Polyurethaneurea composition and method for preparing polyurethaneurea elastic yarn using same

Abstract

The present invention relates to a polyurethaneurea composition using an organic solvent that ensures excellent stability and processability in polyurethane urea, and a method for preparing polyurethane urea elastic yarn. According to the present invention, by using an amide-ether-based solvent, reaction control is enabled, thereby allowing a high-molecular-weight polyurethane polymer to be obtained. The obtained polyurethane elastomer solution exhibits excellent transparency, does not become turbid even after long-term storage, thereby providing excellent storage stability, is not subject to environmental regulations, has high process stability due to a high flash point, and contains a low residual amount in the elastic yarn, thereby providing the advantage of being harmless to the human body when applied to clothing.

Description

Polyurethaneurea composition and method for manufacturing polyurethaneurea elastic yarn using the same

[0001] The present invention relates to a polyurethaneurea composition and a method for manufacturing a polyurethaneurea elastic yarn using the same. More specifically, the invention relates to a polyurethaneurea composition comprising an organic solvent that ensures excellent stability and processability in the polyurethaneurea, and a method for manufacturing a polyurethaneurea elastic yarn.

[0002] Polyurethaneurea elastic fibers, also known as spandex or elastane, are widely used in stockings, sportswear, women's underwear, swimwear, and stretch fabrics due to their excellent elasticity and elastic recovery. Furthermore, polyurethaneurea elastic fibers are interwoven with polyamide, polyester, and natural fibers to serve as elastic materials in various clothing applications, including bras, socks, pantyhose, and swimwear.

[0003] Polyurethaneurea elastic yarn is generally manufactured by reacting a high molecular weight polyol with an excess amount of diisocyanate compound to obtain a prepolymer having isocyanate groups at both ends of the polyol, dissolving the prepolymer in a suitable solvent, and then dry-spinning or wet-spinning the polyurethaneurea polymer solution obtained by chain-extending the prepolymer.

[0004] Dry spinning technology involves dissolving a polymer in an organic solvent to create a spinning solution, which is then extruded through a spinneret to allow the solvent to evaporate and the polymer filaments to solidify, thereby manufacturing fibers. Most commercially available polyurethaneurea elastic yarns are produced using dry spinning technology. The selection of the solvent is critical in dry spinning technology. First, the solvent must possess strong polarity to completely dissolve high molecular weight polymers. If solubility is insufficient, the cross-section of the yarn becomes non-uniform, leading to significant variations in physical properties. Second, when passing through the high-temperature spinneret, the polymer solution must rapidly remove the solvent to minimize the amount of residual solvent in the fiber. This is because solvents are highly toxic, and any residual solvent remaining in the spandex fiber during and after production must be minimized to reduce potential harm to human health.

[0005] Currently, organic polar solvents such as N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and dimethylacetamide (DMAc) are used in the synthesis of polyurethaneurea polymers. These solvents are harmful to the human body due to their carcinogenic and cytotoxic properties, and they also pose environmental, toxicological, and administrative problems. For example, NMP is listed on the "Substances of Very High Concern (SVHC)" list under REACH (Registration, Evaluation, Authorization and Restriction of Chemicals), the European Union regulatory framework for the registration, evaluation, authorization, and restriction of chemicals. DMAc and DMF also have similar issues and are scheduled to be regulated under REACH. Therefore, the development of solvents that can replace them is required.

[0006] [Prior Art Literature]

[0007] [Patent Literature]

[0008] (Patent Document 1) KR 2023-0065317 A

[0009] The present invention aims to solve the problems of the aforementioned prior art. One objective of the present invention is to provide a polyurethaneurea composition that can efficiently and stably synthesize high molecular weight polyurethaneurea polymers, and which uses a solvent that can replace regulated substances such as REACH, so that the reaction solution does not become cloudy during or after the reaction, thereby having high transparency and storage stability, and a method for manufacturing a polyurethaneurea elastic yarn using the same.

[0010] One aspect of the present invention for solving the above-mentioned problem is

[0011] The present invention relates to a polyurethaneurea composition comprising a polyurethaneurea polymer and an amide-ether-based solvent of the following chemical formula 1.

[0012]

[0013] In the above formula, R1, R2, R3 and R4 are independent of each other and are hydrogen or alkyl groups having 1 to 18 carbon atoms.

