JPH07166425A - Polyurethane elastic fiber - Google Patents

Abstract

PURPOSE:To obtain a polyurethane elastic fiber having excellent antimicrobial function. CONSTITUTION:This is a silver-containing polyurethane elastic fiber. An applicable state of silver to be incorporated is a silver ion, a silver salt, silver fine particle or their combination and further the silver ion, the silver fine particle or their combination is preferable because it exhibits excellent antimicrobial activity with a small quantity of silver. The silver content in the fiber is: in a silver ion, 10-5000ppm, preferably 100-1000ppm; in a silver salt or silver fine particle, 0.005-1.0wt.%, preferably 0.025-0.5wt.%. The method to incorporate silver is as follows: in the case of a silver ion, a spinning solution is compounded with a supporting body of the silver ion, preferably a zirconium phosphate-containing ion-exchanger capable of supporting the silver ion, the ingredients are homogeneously dispersed and subsequently the obtained liquid is subjected to spinning; in the case of a silver salt, a spinning solution compounded with a silver salt itself of e.g. trifluoroacetic acid is subjected to spinning; in the case of silver fine particle, a spinning solution is compounded with a silver salt and a reducing agent, the ingredients are homogeneously dispersed and this is subjected to a heat treatment at about 150 deg.C to reduce the silver ion to silver followed by spinning.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyurethane-based elastic fibers having antibacterial properties.

[0002]

As a technique for imparting antibacterial properties to synthetic fibers such as polyester, a so-called kneading method in which a chemical is added to a raw material polymer and then spun is widely used because of excellent washing durability. In the case of polyurethane-based elastic fibers, conventionally known antibacterial agents have poor stability such as liquid diffusibility in a spinning stock solution and poor spinnability.

For this reason, there is no choice but to mix it with an antibacterial polyamide fiber or the like, and a polyurethane elastic fiber having an antibacterial property has not yet been proposed.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a polyurethane-based elastic fiber having antibacterial properties which meets such a demand.

[0005]

That is, the present invention is a polyurethane-based elastic fiber containing silver. The polyurethane-based elastic fiber in the present invention,
Having hydroxyl groups at both ends, molecular weight 400-500
A substantially linear polymer of 0, for example, one or more of polyester diol, polylactone diol, polythioether diol, polyester amide diol, polyether diol, and polycarbonate diol, organic diisocyanate, and polyfunctional active hydrogen atom. A molecule obtained by reacting a chain extender having, for example, hydrazine, polyhydrazide, polyol, polyamine, hydroxylamine, water, and an end-capping agent having a monofunctional active hydrogen atom, for example, a dialkylamine, in one or multiple steps. It is a fiber obtained by spinning an elastic polymer having a urethane group therein.

Alternatively, a chain extender having a polyfunctional active hydrogen atom is added to a prepolymer consisting of a substantially linear polymer having hydroxyl groups at both ends and a molecular weight of 400 to 5000 and an organic diisocyanate, and a monofunctional compound. It is a fiber obtained by spinning while reacting with a terminal stopper having an active hydrogen atom. If desired, the elastic fiber may be
Organic or inorganic compounding agents having a specific chemical structure useful for known polyurethane polymer compositions, for example, gas yellowing inhibitors, ultraviolet absorbers, antioxidants, antifungal agents, barium sulfate, magnesium oxide, Inorganic fine particles such as calcium silicate and zinc oxide, calcium stearate, magnesium stearate, polytetrafluoroethylene,
An anti-tacking agent such as organopolysiloxane may be appropriately blended.

It is preferable that the elastic fiber has a denier of 490 or less and a breaking elongation of 50 to 800%.
Examples of the state of silver contained include silver ions, silver salts, silver fine particles and combinations thereof, and silver ions, silver fine particles and combinations thereof are preferred because they have a smaller content and are excellent in antibacterial effect. The method of incorporating silver ions is not particularly limited, but in the case of silver ions, a method of adding a silver ion carrier to the stock solution for spinning and uniformly dispersing it is preferable because silver ions can be uniformly incorporated inside the fibers. Examples of silver ion carriers include inorganic cation exchangers supporting silver ions, specifically natural zeolites and synthetic zeolites are preferable, and zirconium phosphate ion exchangers are particularly preferable. As a method of supporting silver ions, a method of replacing the cations of the inorganic cation exchanger with silver ions by treating the inorganic cation exchanger with a solution containing silver ions can be preferably used.

For example, when a zirconium phosphate-based ion exchanger is used as the carrier, the calcined zirconium phosphate salt is treated with a strongly acidic solution and then with a silver ion solution to support silver ions at a high concentration. You can
Alternatively, a silver salt such as trifluoroacetic acid may be added as it is. In the case of containing fine silver particles, for example, a silver salt such as trifluoroacetic acid and a reducing agent such as a hindered phenol-based or amine-based reducing agent are added to the spinning solution and uniformly dispersed, followed by heat treatment at about 150 ° C. The method of reducing to silver and spinning is preferable because silver fine particles having a particle size of about 6 to 11 nm can be uniformly contained inside the fiber.

