KR102836618B1 - Biodegradable polyurethaneurea elastic fiber usung ester-based copolymer polyol and method for preparing the same - Google Patents

Abstract

The present invention relates to a biodegradable polyurethane urea elastic yarn and a method for manufacturing the same. The biodegradable polyurethane urea elastic yarn of the present invention has excellent yarn power and can be effectively biodegraded within a short period of time by applying an ester-based polyol.

Description

Biodegradable polyurethane urea elastic fiber using ester-based copolymer polyol and method for preparing the same {BIODEGRADABLE POLYURETHANEUREA ELASTIC FIBER USUNG ESTER-BASED COPOLYMER POLYOL AND METHOD FOR PREPARING THE SAME}

The present invention relates to polyurethane urea elastic yarn and a method for producing the same, and more specifically, to polyurethane urea elastic yarn imparted with excellent biodegradability by applying an ester copolymer polyol, and a method for producing the same.

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

These polyurethane elastic yarns are generally obtained by dry spinning a polymer solution produced by a first polymerization reaction in which a polyol, which is a high molecular weight diol compound, is reacted with an excessive amount of a diisocyanate compound to obtain a prepolymer having isocyanate groups at both terminals of the polyol, and a second polymerization reaction in which the prepolymer is dissolved in an appropriate solvent and a diamine or diol chain extender is added to the solution and reacted.

In addition, as environmental issues have been growing in recent years, the demand for biodegradable polyurethane elastic fibers has been increasing. Accordingly, there is a growing need to replace polymer diols, which account for the largest portion of spandex manufacturing raw materials, with raw materials that have biodegradable properties.

For example, Korean Patent Publication No. 2016-0143845 discloses a method for producing a polymeric glycol composition from renewable bio-derived butanediol and producing an elastomeric fiber using the same. Korean Patent Publication No. 2017-0132039 describes a polyurethane urea elastic yarn produced from a polyether polyol synthesized using castor oil as a starting material.

Biodegradable polyurethane urea elastic fibers manufactured by these conventional techniques have a low biodegradation rate and thus have a limitation in that the biodegradation period is long.

The invention has been made to solve the problems of the prior art described above, and one object of the present invention is to provide a polyurethane urea elastic yarn with improved biodegradability and a method for producing the same.

One aspect of the present invention to achieve the above-described purpose is:

The present invention relates to a biodegradable polyurethane urea elastic yarn comprising polyurethane urea, which is a reaction product of a prepolymer and a chain extender, wherein the prepolymer comprises a reaction product of an ester polyol and a diisocyanate, and the ester polyol is poly(1,4-butanediol sebacate succinate) copolymerized with 1,4-butanediol, sebacic acid, and succinic acid.

The above polyurethane urea elastomer may further include, in addition to the ester polyol, an ether 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.

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

In the present invention, the molecular weight (Mn) of the ester polyol is within the range of 1900 to 2200, and the content of the ester polyol can be 80 to 100 mol%.

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

The polyurethane urea elastic fiber of the present invention may have a biodegradation rate within a range of 0.1%/day to 1.2%/day as measured by the carbon dioxide emission assessment method described in ISO 14855.

Another aspect of the present invention for achieving the above-described purpose is:

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

In the step of obtaining the polyurethane diisocyanate of the present invention, in addition to the ester polyol, an ether 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.

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.

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

Another aspect of the present invention relates to a sanitary product using the polyurethane urea elastic yarn. According to a preferred embodiment of the present invention, a disposable diaper using biodegradable polyurethane urea elastic yarn can be provided.

According to the biodegradable polyurethane urea elastic yarn of the present invention, by applying an ester-based polyol to a polyurethane urea elastic yarn polymer, a biodegradable polyurethane urea elastic yarn can be obtained and the power of the yarn can be further improved. In addition, by preparing a material constituting the above-mentioned copolymer using a bio-derived raw material, bio-based characteristics can be imparted to the polyurethane urea elastic yarn.