[0014] Another aspect of the present invention for solving the above-mentioned problem relates to a method for manufacturing a polyurethaneurea elastic yarn comprising the steps of: dissolving a polyurethaneurea prepolymer in an organic solvent of Formula 1 and then performing a chain extension reaction to obtain a polyurethaneurea solution; and preparing a spinning solution from the obtained polyurethaneurea solution and spinning it.

[0015] [Chemical Formula 1]

[0016]

[0017] In the above formula, R1, R2, R3 and R4 are independent of each other and are hydrogen or alkyl groups having 1 to 18 carbon atoms.

[0018] In the present invention, a polyurethaneurea prepolymer is prepared by polymerizing a polyol and an excess amount of diisocyanate at a capping ratio (CR) of 1.4 to 2.0, and then the polyurethaneurea prepolymer is dissolved in an amide-ether solvent of the following chemical formula 1 to obtain a prepolymer solution, and then a chain extender and a chain terminater are added to the obtained prepolymer solution to synthesize a polyurethaneurea polymer and prepare a polyurethaneurea solution.

[0019] In the present invention, one or more types selected from the group consisting of polytetramethylene ether polyol, polypropylene polyol, polycarbonate diol, and combinations thereof may be used as polyols.

[0020] In the present invention, one or more types selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate may be used as the diisocyanate.

[0021] In the present invention, one or more diamine chain extenders may be used as chain extenders.

[0022] In the present invention, one or more diamine chain extenders selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and combinations thereof may be used.

[0023] One or more selected from the group consisting of diethylamine, monoethanolamine, cyclohexylamine, and dimethylamine may be used as the above-mentioned chain endogenizer.

[0024] In the method of the present invention, polyurethane can be synthesized by solution polymerization, and the polyurethaneurea spinning solution can be spun by dry spinning.

[0025] Another aspect of the present invention for achieving the above-described objective relates to a polyurethane-urea elastic yarn produced by the method for producing a polyurethane-urea elastic yarn described above.

[0026] The residual amount of organic solvent in the polyurethane urea elastic yarn of the present invention can be 0.1% to 0.90%.

[0027] According to the present invention, the polyurethaneurea composition obtained by using an amide-ether-based solvent that has a positive polarity and high solubility in the preparation of the polyurethaneurea composition is transparent and does not become cloudy even after long-term storage, thus having good storage stability, and the reaction is controllable, allowing for the production of various high molecular weight polymers. In addition, the amide-ether-based solvent used in the present invention has a high flash point and low volatility, and as a result, generates less odor, thereby ensuring an improved working environment when applied to the process.

[0028] In addition, according to the present invention, by using a solvent that complies with international regulations such as REACH, it is possible to manufacture a polyurethane-urea elastic yarn having physical properties equivalent to those of a conventional polyurethane-urea elastic yarn even under milder conditions.

[0029] The present invention will be described in more detail below.

[0030] In this specification, the term “polyurethaneurea polymer” basically refers to a long chain synthetic polymer composed of alternating “soft segments” of polyether or polyester and “hard segments” derived from the reaction of isocyanate and diamine chain extender. In this specification, the term “polyurethaneurea” is a term relating to a polymer chain containing both urethane and urea linkers.

[0031] In this specification, the term "fiber" may be a single filament or multiple filaments and may be used interchangeably with "yarn."

[0032] As used in this specification, the term "polyurethaneurea elastic fiber" means "an elastomer fiber in which the fiber-forming material is a long-chain synthetic polymer composed of at least 85% segmented polyurethane." In this specification, the term "polyurethaneurea elastic fiber" may be used interchangeably with "spandex fiber."

[0033] In this specification, the “capping ratio (CR)” is defined as the molar ratio of diisocyanate to polyol used in the prepolymerization step. If multiple diisocyanate compounds and / or polyols are used in the reaction, the average molecular weight should be used when calculating the capping ratio.

[0034] In this specification, "solvent" means an organic solvent capable of forming a homogeneous solution of a polyurethane polymer.

[0035] In this specification, the term "polymerization" includes the term "copolymerization" in its meaning unless otherwise indicated.

[0036] The term “solution-spinning” as used herein includes the manufacture of fibers from a solution, which may be a wet-spinning or dry-spinning process.

