KR100580324B1 - A polyurethane urea elactic fiber, and a process of preparing the same - Google Patents

Abstract

The present invention relates to a polyurethaneurea elastic fiber excellent in weather resistance and a method for producing the same.

The present invention is a polyamide having a strong retention of 90% or more after the formamidine-based UV absorber of the general formula (I) is added to Spinning Dope and left for 24 hours in a fade-o-meta equipped with sunshine carbon arc. Urethane urea elastic fibers are produced.

Wherein R ₁ and R ₂ are alkyl having 1 to 5 carbon atoms.

Weather Resistance, Light Resistance, Polyurethane Urea, Elastic Fiber, UV Absorber

Description

Polyurethane urea elastic fiber and its manufacturing method {A polyurethane urea elactic fiber, and a process of preparing the same}             

The present invention relates to a polyurethaneurea elastic fiber excellent in weather resistance and a method of manufacturing the same.

Polyurethane-based elastic fibers are used in stockings, women's underwear, sportswear and swimwear because of their excellent elasticity and elastic recovery. However, when the polyurethane-based elastic fiber is exposed to the atmosphere, the physical properties and colors of the elastic fiber change due to sunlight, and are easily discolored by the waste gas in the atmosphere. .

In order to compensate for these drawbacks, Korean Patent Application No. 90-10867 describes a method of using a phenolic antioxidant, an amine ultraviolet stabilizer, and a methacrylic lake yellowing agent as an additive. They have the disadvantage of leaching and subliming out of the polymer, causing process problems.

U.S. Patent No. 4548975 describes a method for improving the stabilization effect against oxidation and heat using phenolic antioxidants and phosphite antioxidants, but the properties and colors of the prepared urethane-based elastic fibers are easily changed by sunlight. There is.

Korean Publication 93-11337 describes a method for producing weatherable elastomers using phenolic antioxidants, phosphite antioxidants, semicarbazide yellowing agents, and benzotriazole light stabilizers, but benzotriazole light stabilizers Due to the lack of compatibility with the polyurethane elastomer and leaching, sublimation during spinning there is a problem that adversely affects the fairness.

Korean Patent Application No. 93-28704 describes a method for producing chlorine-resistant elastic fibers using inorganic salts, but this technique does not prevent the deterioration of physical properties of the elastomer against light and heat.

Korean Patent Publication No. 97-7688 describes a composition using a phenolic antioxidant and a metal salt chlorine agent, but this method does not prevent discoloration and deterioration of properties due to light.

Korean Publication 96-11609 improves the resistance to ultraviolet rays and chlorine by using benzophenol-based light and chlorine-resistant chlorine, but has a problem in preventing physical property degradation and yellowing of heat or waste gas.

As described above, a combination containing various stabilizers has been proposed to improve the weather resistance of polyurethane-based elastomers, but the overall weatherability of light resistance, waste gas resistance, chlorine resistance, oxidation resistance, etc. There is no description of how this can be manufactured.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems, and to provide a method capable of producing polyurethaneurea elastic fibers having excellent light resistance with a stable processability by using a new type of UV stabilizer.

The present invention is to provide a polyurethane urea elastic fiber and a method of manufacturing the same, while maintaining the intrinsic properties of elastic fibers such as elasticity and having excellent light resistance and processability.

The present invention relates to a polyurethaneurea elastic fiber and a method of manufacturing the same, while maintaining the intrinsic properties of the elastic fiber and at the same time excellent in process stability and light resistance.

More specifically, the present invention contains a formamidine-based ultraviolet absorber of the following general formula (I), 90% strong retention after standing for 24 hours in a fade-O-Meter equipped with sunshine carbon arc The present invention relates to a polyurethaneurea elastic fiber.

The present invention also relates to a method for producing a polyurethaneurea elastic fiber, characterized in that the formamidine-based ultraviolet absorber of the general formula (I) is added to Spinning Dope.

