Biodegradable polyurethane urea elastic yarn to which ester-based copolymer polyol is applied and manufacturing method thereof

Abstract

The present invention relates to a biodegradable polyurethane urea elastic yarn and a manufacturing method thereof. By applying an ester-based polyol, the biodegradable polyurethane urea elastic yarn of the present invention can be effectively biodegraded in a short time while having excellent yarn power.

Description

Biodegradable polyurethaneurea elastic yarn using ester-based copolymer polyol and method for manufacturing the same

[0001] The present invention relates to a polyurethaneurea elastic yarn and a method for manufacturing the same, and more specifically, to a polyurethaneurea elastic yarn with excellent biodegradability imparted by applying an ester-based copolymer polyol and a method for manufacturing the same.

[0002] Polyurethane elastic yarns are actively used for various purposes due to their unique characteristic of having high elasticity, and depending on the application, polyurethane elastic yarns can be combined with various other fibers such as acrylic, wool, cotton, and silk. In particular, elastic yarns containing 85 parts by weight or more of long-chain soft segments are called polyurethane urea elastic yarns (spandex).

[0003] These polyurethane elastic yarns are generally obtained by dry spinning a polymer solution prepared by a primary polymerization reaction in which a polyol, which is a high molecular weight diol compound, is reacted with an excess amount of a diisocyanate compound to obtain a prepolymer having isocyanate groups at both ends of the polyol, and a secondary polymerization reaction in which the prepolymer is dissolved in a suitable solvent and then a diamine-based or diol-based chain extender is added to the solution to react.

[0004] Furthermore, with the recent growing trend of eco-friendly issues, the demand for biodegradable polyurethane elastic yarns is increasing. Consequently, there is a growing need to replace polymeric diols, which account for the largest portion of spandex manufacturing raw materials, with materials possessing biodegradable properties.

[0005] For example, Korean Patent Publication No. 2016-0143845 discloses a method for preparing a polymeric glycol composition from renewable bio-derived butanediol and using it to produce an elastomer fiber. Korean Patent Publication No. 2017-0132039 describes a polyurethaneurea elastic yarn prepared from a polyether polyol synthesized using castor oil as a starting material.

[0006] Biodegradable polyurethaneurea elastic yarns manufactured by such conventional technology have a limitation in that they have a low biodegradation rate and take a long time to decompose.

[0007] The present invention was devised to solve the problems of the aforementioned prior art, and one objective of the present invention is to provide a polyurethaneurea elastic yarn with improved biodegradability and a method for manufacturing the same.

[0008] One aspect of the present invention for achieving the above-mentioned purpose is,

[0009] The present invention relates to a biodegradable polyurethaneurea elastic yarn comprising a polyurethaneurea that is a reaction product of a prepolymer and a chain extender, wherein the prepolymer comprises a reaction product of an ester-based polyol and a diisocyanate, and the ester-based polyol is poly(1,4-butanediol sebacate succinate) copolymerized from 1,4-butanediol, sebacic acid, and succinic acid.

[0010] In addition to the ester-based polyol, the above polyurethane urea elastic yarn may further comprise an ether-based glycol selected from the group consisting of polyethylene ether glycol, polytrimethylene ether glycol, poly(tetramethylene ether) glycol, poly(tetramethylene-co-2-methyltetramethylene ether) glycol, poly(tetramethylene-co-ethylene ether) glycol, and mixtures thereof.

[0011] The above prepolymer may include reaction products of poly(tetramethylene ether) glycol, poly(1,4-butanediol sebacate succinate), and 4,4-diphenylmethane diisocyanate.

[0012] In the present invention, the molecular weight (Mn) of the ester-based polyol is in the range of 1900 to 2200 g / mole, and the content of the ester-based polyol may be 80 to 100 mol%.

[0013] At least one of the above 1,4-butanediol, sebacic acid, and succinic acid may be a bio-derived component.