[0037] One aspect of the present invention relates to a polyurethaneurea composition comprising a polyurethane polymer and an amide-ether-based solvent of Formula 1 below.

[0038] [Chemical Formula 1]

[0039]

[0040] In the above formula, R1, R2, R3 and R4 are independent of each other and are hydrogen or alkyl groups having 1 to 18 carbon atoms.

[0041] Non-limiting examples of the amide-ether solvent of Formula 1 above include 3-methoxy-N,N-dimethylpropanamide (3-MDPA), 3-methoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-methoxy-N,N-dibutylpropionamide, 3-propoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-dipropylpropionamide, 3-ethoxy-N,N-dipropylpropionamide, 3-ethoxy-N,N-dibutylpropionamide, 3-propoxy-N,N-diethylpropionamide, 3-butoxy-N,N-diethylpropionamide, Examples include 3-butoxy-N,N-diisopropylpropionamide.

[0042] In this specification, the term “alkyl group having 1 to 18 carbon atoms” means an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 carbon atoms or a range comprising two of these integers, which includes 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17 or 1-18 carbon atoms. Examples of straight-chain and branched alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dinethylbutyl, 1,2,2-trimethylpropyl or 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl and 1,1,3,3-tetramethylbutyl group, nonyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-ethylnonyl.It includes 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1,2-pentylheptyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl groups.

[0043] Another aspect of the present invention relates to a method for manufacturing a polyurethaneurea elastic yarn, comprising the steps of: dissolving a polyurethaneurea prepolymer in an organic solvent of Formula 1 and then performing a chain extension reaction to obtain a polyurethaneurea solution; and preparing a spinning solution from the obtained polyurethaneurea solution and spinning it.

[0044] [Chemical Formula 1]

[0045]

[0046] In the above formula, R1, R2, R3 and R4 are independent of each other and are hydrogen or alkyl groups having 1 to 18 carbon atoms.

[0047] In the present invention, a polyurethaneurea prepolymer is prepared by polymerizing a polyol and an excess amount of diisocyanate at a capping ratio (CR) of 1.4 to 2.0, and then the polyurethaneurea prepolymer is dissolved in an amide-ether solvent of Formula 1 to obtain a prepolymer solution, and then a chain extender and a chain terminater are added to the prepolymer solution to synthesize a polyurethaneurea polymer and prepare a polyurethaneurea solution.

[0048] Polyols usable in the present invention include polyether polyols, polycarbonate polyols, and polyester polyols having a number average molecular weight of about 600 to about 3,500. A mixture of two or more polyols or copolymers may be used.

[0049] The polyols usable in the present invention may be exemplified by one selected from the group consisting of polytetramethylene ether polyols, polypropylene polyols, polycarbonate diols, and combinations thereof, but are not necessarily limited to these.

[0050] The diisocyanates used in the manufacture of the polyurethane-urea elastic yarn of the present invention are not particularly limited, but examples thereof may include one or more selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, or isophorone diisocyanate.

[0051] In the reaction for synthesizing polyurethane from a polyol and a diisocyanate using an amide-ether solvent in the present invention, the reaction temperature is typically 20°C to 150°C, preferably 30°C to 120°C, and more preferably 40°C to 110°C.

[0052] When manufacturing polyurethane, a polyol is first reacted with an organic isocyanate and, optionally, a catalyst to form an "NCO-terminated prepolymer" or a "capped polyol." This reaction is generally carried out in the form of a uniformly blended mixture with applied heat at a temperature of 60°C to 95°C for a period of 1 to 6 hours. The amount of each reaction component can be controlled by a capping ratio (CR), defined as the molar ratio of the diisocyanate to the polyol. In the present invention, the capping ratio (CR) of the polyol and the diisocyanate is preferably 1.4 to 2.0.

[0053] Amide-ether solvents possess anodes and high solubility, which can contribute to minimizing cloudiness, maintaining transparency, and ensuring solvent stability during the polyurethaneurea polymerization process. Furthermore, since they are not included in regulated substances such as REACH, they are free from administrative issues. Their high flash point ensures high safety even in high-temperature processes, and their high flash point results in low volatility and consequently less odor, thereby improving the working environment when applied to processes.

