular weight aliphatic dicarboxylic acid having not more than 12 carbon atoms in each molecule. And the condensation polymerization of the diol or a mixture thereof. 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 dodecane carboxylic acid. Examples of suitable polyols for the preparation of polyester polyols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl Glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-nonanediol, and 1, 12-dodecanediol. Linear, difunctional polyester polyols having a melting or softening temperature below 55 ° C are preferred. Examples of polycarbonate diols include polycarbonates having two hydroxyl end groups which are produced by condensation polymerization of an aliphatic diol with phosgene, a dialkyl carbonate or a diaryl carbonate. Examples of suitable diols for the preparation of polycarbonate diols are 1,3-propanediol, 1,4-butanediol 1, 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 a mixture thereof and oligomeric polyester or polyether diol. Linear, difunctional polycarbonate polyols having a melting or softening temperature below 55 ° C are preferred.

Another aspect is a method of producing an elastic rayon comprising polyurethane urethane using a mixed or blended diol, the mixed or blended diol comprising a polyether polyol and a non-reactive having a relatively high concentration PPG with or without a terminal or unsaturated or monool end group. The mixed diol is reacted with an excess of diisocyanate to form an isocyanate-terminated prepolymer, the prepolymer is diluted with an aprotic polar solvent and further terminated with an aliphatic diamine or diamine mixture chain extender and a dialkylamine in a solvent. The agent is reacted and the resulting polyurethaneurea solution is subsequently spun into fibers via a solution spinning process such as a dry spinning process or a wet spinning process. Controlling the molecular weight of the elastomeric rayon polymer polymer before and after fiber formation to overcome the lack of high non-reactive end group/monool concentration in the diol and balance the need for manufacturing processability and product performance . In particular, the molecular weight of the polymer is controlled by maintaining the relative ratio of the individual components involved in chain growth and chain termination reactions such that: (a) isocyanate (NCO) end groups (in milliequivalents) from the prepolymer The concentration ratio of one of the chain amine (NH ₂ ) end groups (in milliequivalents) from the chain extender or chain extender mixture is in the range of 0.99 to 1.01, such as about 1.00, and (b) the dialkylamine from the terminator The sum of the monool end groups from the PPG is less than about 50 meq/kg of polymer, including from about 20 meq/kg to about 40 meq/kg of polymer.

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

Another aspect is fabric. Several methods of making fabrics are known in the art. Examples include knitting or weaving or lamination. Such articles may include from about 1% to about 30% by weight of the elastic rayon fibers of the present invention. These fabrics have a soft stretch without sacrificing restoring force.

Some aspects of the article may be yarns, coated yarns, wovens, non-wovens, knits or laminates. The knitwear can be a warp knit or a circular knit. Suitable laminates can include one or more layers of fabric, film, etc., between which the elastic rayon fibers are placed and adhered or bonded.

Polyurethane ureas for elastic rayon fibers can be prepared by a two-step process.

In the first step, an isocyanate-terminated urethane prepolymer or a blocked diol is formed by reacting a blend of two or more diols with a diisocyanate. In the diol blend, at least one component is a polyether polyol such as poly(tetramethylene ether) glycol (PTMEG) or a copolyether containing at least 50 mole percent of a repeating unit of tetramethylene ether. The diol, and at least one other component of the diol blend is a poly(propylene ether) glycol (PPG) comprising a copolyether having at least 50 mole percent of propylene ether repeating units. PTMEG or its copolyether glycol has at least 50% by weight in the blended diol and a number average molecular weight in the range of from 1000 to 4000 (including 1000 to 3000). The PPG or its copolyether glycol has at least 10% by weight of the blended diol and has a number average molecular weight in the range of from 1000 to 5000. Further, the PPG diol used in the diol blend has from 40 meq/kg to 90 meq/kg, preferably from 40 meq/kg to 70 meq/kg (meq/kg) of the PPG diol. A relatively high concentration of unsaturated or monol end groups within the range. The ratio of the capping ratio used to produce the prepolymer, that is, the ratio of the total number of molar ratios or isocyanate groups (-NCO) of the diisocyanate to the blended diol to the total number of hydroxyl groups (-OH) is controlled at about 1.50 to Within the range of about 2.50. Optionally, in this prepolymerization step, a catalyst may be used to assist the reaction.

In the second step, the urethane prepolymer or the capped glycol is dissolved in a solvent such as N,N -dimethylacetamide (DMAc) to form a solution having a solid content of 30% to 50%. . The diluted blocked diol solution is then chain extended with a mixture of low molecular weight aliphatic primary diamines or diamines, and optionally capped with a small amount of dialkylamine to form a polyurethane urethane solution. The amount of the diamine chain extender used should be controlled in such a way that the total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer are combined with the chain extender or chain extender. The ratio of total primary amine (NH ₂ ) end groups (in milliequivalents) is in the range of 0.99 to 1.01 (such as about 1.00). The termination dose is controlled in such a way that the sum of the dialkylamine from the terminator and the monol end group from the PPG is less than 50 meq/kg of polymer solids, preferably at 20 meq/kg. Up to 40 meq/kg of polymer solids.

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

The additive can be mixed into the polymer solution at any stage after the formation of the polyurethane urea but prior to spinning the solution into fibers. The solids content (including additives) in the polymer solution prior to spinning is typically controlled in the range of from 30.0% to 50.0% by weight of the solution. The viscosity of the solution held in the storage tank prior to spinning is typically controlled in the range of 3,000 poise to 5,000 poise by adjusting the aging time, agitation speed and sump temperature to achieve optimum spinning performance.

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

Examples of PPG diols and copolyether diols include, but are not limited to, Pluracol® polyether polyols from BASF (Wyandotte, Michigan, USA), Multranol® and Arcol® polyethers from Bayer MaterialScience (Leverkusen, Germany) Alcohol, VORANOL polyether polyol from Dow Chemical (Midland, Michigan, USA), Poly-L® polyether polyol from Lonza Group Ltd. (Basel, Switzerland) and from SINOPEC Gaoqiao Petrochemical Co. (Shanghai, China) Polyether polyol.