Wherein R ₁ and R ₂ are alkyl having 1 to 5 carbon atoms.

The present invention is characterized in that the formamidine ultraviolet absorber of the general formula (I) is added to the spinning dope in the manufacturing process of ordinary polyurethaneurea elastic fibers.

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

First, 1.3 to 2.0 moles of the diisocyanate compound is prepolymerized with respect to 1 mole of the diol compound, and then a suitable amount of the solvent is mixed to prepare a solution of the prepolymer in the same manner as in the conventional polyurethaneurea elastic fiber production method.

In the prepolymerization, it is preferable to use a high molecular weight diol compound having a number average molecular weight of 1,500 to 3,000.

Next, a diamine compound and a monoamine compound are added to the prepolymer solution to chain extend and stop the prepolymer to prepare a polyurethaneurea polymer solution (spinning dope).

In this case, the amount of the diamine compound added is 70-99 equivalent% of the prepolymer. The amount of the monoamine compound added is preferably 1 to 30 equivalent% of the prepolymer. In addition, it is more advantageous for the spinning process to adjust the viscosity of the polymer solution to 1,500 to 5,000 poise at 40 ° C.

Next, the polyurethane urea elastic fiber of the present invention is prepared by adding a formamidine-based ultraviolet absorber of the general formula (I) to the polyurethane urea polymer solution (spinning dope) and then spinning them.

Wherein R ₁ and R ₂ are alkyl having 1 to 5 carbon atoms.

Specific examples of the formamidine-based ultraviolet absorbers of formula (I) used in the present invention include N- (4-ethoxycarbonylphenyl) -N-methyl-N-phenylformamidine, N- (4-methoxy Carbonylphenyl) -N-methyl-N-phenylformamidine, N- (4-ethoxycarbonylphenyl) -N-ethyl-N-phenylformamidine, and the like.

The formamidine-based ultraviolet absorber of the general formula (I) is preferably added at 0.1 to 3.0% by weight, more preferably 0.5 to 2.0% by weight, based on the polyurethaneurea polymer (solid content). If the amount is less than 0.1% by weight, the effect of improving the light resistance of the elastic fiber is insignificant, and if the amount is more than 3.0% by weight, the processability such as spinning becomes unstable.

The present invention includes adding a pigment such as titanium oxide or an additive such as an antioxidant, a chlorine resistant agent, a waste gas stabilizer together with a formamidine-based ultraviolet absorber of the general formula (I) to the polyurethaneurea polymer solution. .

Antioxidant can be mainly used hindered phenolic antioxidant, inorganic chloride chlorine such as zinc oxide can be used as chlorine-resistant, semikibazide-based waste gas stabilizer can be used as a waste gas stabilizer. . More specifically, 0.1 to 1.5% by weight of antioxidant, 0.1 to 2.0% by weight of chlorine resistant agent, 0.1 to 2.0% by weight of waste gas stabilizer, 0.05 to 4.0% by weight of titanium oxide, and blue pigment 0.005 ~ to polyurethane urea polymer (solid content) 0.002% by weight can be added.

Formamidine UV absorbers of the general formula (I) used in the present invention are excellent in heat resistance and UV blocking effect as compared to the conventional UV absorbers, without reducing the intrinsic properties of the elastic fibers in the elastic fiber manufacturing process Light resistance and processability can be improved.

The polyurethaneurea elastic fiber of the present invention contains the formamidine ultraviolet absorber of the general formula (I), and has a strong retention of 90% or more after being left in a fade-o-meta equipped with sunshine carbon arc for 24 hours. The content of formamidine ultraviolet absorber of formula (I) relative to the total weight of the fiber is 0.5 to 2.0% by weight.

In the present invention, the physical property evaluation method of the polyurethaneurea elastic fiber is as follows.

1. Light resistance evaluation

The 40 denier polyurethane urea elastic yarn was wound on an aluminum plate and left for 24 hours in a fade-o-meta equipped with a sunshine shine carbon arc. The color change (Δb) and the strong retention before and after the treatment were measured by the KSK 0700 method.