[0054] Polyurethaneurea elastic yarn consists of a hard segment portion and a soft segment portion. The hard segment portion of the elastic yarn can interact with polar solvents, such as amide-ether solvents, to increase solubility, but the relatively non-polar soft segment may interfere with the interaction. In the method for manufacturing polyurethaneurea elastic yarn according to the present invention, the content ratio of the hard segment and the soft segment of the elastic yarn must be adjusted to improve the affinity with the solvent in order to improve the solubility of the solvent.

[0055] In the present invention, a prepolymer is prepared using a polyol and a diisocyanate with a capping ratio (CR) of 1.40 to 2.0. If the capping ratio is less than 1.4, there is a problem with insufficient power enhancement, and if the capping ratio exceeds 2.0, there is a problem with process application due to solubility issues caused by an excessive increase in hard segments.

[0056] After the capping reaction is completed when all hydroxyl (-OH) groups from the polyol molecule are consumed by the isocyanate (-NCO) groups from the diisocyanate to form urethane groups, the weight % (%NCO) of the NCO groups remaining on the prepolymer can be measured. In one embodiment of the present invention, the preferred %NCO range of the prepolymer may be 1.5 to 3.8.

[0057] In the present invention, one or more diamine chain extenders may be used as chain extenders.

[0058] The diamine chain extenders usable in the present invention may include one or more selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and combinations thereof, but are not necessarily limited to these.

[0059] For controlling the molecular weight of polyurethaneurea polymers, one or more chain-ending agents selected from the group consisting of amines having a single functional group, such as diethylamine, monoethanolamine, cyclohexylamine, and dimethylamine, may be used, but are not necessarily limited to these.

[0060] Polyurethane urea elastic yarns may contain additives such as stabilizers and pigments, but such additives should not impair the advantages of the present invention. Such additives include benzotriazole-based stabilizers, ultraviolet absorbers, other light-resistant agents, antioxidants, matting agents, anti-sticking agents, dyes and dye promoters, lubricants (e.g., mineral oil and silicone oil), deodorizers, and antistatic agents. Other examples of additives include polymers of bis(4-isocyanatocyclohexyl)methane and 3-t-butyl3-aza-1,5-pentanediol), titanium oxide, zinc oxide, magnesium stearate, barium sulfate, mixtures of hydrotalcite, huntite and hydromagnesite, and fungicides containing silver, zinc, or compounds thereof.

[0061] In addition, to prevent discoloration and deterioration of physical properties of the polyurethaneurea elastic yarn of the present invention due to ultraviolet rays, atmospheric smog, heat treatment processes associated with spandex processing, etc., a sterically hindered phenolic compound, a benzofuran-one compound, a semicarbazide compound, a benzotriazole compound, a polymeric tertiary amine stabilizer, etc., may be appropriately added to the spinning solution.

[0062] Furthermore, the polyurethane urea elastic yarn of the present invention may include additives such as titanium dioxide, magnesium stearate, etc. in addition to the above components.

[0063] There are no specific restrictions on the method of adding these other additives, and any conventional method, such as titration mixing, may be used. The additives may be mixed into the polymer solution at any stage after the polyurethaneurea polymer is formed and before the solution is spun into fibers. As a representative method, blending by a static mixer or a stirring method may preferably be used after adding to the spinning solution.

[0064] When forming polyurethane elastic fibers by spinning a polyurethaneurea solution obtained by a solution polymerization method, the spinning method is not particularly limited, and known methods such as dry spinning and wet spinning can be appropriately used. However, considering productivity, dry spinning is preferred in that stable spinning is possible for all finenesses from thin to thick threads.

[0065] Another aspect of the present invention relates to a polyurethane-urea elastic yarn produced by the method for producing a polyurethane-urea elastic yarn described above.

[0066] The residual amount of organic solvent in the polyurethane-urea elastic yarn of the present invention can be 0.1% to 0.90%.

[0067] The polyurethane urea elastic yarn of the present invention can be suitably used, for example, in clothing such as innerwear, stockings, socks, sportswear, swimwear, and fashion clothing; clothing materials such as elastic tapes and strings; interior materials for vehicles such as vehicle seats; and sanitary products such as disposable diapers.

[0068] The present invention will be described in more detail below with reference to examples. However, the following examples are intended to illustrate embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Furthermore, in the examples, "parts" and "%" refer to weight standards unless otherwise specified.