The biodegradable polyurethane urea elastic fiber of the present invention can provide a very environmentally friendly advantage as its biodegradation period is shortened to 2 to 3 years.

Hereinafter, preferred embodiments of the present invention will be described in more detail. However, when describing preferred embodiments of the present invention in detail, if it is determined that a specific description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

Additionally, throughout the specification, reference to a component as "including" means that other components may be included, but does not exclude other components, unless otherwise specifically stated.

The term 'polyurethane fiber' as used herein means staple fibers or continuous filaments comprising polyurethane and having an elongation at break greater than 100%. Polyurethane urea elastomeric yarn (Spandex) is an example of a polyurethane elastomeric fiber. The terms 'polyurethane urea elastomeric yarn', 'polyurethane fiber' and 'polyurethane elastomeric yarn' are used interchangeably herein.

As used herein, glycol is defined as a polymeric diol having a hydroxyl group at each chain terminal. The term may be used interchangeably with polyol.

The term "biodegradable" herein generally refers to a material that decomposes, generally by 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 it separates or decomposes (oxidizes) to at least about 80% after 180 days in a controlled composting environment as described in the procedure, when tested in accordance with ISO-44855-1.

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.

One aspect of the present invention to achieve the above-described purpose is:

The present invention relates to a biodegradable polyurethane urea elastic yarn comprising polyurethane urea, which is a reaction product of a prepolymer and a chain extender, wherein the prepolymer comprises a reaction product of an ester polyol and a diisocyanate, and the ester polyol is poly(1,4-butanediol sebacate succinate) copolymerized with 1,4-butanediol, sebacic acid, and succinic acid.

The above polyurethane urea elastic yarn, in addition to ester polyol,

It may further comprise an ether 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.

The above prepolymer may comprise a reaction product of poly(tetramethylene ether) glycol, poly(1,4-butanediol sebacate succinate), and 4,4-diphenylmethane diisocyanate. The poly(tetramethylene ether) glycol suitable for use in the present invention may have a molecular weight (Mn) 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.

In general, adipic acid, which is used to manufacture ester polyols, is difficult to manufacture from bio-derived components, but sebacic acid and succinic acid can be manufactured relatively easily from bio-derived components, so using the two substances can obtain a 100% bio-derived ester polyol.

In the present invention, by applying a copolymer derived from 1,4-butanediol and succinic acid or sebacic acid, a biodegradable polyurethane urea elastic yarn with improved yarn power can be obtained, and by preparing the above-mentioned copolymer with a bio-derived raw material, bio-based properties can be imparted to the polyurethane urea elastic yarn.

The above ester polyol may have a molecular weight (Mn) of 1800 to 2400. By using an ester polyol having a molecular weight in this range, a polyurethane urea elastic yarn having excellent flexibility, strength, elastic recovery, and heat resistance can be obtained.

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

In the present invention, examples of the diisocyanate include known aliphatic, alicyclic or aromatic diisocyanates having two isocyanate groups in the molecule. Specific examples thereof include diisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-trylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate is preferred. In addition, as the diisocyanate, a compound having a blocked isocyanate group that is converted into a free isocyanate group can also be used.

The chain extender can be a diamine chain extender for water or the polyurethaneurea. Combinations of different chain extenders can be included depending on the desired properties of the polyurethaneurea and the fibers produced. 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); 1,2-cyclohexanediamine; 1,4-cyclohexanediamine; 4,4'-methylene-bis(cyclohexylamine); isophorone diamine; 2,2-dimethyl-1,3-propanediamine; meta-tetramethylxylylenediamine; 1,3-diamino-4-methylcyclohexane; 1,3-cyclohexane-diamine; 1,1-methylene-bis(4,4'-diaminohexane); 3-aminomethyl-3,5,5-trimethylcyclohexane; 1,3-pentanediamine (1,3-diaminopentane); m-xylylene diamine.