[0014] The polyurethaneurea elastic yarn of the present invention may have a biodegradation rate measured by the carbon dioxide emission evaluation method described in ISO 14855 in the range of 0.1% / day to 1.2% / day.

[0015] Another aspect of the present invention for achieving the above-mentioned purpose is,

[0016] The present invention relates to a method for manufacturing a biodegradable polyurethaneurea elastic yarn, characterized in that, in the step of manufacturing a polyurethaneurea elastic yarn fiber using a polyurethaneurea polymer, a polyurethane diisocyanate is obtained by reacting an ester-based polyol with a diisocyanate to obtain a polyurethane diisocyanate, and poly(1,4-butanediol sebacate succinate) copolymerized with 1,4-butanediol, sebacic acid, and succinic acid is used as the ester-based polyol.

[0017] In the step of obtaining the polyurethane diisocyanate of the present invention, in addition to the ester-based polyol, an ether-based glycol selected from the group consisting of polyethylene ether glycol, polytrimethylene ether glycol, poly(tetramethylene ether) glycol, poly(tetramethylene-co-2-methyltetramethylene ether) glycol, poly(tetramethylene-co-ethylene ether) glycol, and mixtures thereof may be added.

[0018] In the present invention, polyurethane diisocyanate can be produced by reacting poly(tetramethylene ether) glycol, poly(1,4-butanediol sebacate succinate), and 4,4-diphenylmethane diisocyanate.

[0019] At least one of 1,4-butanediol, sebacic acid, and succinic acid constituting the ester-based polyol may be a bio-derived component.

[0020] Another aspect of the present invention relates to a sanitary product using the polyurethaneurea elastic yarn. According to a preferred embodiment of the present invention, a disposable diaper made using a biodegradable polyurethaneurea elastic yarn may be provided.

[0021] According to the biodegradable polyurethaneurea elastic yarn of the present invention, a biodegradable polyurethaneurea elastic yarn can be obtained by applying an ester-based polyol to the polyurethaneurea elastic yarn polymer, and the power of the yarn can be further improved. Additionally, bio-based properties can be imparted to the polyurethaneurea elastic yarn by preparing the materials constituting the aforementioned copolymer with bio-derived raw materials.

[0022] The biodegradable polyurethane urea elastic yarn of the present invention can provide very eco-friendly advantages by shortening the biodegradation period to 2 to 3 years.

[0023] Preferred embodiments of the present invention will be described in more detail below. However, in describing the preferred embodiments of the present invention in detail, specific descriptions of related known functions or configurations are omitted if it is determined that such detailed descriptions may unnecessarily obscure the essence of the present invention.

[0024] Furthermore, throughout the specification, the term 'comprising' a component means that, unless specifically stated otherwise, it does not exclude other components but rather allows for the inclusion of additional components.

[0025] As used herein, the term "polyurethane fiber" refers to a staple fiber or continuous filament comprising polyurethane and having an elongation at break exceeding 100%. Polyurethaneurea elastic yarn (Spandex) is an example of a polyurethane elastic fiber. In this specification, the terms "polyurethaneurea elastic yarn," "polyurethane fiber," and "polyurethane elastic yarn" are used interchangeably.

[0026] As used in this specification, glycol is defined as a polymeric diol having a hydroxyl group at each chain end. This term may be used interchangeably with polyol.

[0027] In this specification, the term “biodegradable” generally refers to a material that decomposes due to the action of naturally occurring microorganisms such as bacteria, fungi, and algae, environmental heat, moisture, or other environmental factors. The biodegradability of a material is that, when tested according to ISO-44855-1, at least 80% is separated or decomposed (oxidized) after 180 days in a controlled composting environment.

[0028] Poly(tetramethylene ether glycol) (PTMEG) is defined as a glycol made using 1,4-butanediol or tetrahydrofuran (THF) as the main monomer component, and also includes homopolymers and copolymers containing tetramethylene ether repeating units.