[0069] Examples

[0070] Example 1

[0071] A polyurethane prepolymer was prepared by thoroughly mixing a polytetramethylene polyol with a molecular weight of about 1800 and 4,4'-diphenylmethane diisocyanate at a capping ratio of 1.40 at a temperature of about 90°C for 120 minutes to obtain an NCO% of 1.535%.

[0072] 90 mol% ethylenediamine and 10 mol% 1,2-diaminopropane were used as chain extenders, and diethylamine was used as a chain terminater. 3-methoxy-N,N-dimethylpropanamide (3-MDPA) was used as a solvent to obtain a polyurethaneurea solution with a solid content of 40%.

[0073]

[0074] Example 2

[0075] 4,4'-diphenylmethane diisocyanate and polytetramethylene glycol were prepared with a capping ratio (CR) of 1.65 to achieve an NCO% of 2.46%. Ethylenediamine at 80 mol% and 1,2-diaminopropane at 20 mol% were used as chain extenders, and diethylamine was used as a chain terminater. 3-methoxy-N,N-dimethylpropanamide (3-MDPA) was used as the solvent to obtain a polyurethaneurea solution with a solid content of 35%.

[0076]

[0077] Example 3

[0078] A polyurethaneurea solution was obtained by carrying out the same procedure as in Example 1, except that the solid content of the polyurethaneurea solution was prepared to be 37%.

[0079]

[0080] Example 4

[0081] 4,4'-diphenylmethane diisocyanate and polytetramethylene polyol were prepared with a capping ratio (CR) of 1.72 to achieve an NCO% of 2.70%. Ethylenediamine was used at 100 mol% as a chain extender, and diethylamine was used as a chain terminater. The ratio of the chain extender to the chain terminater was set to 8:1, and the amines used were prepared at a total concentration of 7 mol%. 3-methoxy-N,N-dimethylpropanamide (3-MDPA) was used as the solvent to obtain a polyurethaneurea solution with a final polymer solid content of 35 wt%.

[0082]

[0083] Example 5

[0084] 4,4'-diphenylmethane diisocyanate and polytetramethylene polyol were prepared with a capping ratio (CR) of 1.85 to achieve an NCO% of 3.10%. Ethylenediamine 50 mol% and 1,2-diaminopropane 20 mol% were used as chain extenders, and diethylamine was used as a chain terminater.

[0085] The ratio of chain extender to chain terminater was set to 20:1, the amine used was prepared at a total concentration of 7 mol%, and 3-methoxy-N,N-dimethylpropanamide (3-MDPA) was used as the solvent to obtain a polyurethaneurea solution with a final polymer solid content of 40 wt%.

[0086]

[0087] Example 6

[0088] 4,4'-diphenylmethane diisocyanate and polytetramethylene glycol were prepared with a capping ratio (CR) of 2.00 to achieve an NCO% of 3.591%. Ethylenediamine was used at 100 mol% as a chain extender, and diethylamine was used as a chain terminater. The ratio of the chain extender to the chain terminater was set to 13:1, and the amines used were prepared at a total concentration of 7 mol%. 3-methoxy-N,N-dimethylpropanamide (3-MDPA) was used as the solvent to obtain a polyurethaneurea solution with a final polymer solid content of 33 wt%.

[0089]

[0090] Example 7

[0091] A polyurethaneurea elastic fiber spinning solution was obtained by adding and mixing 1.5 wt% of ethylenebis(oxyethylene)bis-(3-(5-t-butyl-4-hydroxy-m-toyl)-propionate), 0.5 wt% of 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, 1 wt% of 1,1,1',1'-tetramethyl-4,4'-(methylene-di-p-phenylene)disemicarbazide, 1 wt% of poly(N,N-diethyl-2-aminoethyl methacrylate), and 0.1 wt% of titanium dioxide as additives relative to the solid content of the polyurethaneurea solution of Example 1.

[0092] The spinning solution obtained as above was used to produce 40 denier 3-filament polyurethaneurea elastic fibers by dry spinning at a speed of 900 m / min, and the physical properties were evaluated and are shown in Table 2 below.

[0093]

[0094] Comparative Examples 1 to 3

[0095] A polyurethaneurea solution was obtained by carrying out the same procedure as in Examples 2, 4, and 5, except that dimethylacetamide (DMAc) was used as the solvent. Its physical properties were evaluated and are shown in Table 1 below.