Examples of compounds that can be used as chain terminators during the 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-pipecoline, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropylmorpholine, 4-aminomethyl-1-butylpiperidine, dimethylaminoethoxypropylamine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropylmorpholine, and 4-aminomethyl-1-butylpiperidine are exemplified.

The polyurethane urea elastic yarn of the present invention may contain additional stabilizers, pigments, etc. These additives should not impair the advantages of the present invention. Among the additives, there are benzotriazole-based stabilizers, ultraviolet light absorbers, other light-resistant agents, antioxidants, anti-adhesives, lubricants such as mineral oils and silicone oils, antistatic agents, etc. 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, bactericides containing silver, zinc or compounds thereof, deodorants, various antistatic agents, phosphoric acid, etc. The additives may be mixed into the polymer solution at any stage after the polyurethane urea is formed and before the solution is spun into fibers.

The polyurethane urea elastic yarn of the present invention is characterized in that it contains an ester-based polyol in the polyurethane main chain, and has 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 polyurethane urea elastic yarn of the present invention may be enzymatic, hydrolytic, oxidative degradation, and/or degradation due to the action of electromagnetic radiation, for example, ultraviolet light, and may mainly occur due to the action of microorganisms such as bacteria, yeast, mold, and algae.

In the present invention, when the capping reaction is performed to prepare the prepolymer, the molar ratio (capping ratio, CR) of the ester 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 polyurethane urea elastic yarn becomes too low, and if the capping ratio exceeds 1.9, the polymerization processability is not good, making it difficult to apply it to the actual production of polyurethane urea elastic yarn. In addition, in the present invention, if the capping ratio (CR) is in the range of 1.7 to 1.9, a polyurethane urea elastic yarn having a power of 13.5 g or more can be obtained.

Another aspect of the present invention relates to a method for producing a biodegradable polyurethane urea elastic yarn. In the present invention, in producing a polyurethane urea elastic yarn using a polyurethane urea polymer, in the step of reacting an ester polyol and a diisocyanate to obtain a polyurethane diisocyanate, poly(1,4-butanediol sebacate succinate) copolymerized with 1,4-butanediol, sebacic acid, and succinic acid is used as the ester polyol.

In the present invention, in addition to poly(1,4-butanediol sebacate succinate) as a polyol, an ether 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 can be used together. Polytetramethylene ether glycol can be used as the polyether glycol. The molecular weight (Mn) of the polyether glycol is preferably 1800 to 3100, and if it is less than 1800, the elongation of the fiber is low, which causes a problem in that the function as a polyurethane urea elastic yarn fiber is deteriorated, and if it exceeds 3100, the degree of crystallinity is too high, so that elasticity is not expressed normally.

In one specific example, a mixture of polytetramethylene glycol (PTMG) and poly(1,4-butanediol sebacate succinate) as an ester polyol is stirred with 4,4'-diphenylmethane diisocyanate to perform a capping reaction, thereby preparing a polyurethane urea prepolymer. At this time, the reaction proceeds at a capping ratio (CR), which is a molar ratio of the ester polyol and the diisocyanate compound, in a range of 1.4 to 1.9.

At least one of the above 1,4-butanediol, sebacic acid and succinic acid may be a bio-derived component. When a copolymer derived from 1,4-butanediol and succinic acid or sebacic acid is applied to a polyurethane urea elastic fiber polymer and the reaction is further performed at a capping ratio (CR) of 1.7 to 1.9, a polyurethane urea elastic fiber with improved power can be obtained.

A prepolymer solution obtained by dissolving a prepolymer in a solvent and an imine solution in which a chain extender and a chain terminator are dissolved in a solvent are reacted to prepare a polyurethane urea spinning stock, and then the polyurethane urea spinning stock is spun and wound to produce a polyurethane urea elastic yarn. An organic solvent that dissolves a polymer usable in the preparation of the polyurethane solution may be an organic solvent commonly used in the relevant field. For example, the organic solvent may be at least one of N,N'-dimethylformamide, N,N'-dimethylacetamide, tetramethylurea, and hexamethyl phosphonoamide, but is not limited thereto. At this time, the solvent is preferably dimethylacetamide. Thereafter, the obtained polyurethane solution is used to produce polyurethane urea elastic yarn through a fiber spinning process such as dry spinning or melt spinning.

