KR20060036972A - Method of manufacturing a polyurethaneurea elastic fiber with excellent antimicrobe - Google Patents

Abstract

The present invention relates to a method for producing a polyurethane urea elastic yarn excellent in antibacterial deodorization, when manufacturing a polyurethane urea elastic yarn by dry spinning a polyurethane urea solution, silver nanoparticles having an average particle diameter of 1 ~ 50nm is dispersed N, N'-dimethylacetamide solution is characterized in that it is added to the polyurethaneurea spinning solution which is dry spinning.

Since the present invention is added to the polyurethane urea spinning solution in a state in which silver nanoparticles are dispersed in a N, N'-dimethylacetamide solution, the viscosity of the polyurethane urea solution that is dry-spun is easily controlled, and antibacterial and deodorizing properties at a low manufacturing cost. This excellent polyurethaneurea elastic yarn can be manufactured.

Elastic yarn, polyurethane urea, antibacterial deodorization, silver, nanoparticles, dispersion, dimethylacetamide.

Description

Method of manufacturing a polyurethaneurea elastic fiber with excellent antimicrobe}

The present invention relates to a method for producing a polyurethane urea elastic yarn having excellent antibacterial deodorization, and more particularly to a method for producing a polyurethane urea elastic yarn containing silver nanoparticles while maintaining the inherent physical properties of the elastic yarn as it is. It is about.

Polyurethane urea elastic yarn is excellent in elasticity and elastic recovery power, and is widely used in stockings, women's underwear, and stretch fabrics, and is continuously being used for aerobic wear and swimwear. However, many types of bacteria and fungi are attached to and inhabited by various secretions from the body. Of these, they are attached to fabrics, but they do not harm the human body, but they deteriorate, color, and contaminate the clothes. Some may cause odors, and some may directly harm the human body. In particular, there are many cases in which elastic yarn is used in girdle and bra of women, and in this case, a problem occurs that bacteria or fungi inhabit the elastic yarn due to sweating and thus adversely affect hygiene and health.

In order to solve such a problem, a conventional method for imparting antimicrobial properties to polyurethane urea elastic yarn is US Pat. No. 4,837,292. In the soft segment, poly (pentane-1,5-carbonate) diol, which is a polycarbonate diol type of aliphatic diol, or The method of providing antimicrobial property is disclosed by using the copolymer.

However, since the method does not add a separate antimicrobial agent, there was a problem of low antimicrobial effect.

In addition, Korean Patent Publication No. 199-004530 discloses a method of adding an inorganic antimicrobial agent in which sterile metal ions are ion-exchanged to a crystalline aluminosilicate zeolite, which is a porous inorganic material, to a polyurethaneurea elastic yarn.

However, since the silicate zeolite itself exhibits strong adsorption characteristics, when water is adsorbed, the silicate zeolite reacts rapidly with the diisocyanate as a raw material during the polymerization of the elastic yarn to form urea or burette or allophanate. The role of crosslinking the polymer to increase the viscosity of the polymer and to form a gel to rapidly increase the pressure of the filter, there was a problem that the trimming occurs frequently during spinning.

In addition, Korean Patent Publication No. 1995-95734 discloses a method for adding a non-porous inorganic ceramic containing silver or zirconium to a polyurethaneurea elastic yarn.

However, the method has a problem that yellowing of the elastic yarn when adding a large amount of non-porous inorganic ceramics, low antibacterial when added less.                         

In addition, Korean Patent No. 131831 discloses a method of using an oxybisphenoxacin-based compound as an antibacterial deodorant. However, the oxybisphenoxacin-based compound used as an antimicrobial deodorant has a low heat resistance compared to an inorganic ceramic antimicrobial agent, and thus high temperature radiation. A problem occurred.