[0029] One aspect of the present invention for achieving the above-mentioned purpose is,

[0030] The present invention relates to a biodegradable polyurethaneurea elastic yarn comprising a polyurethaneurea that is a reaction product of a prepolymer and a chain extender, wherein the prepolymer comprises a reaction product of an ester-based polyol and a diisocyanate, and the ester-based polyol is poly(1,4-butanediol sebacate succinate) copolymerized from 1,4-butanediol, sebacic acid, and succinic acid.

[0031] The above polyurethane urea elastic yarn is added to an ester-based polyol,

[0032] It may further include an ether-based glycol selected from the group consisting of polyethylene ether glycol, polytrimethylene ether glycol, poly(tetramethylene ether) glycol, poly(tetramethylene-co-2-methyltetramethylene ether) glycol, poly(tetramethylene-co-ethylene ether) glycol, and mixtures thereof.

[0033] The above prepolymer may comprise reaction products of poly(tetramethylene ether) glycol, poly(1,4-butanediol sebacate succinate), and 4,4-diphenylmethane diisocyanate. Poly(tetramethylene ether) glycol suitable for use in the present invention may have a number average molecular weight of about 1500 to about 4000, preferably about 1600 to about 2500, more preferably about 1800 to about 2000. At least one of 1,4-butanediol, sebacic acid, and succinic acid constituting the poly(1,4-butanediol sebacate succinate) constituting the above prepolymer may be a bio-derived component.

[0034] In general, adipic acid, which is used to manufacture ester-based polyols, is difficult to produce using bio-derived components, but sebacic acid and succinic acid can be produced relatively easily using bio-derived components, so using these two substances allows for the production of 100% bio-derived ester-based polyols.

[0035] In the present invention, a biodegradable polyurethaneurea elastic yarn with improved yarn power was obtained by applying a copolymer derived from 1,4-butanediol and succinic acid or sebacic acid, and bio-based properties can be imparted to the polyurethaneurea elastic yarn by preparing the aforementioned copolymer with a bio-derived raw material.

[0036] The above ester-based polyol may have a number average molecular weight (Mn) of 1800 to 2400 g / mole. By using an ester-based polyol having a number average molecular weight in this range, a polyurethaneurea elastic yarn having excellent flexibility, strength, elastic recovery, and heat resistance can be obtained.

[0037] The content of the above ester-based polyol is 80 mol% to 100 mol%. If the content of the ester-based polyol is less than 80 mol%, the biodegradability may be insufficient.

[0038] Examples of diisocyanates in the present invention include known aliphatic, alicyclic, or aromatic diisocyanates having two isocyanate groups within the molecule. Specifically, examples include diisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-trilene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate, and preferably, 4,4'-diphenylmethane diisocyanate. Additionally, as a diisocyanate, a compound having a blocked isocyanate group that converts into a free isocyanate group may be used.

[0039] The chain extender may be a diamine chain extender for water or polyurethaneurea. Depending on the desired properties of the polyurethaneurea and the resulting fiber, combinations of different chain extenders may be included. Non-limiting examples of suitable diamine chain extenders include hydrazine, 1,2-ethylenediamine; 1,4-butanediamine; 1,2-butanediamine; 1,3-butanediamine; 1,3-diamino2,2-dimethylbutane; 1,6-hexamethylenediamine; 1,12-dodecanediamine; 1,2-propanediamine; 1,3-propanediamine; 2-methyl-1,5-pentanediamine; 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane; 2,4-diamino-1-methylcyclohexane; N-methylamino-bis(3-propylamine); It may include 1,2-cyclohexanediamine; 1,4-cyclohexanediamine; 4,4'-methylene-bis(cyclohexylamine); isophorone diamine; 2,2-dimethyl-1,3-propanediamine; meta-tetramethylxylenediamine; 1,3-diamino-4-methylcyclohexane; 1,3-cyclohexanediamine; 1,1-methylene-bis(4,4'-diaminohexane); 3-aminomethyl-3,5,5-trimethylcyclohexane; 1,3-pentanediamine (1,3-diaminopentane); and m-xylylene diamine.