2. Waste gas resistance evaluation

The 40 denier polyurethane urea elastic yarn was wound on an aluminum plate and treated at 650 ppm NO ₂ gas concentration for 1 hour, and the color change before and after the treatment was measured.

3. Chlorine Resistance Evaluation

After 40 hours of treatment with 40 denier polyurethane urea elastic yarn in an aqueous solution of 30 ppm chlorine concentration, discoloration and strong retention were measured.

4. Evaluation of oxidation resistance (heat resistance)

The 40 denier polyurethane urea elastic yarn was stretched and fixed twice, followed by heat treatment at 180 ° C. for 60 seconds to measure the strong retention before and after treatment.

5. Strong maintenance rate (%)

× 100Strong retention rate (%) =

× 100

Example 1

2 moles of 4,4'-diphenylmethane diisocyanate was mixed with 1 mole of polytetramethylene glycol having a molecular weight of 1,800 and reacted at 90 ° C. for 90 minutes to synthesize a prepolymer having an isocyanate at the sock end.

After cooling the prepolymer to 40 ° C., N, N′-dimethylacetamide was added to prepare a solution containing about 45% of the prepolymer. Lower the prepolymer solution to 5 ° C and stir vigorously while slowly stirring the N, N'-dimethylacetamide solution containing 96 equivalent% of ethylenediamine and 6 equivalent% of diethylamine to the prepolymer. To prepare a final polyurethaneurea solution.

1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzene) -1,3,5-triazine-2,4,6- (1H in the obtained polyurethaneurea solution , 3H, 5H) Triion antioxidant 1.2% by weight, based on the solid content of the polyurethaneurea solution, 1,1,1 ', 1'-tetramethyl-4,4'-(methylene-di-p-phenylene) di 1.0% by weight of semicarbazide waste gas stabilizer, 1.2% by weight of zinc oxide chlorine agent, 2.0% by weight of N- (4-ethoxycarbonylphenyl) -N-methyl-N-phenylformamidine UV absorber, oxidation Titanium 2% by weight, blue pigment (ultramarine blue) was added 0.003% by weight in a 220 ℃ atmosphere to prepare a polyurethane denier polyurethane urea of 40 denier.

Light resistance, oxidation resistance (heat resistance), chlorine resistance, and waste gas resistance of the fibers were evaluated and shown in Table 1 below.

Example 2

A polyurethaneurea elastic fiber was prepared in the same manner as in Example 1 except that 1.5 wt% of an additive N- (4-ethoxycarbonylphenyl) -N-methyl-N-phenylformamidine ultraviolet absorbent was used. Light resistance, oxidation resistance (heat resistance), chlorine resistance, and waste gas resistance of the fibers were evaluated and shown in Table 1 together.

Example 3

Polyurethaneurea elastic fibers were prepared in the same manner as in Example 1 except that 1.0 wt% of an additive N- (4-ethoxycarbonylphenyl) -N-methyl-N-phenylformamidine UV absorber was used. Light resistance, oxidation resistance (heat resistance), chlorine resistance, and waste gas resistance of the fibers were evaluated and shown in Table 1 together.

Example 4

Polyurethaneurea elastic fiber was prepared in the same manner as in Example 1 except that 0.5 wt% of an additive N- (4-ethoxycarbonylphenyl) -N-methyl-N-phenylformamidine UV absorber was used. Light resistance, oxidation resistance (heat resistance), chlorine resistance, and waste gas resistance of the fibers were evaluated and shown in Table 1 together.

Comparative Example 1

After the polyurethane urea elastic fiber was prepared in the same manner as in Example 1 without adding any additives to the polymer solution, the fibers were evaluated for light resistance, oxidation resistance (heat resistance), chlorine resistance, and waste gas resistance. 1 is shown together.