In addition, Korean Patent No. 163496, Korean Laid-Open Patent No. 2000-27866 and Korean Laid-Open Patent No. 2000-59821 support inorganic ceramics containing 2 to 60% by weight of silver and zirconium metal ions or 4% by weight of silver. Published method of adding inorganic inorganic ceramics to polyurethaneurea elastic yarn

However, in the above methods, since the amount of silver supported in the inorganic ceramic is more than 2% by weight, the product containing the silver is easily browned due to the easy discoloration (browning) of silver, resulting in a loss of appearance. There was a problem that the manufacturing cost is increased by.

In addition, Korean Patent Laid-Open Publication No. 2002-0095604 discloses a method in which an inorganic ceramic loaded with 0.1 to 2% by weight of silver and 20 to 50% by weight of zinc is added to 0.2 to 2% by weight based on the total weight of the polyurethaneurea elastic yarn. have.

However, the method has a high content of zinc (Zn) of 20 to 50% by weight, which may cause environmental problems. Further, the particle size of the silver zeolite compound is about 2 μm, which causes a problem of deterioration in spinning.

In addition, Korean Patent Publication No. 2003-0010003 discloses a glass compound having 50 to 79 mol% of ZnO, 20 to 50 mol% of SiO ₂ , and 1 to 10 mol% of alkali metal oxide, and having an average particle size of 5 μm or less as an antimicrobial agent. The method of adding 0.2 to 5 weight% to polyurethane urea elastic yarn is published.

However, the above method has a problem in that when the ZnO is supported on the silicate zeola art, sufficient antimicrobial activity is not exerted because inorganic metals such as Zn are present as a stable chelating compound rather than as cations.

In addition, in Korean Patent Laid-Open Publication No. 2003-0038585, silver nanoparticles are stably formed under a solvent by forming and dispersing silver nanoparticles in a polyol using a urethane acrylate precursor having surfactant activity and reacting with diisocyanate. A method for preparing a dispersed polyurethane nanocomposite is disclosed.

However, the method is a technique for synthesizing the polyurethane nanocomposites in the absence of solvent, it is difficult to control the viscosity in the manufacturing process of polyurethane urea elastic yarn by diluting the polymer synthesized with a solvent such as N, N'- dimethylacetamide and dry spinning There was a problem that can not be applied.

An object of the present invention is to solve the conventional problems described above, to produce a polyurethane urea elastic yarn using silver nanoparticles that can exhibit a high antibacterial effect in a small amount because the specific surface area is wider than the general inorganic antimicrobial agent It is to provide a method.

According to the present invention, after dispersing silver nanoparticles expressing high antimicrobial effect in a smaller amount than general inorganic antimicrobial agent in N, N'-dimethylacetamide solution, it is a polyurethane urea spinning solution (spinning dope) which is dry spinning In addition, to provide a method for producing a polyurethane urea elastic yarn containing silver nanoparticles.

According to the present invention, a method for preparing a polyurethaneurea elastic yarn having excellent antibacterial and deodorizing properties according to the present invention is to mix and react a high molecular weight diol compound and an excess diisocyanate compound and then add a solvent to the prepolymer. In preparing a solution and then dry spinning a polyurethaneurea spinning solution prepared by reacting the prepolymer solution with a diamine as a chain extender and a monoamine as a chain stopper to prepare a polyurethaneurea elastic yarn, the average particle diameter is 1 to 50 nm. Phosphorus silver N-N'- dimethylacetamide solution in which the nanoparticles are dispersed is characterized in that it is added to the polyurethane urea spinning solution that is dry spinning.

Hereinafter, the present invention will be described in detail.

First, a prepolymer is prepared by mixing and reacting a high molecular weight diol compound and an excess of diisoanate compound, and adding and mixing a solvent thereto to prepare a prepolymer solution.

At this time, it is preferable that the number average molecular weight of the said diol compound is 1,500-3,000, and it is preferable that the molar ratio of a high molecular weight diol compound and a diisocyanate compound is 1: 1.3-2.0.