[0040] Examples of compounds that can be used as chain termination agents during polyurethane polymerization used in the present invention include the following compounds. Amine compounds such as dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, N,N-diisopropylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, dimethylaminoethoxypropylamine, diethanolaminopropylamine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropylmorpholine, 4-aminomethyl-1-butylpiperidine, dimethylaminoethoxypropylamine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropylmorpholine, and 4-aminomethyl-1-butylpiperidine are exemplified.

[0041] The polyurethaneurea elastic yarn of the present invention may contain additional stabilizers, pigments, etc. Such additives must not impair the advantages of the present invention. Among the said additives are benzotriazole-based stabilizers, ultraviolet light absorbers, other light-resistant agents, antioxidants, anti-adhesion agents, lubricants such as mineral oil and silicone oil, and antistatic agents. Other examples of additives may include hindered phenol-based stabilizers, hindered amine stabilizers, inorganic pigments such as titanium oxide, zinc oxide, and carbon black, metal salts such as magnesium stearate and barium sulfate, mixtures of huntite and hydromagnesite, disinfectants containing silver, zinc, or compounds thereof, deodorizers, various antistatic agents, phosphoric acid, etc. The additives may be mixed into the polymer solution at any stage after the polyurethaneurea is formed and before the solution is spun into fibers.

[0042] The polyurethaneurea elastic yarn of the present invention is characterized by including an ester-based polyol in the polyurethane main chain, and having a biodegradation rate of 0.1% / day to 1.2% / day when measured by the carbon dioxide emission evaluation method described in ISO 14855. The biodegradation of the polyurethaneurea elastic yarn of the present invention may be enzymatic, hydrolytic, oxidative degradation and / or degradation caused by the action of electromagnetic radiation, e.g., ultraviolet rays, and may mainly occur due to the action of microorganisms such as bacteria, yeast, mold, and algae.

[0043] In the present invention, when proceeding with the capping reaction to prepare a prepolymer, the molar ratio (capping ratio, CR) of the ester-based polyol and the diisocyanate is 1.4 to 1.9, and more preferably 1.7 to 1.9. In the present invention, if the capping ratio (CR) is less than 1.4, the power of the polyurethaneurea elastic yarn becomes too low, and if the capping ratio exceeds 1.9, the polymerization processability is poor, making it difficult to apply to the actual manufacture of polyurethaneurea elastic yarn. Furthermore, in the present invention, if the capping ratio (CR) is in the range of 1.7 to 1.9, a polyurethaneurea elastic yarn with a power of 13.5g or more can be obtained.

[0044] Another aspect of the present invention relates to a method for manufacturing a biodegradable polyurethaneurea elastic yarn. In the present invention, when manufacturing a polyurethaneurea elastic yarn using a polyurethaneurea polymer, in the step of obtaining a polyurethane diisocyanate by reacting an ester-based polyol with a diisocyanate, a poly(1,4-butanediol sebacate succinate) copolymerized with 1,4-butanediol, sebacic acid, and succinic acid is used as the ester-based polyol.

[0045] In the present invention, in addition to poly(1,4-butanediol sebacate succinate) as a polyol, an ether-based glycol selected from the group consisting of polyethylene ether glycol, polytrimethylene ether glycol, poly(tetramethylene ether) glycol, poly(tetramethylene-co-2-methyltetramethylene ether) glycol, poly(tetramethylene-co-ethylene ether) glycol, and mixtures thereof may be used together. Polytetramethylene ether glycol may be used as the polyether glycol. The number average molecular weight of the polyether glycol is preferably 1800 to 3100 g / mole; if it is less than 1800 g / mole, the elongation of the fiber is low, which causes a problem of reduced function as a polyurethaneurea elastic yarn fiber, and if it exceeds 3100 g / mole, the degree of crystallization is too high, so elasticity is not expressed normally.