[0096]

[0097] Comparative Example 4

[0098] A polyurethaneurea solution was obtained by carrying out the same procedure as in Example 1, except that dimethyl sulfoxide (DMSO) was used as the solvent. Its physical properties were evaluated and are shown in Table 1 below.

[0099]

[0100] Comparative Example 5

[0101] A polyurethaneurea solution was obtained by carrying out the same procedure as in Example 1, except that Cyrene™ was used as the solvent. Its physical properties were evaluated and are shown in Table 1 below.

[0102]

[0103] Comparative Example 6

[0104] A polyurethaneurea solution was obtained by carrying out the same procedure as in Example 1, except that 4,4'-diphenylmethane diisocyanate and polytetramethylene glycol were used at a capping ratio (CR) of 1.20, and the physical properties were evaluated and are shown in Table 1 below.

[0105]

[0106] Comparative Example 7

[0107] The procedure was carried out in the same manner as in Example 6, except that the capping ratio (CR) of 4,4'-diphenylmethane diisocyanate and polytetramethylene polyol was 2.10, to obtain a polyurethaneurea solution, and its physical properties were evaluated and are shown in Table 1 below.

[0108]

[0109] Comparative Example 8

[0110] A 40-denier 3-filament polyurethaneurea elastic fiber was prepared by carrying out the same procedure as in Example 7, except that the polyurethaneurea solution of Comparative Example 1 was used, and its physical properties were evaluated and are shown in Table 2 below.

[0111]

[0112] Test example

[0113] The physical properties of the polyurethaneurea solutions prepared in Examples 1-6 and Comparative Examples 1-7 and the polyurethaneurea elastic yarns prepared in Examples 7 and Comparative Example 8 were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

[0114] (1) NCO% = [100 × 2 × NCO formula weight × (capping ratio - 1)] / (diisocyanate molecular weight × capping ratio) + polyol molecular weight

[0115] (2) Strength and elongation of the yarn: Measurements were taken using an automatic strength and elongation measuring device (manufacturer: Textechno, model name: MEL) with a sample length of 10 cm and a tensile speed of 100 cm / min. At this time, the strength and elongation values ​​at break were measured, and the 200% modulus of the load applied to the yarn when the yarn is stretched by 200% was also measured.

[0116] (3) Yarn Power (5 th unload @200%): Using an automatic tensile strength measuring device (manufacturer: Textechno, model name: MEL), a sample length of 10 cm × 20 strands is stretched 300% five times at a tensile speed of 100 cm / min, and the power at the 200% section during the fifth recovery is measured and then divided by the number of strands and denier (de).

[0117] (4) Turbidity: To evaluate the storage stability of the polyurethaneurea elastomer solution, the turbidity of the secondary polymer (polyurethane polymer immediately after reacting the polyurethane prepolymer with the chain extender and chain terminater) was measured 5 times using Turbidity Meters (Manufacturer: HANNA instruments, Model: HI 98703) and the minimum value was used.

[0118] (5) Turbidity change rate: The turbidity of the secondary polymer was measured at 24-hour intervals while storing it in a 40℃ oven.

[0119] Turbidity change rate [NTU / hr] = (Turbidity after 72 hours - Initial turbidity) / 72

[0120] (6) Toxicity in solvent: The presence or absence of toxicity was determined through the REACH SVHC Candidate List of substances of very high concern for Authorisation - ECHA (European Chemical Agency).

[0121] (7) Flash point measurement: The measurement method followed the ASTM D 1310-86 standard, and the procedure is as follows, and the results are shown in Table 3.

[0122] ① 70 ml of each sample of solvent and polyurethaneurea solution was placed in a sample cup and heated starting from a temperature about 20℃ lower than the predicted flash point.

[0123] ② The heating rate was adjusted to 1 ± 0.25℃.

[0124] ③ For every 0.5℃ increase in temperature, the test salt was brought close to the surface of the flammable liquid for 1 second.

[0125] ④ When ignition occurred, the duration of the ignition was measured using a timer.

[0126] ⑤ The temperature at which the ignition duration was 5 seconds or more was recorded as the combustion point.