Examples of diisocyanates that may be used include, but are not limited to, 4,4'-methylenebis(phenylisocyanate) (also known as 4,4'diphenylmethane diisocyanate (MDI)), 2, 4'-methylenebis(phenylisocyanate), 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-diisocyanate, 2,6-di Toluene isocyanate, toluene 2,4-diisocyanate, and mixtures thereof. Examples of specific polyisocyanate components include Takenate® 500 (Mitsui Chemicals), Mondur® MB (Bayer), Lupranate® M (BASF), and lsonate® 125 MDR (Dow Chemical), and combinations thereof.

Examples of suitable diamine chain extenders include one or more diamines selected from the group consisting of 1,2-ethylenediamine, 1,4-butanediamine, 1,2-butanediamine, 1,3-butane Amine, 1,3-diamine-2,2-dimethylbutane, 1,6-hexanediamine, 1,12-dodecanediamine, 1,2-propylenediamine, 1,3-propane Diamine, 2-methyl-1,5-pentanediamine, 1-amino-3,3,5-trimethyl-5-aminemethylcyclohexane, 2,4-diamine-1-methyl Cyclohexane, N-methylamino-bis(3-propylamine), 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-methylene-bis(cyclohexylamine) ), isophorone diamine, 2,2-dimethyl-1,3-propanediamine, m-tetramethylxylenediamine, 1,3-diamine-4-methylcyclohexane, 1 , 3-cyclohexane-diamine, 1,1-methylene-bis(4,4'-diaminohexane), 3-aminomethyl-3,5,5-trimethylcyclohexane , 1,3-pentanediamine (1,3-diaminopentane), m-xylylenediamine and Jeffamine® (Texaco).

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

Exemplary and non-limiting list of additives included as appropriate include antioxidants, UV stabilizers/screening agents, colorants, pigments, crosslinkers, antimicrobial agents, microencapsulated additives, flame retardants, anti-adhesive additives (metal Stearates), anti-chlorine degradation additives, dyeability and/or dyeing agents, matting agents such as titanium dioxide, stabilizers such as hydrotalcite, mixtures of carrasite and bauxite, and combinations thereof. Other can be included in elastic man-made fibers Additives in the composition are, for example, adhesion promoters, antistatic agents, optical brighteners, conductive additives, luminescent additives, lubricants, organic and inorganic fillers, preservatives, conditioning agents, wetting agents, stabilizers (blocked) Phenol, zinc oxide, hindered amines, slip agents (polyoxygenated oils), and combinations thereof.

The polyurethane urethane polymer solution prepared as described above is then spun into elastic rayon fibers by a dry spinning method as known in the art.

The features and advantages of the present invention are more fully shown by the following examples, which are set forth herein.

testing method

The viscosity of the polymer solution was determined according to the method of ASTM D1343-69 using a DV-8 type ball viscous meter (Duratech Corp., Waynesboro, VA), operated at 40 ° C and reported as berth.

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

The percentage of isocyanate of the blocked diol prepolymer (% NCO) is based on the method of S. Siggia. "Quantitative Organic Analysis via Functional Group" 3rd edition, Wiley & Sons, New York, pp. 559-561 (1963). Titration to determine.

The strength and elastic properties of the elastic rayon and film are measured according to the general method of ASTM D 2731-72. Three filaments, 2 吋 (5 cm) gauge length and 0-300% elongation cycle were used for each measurement. The sample was cycled five times at a constant elongation rate of 50 cm/min. The load force (TP2) (the stress on the elastic rayon during the initial extension) was measured at 200% elongation in the first cycle and reported in the given denier of denier. The unloading force (TM2) is the stress of the fifth unloading cycle with an extension of 200% and is also reported in grams. The percent elongation at break (ELO) and the tensile strength (TEN) were measured on the sixth extended cycle. Stress decay (%SD) was measured as a percentage of stress reduction at 300% in the fifth cycle after a 30 second delay.

%SD=(5LP-5UP)×100/5LP

Among them, 5LP and 5UP in terms of gram force are respectively the load force and unloading force under the 300% extension of the sample.

Percentage of permanent deformation was also measured for samples that had been subjected to five 0-300% elongation/relaxation cycles. Then calculate the percentage of permanent deformation as follows, %SET: %SET=100×(Lf-Lo)/Lo

Wherein Lo and Lf are the lengths of the filaments (yarns) when held straight before tension and before the five elongation/relaxation cycles, respectively.

Instance

Terathane® 1800 is a linear poly(tetramethylene ether) glycol (PTMEG) having a number average molecular weight of 1,800 g/mol (available from Invista, S.à.rL, Wichita, KS); Pluracol® 1062 is A linear polypropylene polyol having a primary hydroxyl end group comprising 18% by weight of ethylene oxide capped based on the total weight of the polyol, and having a number average molecular weight of 4000 g/mol, which is commercially available from BASF Corporation, Wyandotte, Mich. The diol had a maximum unsaturation of 65 meq/kg according to its specifications, and the unsaturation of the specific batch used for the elastic rayon of the present invention was determined by the supplier to be 59 meq/kg.