[0046] In one embodiment, a polyurethaneurea prepolymer is prepared by carrying out a capping reaction by stirring a mixture of polytetremethylene glycol (PTMG) and poly(1,4-butanediol sebacate succinate) as an ester-based polyol with 4,4'-diphenylmethane diisocyanate. At this time, the reaction is carried out with a capping ratio (CR), which is the molar ratio of the ester-based polyol to the diisocyanate compound, between 1.4 and 1.9.

[0047] At least one of the above 1,4-butanediol, sebacic acid, and succinic acid may be a bio-derived component. By applying a copolymer derived from 1,4-butanediol and succinic acid or sebacic acid to a polyurethaneurea elastomer polymer and further proceeding the reaction with a capping ratio (CR) between 1.7 and 1.9, a polyurethaneurea elastomer with improved power can be obtained.

[0048] A polyurethaneurea spinning solution can be prepared by reacting a prepolymer solution obtained by dissolving a prepolymer in a solvent with an imine solution in which a chain extender and a chain terminater are dissolved in a solvent, and then the polyurethaneurea spinning solution can be spun and wound to produce a polyurethaneurea elastic yarn. The organic solvent used to dissolve the polymer when preparing the polyurethane solution may be an organic solvent commonly used in the field. For example, the organic solvent may be at least one of N,N'-dimethylformamide, N,N'-dimethylacetamide, tetramethylurea, and hexamethylphosphonoamide, but is not limited to the above types. In this case, it is preferable that the solvent be dimethylacetamide. Subsequently, the obtained polyurethane solution is used to manufacture polyurethaneurea elastic yarn through a fiber spinning process such as dry spinning or melt spinning.

[0049] The polyurethaneurea elastic yarn produced by the method of the present invention has a power of 13.5 or higher, and a biodegradation rate of 0.1% / day to 1.2% / day as measured by the carbon dioxide emission evaluation method described in ISO 14855.

[0050] In the preparation of the above-mentioned spinning solution, rosin or a rosin derivative may be further added.

[0051] The step of preparing the above prepolymer may involve mixing the above polyurethaneurea polymer, an antioxidant, an anti-yellowing agent, an anti-sticking agent, and a dye-fixing promoter, and then milling the mixture with a grinder mill to produce a buffer polymer in the form of a slurry. The antioxidant and the anti-yellowing agent may include at least one of phenolic, phosphorus-based, sulfur-based, and amine-based compounds, and an antioxidant commonly used in the field may be used. Additionally, a polyurethane-based compound may be used as the dye-fixing promoter, and a dye-fixing promoter commonly used in the field may be used.

[0052] To manufacture polyurethaneurea elastic yarn, dry spinning or wet spinning may be used. However, in the case of wet spinning, production must be carried out at a lower speed compared to dry spinning due to the characteristics of the process. Therefore, according to a preferred embodiment of the present invention, it is preferable to dry spin the spinning solution. Dry spinning manufactures elastic yarn by passing the spinning solution through a spinning die into a spinning chamber and twisting it. At this time, a gas passes through the chamber to evaporate the solvent contained in the polymer solution, thereby manufacturing the elastic yarn. When dry spinning, the spinning temperature may be 200°C to 300°C, and the spinning speed may be 400 m / min to 1500 m / min.

[0053] Polyurethaneurea elastic yarn may be used alone or may be combined, twisted, or blended with any other fiber. Examples of such fibers include nylon, polyester, cotton, wool, jute, sisal, flax, bamboo, polypropylene, polyethylene, polyfluorocarbon, rayon, cellulose, and acrylic fibers. The polyurethaneurea elastic yarn of the present invention may also be coated with a conventional known fiber and used as a coated elastic fiber.