[0127] Capping Ratio (CR) Chain Extender Solvent Solution Concentration (%) Solution Appearance Intrinsic Viscosity (IV) Turbidity (NTU) Turbidity Change Rate (NTU / hr) Presence or Absence of Toxicity Example 1 1.40 EDA:12 PDA=90:103-MDPA40 Colorless, Transparent 1.12 0.30 None Example 2 1.65 EDA:12 PDA=80:203-MDPA35 Colorless, Transparent 0.92 0.30 0.312 None Example 3 1.65 EDA:12 PDA=80:203-MDPA37 Colorless, Transparent 0.95 0.33 0.425 None Example 41.72 EDA:12PDA=100:03-MDPA35 Colorless, Transparent 1.05 0.38 0.434 None Example 5 1.85 EDA:12PDA=50:503-MDPA40 Colorless, Transparent 1.12 0.41 0.451 None Example 6 2.00 EDA:12PDA=100:03-MDPA33 Colorless, Transparent 0.98 0.45 0.502 None Comparative Example 1 1.65 EDA:12PDA=80:20DMAc35 Colorless, Transparent 0.95 0.41 0.355 Present Comparative Example 2 1.72 EDA:12PDA=100:0DMAc35 Colorless, Transparent 0.97 0.48 0.492 Present Comparative Example 31.85 EDA:12 PDA=50:50 DMC40 Colorless, Transparent 1.10 0.53 0.411 Present Comparative Example 41.65 EDA:12 PDA=80:20 DMSO35 White, Opaque 0.52 10 or more Unmeasurable None Comparative Example 51.65 EDA:12 PDA=80:20 Cyrene35 Yellow, Opaque 0.45 10 or more Unmeasurable None Comparative Example 61.20 EDA:12 PDA=90:103-MDPA40 Colorless, Transparent 0.23 0.27 0.105 None Comparative Example 72.10 EDA:12 PDA=100:03-MDPA33 Colorless, Transparent 1.20 0.88 1.001 None

[0128] Capping Ratio (CR) Chain Extender Solvent Solution Concentration Strength (g / d) Elongation (%) 200% Modulus (g) Yarn Power (g) Example 7 1.65 EDA:12 PDA=80:20 3-MDPA 35 1.17 48 7 7.5 1.14 Comparative Example 8 1.65 EDA:12 PDA=80:20 DMac 35 1.23 47 5 7.2 1.18

[0129] Classification Solvent Solvent Flash Point (°C) Polyurethane Urea Solution Flash Point (°C) Example 5 DMAc6161 Example 63-MDPA99100

[0130] As confirmed by the results in Tables 1 to 3 above, using the amide-ether-based organic solvent of the present invention, it was possible to obtain a polyurethaneurea solution having excellent solubility and solution stability under various polyurethaneurea compositions and solution concentration conditions, and when polyurethaneurea elastic yarn was manufactured using this, an elastic yarn with physical properties similar to existing ones could be obtained. In addition, process stability could be secured with a high flash point.

[0131] [Aspects]

[0132] Aspect 1. A polyurethaneurea composition comprising a polyurethaneurea polymer and an amide-ether-based solvent of the following chemical formula 1.

[0133] [Chemical Formula 1]

[0134]

[0135] In the above formula, R1, R2, R3 and R4 are independent of each other and are hydrogen or alkyl groups having 1 to 18 carbon atoms.

[0136] A method for manufacturing a polyurethaneurea elastic yarn comprising: a step of dissolving a polyurethaneurea prepolymer in an organic solvent of the following chemical formula 1 and then performing a chain extension reaction to obtain a polyurethaneurea solution; and a step of preparing a spinning solution with the obtained polyurethaneurea solution and spinning it.

[0137] [Chemical Formula 1]

[0138]

[0139] In the above formula, R1, R2, R3 and R4 are independent of each other and are hydrogen or alkyl groups having 1 to 18 carbon atoms.

[0140] A method for manufacturing a polyurethaneurea elastic yarn according to Aspect 2, wherein the method comprises the step of preparing a polyurethaneurea prepolymer by polymerizing a polyol and an excess amount of diisocyanate at a capping ratio (CR) of 1.4 to 2.0, and then preparing a polyurethaneurea solution by adding a chain extender and a chain terminater to a prepolymer solution obtained by dissolving the polyurethaneurea prepolymer in a solvent of Formula 1.

[0141] A method for manufacturing a polyurethane-urea elastic yarn according to side 2 or side 3, wherein the diisocyanate is one or more selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

[0142] A method for manufacturing a polyurethane-urea elastic yarn, characterized in that, in any one of sides 2 to 4, the chain extender is one or more diamine chain extenders.