N, N'-dimethylacetamide etc. are used as a solvent.

Next, a polyurethaneurea spinning solution is prepared by reacting the prepolymer solution with a diamine as a chain extender and a monoamine as a chain stopper.

At this time, the diamine is preferably added 94 to 97.5 equivalent% of the prepolymer, and 6 to 11 equivalent percent of the monoamine.

Moreover, it is preferable that the viscosity of a polyurethaneurea spinning solution is 1,500-5,000 poise at 10 degreeC.

It is preferable that diamine which is a chain extending agent is comprised from 70-90 mol% of ethylenediamine and 10-30 mol% of 1, 2- diamino propane, and it is preferable that the monoamine which is a chain stopper is diethyleneamine.

The method for preparing the polyurethaneurea spinning solution described above is only one embodiment of the present invention, and the present invention is not limited to the method for preparing the polyurethaneurea spinning solution.

In other words, the present invention encompasses all conventional methods for producing a polyurethaneurea spinning solution.

Next, in the present invention, N-N'-dimethylacetamide solution in which silver nanoparticles having an average particle diameter of 1 to 50 nm is dispersed is added to the polyurethaneurea spinning solution prepared as described above, and then, this is a conventional method. Dry spinning according to the polyurethane urea elastic yarn is produced.

As such, in the present invention, silver nanoparticles having an average particle diameter of 1 to 50 nm are dispersed in an N-N'-dimethylacetamide solution to prepare an N-N'-dimethylacetamide solution in which silver nanoparticles are dispersed. It is characterized in that it is added to the polyurethane urea spinning solution immediately before dry spinning.

When the average particle diameter of the silver nanoparticles exceeds 50 nm, the specific surface area of the silver nanoparticles may be reduced, which may cause a problem in that the antimicrobial effect is not effectively expressed. When the average particle diameter of the silver nanoparticles is lower than 1 nm, the price is not economical.

The content of the silver nanoparticles dispersed in the N-N'-dimethylacetamide solution is preferably 0.001 to 0.01% by weight based on the weight of the polymer (solid content) in the polyurethaneurea solution.

When the content is less than 0.001% by weight, the antimicrobial effect of the polyurethane urea elastic yarn may not be effectively expressed. When the content is more than 0.01% by weight, the dispersion of the silver nanoparticles in the spinning solution becomes uneven or the discoloration of the spinning solution is discolored. The quality of may be degraded.

In addition, a small amount of additives such as antioxidants, ultraviolet absorbers, dyeing enhancers and titanium oxide may be added to the polyurethaneurea spinning solution.

In the present invention, since the silver nanoparticles are added to the polyurethaneurea spinning solution in a state dispersed in the N-N'-dimethylacetamide solution, viscosity control of the spinning solution is facilitated.                     

In addition, since silver nanoparticles have a smaller particle size than a general inorganic antimicrobial agent, the specific surface area is relatively high, and even if a small amount is added, a high antibacterial deodorization effect can be obtained.

As a result, the polyurethane urea elastic yarn produced by the present invention is very excellent antibacterial deodorizing effect.

For example, the circular knitted fabric was knitted with a polyurethane urea elastic yarn prepared according to the present invention, and then the reduction rate (%) of Staphylococcus aureus was measured by KS K 0693 fabric antibacterial test method.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.