The content of silver with respect to the polyurethane elastic fiber may be appropriately selected in consideration of desired performance, economical efficiency and spinnability. For example, with silver ion, it is 10 ppm.
~ 5000ppm, preferably 100ppm-1000p
pm, silver salt and silver fine particles, 0.005-1.0 polymerization%
0.025 to 0.5 polymerization% is preferable. or,
The fine silver particles have a particle size of 1 to 100 nm, preferably 5 to 50 n.
m is good.

The silver ion content is the amount of silver ions measured by the light emitting plasma method. The polyurethane elastic fiber of the present invention may be used alone or in combination with other fibers, for example, synthetic fibers such as polyamide fiber and polyester fiber, regenerated fiber such as cupra, rayon and acetate, cotton, wool, hemp, silk and the like. It is used for conventional polyurethane elastic fibers such as pantyhose, innerwear, sportswear, etc. by mixing it with filament yarn or spun yarn of natural fiber.

Further, various functions can be imparted by kneading the following materials into the polyurethane elastic fiber. For example, in order to impart hygroscopicity or water absorption, a sodium acrylate polymer (trade name Sumika gel), a copolymer of isobutylene and maleic acid (trade name KI gel) has
Iron oxide, aluminum oxide, copper iodide, trade name radium powder (natural ore; manufactured by Nippon Environmental Chemicals Co., Ltd.), Mn
-Ni-Co-Fe-Cu oxide sintered body (trade name FIR
AC), for deodorization, trade name Shu-cut (manufactured by Nippon Environmental Chemicals Co., Ltd.), for thread / thread (F / F) and thread / metal (F / M) friction, aluminum oxide, titanium oxide However, the addition of a reactive dye having a sodium sulfonate group in the triazine skeleton (trade name: Sandspace, manufactured by Sand Co.) is effective for cationic dyeing.

Further, regarding heat storage, zinc oxide, Z
irconium Complex ZSP (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd .; zirconium as a skeleton, to which a phosphate group is coordinated, and other monomers are bonded through the phosphate group to form a polymer), Ceragit AL-F-9 (OK
Trading Company; A1 ₂ O ₃ / SiO ₂ / Na ₂ O / K
₂ O / Fe ₂ O ₃ ) and zirconium carbide are effective.

[0013]

EXAMPLES The present invention will be described in detail below with reference to examples.
The antibacterial property was measured by the following method. Antibacterial property; Processing effect evaluation test manual for antibacterial and deodorant processed products: Shake flask method (textile product hygiene processing council, March 1988) was used. The strain used is Staphylococcus auveu.
s), add a predetermined amount of the test bacterial solution into the Erlenmeyer flask,
Furthermore, 0.75 g of a measurement test piece was added, and after shaking with wrist action (330 rpm, 1 hr), the viable cell count in the flask was measured by culture, and the sterilization rate was calculated by the following formula.

Sterilization rate = (AB) / A × 100% A: Number of bacteria per 1 ml of test solution in Erlenmeyer flask before shaking B: Bacteria per 1 mL of test solution in Erlenmeyer flask after shaking number

[0015]

Example 1 1000 g of polytetramethylene glycol having an average molecular weight of 1200 and 312 g of 4,4′-diphenylmethane diisocyanate were reacted in a nitrogen gas stream at 95 ° C. for 90 minutes while stirring to obtain a prepolymer having an isocyanate group remaining. It was Then, after cooling this to room temperature, 2360 g of dry dimethylformamide was added and dissolved to obtain a prepolymer solution. On the other hand, 23.4 g of ethylenediamine and 3.7 g of diethylamine were dissolved in 1570 g of dry dimethylformamide, and the prepolymer solution was added thereto at room temperature to obtain a polyurethane solution having a viscosity of 1200 poise (30 ° C.).

To this viscous polymer solution, 2% by weight of 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 2- (2'-hydroxy-3'-t-butyl-) was added. 0.7% by weight of 5'-methylphenyl) -5-chloro-benzotriazole was added. In this polymer solution, 99.7 parts by weight of the polymer and 0.1% of silver trifluoroacetate were added.
Parts by weight and 0.2 part by weight of a hindered phenol-based reducing agent were added and dry-spun to obtain 40d / 4f polyurethane elastic fibers.

As a result of evaluating the quantity of silver and the antibacterial property of this polyurethane elastic fiber, 0.05% by weight of silver fine particles having a particle size of 6 to 11 nm was uniformly contained, and the antibacterial property was 99%. It was The antibacterial property of the conventional polyurethane-based elastic fiber containing no silver was 0%.

[0018]

Example 2 Silver ions were adsorbed on zirconium phosphate to prepare silver ion-supporting fine particles having an average particle size of 0.8 μm. The silver ion content was 3.5% by weight. The fine particles were added to the polymer solution of Example 1 in an amount of 2% by weight based on the weight of the polymer.
It was added and dry-spun to obtain a polyurethane elastic fiber of 40d / 4f.

As a result of quantitative determination of silver ions and antibacterial property of this polyurethane elastic fiber by the light emitting plasma method, the silver ion content was 350 ppm and the antibacterial property was 99%.
Met.

[0020]

EFFECTS OF THE INVENTION The present invention provides a polyurethane-based elastic fiber having excellent antibacterial properties.

Claims (1)

[Claims] 1. A polyurethane-based elastic fiber containing silver.