Isonate® 125MDR is a pure mixture of diphenylmethane diisocyanate (MDI) containing 98% 4,4'-MDI isomer and 2% 2,4'-MDI isomer (available from Dow Company, Midland, Michigan); Dytek® A is 2-methyl-1,5-pentanediamine (MPMD) (available from Invista, S.à.rL, Wichita, KS); Terathane® 2900 is a number of 2,900 g/mol Linear molecular weight poly(tetramethylene ether) glycol (PTMEG) (available from Invista, S.à.rL, Wichita, KS and Wilmington, DE); Terathane® E 2049 is tetrahydrofuran and ethylene oxide a chain copolyether diol having a number average molecular weight of 2,000 g/mol and a stretching ethyl ether repeating unit of about 49 mole percent from Invista, S.à.rL, Wichita, KS and Wilmington, DE; Terathane® E 2549 is a linear copolyether diol of tetrahydrofuran and ethylene oxide having a number average molecular weight of 2,500 g/mol and a stretching ethyl ether repeating unit of about 49 mole percent from Invista, S.à.rL, Wichita , KS and Wilmington, DE; Terathane® E 2538 is a linear copolyether glycol of tetrahydrofuran and ethylene oxide having a number average molecular weight of 2,500 g/mol and a stretch of about 38 mole percent a repeating unit of an ether from Invista, S.à.rL, Wichita, KS and Wilmington, DE; PTG-L2200 is a linear copolyether glycol of tetrahydrofuran and 3-methyl-tetrahydrofuran having 2,200 g/mol a number average molecular weight and a 2-methyl-tetramethylene ether repeating unit of about 8 mole percent from Hodogaya Chemical., Ltd., Tokyo, Japan; PTG-L3500 is a straight line of tetrahydrofuran and 3-methyl-tetrahydrofuran a chain copolyether diol having a number average molecular weight of 3,500 g/mol and a 2-methyl-tetramethylene ether repeating unit of about 13 mole percent from Hodogaya Chemical Co., Ltd., Tokyo, Japan; Desmophen® C 2200 is a linear aliphatic polycarbonate diol having a number average molecular weight of 2,000 g/mol (CAS number 101325-00-2) available from Bayer MaterialScience, Pittsburgh, PA; polycaprolactone- block - polytetrahydrofuran - block - polycaprolactone diol triblock copolymer having a number of from about 2000g / mol average molecular weight of which from Sigma-Aldrich Co., St.Louis, MO ; VORANOL TM 222- 056 polyol is a linear polyether diol based on propylene oxide, wherein ethylene oxide is capped at the end, and the VORAN OL ^TM 222-056 polyol having a number 2,000g / mol of average molecular weight, commercially available from Dow Company, Midland, Michigan. The unsaturation of a particular batch of elastomeric rayon used in the present invention is provided by the supplier at 50 meq/kg; EDA for ethylenediamine; DETA for diethyltriamine; DEA for N as a chain terminator N-diethylamine

Fiber Example 1 (Comparative Example)

100.00 parts by weight of Terathane ^® 1800 diol and 23.47 parts of Isonate® 125MDR MDI were mixed and reacted at a capping ratio (NCO/OH) of 1.69 to form an isocyanate-terminated prepolymer, wherein the percentage of isocyanate groups (-NCO) is 2.60% of the prepolymer. This prepolymer was then dissolved in 165.52 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of amines in DMAc solution using a high speed disperser to form a homogeneous polyamine group having a viscosity of about 34.8% polymer solids and a viscosity of 2600 poise (measured at 40 ° C). The acid ester urea solution containing 1.94 parts EDA, 0.42 parts Dytek*A, 0.03 parts DETA, 0.42 parts DEA and 71.05 parts DMAc. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.05 and the end group concentration from the diethylamine terminator is about 45 meq/kg of polymer solids.

The polymer solution is mixed with a slurry of the additive comprising 4.0% anti-bleach, 0.17% matting agent, 1.35% antioxidant, 0.5% co-dyeing agent, 0.3% spinning aid and 0.4% based on the weight of the solid. Anti-adhesive additive. This mixture was spun into a 40 denier elastic rayon yarn having a winding speed of 4 filaments at a winding speed of 930 meters per minute. The properties of the as-spun yarn of this test article were measured and are listed in Table 1.

Fiber Example 2:

Blending 44.49 parts by weight of Terathane® 1800 diol with 22.25 parts by weight of Pluracol® 1062 polyol, and reacting the blended diol with 13.26 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 1.75 To form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) is 2.38% of the prepolymer. This prepolymer was then dissolved in 99.60 parts of N,N-dimethylacetamide (DMAc). A mixture of the diluted prepolymer solution and 11.41 parts of the diamine extender in a 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 DMAc using a high speed disperser The solution (containing 0.07 parts of DEA and 7.93 parts of DMAc) and the additional 34.01 parts of DMAc were reacted to form a homogeneous polyurethaneurea solution having a concentration of about 35.0 at 40 °C. % polymer solids and 2,600 poise viscosity. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00, and the end group concentration from the diethylamine terminator is about 12 meq/kg of polymer solids and the monool end group from PPG is about 16 meq/kg (meq/kg) of polymer solids. .

The polymer solution is mixed with a slurry of an additive comprising 4.0% anti-bleach, 0.17% matting agent, 1.35% antioxidant, 0.5% co-dyeing agent, 0.3% spinning aid and 0.4% by weight of solids. Anti-adhesive additive. This mixed solution was spun at a winding speed of 930 m/min into a 40 denier elastic rayon yarn having four filaments wound together. The properties of the as-spun yarn of this test article were measured and are listed in Table 1.

Fiber Example 3 (Comparative Example)

200.00 parts by weight of Terathane® 1800 diol was blended with 100.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was reacted with 59.84 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 1.75. To form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) is 2.40% of the prepolymer. This prepolymer was then dissolved in 578.22 parts of N,N-dimethylacetamide (DMAc). A mixture of the diluted prepolymer solution and 201.86 parts of the diamine extender in a 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 DMAc solution (containing 0.70) using a high speed disperser The DEA in DEA and 7.30 parts of DMAc) is reacted to form a homogeneous polyurethaneurea solution having a viscosity of about 32.0% polymer solids and a viscosity of 3011 poise at 40 °C. . In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.02, and the end group concentration from the diethylamine terminator is about 20 meq/kg polymer solids and the monool end group from PPG is about 18 meq/kg polymer solids. .

