KR100445313B1 - Antibacterial Spandex - Google Patents

Abstract

The present invention relates to an antimicrobial elastic fiber, and more particularly, it is composed of 50 to 78 mol% of ZnO, 21 to 49 mol% of SiO ₂ , and 1 to 10 mol% of alkali metal oxide as an antimicrobial agent, and has an average particle size of 0.1 μm. The present invention relates to an antimicrobial spandex fiber containing 0.2 to 5% by weight of glass compounds having a diameter of 5 μm or less, and does not cause yellowing problems even after the spinning process, and provides an elastic yarn semi-permanently given antimicrobial properties.

Description

Antibacterial Elastic Fiber {Antibacterial Spandex}

The present invention relates to an antimicrobial elastic fiber, and more particularly, by using a glass compound composed of ZnO, SiO ₂ , and alkali metal oxide as an antimicrobial agent does not cause yellowing problems even after spinning process, excellent antibacterial It relates to an elastic fiber.

Polyurethane-based elastic fibers have been widely used in stockings, women's underwear and stretch fabrics because of their excellent elasticity and elasticity, and their use as aerobic and accommodating clothes continues to expand. However, many kinds of bacteria and molds adhere to the clothes by various secretions discharged from the body. Of these, they are attached to the fabric and do not harm the human body. In some cases, it directly causes harm to the human body. In particular, there are many cases in which elastic fibers are used as girdle and braser of women, but in this case, bacteria or fungi may inhabit the elastic fibers due to secretions caused by sweat or the like.

As a method for imparting antimicrobial properties to polyurethane elastic fibers, US Pat. No. 4,837,292 is a polysegment of polycarbonate diols among the aliphatic diols as soft segments and poly (hexane-1,6-diol). A method of imparting antimicrobial properties by using carbonate) diol or a copolymer thereof has been disclosed. This is a method of giving antimicrobial properties using the physical properties of the raw material itself without adding a separate antimicrobial agent, but there is a problem of low antibacterial effect.

In addition, as in Korea Patent Publication No. 1993-9999, since the zeolite itself exhibits strong adsorption characteristics when used as an antimicrobial agent by ion-exchanging bactericidal metal ions to the crystalline aluminosilicate zeolite, which is a porous inorganic material, as an inorganic antimicrobial agent, When moisture is adsorbed, it reacts rapidly with the diisocyanate as a raw material during the polymerization process in the elastic fiber manufacturing process to form urea or to form a burette or allophanate to crosslink the polymer to increase the viscosity of the polymer and form a gel. As a result, the pressure of the filter is rapidly increased, which causes frequent trimming during spinning.

In Korean Patent No. 103406, non-porous inorganic ceramics containing silver or zirconium are used to impart antimicrobial properties to elastic fibers, but in this case, a problem occurs in that the spandex yellows.

The present invention is to solve the problems of the prior art, it is an object of the present invention to provide an antimicrobial elastic yarn semi-permanently given antibacterial even after the spinning process does not cause a yellowing problem.

That is, the present invention is composed of 50 to 78 mol% of ZnO, 21 to 49 mol% of SiO ₂ , and 1 to 10 mol% of alkali metal oxide as an antimicrobial agent, and a glass compound having an average particle size of 0.1 μm or more and 5 μm or less compared to yarns. It relates to an antimicrobial spandex fiber comprising 0.2 to 5% by weight.

Hereinafter, the present invention will be described in more detail.

In the present invention, ZnO is composed of 50 to 78 mol%, SiO ₂ 21 to 49 mol%, alkali metal oxide 1 to 10 mol%, and an average particle size of 0.1 μm or more and 5 μm or less is used. The antimicrobial agent is a non-porous antimicrobial agent, there is almost no adsorption of moisture, there is no fear of gel generation when introduced into the polymer, and does not cause a dye non-uniformity problem during the dyeing process.