The polyurethane urea elastic yarn manufactured by the method of the present invention has a power of 13.5 g or more 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.

In the production of the above-mentioned radiation source, rosin or a rosin derivative may be further added.

The step of preparing the above prepolymer can be performed by mixing the polyurethane urea polymer, an antioxidant, an anti-yellowing agent, an anti-adhesion agent, and a dyeing promoter, and then milling the mixture with a grinder-mill to prepare a slurry-shaped buffer polymer. The antioxidant and the above-mentioned anti-yellowing agent can include at least one of a phenol-based, phosphorus-based, sulfur-based, and amine-based compound, and an antioxidant commonly used in the art can be used. In addition, a polyurethane-based compound can be used as the dyeing promoter, and a dyeing promoter commonly used in the art can be used.

In order to manufacture polyurethane urea elastic yarn, dry spinning or wet spinning can be used. However, in the case of wet spinning, production can only be done at a lower speed than dry spinning due to the process characteristics. Therefore, according to a preferred embodiment of the present invention, it is preferable to dry spin the spinning raw material. Dry spinning manufactures elastic yarn by passing the spinning raw material through a spinneret into a spinning chamber and twisting it. At this time, gas passes through the chamber to evaporate the solvent contained in the polymer solution, thereby manufacturing elastic yarn. In dry spinning, the spinning temperature can be 200°C to 300°C, and the spinning speed can be 400 m/min to 1500 m/min.

The polyurethane urea elastic yarn may be used alone or may be twisted, twisted or blended with any other fiber. Such fibers include nylon, polyester, cotton, wool, jute, sisal, flax, bamboo, polypropylene, polyethylene, polyfluorocarbon, rayon, cellulose and acrylic fibers. The polyurethane urea elastic yarn of the present invention may also be covered with conventionally known fibers and used as a covered elastic fiber.

Another aspect of the present invention relates to a sanitary product using the polyurethane urea elastic yarn. According to a preferred embodiment of the present invention, the sanitary product may be a disposable diaper using a biodegradable polyurethane urea elastic yarn, and in particular, the elastic yarn may be applied to a leg flap portion and a cuff portion of the disposable diaper. Furthermore, the elastic yarn may be appropriately applied to other portions of the diaper, such as a waist portion or a diaper body portion, in addition to the leg flap portion and the cuff portion of the disposable diaper without any special limitation.

Hereinafter, the present invention will be specifically described 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 %.

Example

Manufacturing example 1

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

Example 1

A mixture of (1,4-butanediol sebacate succinate) (molecular weight (Mn) 1800-2400) copolymerized with 1,4-butanediol, succinic acid extracted from castor oil, and sebacic acid extracted from sugar cane in a molar ratio of 5:1.7:3.3 was stirred at 90°C for 3 hours to perform a capping reaction with 4,4'-diphenylmethane diisocyanate in a molar ratio of 1:1.85 (Capping Ration, CR 1.85) to prepare polyurethaneurea diisocyanate. This diisocyanate was dissolved in dimethylacetamide (DMAc), and an amine solution diluted to a concentration of 7% in dimethylacetamide was added. The amine used at this time was a mixture of ethylenediamine, a chain extender, and diethylamine, a chain terminator, in an equivalent ratio of 7:1. By reacting diisocyanate and amine in this way, a polyurethane urea spinning solution having a solid content of 41.5% and an inherent viscosity of 1.03, which has a higher equivalent ratio of amine groups than NCO, was produced. The obtained spinning solution was dry-spun at 250°C and 500 m/min to produce a 680 Dtex biodegradable polyurethane urea elastic yarn.

Examples 2-5

A biodegradable polyurethane urea elastic yarn of 680 Dtex was manufactured in the same manner as in Example 1, except that the capping ratio (CR) was changed as shown in Table 1 below.