Due to frequent fractures in the spinning chamber, this polymer solution could not be spun into 40 denier fibers with 4 filaments.

Fiber Example 4: (Comparative Example)

200.00 parts by weight of Terathane® 2000 diol was blended with 100.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was reacted with 56.78 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 1.82. To form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) is 2.46% of the prepolymer. This prepolymer was then dissolved in 575.30 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of 203.78 parts of the diamine extender in DMAc solution (containing 5.51 parts EDA, 1.18 parts Dytek® A and 197.08 parts DMAc) using a high speed disperser to form a polymerization having about 32.0%. A homogeneous solid polyurethane solution of solids. The viscosity of the solution was too high to be measured by the ball drop method at 40 °C. In this polymer, the ratio of total isocyanate (NCO) end groups (in milliequivalents) from the prepolymer to total primary amine (NH ₂ ) end groups from the chain extender or chain extender mixture is about 1.03, And the terminal group concentration is only the monool end group derived from PPG at about 18 meq/kg of polymer solids.

Due to frequent fractures in the spinning chamber, this polymer solution could not be spun into 40 denier fibers with 4 filaments.

Fiber Example 5:

200.00 parts by weight of Terathane® 2000 diol was blended with 100.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was reacted with 56.74 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 1.75. To form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) is 2.45% of the prepolymer. This prepolymer was then dissolved in 513.65 parts of N,N-dimethylacetamide (DMAc). A mixture of 203.78 parts of the 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 DMAc solution (containing 0.16) using a high speed disperser The DEA reacts with DEA in 1.66 parts of DMAc) to form a homogeneous polyurethaneurea solution which has 32.0% polymer solids and 2541 measured by the ball drop method at 40 °C. The viscosity of the mooring. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.02, and the end group concentration from the diethylamine terminator is about 6 meq/kg polymer solids and the monool end group from PPG is about 18 meq/kg polymer solids. .

This polymer solution was spun at a winding speed of 930 meters per minute into a 40 denier elastic rayon yarn having four filaments wound together. The properties of the as-spun yarn of this test article were measured and are listed in Table 1.

Fiber Example 6:

200.00 parts by weight of Terathane® 1800 diol was blended with 100.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was reacted with 62.17 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 1.82. To form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) is 2.60% of the prepolymer. This prepolymer was then dissolved in 566.84 parts of N,N-dimethylacetamide (DMAc). A mixture of the diluted prepolymer solution and 224.08 parts of the diamine extender in a DMAc solution (containing 6.06 parts of EDA, 1.30 parts of Dytek® A and 216.72 parts of DMAc) and 1.86 parts of DMAc solution (containing 0.16) using a high speed disperser The DEA is reacted with DEA in 1.70 parts of DMAc) to form a homogeneous polyurethaneurea solution having about 32.0% polymer solids by a ball drop method at 40 ° C and Viscosity of 4,795 poise. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00, and the end group concentration from the diethylamine terminator is about 6 meq/kg of polymer solids and the monool end group from PPG is about 18 meq/kg (mq/kg) of polymer solids. .

This polymer solution was spun at a winding speed of 930 meters per minute into a 40 denier elastic rayon yarn having four filaments wound together. The properties of the as-spun yarn of this test article were measured and are listed in Table 1.

The above fiber examples 2, 5 and 6 illustrate the use of a diol blend of a PTMEG diol with a PPG diol having a high concentration of unsaturated end groups or a monol content to produce an elastic rayon. These elastic rayon fibers provide unique properties such as lower load forces, high unloading forces, and high elongation at break compared to elastic rayon fibers made only with PTMEG. However, in order to obtain the necessary polymer structure and molecular weight to produce the elastic rayon fibers, as described and exemplified in the present invention, the relative ratio of components must be strictly controlled in the manufacture of elastic rayon polymers by blending PTMEG with PPG. .

Fiber Example 7:

200.00 parts by weight of PTG-L2200 diol (Hodogaya Chemical Co., Ltd.) was blended with 100.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was combined with 51.05 parts of Isonate® 125MDR MDI at the end cap ratio (NCO). /OH) was reacted at 1.70 to form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) was 2.06% of the prepolymer. This prepolymer was then dissolved in 595.23 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of 168.01 parts of a diamine extender in a 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 polymerization having about 32.0%. A homogeneous solid polyurethane solution of solids. In this polymer, the total isocyanate (NCO) end group from the prepolymer (in milliequivalents) The ratio of total primary amine (NH2) end groups (in milliequivalents) from the chain extender or chain extender mixture is about 1.00, and the monool end group from PPG is about 16.5 meq/kg (meq) /kg) polymer solids.

This polymer solution was spun at a winding speed of 850 m/min into a 40 denier elastic rayon yarn having three filaments entangled together. The properties of the as-spun yarn of this test article were measured and are listed in Table 2.

Fiber Example 8:

134.00 parts by weight of Terathane® 2900 diol was blended with 66.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was reacted with 28.25 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 1.80. To form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) is 1.84% of the prepolymer. This prepolymer was then dissolved in 395.00 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of 100.33 parts of a diamine extender in a 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 polymerization having about 32.0%. A homogeneous solid polyurethane solution of solids. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00 and the monool end group from PPG is about 16.8 milliequivalents per kilogram (meq/kg) of polymer solids.

This polymer solution was spun at a winding speed of 850 m/min into a 40 denier elastic rayon yarn having three filaments entangled together. The properties of the as-spun yarn of this test article were measured and are listed in Table 2.