[0143] A method for manufacturing a polyurethane-urea elastic yarn, wherein, in any one of the above sides 2 to 5, the diamine chain extender is one or more selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine, and 1,4-cyclohexanediamine.

[0144] A method for manufacturing a polyurethane-urea elastic yarn, characterized in that, in any one of the above sides 2 to 6, the chain termination agent is one or more selected from the group consisting of diethylamine, monoethanolamine, cyclohexylamine, and dimethylamine.

[0145] Side 8. A method for manufacturing a polyurethane-urea elastic yarn, wherein in any one of Side 2 to Side 6, the method is characterized by dry spinning a polyurethane-urea spinning solution.

[0146] Side 9. A polyurethane-urea elastic yarn manufactured by the method of manufacturing a polyurethane-urea elastic yarn of any one of Sides 2 to 8 above.

[0147] Side 10. The polyurethane-urea elastic yarn according to Side 9, characterized in that the residual solvent amount of the polyurethane-urea elastic yarn is 0.1% to 0.90%.

[0148] Although the present invention has been described in detail above, such description is for the purpose of illustrating the invention, and it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the scope of the invention. Accordingly, all such changes and modifications should be understood as being included within the scope of protection of the present invention as defined by the appended claims.

[0149] All optional and preferred features and variations of the embodiments and dependent claims described herein may be used in all aspects taught herein. Furthermore, all optional and preferred features and variations of the embodiments described herein, as well as individual features of the dependent claims, are combined and interchangeable with one another. It will be understood that polyurethaneurea compositions and polyurethaneurea elastic yarns can be designed for specific applications by using various combinations of the arrangements described above. It will be understood that the features described herein may all be used together in a single system. In other embodiments, some features may be omitted. Features may be used in any compatible arrangement. Many variations and modifications not explicitly described above are possible without departing from the scope defined in the appended claims.

Claims

1. A polyurethaneurea composition comprising a polyurethaneurea polymer and an amide-ether-based solvent of the following chemical formula 1. [Chemical Formula 1] In the above formula, R1, R2, R3 and R4 are independent of each other and are hydrogen or alkyl groups having 1 to 18 carbon atoms.

2. A method for manufacturing a polyurethaneurea elastic yarn comprising: a step of dissolving a polyurethaneurea prepolymer in an organic solvent of the following chemical formula 1 and then performing a chain extension reaction to obtain a polyurethaneurea solution; and a step of preparing a spinning solution using the obtained polyurethaneurea solution and spinning it. [Chemical Formula 1] In the above formula, R1, R2, R3 and R4 are independent of each other and are hydrogen or alkyl groups having 1 to 18 carbon atoms.

3. In paragraph 2, the above method A method for manufacturing a polyurethaneurea elastic yarn, characterized by including the step of preparing a polyurethaneurea prepolymer by polymerizing a polyol and an excess amount of diisocyanate at a capping ratio (CR) of 1.4 to 2.0, and then preparing a polyurethaneurea solution by adding a chain extender and a chain terminater to a prepolymer solution obtained by dissolving the polyurethaneurea prepolymer in a solvent of Formula 1.

4. A method for manufacturing a polyurethane-urea elastic yarn according to claim 3, wherein the diisocyanate is one or more selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

5. A method for manufacturing a polyurethane-urea elastic yarn according to claim 3, characterized in that the chain extender is one or more diamine chain extenders.

6. A method for manufacturing a polyurethane-urea elastic yarn according to claim 5, wherein the diamine chain extender is one or more selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine.

7. A method for manufacturing a polyurethane urea elastic yarn according to claim 3, characterized in that the chain termination agent is one or more selected from the group consisting of diethylamine, monoethanolamine, cyclohexylamine, and dimethylamine.

8. A method for manufacturing a polyurethane urea elastic yarn according to paragraph 3, characterized in that the method involves dry spinning a polyurethane urea spinning solution.

9. A polyurethane-urea elastic yarn manufactured by the method for manufacturing a polyurethane-urea elastic yarn according to any one of paragraphs 2 through 8.

10. The polyurethaneurea elastic yarn according to claim 9, characterized in that the residual solvent amount of the polyurethaneurea elastic yarn is 0.1% to 0.90%.

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