Example 1

1.7 moles of 4,4′-phenylmethane diisocyanate was mixed with 1 mole of polytetramethylene glycol having a number average molecular weight of 1800 and reacted at 90 ° C. for 90 minutes to synthesize a prepolymer having an isocyanate at the sock end. The prepolymer was cooled to 40 ° C. and then N-N'-dimethylacetamide was added to prepare about 45% of the prepolymer solution. Lower the prepolymer solution to 5 ° C. and stir vigorously to prepare 96% by weight of a chain extender composed of 75 mol% of ethylenediamine and 25 mol% of 1,2-diaminopropane and a chain stopper of diethyleneamine. Polyurethane urea spinning solution was prepared by chain extension and chain termination while slowly adding N-N'-dimethylacetamide solution containing 4 equivalent%. To the obtained polyurethane urea spinning solution, silver nanoparticles having an average particle diameter of 20 nm were added to the weight of the polymer (solid content) in the polyurethane urea spinning solution while adding a small amount of a conventional antioxidant, ultraviolet absorber, dyeing enhancer and titanium oxide. N-N'-dimethylacetamide solution dispersed in 0.001% by weight was added to the antimicrobial agent, followed by dry spinning to prepare a polyurethane denier polyurethane of 40 denier.

After the circular knitted fabric was knitted with the prepared polyurethaneurea elastic yarn, the antimicrobial activity and the spinning stock solution measured by the fabric antibacterial test method of KS K 0693 are shown in Table 2.

Examples 2 to 3 and Comparative Example 1

Polyurethane urea elastic yarn was prepared in the same process and conditions as in Example 1 except that the content and average particle diameter of silver-nanoparticles dispersed in the N-N'-dimethylacetamide solution were changed as shown in Table 1.

After the circular knitted fabric was knitted with the prepared polyurethaneurea elastic yarn, the antimicrobial activity and the spinning stock solution measured by the fabric antibacterial test method of KS K 0693 are shown in Table 2.

Manufacture conditions division Example 1 Example 2 Example 3 Comparative Example 1 Content of Silver Nanoparticles Dispersed in N-N'-Dimethylacetamide Solution (wt%) 0.001 0.005 0.01 0 Silver-nanoparticle average particle diameter (nm) 20 10 40 -

In Comparative Example 1, N-N'-dimethylacetamide solution containing silver nanoparticles was not added to the polyurethaneurea spinning solution.

Antimicrobial and Radiation Solution division Example 1 Example 2 Example 3 Comparative Example 1 Antimicrobial activity Reduction rate of pneumococci (%) 99.9 99.9 99.9 70.0 Staphylococcus aureus reduction rate (%) 96.3 99.8 99.5 50.5 Radiant Color and Dispersion State Good Good Good Good

In the present invention, since the silver nanoparticles are added to the polyurethaneurea spinning solution in a state of being dispersed in a N-N'-dimethylacetamide solution, the viscosity of the spinning solution can be easily controlled and inexpensive manufacturing cost is low.

In addition, the polyurethane urea elastic yarn prepared by the present invention is very excellent in antibacterial to various bacteria.

Claims (5)

After mixing and reacting a high molecular weight diol compound and an excess diisocyanate compound, a solvent is added thereto to prepare a prepolymer solution, followed by reacting the prepolymer solution with a diamine as a chain extender and a monoamine as a chain stopper. In manufacturing the polyurethane urea elastic yarn by dry spinning the polyurethane urea spinning solution, the N-N'-dimethylacetamide solution in which silver nanoparticles having an average particle diameter of 1 to 50 nm is dispersed is dried before the polyurethane A method for producing a polyurethane urea elastic yarn having excellent antibacterial and deodorizing property, which is added to a urea spinning solution. The antimicrobial deodorizing property according to claim 1, wherein the content of the silver nanoparticles dispersed in the N-N'-dimethylacetamide solution is 0.001 to 0.01 wt% based on the weight of the polymer (solid content) in the polyurethaneurea solution. Excellent polyurethaneurea elastic yarn manufacturing method. The method according to claim 1, wherein the diamine, which is a chain extender, comprises 70 to 90 mol% of ethylenediamine and 10 to 30 mol% of 1,2-diaminopropane. The method for producing a polyurethaneurea elastic yarn having excellent antibacterial and deodorizing property according to claim 1, wherein the monoamine which is a chain stopper is diethyleneamine. The method according to claim 1, wherein the number average molecular weight of the high molecular weight diol compound is 1,500 to 3,000.