Fiber Example 9:

150.00 parts by weight of PTG-L3500 diol (Hodogaya Chemical Co., Ltd.) was blended with 50.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was combined with 23.55 parts of Isonate® 125MDR MDI at the end cap ratio (NCO). /OH) was reacted at 1.70 to form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) was 1.50% of the prepolymer. This prepolymer was then dissolved in 404.47 parts of N,N-dimethylacetamide (DMAc). A mixture of the diluted prepolymer solution and 77.50 parts of the diamine extender in a 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 DMAc solution (containing 0.10) using a high speed disperser The DEA was reacted with DEA in 1.03 parts of DMAc) to form a homogeneous polyurethaneurea solution having about 32.0% polymer solids. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00, and the end group concentration from the diethylamine terminator is about 6 meq/kg of polymer solids and the monool end group from PPG is about 13 meq/kg (meq/kg) of polymer solids. .

This polymer solution was spun at a winding speed of 850 m/min into a 40 denier elastic rayon yarn having three filaments entangled together. The properties of the as-spun yarn of this test article were measured and are listed in Table 2.

Fiber Example 10:

150.00 parts by weight of Desmophen® C 2200 diol (Bayer MaterialScience LLC) was blended with 50.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was combined with 40.46 parts of Isonate® 125MDR MDI at the end cap ratio (NCO/OH). The reaction was carried out at 1.80 to form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) was 2.50% of the prepolymer. This prepolymer was then dissolved in 382.60 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of 143.06 parts of the diamine extender in DMAc solution (containing 3.87 parts EDA, 0.83 parts Dytek® A and 138.36 parts DMAc) using a high speed disperser to form a polymerization having about 32.0%. A homogeneous solid polyurethane solution of solids. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00 and the monool end group from PPG is about 12 meq/kg (meq/kg) polymer solids.

This polymer solution was spun at a winding speed of 850 m/min into a 40 denier elastic rayon yarn having three filaments entangled together. The properties of the as-spun yarn of this test article were measured and are listed in Table 2.

Fiber Example 11:

225.00 parts by weight of Terathane® E 2049 diol (Invista) was blended with 75.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was combined with 61.87 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 2.00. The reaction is carried out to form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) is 2.49% of the prepolymer. This prepolymer was then dissolved in 547.14 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of 247.22 parts of a diamine extender in a DMAc solution (containing 6.69 parts EDA, 1.44 parts Dytek® A and 239.10 parts DMAc) using a high speed disperser to form a polymerization having about 32.0%. A homogeneous solid polyurethane solution of solids. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00 and the monool end group from PPG is about 12 meq/kg (meq/kg) polymer solids.

This polymer solution was spun at a winding speed of 850 m/min into a 40 denier elastic rayon yarn having three filaments entangled together. The properties of the as-spun yarn of this test article were measured and are listed in Table 2.

Fiber Example 12:

225.00 parts by weight of Terathane® E 2538 diol was blended with 75.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was combined with 52.97 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 1.95. The reaction is carried out to form an isocyanate-terminated prepolymer wherein the percentage of isocyanate groups (-NCO) is 2.45% of the prepolymer. This prepolymer was then dissolved in 565.39 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of 205.80 parts of the diamine extender in DMAc solution (containing 5.57 parts EDA, 1.20 parts Dytek® A and 199.04 parts DMAc) using a high speed disperser to form a polymerization having about 32.0%. A homogeneous solid polyurethane solution of solids. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00 and the monool end group from PPG is about 12 meq/kg (meq/kg) polymer solids.

This polymer solution was spun at a winding speed of 850 m/min into a 40 denier elastic rayon yarn having three filaments entangled together. The properties of the as-spun yarn of this test article were measured and are listed in Table 2.

Fiber Example 13:

225.00 parts by weight of Terathane® E 2549 diol (Invista) was blended with 75.00 parts by weight of Pluracol® 1062 polyol, and the blended diol was combined with 51.71 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 1.90. The reaction is carried out to form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) is 2.26% of the prepolymer. This prepolymer was then dissolved in 571.73 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of 195.76 parts of the diamine extender in DMAc solution (containing 5.29 parts EDA, 1.14 parts Dytek® A and 189.33 parts DMAc) using a high speed disperser to form a polymerization having about 32.0%. A homogeneous solid polyurethane solution of solids. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00 and the monool end group from PPG is about 12 meq/kg (meq/kg) polymer solids.

This polymer solution was spun at a winding speed of 850 m/min into a 40 denier elastic rayon yarn having three filaments entangled together. The properties of the as-spun yarn of this test article were measured and are listed in Table 2.

Fiber Example 14:

The parts by weight of Terathane® 1800 200.00 diol (Invista) ^(TM) and 100.00 parts by weight of 222-056 polyol blend Voranol, and make this diol blend with 68.57 parts of Isonate® 125MDR MDI terminated at the ratio (NCO / OH) of The reaction was carried out in the case of 1.70 to form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) was 2.55% of the prepolymer. This prepolymer was then dissolved in 580.73 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of 225.65 parts of a diamine extender in a DMAc solution (containing 6.10 parts EDA, 1.31 parts Dytek® A and 218.24 parts DMAc) using a high speed disperser to form a polymerization having about 32.0%. A homogeneous solid polyurethane solution of solids. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00 and the monool end group from PPG is about 13 meq/kg polymer solids.

This polymer solution was spun at a winding speed of 850 m/min into a 40 denier elastic rayon yarn having three filaments entangled together. The properties of the as-spun yarn of this test article were measured and are listed in Table 2.

Fiber Example 15:

150.00 parts by weight of polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone diol (Sigma-Aldrich) having an average Mn of about 2000 was blended with 50.00 parts by weight of Pluracol® 1062 polyol, and this was The blended diol was reacted with 41.25 parts of Isonate® 125MDR MDI at a capping ratio (NCO/OH) of 1.85 to form an isocyanate-terminated prepolymer in which the percentage of isocyanate groups (-NCO) was prepolymer 2.62%. This prepolymer was then dissolved in 376.73 parts of N,N-dimethylacetamide (DMAc). The diluted prepolymer solution was reacted with a mixture of 151.48 parts of a diamine extender in a 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 polymerization having about 32.0%. A homogeneous solid polyurethane solution of solids. In this polymer, the total isocyanate (NCO) end group (in milliequivalents) from the prepolymer and the total primary amine (NH ₂ ) end group (in milliequivalents) from the chain extender or chain extender mixture The ratio is about 1.00 and the monool end group from PPG is about 12 meq/kg (meq/kg) polymer solids.