Among the components, ZnO is a substance that provides antimicrobial activity. If the content thereof exceeds 78 mol%, it is difficult to make a glass compound, and if the content is less than 50 mol%, the antimicrobial activity is insufficient. As the alkali metal oxides, oxides of alkali metals Na, K and Li may be used, and two or three kinds thereof may be used together. Alkali metal oxides play a very important role in imparting discoloration resistance and water resistance to the antimicrobial agent. When the alkali metal oxide exceeds 10 mol%, the water solubility of the antimicrobial agent becomes large, and the antimicrobial property is poor, which does not bring a persistent antimicrobial property, and damage to discoloration resistance and water resistance.

When SiO _{2, which} is a glass forming component of the antimicrobial agent, exceeds 49 mol%, the water solubility is increased and the antimicrobial properties are lowered. When it is less than 21 mol%, it is difficult to obtain a stabilized glass forming component. The essential glass forming component in the present invention is SiO _2, but other glass forming components can be used in place of a part of the SiO ₂ component. As other glass components, P ₂ 0 ₅ , Al ₂ 0 ₃ , Ti0 ₂ , ZrO _2, or the like is preferably used. The content of the other glass components is preferably 0.1 to 19 mol% or less.

The segmented polyurethane polymer used to prepare the elastic yarn of the present invention is prepared by reacting organic diisocyanate and polymer diol to prepare a polyurethane precursor, as known in the art, and then dissolving it in an organic solvent and then diamine and mono Prepared by reacting with an amine.

The organic diisocyanate used in the present invention includes diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated P, P methylene diisocyanate and the like. As the polymer diol, polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and the like may be used. The diamines are used as chain extenders, and examples thereof include ethylenediamine, propylenediamine, hydrazine, and the like. In addition, the monoamine is used as a chain stopper, examples thereof include diethylamine, monoethanolamine, dimethylamine and the like. As the additive, UV stabilizers, antioxidants, NOx gas yellowing inhibitors, anti-sticking agents, dyeing enhancers, chlorine resistant agents and the like can be used.

Antibacterial agent used in the present invention is preferably added to 0.2 to 5% by weight relative to the yarn. If the amount of the antimicrobial agent is less than 0.2% by weight, there is no antimicrobial effect. If the amount of the antimicrobial agent is more than 5% by weight, it causes a decrease in the properties of spandex yarn and further antimicrobial effect cannot be expected. The antimicrobial agent used in the present invention may be added by mixing with other additives, and other additives may be added first and then immediately before spinning.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are intended to illustrate the present invention and are not intended to limit the present invention.

Example : Preparation of Segment Polyurethane Polymer

518 g of diphenylmethane-4,4'-diisocyanate and 2328 g of polytetramethylene ether glycol (molecular weight 1800) were reacted with stirring at 85 ° C. for 90 minutes in a nitrogen gas stream, and a polyurethane precursor containing an isocyanate at both ends was reacted. Prepared. After the polyurethane precursor was cooled to room temperature, 4643 g of dimethylacetamide was added thereto and dissolved to obtain a polyurethane precursor solution. Subsequently, a solution obtained by dissolving 54 g of propylenediamine and 9.1 g of diethylamine in 1889 g of dimethylacetamide was added to the polyurethane precursor solution at 10 ° C. or lower to prepare a segmented polyurethane polymer solution. A conventional UV stabilizer, antioxidant, yellowing inhibitor, and the like were added to the polymerized product, and an antimicrobial agent was added thereto. The antimicrobial agent contains 12.1% by weight of yarn using a glass compound composed of 62.1 mol% of ZnO, 31.1 mol% of SiO ₂ , 2.5 mol% of P ₂ 0 ₅ , 2.3 mol% of Al ₂ O ₃ , and ₂ mol% of Na ₂ O. Was added to be. After degassing this spinning stock solution, 4 filament 40 denia elastic yarn was prepared by adjusting the spinning temperature to 250 ° C. in a dry spinning process. The elastic yarn thus obtained was knitted spandex circular knitted fabric as a specimen using a Hona knitting machine (KT-400, 4 inches in diameter, 400 submerged, Nagakaseiki, Japan), and then using a conventional spandex refining method To refine the spandex circular knit to evaluate the physical properties and the results are shown in Table 1.