Comparative Example 2

1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzene) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) Polyurethane urea elastic fiber was prepared in the same manner as in Example 1, except that only 0.5% by weight of a triion antioxidant was added, and then the light resistance, oxidation resistance (heat resistance), chlorine resistance, and waste gas resistance of the fiber were obtained. The evaluation is shown in Table 1 together.

Comparative Example 3

1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzene) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) Polyurethane urea elastic fiber was prepared in the same manner as in Example 1 except that only 0.5% by weight of triion antioxidant and 0.5% by weight of zinc oxide chlorine agent were added. Heat resistance), chlorine resistance, and waste gas resistance were evaluated and shown in Table 1 below.

Comparative Example 4

Polyurethane urea elastic fibers were prepared in the same manner as in Example 1 except that N- (4-ethoxycarbonylphenyl) -N-methyl-N-phenylformamidine UV absorber was not added to the polymer solution. About this fiber, light resistance, oxidation resistance (heat resistance), chlorine resistance, and waste gas resistance were evaluated and shown in Table 1 together.

Property evaluation result division Light resistance Oxidation resistance Waste gas resistance Chlorine Tolerance Δb Strong retention rate (%) Strong retention rate (%) Δb Strong retention rate (%) Δb Strong retention rate (%) Example 1 0.1 99.1 97.0 0.15 98.0 2.40 98.2 Example 2 0.3 98.0 95.0 0.16 98.0 2.38 98.0 Example 3 0.4 97.3 95.0 0.16 97.3 2.38 97.6 Example 4 0.9 94.6 93.2 0.17 97.0 2.45 97.2 Comparative Example 1 16.3 68.9 62.3 7.2 72.1 8.9 73.8 Comparative Example 2 14.7 69.3 82.9 7.2 73.2 8.5 73.5 Comparative Example 3 14.8 69.2 83.1 7.0 76.1 3.3 92.1 Comparative Example 4 13.9 72.1 86.1 0.56 83.9 2.92 93.1

Since the formamidine-based ultraviolet absorber used in the present invention is excellent in heat resistance and UV blocking effect, the polyurethaneurea elastic fiber of the present invention is particularly excellent in weather resistance such as light resistance while maintaining the intrinsic properties such as elasticity. In addition, the production method of the present invention can produce a polyurethane urea elastic fiber under a long-term stable process.

Claims (7)

A method for producing a polyurethaneurea elastic fiber, characterized in that the formamidine-based ultraviolet absorber of the general formula (I) is added to a spinning dope.

Wherein R ₁ and R ₂ are alkyl having 1 to 5 carbon atoms. The formamidine UV absorber according to claim 1, wherein the formamidine-based ultraviolet absorber is N- (4-ethoxycarbonylphenyl) -N-methyl-N-phenylformamidine, N- (4-methoxycarbonylphenyl) -N-methyl- N-phenylformamidine or N- (4-ethoxycarbonylphenyl) -N-ethyl-N-phenylformamidine. The method for producing a polyurethaneurea elastic fiber. The method for producing a polyurethaneurea elastic fiber according to claim 1, wherein the formamidine-based ultraviolet absorber is added in an amount of 0.1 to 3.0% by weight based on the polyurethaneurea polymer (solid content). The method for producing a polyurethaneurea elastic fiber according to claim 1, wherein the formamidine-based ultraviolet absorber is added in an amount of 0.5 to 2.0% by weight based on the polyurethaneurea polymer (solid content). Polyurethane urea elastic fiber, characterized in that the strength retention is 90% or more after 24 hours left in the fade-o-meta equipped with sunshine carbon arc. Strong retention rate (%) =

× 100 A polyurethane urea elastic fiber, wherein the fiber contains a formamidine-based ultraviolet absorber of the general formula (I) below.

Wherein R ₁ and R ₂ are alkyl having 1 to 5 carbon atoms. The polyurethaneurea elastic fiber according to claim 6, wherein the ultraviolet absorbent content is 0.5 to 2.0% by weight based on the total weight of the fiber.