JPH0681215A - Polyurethane-based elastic yarn - Google Patents

Abstract

PURPOSE:To improve chlorine deterioration resistance of polyurethane-based elastic yarn. CONSTITUTION:Polyurethane or polyurethane solution is blended with a solid solution of MgO/ZnO and spun to give a polyurethane elastic yarn having excellent chlorine deterioration resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyurethane elastic fibers. More specifically, to the polyurethane (hereinafter, polyurethane is a general term for polyurethane and polyurethaneurea in the present invention) or a polyurethane solution, the MgO / ZnO solid solution shown in the text is added in an amount of 0.1 to 20% by weight based on the weight of the fiber. The present invention relates to a polyurethane elastic fiber obtained by spinning, which prevents deterioration in various chlorine-containing environments.

[0002]

2. Description of the Prior Art Polyurethane elastic fibers obtained from 4,4'-diphenylmethane diisocyanate, polyhydroxy polymers having a relatively low degree of polymerization and polyfunctional active hydrogen compounds have a high degree of rubber elasticity. It has excellent mechanical properties such as tensile stress and recovery, and also has excellent thermal behavior. Therefore, it has been widely noticed and used as a functional material for clothing such as foundations, socks, and sportswear.

However, when a product using elastic fibers mainly composed of such long-chain synthetic elastic segmented polyurethane is exposed to a chlorine-water environment such as a detergent using chlorine bleaching, the physical properties of the segmented polyurethane are deteriorated. It is known that a considerable reduction occurs. It is known that a swimsuit composed of polyurethane fibers and polyamide fibers is deteriorated in physical properties of fibers when exposed to water containing an active chlorine concentration of 0.5 to 3 ppm in a swimming pool for a long time. There is.

Improvements have been made in imparting deterioration preventive properties against such chlorine-induced deterioration or imparting resistance to deterioration. For example, zinc oxide (Japanese Patent Publication No. 60-43444), magnesium oxide, aluminum oxide (Japanese Patent Publication No. 61-35283) are described as chlorine deterioration inhibitors.

[0005]

However, when the product such as the above-mentioned knitted or knitted fabric using the polyurethane elastic fiber containing the chlorine deterioration inhibitor is exposed to dyeing, finishing, processing, etc., especially at the time of dyeing. When an acid such as acetic acid or formic acid is used as the acid, the pH of the dyeing solution is low, and the chlorine deterioration inhibitor contained in the dye is eluted, and although the raw fiber has resistance to chlorine, There is a problem that resistance is almost lost in products that have undergone dyeing and the like.

[0006]

The present invention has solved the above-mentioned problems of the prior art and has arrived at an epoch-making present invention. That is, the present invention relates to a polyurethane-based elastic fiber characterized by containing 0.1 to 20% by weight of the MgO / ZnO solid solution shown in the text with respect to the weight of the fiber.

The polyurethane-based elastic fiber in the present invention is an elastic fiber obtained by spinning a polymer composition mainly composed of the following polyurethane. As the polyurethane in the present invention, a polymer having a number average molecular weight of 600 or more, preferably 1000 to 5000 and a melting point of 60 ° C. or less, an isocyanate mainly composed of an organic diisocyanate, and a molecular weight of 400 or less. The polymer obtained by reacting the polyfunctional active hydrogen compound of is mentioned.

As the polymer diol, polytetramethylene ether glycol, polyethylene glycols such as polyethylene propylene ether glycol, ethylene glycol, 1,6-hexanediol are used. ,
At least one of glycols such as 1,4-butanediol and neopentyl glycol and at least one dicarboxylic acid such as adipic acid, suberic acid, azelaic acid, sebacic acid, β-methyladipic acid and isophthalic acid. Polyester glycols obtained by reacting with one kind, polycaprolactone glycol, polyhexamethylene dicar
Examples thereof include one type of polymer diol such as bonnet glycol, or a mixture or copolymer of two or more types thereof.

As the organic diisocyanate, 4
.4'-diphenylmethane diisocyanate, 1.5-
Naphthalene diisocyanate, 1.4-phenylene diisocyanate, 2.4-tolylene diisocyanate, hexamethylene diisocyanate, 1.4-cyclohexane diisocyanate, 4. Examples thereof include one or a mixture of two or more organic diisocyanates such as 4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate. Further, a small amount of triisocyanate may be used together.

Examples of polyfunctional active hydrogen compounds are ethylenediamine, 1.2-propylenediamine, hexamethylenediamine, xylylenediamine, 4.4'-diphenylmethanediamine, hydrazine, 1.4-diaminopiperazine and ethylene glycol. 1,4-butanedio
1, 1,6-hexanediol, water and the like, or a mixture of two or more thereof. If desired, these compounds may be used in a small amount in combination with a terminating agent such as monoamine or monoalcohol. However, preferred are diamines alone or mainly.