This polymer solution was spun at a winding speed of 850 m/min into a 40 denier elastic rayon yarn having three filaments entangled together. The properties of the as-spun yarn of this test article were measured and are listed in Table 2.

Example of fabric of fiber of fiber example 2:

The following examples demonstrate the invention and its ability to make a variety of weight fabrics. Accordingly, the examples are considered to be illustrative in nature and not limiting. The fabrics from Examples 1 to 9 were woven. The fabrics from Examples 10 to 20 were circular knitwear. In each instance, D48 elastic fiber refers to the fiber of Example 2.

For each of the following wovens, 100% cotton staple fiber spun yarn was used as the warp yarn. It consists of two types of yarn: 7.0Ne OE yarn with irregularly arranged pattern and 8.5Ne OE yarn. The yarn is dyed in an indigo color in the form of a rope before warping. It is then sized and used to make a braided warp beam.

D48 elastic fiber/cotton core spun yarn (CSY) and D48 elastic fiber/polyester deformed air-jet coated yarn (AJY) were used as the weft. Table 3 lists the materials and processing conditions for producing the core spun yarn and the air-covered yarn of each example. Elastomeric yarns are available from Invista, s.á.r.L., Wichita, KS. For example, 40d in the row of elastic fibers means 40 denier; and 3.3x means the draw ratio (mechanical draw ratio) of the elasticity applied by the core spinning machine. In the line of "hard yarn", 16's is based on the British cotton system (English Cotton Count System) The linear density of the spun yarns measured. The remaining items in Table 3 are clearly labeled.

The stretched woven fabric was then produced using the core spun yarn and the air-coated yarn of each of the examples in Table 3. The core spun yarn and the air coated yarn are used as weft yarns. Table 4 summarizes the weaving patterns and quality characteristics of the yarns, fabrics used in the fabric. Some additional annotations for each of the examples are given below. The fabric was woven on a Donier air jet loom unless otherwise stated. The loom speed is 500 latitude/min. The width of the fabric in the loom and in the state of the original embryo is about 76 吋 and about 72 分别, respectively.

Each of the protoplasts in the examples is completed by scouring, desizing, relaxing, and adding a softening agent.

"Table 3 weft specifications", "Table 4 fabric example list" and "Table 5 CK fabric example list" refer to the fabric examples described below.

In Table 4, AJY is an air-coated yarn and CSY is a core-spun yarn having an elastic rayon core.

Fabric Example 1C: Stretch denim with standard elastic AJY

This is a comparative example and is not in accordance with the present invention. The warp yarn is a mixed yarn of 7.0Ne count and 8.4Ne count. The warp yarns were dyed in indigo before warping. The weft yarn is a 300d/192 filament polyester air-coated yarn with 40D T162B Lycra® elastic rayon. The Lycra® fiber was drawn 3.3× during the coating process. Table 4 lists the fabric properties. This fabric had a weight (10.1 OZ/Y ² ), a stretch (32.4%), a growth (4.1%) and a fabric recovery of 84.18%.

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

This sample had the same fabric structure as in Example 1. The difference is the air-coated yarn in the weft direction, which contains 40D D48 LYCRA® fiber. This fabric used the same warp yarns and structure as in Example 1. Further, the weaving and finishing treatments were the same as in Example 1. Table 4 summarizes the test results. I can see that this sample has a low fabric growth (3.3%) and a high fabric recovery (86.30%) compared to the fabric of Example 1.

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

This sample had the same fabric structure as in Examples 1 and 2. The difference is the air-coated yarn in the weft direction, which contains 70D D48 LYCRA® fiber. Table 4 summarizes the test results. Because of the higher denier D48, this sample had high stretch (39.3%), low fabric growth (3.1%), and high fabric recovery (90.14%) compared to the fabrics of Examples 1 and 2.

Fabric Example 4: Heat-set stretched denim with 40D D48 elastic AJY

This sample had the same fabric structure and treatment as in Example 2. The difference is that the fabric is heat set at 380 °F for 45 seconds. The fabric performance listed in Table 4 shows that D48 elastic fiber can withstand Heat setting treatment. After heat setting, the fabric has low shrinkage and good dimensional stability. The weft shrinkage of the fabric decreased from -5.85% of the unheated fabric of Example 2 to -2.73% of the heat set fabric of this example.

Fabric Example 5C: Stretch denim with standard elastic CSY

This is a comparative example and is not in accordance with the present invention. The warp yarn is a mixed yarn of 7.0Ne count and 8.4Ne count. The warp yarn was dyed in indigo before warping. The weft yarn is a 16Ne core spun yarn with 70D T162B Lycra® elastic rayon. Lycra® fiber draws 3.8× during the coating process. Table 4 lists the fabric properties. This fabric has a weight (11.60 g/m ² ), a stretch (44.4%), a growth (5.6%), and a fabric recovery rate (84.23%).

Fabric Example 6: Stretch denim with 70D D48 CSY

This sample had the same fabric structure as Example 5C. The difference is the weft-core core-spun yarn, which contains 70D D48 LYCRA® fiber. This fabric used the same warp yarns and structure as in Example 5C. Further, the weaving and finishing treatment was the same as in Example 5C. Table 4 summarizes the test results. I can see that this sample has similar performance to sample 5C: fabric stretch (43%), fabric growth (5.7%), and fabric recovery (83.4%).