[0054] Another aspect of the present invention relates to a sanitary product using the polyurethaneurea elastic yarn. According to a preferred embodiment of the present invention, the sanitary product may be provided as a disposable diaper incorporating a biodegradable polyurethaneurea elastic yarn, and in particular, may be applied to the leg flap and cuff portions of the disposable diaper. Furthermore, the elastic yarn may be appropriately applied to other parts of the diaper, such as the waist portion or the body portion of the diaper, without special limitations, in addition to the leg flap and cuff portions of the disposable diaper.

[0055] The present invention will be described in detail below through examples; however, the following examples and test examples are merely illustrative of one form of the present invention, and the scope of the present invention is not limited by the following examples. In the examples, the term "percent" or the symbol "%" means weight percent.

[0056] Examples

[0057] Preparation Example 1

[0058] Poly(1,4-butanediol sebacate succinate) was obtained by copolymerizing 1,4-butanediol, succinic acid extracted from castor oil, and sebacic acid extracted from sugarcane in a molar ratio of 5:1.7:3.3 through an esterification reaction under a titanium catalyst. The titanium catalyst was removed after the esterification reaction.

[0059]

[0060] Example 1

[0061] Polyurethaneurea diisocyanate was prepared by performing a capping reaction at 90°C for 3 hours with 4,4'-diphenylmethane diisocyanate at a molar ratio of 1:1.85 (Capping Ration, CR 1.85) using a mixture of (1,4-butanediol sebacate succinate) (molecular weight 1800-2400 g / mol), which is copolymerized of 1,4-butanediol, succinic acid extracted from castor oil, and sebacic acid extracted from sugarcane in a molar ratio of 5:1.7:3.3. This diisocyanate was dissolved in dimethylacetamide (DMAc), and an amine solution diluted to a concentration of 7% in dimethylacetamide was added. The amines used were ethylenediamine, a chain extender, and diethylamine, a chain terminater, mixed in an equivalent ratio of 7:1. In this way, a polyurethaneurea spinning solution with a solid content of 41.5% was prepared by reacting a diisocyanate with an amine, such that the equivalent ratio of amine groups is greater than that of NCO and the intrinsic viscosity is 1.03. Then, the obtained spinning solution was dry-spun at 250°C and 500 m / min to produce a biodegradable polyurethaneurea elastic yarn with a thickness of 680 Dtex.

[0062]

[0063] Examples 2~5

[0064] A biodegradable polyurethaneurea elastic yarn of 680 Dtex was produced by carrying out the same procedure as in Example 1, except that the capping ratio (CR) was changed as shown in Table 1 below.

[0065]

[0066] Examples 6~7

[0067] A biodegradable polyurethaneurea elastic yarn of 680 Dtex was produced by carrying out the same procedure as in Example 1, except that the content of poly(1,4-butanediol sebacate succinate) was varied as shown in Table 1 below.

[0068]

[0069] Comparative Example 1

[0070] A biodegradable polyurethaneurea elastic yarn of 680 Dtex was produced by carrying out the same procedure as in Example 1, except that the content of poly(1,4-butanediol sebacate succinate) was varied as shown in Table 1 below.

[0071]

[0072] Comparative Example 2

[0073] A biodegradable polyurethaneurea elastic yarn of 680 Dtex was prepared by carrying out the same procedure as in Example 1, except that only PTMG was used instead of an ester-based polyol.

[0074]

[0075] Comparative Example 3

[0076] A biodegradable polyurethaneurea elastic yarn of 680 Dtex was prepared by carrying out the same procedure as in Example 5, except that only PTMG was used instead of an ester-based polyol.

[0077]

[0078] Test example

[0079] The physical properties of the polyurethaneurea elastic yarns prepared in Examples 1-7 and Comparative Examples 1-3, respectively, were evaluated using the following method, and the results are shown in Table 1 below.

[0080] -Yarn Power: The polyurethaneurea elastic yarn obtained in the example was subjected to 300% stretching and shrinking 5 times after fixing the yarn length 5 th Unload power at 200% was measured.

[0081] - Adhesive properties (creep): After manufacturing diapers using the polyurethaneurea elastic yarns obtained in the examples and comparative examples, the adhesive properties were evaluated using the corresponding samples as follows.