The polyurethane-based composition is spun into elastic fibers, but is not particularly limited, but it is preferable to dissolve the polyurethane-based composition in a solvent and dry-spin it. N.N-dimethylformamide as a solvent,
Examples include N · N-dimethylacetamide, tetramethylurea, hexamethylphosphonamide, and the like, but the invention is not limited thereto. Compositions other than polyurethane that make up the polyurethane-based composition include stabilizers such as lubricants, ultraviolet absorbers, anti-yellowing agents, pigments, antistatic agents,
Examples include surface treatment agents, flame retardants, antifungal agents, and reinforcing agents.

The MgO / ZnO solid solution used in the present invention is the PERICLAS phase diagram of MgO and ZnO shown in FIG.
It is a range represented by E S S and ZINCITE S S, and is a part recognized as a single crystal of MgO and ZnO as a crystal system (Journal o
f American Ceramic Societ
y byE. R. SEGNIT and A. E. HO
LLAND vol. 48, No8 p. 409-41
3). In the range other than that, it is merely a mixed region of MgO and ZnO, and elution increases in the dyeing process. The addition of the MgO / ZnO solid solution to the polyurethane solution is not particularly limited, but the average particle size is 0.05 to 3 μm.
It is preferable to add as m particles. The amount of the chlorine water deterioration inhibitor such as these metal oxides added is appropriately 0.1 to 20% by weight with respect to the polyurethane, and preferably,
It is 1.0 to 3.0% by weight.

The polyurethane elastic fiber used in the present invention preferably has a denier in the range of 20 to 100, preferably 40 to 80. These elastic fibers are used in the state of covering yarn or bare yarn.

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Moreover,% in the examples is% by weight.

【Example】

-Example 1, Comparative Example 1-Polytetramethylene ether glycol having a hydroxyl group at both ends and a number average molecular weight of 2000 and 4.4'-diphenylmethane diisocyanate in a molar ratio of 1: 2. To produce a prepolymer, followed by chain extension with 1.2 propylenediamine, and 2000 poise (30 ° C.) at a polymer concentration of 30% (solvent dimethylformamide).
A polyurethane solution having a viscosity of MgO / Zn dispersed in dimethylformamide with an attritor in this solution
3% of O solid solution (MgO / ZnO = 65/35 (average particle size is 0.1 to 2 μm) is added to polyurethane,
Further, an antioxidant, an ultraviolet absorber and a gas yellowing inhibitor were added and mixed and stirred to obtain a spinning dope.

After defoaming, the spinning solution was spun out from a spinneret having a hole diameter of 0.2 mm and a hole number of 5 and extruded into a spinning tower in which heated air at 180 ° C. was flowed to perform false twisting at a rotation speed of 10,000 rpm. Then, while applying 6% of the oil agent to the yarn, it was wound at a spinning speed of 500 m / min to obtain 40 denier and 5 filaments of polyurethane elastic fiber (A). For comparison,
A polyurethane elastic fiber (B) was obtained in the same manner as in (A) except that no MgO / ZnO solid solution was added.

The polyurethane elastic fibers (A) and (B) thus obtained were refined, relaxed, dried and heat set, and then dyed. Dyeing is dye; Kayacyl
It was carried out under the conditions of Blue BR, 5% owf (acid dye), 40 ° C. to 95 ° C. for 30 minutes, and 95 ° C. for 30 minutes (bath ratio 1:13). Acetic acid 0.4g / l, ammonium sulfate 2 in the dye bath
g / l and an anionic leveling agent 1.2 g / l were used.

Example 2-MgO / ZnO = 2/98 as MgO / ZnO solid solution
Polyurethane elastic fibers (C) and dyed polyurethane elastic fibers were prepared by the same formulation as in Example 1 except that 3% of was added.

Comparative Example 2 MgO / ZnO = 65/3 as a MgO / ZnO solid solution.
Polyurethane elastic fibers (D) and dyed polyurethane elastic fibers were prepared in the same manner as in Example 1 except that 0.05% was added.

Comparative Example 3 Polyurethane elastic fiber (with the same formulation as in Example 1 except that MgO and ZnO were added individually so that MgO / ZnO = 65/35 so that the total amount was 3%) E) and dyed polyurethane elastic fibers were prepared.

Deterioration of each yarn obtained by the above-mentioned method by chlorine water was measured. The condition of this deterioration test is that each yarn is elongated by 40% in the warp direction, immersed in 30 ppm chlorine water (pH = 7.5) at 30 ° C. for 6 hours, the strength before and after immersion is measured, and the deterioration ( (Brittleness) was determined. The results are shown in Table 1.

[0021]

[Table 1]

[0022]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a product having excellent chlorine resistance, which is capable of improving the deterioration of chlorine in polyurethane elastic fibers used in a chlorine-containing environment due to chlorine.

[Brief description of drawings]

FIG. 1 shows a phase diagram of MgO and ZnO.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location // C08K 3/20 C08L 75/04 NFY 8620-4J (72) Inventor Koji Shirahaku Otsu, Shiga Prefecture 2-1-1 Katata, Ichi, Toyobo Research Institute (72) Inventor Hajime, Hajime 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Research Institute

Claims (1)

[Claims] 1. A polyurethane-based elastic fiber, characterized in that the MgO / ZnO solid solution shown in the text is contained in an amount of 0.1 to 20% by weight based on the weight of the fiber.