Examples 6-7

A biodegradable polyurethane urea elastic yarn having a thickness of 680 Dtex was manufactured in the same manner as in Example 1, except that the content of poly(1,4-butanediol sebacate succinate) was changed as shown in Table 1 below.

Comparative Example 1

A biodegradable polyurethane urea elastic yarn having a thickness of 680 Dtex was manufactured in the same manner as in Example 1, except that the content of poly(1,4-butanediol sebacate succinate) was changed as shown in Table 1 below.

Comparative Example 2

A biodegradable polyurethane urea elastic yarn of 680 Dtex was manufactured in the same manner as in Example 1, except that only PTMG was used without using an ester-based polyol.

Comparative Example 3

A biodegradable polyurethane urea elastic yarn of 680 Dtex was manufactured in the same manner as in Example 5, except that only PTMG was used without using an ester polyol.

Exam example

The physical properties of the polyurethane urea elastic yarns manufactured in each of Example 1-7 and Comparative Example 1-3 were evaluated using the following method, and the results are shown in Table 1 below.

- Power of yarn: The polyurethane urea elastic yarn obtained in the example was fixed in length and then subjected to 300% elongation and contraction 5 times to measure the ^5th unload power @ 200%.

- Adhesive properties (creep): After manufacturing a diaper using the polyurethane urea elastic yarn obtained in the examples and comparative examples, the adhesive properties were evaluated using the samples as follows.

1. Extend the adhesive portion containing the polyurethane urea elastic fiber to the maximum length of the diaper and secure it to a plastic plate measuring 30 cm in width and 50 cm in length.

2. Using a permanent marker, mark 100 mm on both sides (total 200 mm) from the center.

3. Cut the marked area with a knife and use a ruler to measure the extent to which the polyurethane urea elastic fiber has come out of the center.

4. The adhesive properties (creep) are calculated as follows.

Adhesive properties (creep) (%) = length pulled out / 200 * 100 (%)

-Biodegradability: According to KS M ISO 14855-1:2010, biodegradability was measured using the polyurethane urea elastic fiber obtained in the example as a test material.

-Stress retention rate: The polyurethane urea elastic yarn obtained in the example was fixed in length and then subjected to 300% elongation and contraction five times, and the stress retention rate was measured by calculating the ratio of the 5th unload/load.

division Polyol CR Yarn
Power (g) Stress
Maintenance rate (%) splice
characteristic(%) Biodegradability
(%/day) Example 1 Poly(1,4-butanediol sebacate succinate) 100 mol% 1.85 14.4 61 33 1.05 Example 2 Poly(1,4-butanediol sebacate succinate) 100 mol% 1.70 13.6 64 35 0.97 Example 3 Poly(1,4-butanediol sebacate succinate) 100 mol% 1.60 12.3 73 38 0.98 Example 4 Poly(1,4-butanediol sebacate succinate) 100 mol% 1.50 11.5 75 37 0.96 Example 5 Poly(1,4-butanediol sebacate succinate) 100 mol% 1.40 11 78 37 0.95 Example 6 Poly(1,4-butanediol sebacate succinate) 90 mol%, PTMG 10 mol% 1.85 14.2 59 34 0.54 Example 7 Poly(1,4-butanediol sebacate succinate) 80 mol%, PTMG 20 mol% 1.85 14.1 56 35 0.31 Comparative Example 1 Poly(1,4-butanediol sebacate succinate) 70 mol%, PTMG 30 mol% 1.70 12.3 55 37 0.09 Comparative Example 2 PTMG 100 mol% 1.70 12.1 52 39 0.01 Comparative Example 3 PTMG 100 mol% 1.40 10.9 60 38 0.01