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

This sample had the same fabric structure as Examples 5C and 6. The difference is the draw ratio of the elastic fibers in the core spun yarn. The draw ratio of the 70D D48 LYCRA® fiber in this example was 4.6 x relative to 3.8 x in the above two examples. Table 4 summarizes the fabric results. This sample had a fabric stretch (45.4%), fabric growth (5.6%), and fabric recovery (84.59%) similar to the fabric of Example 5. This indicates that the D48 fiber can stretch more than the conventional elastic rayon during the yarn coating process. The high draft ratio provides the textile mill with the ability to use lower levels of elastic rayon and reduce the cost of raw materials.

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

This sample had the same fabric structure and treatment as in Example 6. The difference is the weft-core core spinning yarn, which contains 40D D48 LYCRA® fiber. Fabric performance listed in Table 4 It is shown that 40D D48 elastic fibers can be used to make good fabrics with acceptable performance.

Fabric Example 9: Heat-set stretched denim with 70D D48 elastic CSY

This sample had the same fabric structure and treatment as in Example 6. The difference is for this fabric at 380. F heat setting for 45 seconds. The fabric performance listed in Table 4 shows that the D48 elastic fiber can withstand heat setting treatment. After heat setting, the fabric has low shrinkage and good dimensional stability. The weft shrinkage of the fabric was reduced from -9.75% of the unheated fabric of Example 6 to -3.65% of the heat set fabric of this example.

Table 5 lists examples of circular fabrics. The fabrics from Examples 10 to 15 were low-content elastic rayon cotton CK fabrics. The fabrics from Examples 16 to 20 were high elastic rayon content CK fabrics having nylon and polyester filaments. All fabrics are single jersey fabrics made with 28 standard size machines.

Fabric Example 10C: Cotton Stretch CK

This is a comparative example and is not in accordance with the present invention. The hard yarn is a 32Ne cotton ring spinning yarn. The elastic fiber is 40D T162B Lycra® elastic rayon. The Lycra® fiber was drawn at 3.5× during knitting in a 28 gauge machine. After dyeing and finishing of the fabric, heat setting was carried out at 380 °F for 45 seconds. Table 5 lists the fabric properties. This fabric had a weight (314 g/m ² ), a stretch (129.8% × 124.6%), and a shrinkage ratio (-4.25% × -0.71%).

Fabric Example 11: Cotton stretch with CK fiber CK

This sample had the same fabric structure as Example 10C. The difference is elastic fiber: 40D D48 LYCRA® fiber spun at 95o meters/min. Table 5 summarizes the fabric results. It can be seen that this sample has a light fabric weight (282 g/m ² ), a similar degree of stretch (128.4% x 129.4%), and a lower shrinkage (-3.65 x -0.36%) than the fabric of Example 10C. D48 fibers can be used to make good CK fabrics with light weight, soft stretch and low shrinkage.

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

The elastic fiber was 40D/4f D48 spun at a speed 10% higher than the fiber in Example 11. The fiber spinning speed was 1140 meters per minute. The results of the fabrics listed in Table 5 indicate that this high speed D48 has high elasticity, a higher degree of stretch and a higher shrinkage, which results in a slightly heavier weight. Fabric performance is acceptable.

Fabric Example 13C: Cotton Stretch CK (Preheat Setting)

This is a comparative example and is not in accordance with the present invention. The hard yarn is a 32Ne cotton ring spinning yarn. The elastic fiber is 40D T162B Lycra® elastic rayon. The Lycra® fiber was drawn at 3.5× during knitting in a 28 gauge machine. After preheating and setting in the original embryo stage, the fabric is dyed and finished. Preheating was set at 380 °F for 30 seconds. Table 5 lists the fabric properties. This fabric had a weight (189 g/m ² ), a stretch (75.7% × 113.6%), and a shrinkage ratio (-5.2% × 0.0%).

Fabric Example 14: Cotton stretch CK with D48 fiber (preheat setting)

This sample had the same fabric structure as Example 13C. The difference is elastic fiber: 40D D48 LYCRA® fiber spun at 950 m/min. From Table 5, it can be seen that this sample has a fabric weight (194 g/m ² ) similar to that of the fabric of Example 13C, a similar degree of stretching (76.3% × 113.9%), and a low shrinkage ratio (-3.64% × - 1.43%). This result confirms that D48 fibers can be used in preheating shaped stretch CK fabrics.

Fabric Example 15: Cotton stretch CK with D48 fiber spun at high speed (preheat setting)

The elastic fiber was 40D/4f D48 spun at a speed 10% higher than the fiber of Example 14. The fiber spinning speed was 1140 meters per minute. The fabrics listed in Table 5 show that this high speed D48 fiber can be used in preheating shaped CK fabrics. Fabric performance is acceptable.

Fabric Example 16: High tensile CK with 70D D48 fiber

The hard yarn is 150D/200f T935 COOLMAX® polyester filament. Elastane is 70D/5f D48 Lycra® elastic rayon. The Lycra® fiber was drawn at 2.8 x during knitting in a 28 gauge machine. The LYCRA® fiber content in the fabric was 13.9% by weight. After preheating and setting at 190 ° C for 40 seconds, the fabric was dyed and finished. Table 5 lists the fabric properties. This fabric has a weight (232 g/m ² ), a stretch (85% x 123%), and a shrinkage ratio (-0.3% x -0.3%).

Fabric Example 17: High content stretch CK with 70D D48 fiber

The hard yarn is 71D/68f Tactel® nylon filament. Elastane is 70D/5f D48 Lycra® elastic rayon. The Lycra® fiber was drawn at 2.8 x during knitting in a 28 gauge machine. The LYCRA® fiber content in the fabric was 25.9% by weight. After preheating and setting at 190 ° C for 40 seconds, the fabric was dyed and finished. Table 5 lists the fabric properties. This fabric had a weight (354 g/m ² ), a stretch (209% × 183%), and a shrinkage ratio (-1.3% × -0.2%). The fabric has a soft hand and high restoring power.