[0082] 1. Extend the adhesive portion into which polyurethane urea elastic yarn is inserted to the maximum length of a diaper and fix it to a plastic plate measuring 30 cm in width and 50 cm in length.

[0083] 2. Mark the 100mm sections on both the left and right sides (total 200mm) from the center using an oil-based pen.

[0084] 3. Cut the marked part with a knife and measure the extent to which the polyurethane urea elastic fiber protrudes into the center using a ruler.

[0085] 4. Adhesion properties (creepability) are calculated as follows.

[0086] Adhesion properties (Creep) (%) = Protruding length / 200 × 100 (%)

[0087] - Biodegradability: According to KS M ISO 14855-1:2010, the biodegradability was measured using the polyurethaneurea elastic yarn obtained in the example as a test material.

[0088] - Stress retention rate: The polyurethaneurea elastic yarn obtained in the example was subjected to 300% stretching and shrinking 5 times after fixing the yarn length 5 th The stress retention rate was measured by calculating the ratio of unload to load.

[0089] Classification Polyol CR Yarn Power (g) Stress Retention Rate (%) Adhesion Characteristics (%) Biodegradability (% / day) Example 1 Poly(1,4-Butanediol Sebacate Succinate) 100 mol% 1.85 14.46 133 1.05 Example 2 Poly(1,4-Butanediol Sebacate Succinate) 100 mol% 1.70 13.66 435 0.97 Example 3 Poly(1,4-Butanediol Sebacate Succinate) 100 mol% 1.60 12.37 338 0.98 Example 4 Poly(1,4-Butanediol Sebacate Succinate) 100 mol% 1.50 11.57 537 0.96 Example 5 Poly(1,4-Butanediol Sebacate Succinate) 100 mol% 1.40 1178 370.95 Example 6 Poly(1,4-butanediol sebacate succinate) 90 mol%, PTMG 10 mol% 1.85 14.25 9340.54 Example 7 Poly(1,4-butanediol sebacate succinate) 80 mol%, PTMG 20 mol% 1.85 14.15 6350.31 Comparative Example 1 Poly(1,4-butanediol sebacate succinate) 70 mol%, PTMG 30 mol% 1.70 12.35 5370.09 Comparative Example 2 PTMG 100 mol% 1.70 12.15 2390.01 Comparative Example 3 PTMG 100 mol% 1.40 10.96 380.01

[0090] As confirmed by the results in Table 1 above, when poly(1,4-butanediol sebacate succinate) in the polymer diol is applied at a rate of 80 mol% or more during the manufacture of polyurethaneurea elastic yarns according to the present invention as in Examples 1 to 7, it was confirmed that the product maintains power and adhesive properties similar to Comparative Examples 1 to 3, which were manufactured with 100 mol% PTMG, and exhibits biodegradability of 0.1% / day or more, thereby shortening the biodegradation period and making it very eco-friendly. In addition, while the power of the general polyurethaneurea elastic yarn of Comparative Example 2, which was manufactured with 100 mol% of conventional PTMG, was only 12.1g at a capping ratio (CR) of 1.70, the power of the polyurethaneurea elastic yarn of Example 2 according to the present invention was improved to 13.6g at a capping ratio (CR) of 1.70, and in the case of Examples 1, 6, and 7, when the capping ratio (CR) was increased to 1.85, the power of the elastic yarn was further improved to 14g or more.

[0091] Although preferred embodiments of the present invention have been described in detail above, they are merely for illustrative purposes. A person skilled in the art to which the present invention pertains will be able to realize changes and modifications that can be made without departing from the spirit of the present invention, and such changes and modifications are intended to be included within the scope of protection of the present invention.

Claims

1. A polyurethaneurea elastic yarn obtained by dry spinning a polymer solution containing polyurethaneurea, which is a reaction product of a prepolymer and a chain extender, wherein the prepolymer comprises a reaction product of an ester-based polyol and a diisocyanate, and the ester-based polyol included in the prepolymer is poly(1,4-butanediol sebacate succinate) copolymerized with 1,4-butanediol, sebacic acid, and succinic acid.