As confirmed through the results in Table 1 above, when poly(1,4-butanediol sebacate succinate) in the polymer diol was applied at 80 mol% or more in the manufacture of polyurethane urea elastic fibers as in Examples 1 to 6 according to the present invention, power and adhesive properties similar to those of Comparative Examples 1 to 3 manufactured with 100 mol% of the existing PTMG were maintained, and a biodegradability of 0.1%/day or more was shown, confirming that the biodegradation period was shortened and it was very environmentally friendly. In addition, in the case of the general polyurethane urea elastic yarn of Comparative Example 2 manufactured with 100 mol% of existing PTMG, the power was limited to 12.1 g at a capping ratio (CR) of 1.70, whereas in the case of the polyurethane urea elastic yarn of Example 2 according to the present invention, the power was improved to 13.6 g at a capping ratio (CR) of 1.70, and in the cases 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 14 g or more.

In the above, preferred embodiments of the present invention have been specifically described, but these are for illustrative purposes only. Those skilled in the art 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 protection scope of the present invention.

Claims (15)

A biodegradable polyurethane urea elastic yarn obtained by dry spinning a polymer solution containing polyurethane urea, which is a reaction product of a prepolymer and a chain extender, wherein the prepolymer contains a reaction product of an ester polyol and a diisocyanate, and the ester polyol contained in the prepolymer is poly(1,4-butanediol sebacate succinate) copolymerized with 1,4-butanediol, sebacic acid, and succinic acid.
In the first paragraph, the biodegradable polyurethane urea elastic yarn is characterized in that the polyurethane urea elastic yarn comprises, in addition to the ester polyol, an ether 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.
A biodegradable polyurethane urea elastic yarn, characterized in that in claim 1, the prepolymer comprises a reaction product of poly(tetramethylene ether) glycol, poly(1,4-butanediol sebacate succinate), and 4,4-diphenylmethane diisocyanate.
In the first paragraph, a biodegradable polyurethane urea elastic yarn, characterized in that the molecular weight (Mn) of the ester polyol is 1800 to 2400.
In the first paragraph, a biodegradable polyurethane urea elastic yarn characterized in that the polymer diol used in the preparation of the prepolymer has an ester polyol content of 80 to 100 mol% and an ether polyol content of 0 to 20 mol%.
A biodegradable polyurethane urea elastic yarn, characterized in that in claim 1, at least one of the 1,4-butanediol, sebacic acid and succinic acid is a bio-derived component.
In the first paragraph, a biodegradable polyurethane urea elastic fiber having a capping ratio (CR), which is a molar ratio of the ester polyol and the diisocyanate, of 1.4 to 1.9.
A biodegradable polyurethane urea elastic yarn, characterized in that in claim 7, the capping ratio (CR) is 1.7 to 1.9 and the power is 13.5 g or more.
In the first paragraph, the polyurethane urea elastic yarn is a biodegradable polyurethane urea elastic yarn, characterized in that the biodegradation rate measured by the carbon dioxide emission assessment method described in ISO 14855 is 0.1%/day to 1.2%/day.
A method for producing biodegradable polyurethane urea elastic fiber using a polyurethane urea polymer, characterized in that in the step of reacting an ester polyol and a diisocyanate to obtain polyurethane diisocyanate, poly(1,4-butanediol sebacate succinate) copolymerized with 1,4-butanediol, sebacic acid, and succinic acid is used as the ester polyol.
A method for producing biodegradable polyurethane urea elastic yarn, characterized in that in the step of obtaining polyurethane diisocyanate, in addition to an ester polyol, an ether 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 is added.
A method for producing biodegradable polyurethane urea elastic fiber, wherein the method comprises a step of reacting poly(tetramethylene ether) glycol, poly(1,4-butanediol sebacate succinate) and 4,4-diphenylmethane diisocyanate to produce polyurethane diisocyanate.
A method for producing a biodegradable polyurethane urea elastic fiber, characterized in that in claim 10, at least one of the 1,4-butanediol, sebacic acid and succinic acid is a bio-derived component.
A biodegradable sanitary product manufactured using the polyurethane urea elastic yarn of any one of claims 1 to 9.
A biodegradable 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 leg flap portion and cuff portion of the diaper.