Fabric Example 18: High tensile CK with 40D D48 fiber

70D/72f 564DT polyester filaments were used as the hard yarn. 40D/4f D48 Lycra® elastic rayon is used as the elastic yarn. The Lycra® fiber was drawn at 2.8 x during knitting in a 28 gauge machine. The LYCRA® fiber content in the fabric was 17.3% by weight. After preheating and setting at 190 ° C for 40 seconds, the fabric was dyed and finished. The fabric properties listed in Table 5 show that 40D D48 fibers provide good stretch and recovery for polyester based CK fabrics.

Fabric Example 19: High content stretch CK with 40D D48 fiber

This fabric differs from Example 18 as a hard yarn. Use 80D/68f Supplex® nylon filaments. Elastane is 40D/4f D48 Lycra® elastic rayon. The Lycra® fiber was drawn at 2.8 x during knitting. After preheating and setting at 190 ° C for 40 seconds, the fabric was dyed and finished. The LYCRA® fiber content in the fabric was 16.1% by weight. Table 5 lists the fabric characteristics as: weight (207 g/m ² ), stretch (192% × 189%), and shrinkage (to 1.4% × -0.7%). The fabric also has a soft hand and high restoring power.

Fabric Example 20: High tensile CK with 140D D48 fiber

The hard yarn is 162D/136f nylon filament. The elastic fiber is 140D/10f D48 Lycra® elastic rayon. Lycra® fibers were drawn at 2.0× during knitting in a 28 gauge machine. The LYCRA® fiber content in the fabric was 29% by weight. After preheating and setting at 190 ° C for 40 seconds, the fabric was dyed and finished. This fabric had a weight (309 g/m ² ), a stretch (99% × 163%), and a shrinkage ratio (-0.6% × -0.9%). The fabric has a restoring force of 550 x 444 grams at 30% elongation, which is almost three times larger than a standard cotton stretch CK fabric. This fabric is ideal for making high-energy shaped garments.

Although the present invention has been described as a preferred embodiment of the present invention, it will be appreciated by those skilled in the art that this invention can be modified and modified without departing from the spirit of the invention, and Modifications are included within the true scope of the invention.

Claims (20)

An article comprising a polyurethane furic acid urea, wherein the polyurethane product is a reaction product of: (a) a prepolymer comprising the reaction product of (i) comprising PPG and at least one a polyol of another polyol; and (ii) a diisocyanate; and (b) a diamine chain extender and, optionally, a dialkylamine chain terminator; wherein the total isocyanate (NCO) end group from the prepolymer The ratio of total primary amine (NH ₂ ) end groups from the diamine chain extender is from about 0.99 to about 1.01; and the non-reactive end groups from the PPG and the dioxane in the polyurethane The combined amount of the base end groups is less than about 50 meq/kg. The article of claim 1 wherein the at least one other polyol comprises PTMEG. The article of claim 1 further comprising (c) a chain terminator. The article of claim 3, wherein the chain terminator comprises a dialkylamine chain terminator. The article of claim 1 wherein the polyol has a number average molecular weight of from about 600 to about 3,500. The article of claim 1 wherein the PPG has a number average molecular weight of from about 1000 to about 5,000. The article of claim 1, wherein the polyol comprising PPG blended together with at least one other polyol has a number average molecular weight of from about 1000 to about 4,000. The article of claim 1 wherein the prepolymer has a capping ratio of from about 1.50 to about 2.50. The article of claim 1 wherein the PPG has a content of from about 40 meq/kg to about 90 meq/kg, such as from about 45 meq/kg to about 90 meq/kg or from about 50 meq/kg to about 90 meq/kg or from about 50 meq/kg to about 70 meq. /kg or about 45meq/kg to about 70 Non-reactive end groups of meq/kg. The article of claim 1 wherein the polyurethaneurea has an intrinsic viscosity of from about 0.93 dL/g to about 1.02 dL/g. The article of claim 1 wherein the polyurethane urea has a total non-reactive end group in an amount from about 10 meq/kg to about 45 meq/kg, such as from about 20 meq/kg to 40 meq/kg. The article of claim 1 wherein the diisocyanate comprises diphenylmethane diisocyanate (MDI). The article of claim 1 wherein the diamine chain extender comprises a blend of a diamine chain extender. The article of claim 1 wherein the article is an elastomeric fiber. An article comprising at least one elastomeric fiber comprising a polyurethane furanate as a reaction product of: (a) a capped diol (i) comprising a reaction product of: a PPG and at least one polyol of another polyol; and (ii) a diisocyanate; and (b) a diamine chain extender and optionally a dialkylamine chain terminator; wherein the total isocyanate from the prepolymer ( The ratio of the NCO) end group to the total primary amine (NH ₂ ) end group derived from the diamine chain extender is from about 0.99 to about 1.01; and the amount of non-reactive end group and dialkyl urea end group is less than about 50meq/kg. The article of claim 15 further comprising (c) a chain terminator. The article of claim 16, wherein the chain terminator comprises a dialkylamine chain terminator. The article of claim 15 wherein the article is a coated yarn, a woven, a non-woven, a knit or a laminate. The article of claim 15 wherein the knitwear is selected from the group consisting of warp knits and circular knits. A method of making an elastic rayon comprising: (a) providing a polyol comprising PTMEG and PPG; (b) providing a diisocyanate; (c) contacting the polyol with the diisocyanate to form a capped diol; d) providing the diamine in an amount to control the ratio of the total isocyanate (NCO) end group from the prepolymer to the total primary amine (NH ₂ ) end group derived from the diamine chain extender in an amount of from about 0.99 to about 1.01 a chain extender; (e) providing a dialkylamine chain terminator in an amount to control the molecular weight of the polymer by a non-reactive end group and a dialkyl urea end group in the polyurethane urea The combined amount is less than about 50 meq/kg; (f) contacting the capped diol, the chain extender, and the chain terminator composition in a solvent to form a solution of polyurethane urea; (g) spinning the polyurethane of the solution to form an elastic rayon.