Comparative example

As an antimicrobial agent, the same as in Example 1 except that 3.8% by weight of silver disclosed in Example 1 of Korean Patent Publication No. 1995-734 and 35% by weight of zirconium were added with a nonporous inorganic antimicrobial ceramic having an average particle diameter of 0.4 μm. The physical properties were evaluated, and the results are shown in Table 1.

[Property evaluation method]

(1) antimicrobial evaluation

Staphylococcus aureus (ATCC6538, Staphylococcus aureus) and Escherichia coli (ATCC8739, Escherichia coli) were selected as test bacteria, and after the preculture and main culture, the test cell suspension was made and the sample was added to shake culture (300rpm × 1hr, 25 ℃ ± 5) After counting the bacterial counts, the bacterial counts were evaluated by the shake flask method by comparing the first bacterial counts with the bacterial counts after shaking culture. 100 g of the elastic yarn circular knitted fabric was washed in a 10-liter solution containing 35 g of detergent for 10 minutes, and the elastic yarn circular knitted fabric was repeatedly dried 20 times to evaluate the antimicrobial activity mentioned above.

(2) evaluation of discoloration resistance

The following evaluation was performed with the refined spandex circular knitted fabric length 10cm.

① UV test

Accelerated Weathering Tester (Q-Panel, USA) was used, and UV lamps used UV B lamps. The temperature was fixed at 60 ° C. and the samples were treated for 24 hours.

② Heat resistance test

The treatment was performed for 20 minutes at 200 ° C. in a Geer Oven (Toyoseiki, Japan) where air circulation was possible.

③ NOx gas test

Prepare a NOx gas generating solution with a mixed solution of 300mmL of ion-exchanged water, 85% aqueous solution of phosphate 8mL sodium acetate (NaNO ₂ ) (10g / L), and then put the solution in a sealed container, and place the sample at room temperature, Treated with NOx gas for 24 hours. The discoloration resistance evaluation measured the "b" value (yellowing value) using the color-view (Gardner, USA).

Antibacterial before washing Antibacterial after washing Discoloration resistance Staphylococcus aureus Escherichia coli Staphylococcus aureus Escherichia coli Initial value (b value) UV light (b value) Flame resistance (b value) NOx property (b value) Example 99.5 99.6 99.1 99.0 0.22 20.95 8.69 12.71 Comparative example 99.4 99.6 99.0 99.0 9.34 24.71 24.68 22.27

* The lower the "b value" in discoloration resistance, the better

Spandex to which the antimicrobial agent of the present invention is applied is excellent in antimicrobial properties and does not cause problems of spandex yellowing, so it is suitable for application to spandex.

Claims (3)

As an antimicrobial agent, it is composed of 50 to 78 mol% of ZnO, 21 to 49 mol% of SiO ₂ , and 1 to 10 mol% of alkali metal oxide, and 0.2 to 5% by weight of glass compounds having an average particle size of 0.1 μm or more and 5 μm or less. Antimicrobial spandex fiber comprising. The antimicrobial spandex fiber according to claim 1, wherein the alkali metal oxide is at least one oxide selected from the group consisting of Na, K, and Li. As an antibacterial agent, i) 50 to 77.9 mol% of ZnO, ii) 21.1 to 49 mol of SiO ₂ and at least one other glass component selected from the group consisting of P ₂ 0 ₅ , Al ₂ 0 ₃ , TiO ₂ and ZrO ₂ % And iii) an antimicrobial spandex fiber composed of 1 to 10 mol% of an alkali metal oxide and containing 0.2 to 5% by weight of the glass compound having an average particle size of 0.1 µm or more and 5 µm or less, wherein ii) SiO ₂ and In the above mixture of other glass components, the SiO ₂ content is necessarily 21 mol% or more, and the other glass components include 0.1 to 19 mol% of the antimicrobial spandex fiber.