2. The biodegradable polyurethaneurea elastic yarn according to claim 1, characterized in that the polyurethaneurea elastic yarn further comprises, in addition to the ester-based polyol, an ether-based glycol selected from the group consisting of polyethylene ether glycol, polytrimethylene ether glycol, poly(tetramethylene ether) glycol, poly(tetramethylene-co-2-methyltetramethylene ether) glycol, poly(tetramethylene-co-ethylene ether) glycol, and mixtures thereof.

3. A biodegradable polyurethaneurea elastic yarn according to claim 1, characterized in that the prepolymer comprises a reaction product of poly(tetramethylene ether) glycol, poly(1,4-butanediol sebacate succinate), and 4,4-diphenylmethane diisocyanate.

4. A biodegradable polyurethaneurea elastic yarn according to claim 1, characterized in that the molecular weight (Mn) of the ester-based polyol is 1800 to 2400 g / mole.

5. The biodegradable polyurethaneurea elastic yarn according to claim 1, characterized in that the polymer diol used in the preparation of the prepolymer has an ester-based polyol content of 80 to 100 mol% and an ether-based polyol content of 0 to 20 mol%.

6. A biodegradable polyurethaneurea elastic yarn according to claim 1, characterized in that at least one of the 1,4-butanediol, sebacic acid, and succinic acid is a bio-derived component.

7. The polyurethaneurea elastic yarn according to claim 1, wherein the capping ratio (CR), which is the molar ratio of the ester-based polyol to the diisocyanate, is 1.4 to 1.

9.

8. A biodegradable polyurethaneurea elastic yarn according to claim 7, characterized in that the capping ratio (CR) is 1.7 to 1.9 and the power is 13.5 g or more.

9. The biodegradable polyurethaneurea elastic yarn according to claim 1, characterized in that the polyurethaneurea elastic yarn has a biodegradation rate of 0.1% / day to 1.2% / day as measured by the carbon dioxide emission evaluation method described in ISO 14855.

10. A method for manufacturing a biodegradable polyurethaneurea elastic yarn, characterized in that, in the step of obtaining a polyurethane diisocyanate by reacting an ester-based polyol with a diisocyanate to produce a polyurethane urea elastic yarn using a polyurethaneurea polymer, poly(1,4-butanediol sebacate succinate) copolymerized with 1,4-butanediol, sebacic acid, and succinic acid is used as the ester-based polyol.

11. A method for manufacturing a biodegradable polyurethaneurea elastic yarn according to claim 10, wherein, in the step of obtaining a polyurethane diisocyanate, the method further adds an ether-based glycol selected from the group consisting of polyethylene ether glycol, polytrimethylene ether glycol, poly(tetramethylene ether) glycol, poly(tetramethylene-co-2-methyltetramethylene ether) glycol, poly(tetramethylene-co-ethylene ether) glycol, and mixtures thereof, in addition to the ester-based polyol.

12. A method for manufacturing a biodegradable polyurethaneurea elastic yarn according to claim 10, wherein the method comprises the step of reacting poly(tetramethylene ether) glycol, poly(1,4-butanediol sebacate succinate) and 4,4-diphenylmethane diisocyanate to produce a polyurethane diisocyanate.

13. A method for manufacturing a biodegradable polyurethaneurea elastic yarn according to claim 10, characterized in that at least one of the above 1,4-butanediol, sebacic acid, and succinic acid is a bio-derived component.

14. A biodegradable sanitary product manufactured using a polyurethaneurea elastic yarn according to any one of paragraphs 1 to 9.

15. The sanitary product according to claim 14, wherein the sanitary product is a diaper, and the polyurethane-urea elastic yarn is used in the leg flap portion, cuff portion, or both the leg flap portion and the cuff portion of the diaper.