KR20110079377A - Producing method of polyurethanure elastic fiber having improved dying property - Google Patents

Abstract

PURPOSE: A method for manufacturing polyurethane urea elastic fiber is provided to improve dyeing property of the elastic fiber. CONSTITUTION: A polyurethane urea elastic fiber with improved dyeing property is fabricated using dyeing deposition agent by mixing 0.3-1.0 weight% of acrylic dyeing deposition agent and 0.5-2.0 weight% of urethane dyeing deposition agent. The elastic fiber is prepared by dissolving a solid powder in dimethyl acetamide. The solid power is selected from the group consisting of poly(acrylamide), poly(2-diethylamino)ethylmethacrylate, poly(N,N-diethylacrylamide), poly(N,N-dimethylacrylamide), and poly(N-vinylacetamide).

Description

Producing method of polyurethanure Elastic Fiber having improved dying property

The present invention relates to a method for producing a polyurethaneurea elastic yarn with improved dyeability, and more particularly, to a method for producing a polyurethaneurea elastic yarn with improved dyeability, characterized in that a mixture of an acrylic dye enhancer and a urethane dye enhancer.

Polyurethane generally reacts with a polyol, a high molecular weight diol compound, and an excess of diisocyanate compound to obtain a prepolymer having an isocyanate group at both ends of the polyol, and dissolving the prepolymer in a suitable solvent. Thereafter, the solution is prepared by a secondary polymerization reaction in which a diamine-based or diol-based chain extender is added and reacted.

In general, polyurethane fibers may be used in combination with various other fibers such as acrylic, wool, cotton, silk, etc., depending on the application, and particularly, elastic fibers having a long chain segment content of 85% by weight or more are called spandex.

Polyurethane fibers are being actively used for various purposes because of their inherent characteristics with high elasticity, and as the use thereof is expanded, new additional properties are continuously required for existing polyurethane fibers. Until now, a number of polyurethane fibers, which have been further strengthened in heat resistance and elastic recovery, have been developed, and in recent years, the demand for polyurethane fibers having high heat setability has gradually increased.

As a general technique for improving the dyeability of polyurethane used in the manufacture of artificial leather, spandex and the like, 1) a method of introducing a tertiary nitrogen atom into a polyurethane polymer chain (Japanese Patent Publication 62-23097), 2) A method of introducing a salt of an organic acid or an inorganic acid and a tertiary amine into a polyurethane polymer chain (Japanese Patent Publication 75-17520), 3) introducing a tertiary or quaternary nitrogen atom to the terminal of the polyurethane polymer chain. Methods (Japanese Patent Publication No. 69-16386), 4) a method of using a low molecular diamine as a chain extender (Japanese Patent Publication No. 59-108021), and the like.

However, methods 1) and 2) tend to become gels during the reaction, and method 3) has a problem that it is difficult to control the amount of nitrogen atoms introduced. In addition, method 4) using a low molecular weight diamine as a chain extender may improve dyeing property, but has a problem of lowering softness and elasticity.

In addition, in the prior art (Application No. 93-9904, name of the invention: Polyurethane resin composition with improved dyeability), organic diisocyanate, high molecular diol, low molecular diol containing no nitrogen, high molecular triol, organic solvent Although the above problems have been partially compensated for by the addition of low molecular weight diols containing nitrogen atoms to the polyurethane, the low molecular weight diols containing nitrogen atoms are added together to synthesize the polyurethane to improve dyeability. Although the problem has been somewhat compensated for, it is difficult to sufficiently improve the dyeability of polyurethane because it causes a decrease in physical properties when a certain amount of a low molecular diol containing nitrogen atoms is added to improve dyeability.

On the other hand, in order to improve the dyeability of polyurethane urea elastic yarn conventionally, an acrylic dye enhancer or a urethane dye enhancer was used. However, when increasing the content of the dyeing enhancer to increase the dyeability of polyurethane urea elastic yarn, there were problems such as the change of physical properties of the elastic yarn and the occurrence of scum when knitting the fabric.

The present invention has been invented to solve the above problems, the present invention is to provide a method for producing a polyurethane urea elastic yarn with improved dyeability, characterized in that the mixture using an acrylic dye enhancer and a urethane dye enhancer. .

Polyurethane urea elastic yarn manufacturing method improved dyeing properties according to the present invention is characterized by using a mixture of the dye-promoting agent 0.3 ~ 1.0% by weight acrylic dyeing accelerator and 0.5 ~ 2.0% by weight of the urethane dyeing accelerator.

In the present invention, by using an acrylic dye-enhancing agent and a urethane dye-enhancing agent mixed dyeing enhancer can be expected to improve the dyeability of polyurethane urea elastic yarn in the dyeing method of the dyeing method and the padding method when dyeing with acid dyes. .

Hereinafter, the present invention will be described.

The present invention is characterized by using an acrylic dye enhancer and a urethane dye enhancer to improve the dyeability of the elastic yarn. Conventionally, there are problems such as changes in the properties of elastic yarn when the content of the dye enhancer is increased by using the acrylic dye enhancer and the urethane dye enhancer separately. In the present invention, acrylic dye enhancers and urethane dye enhancers are used. Use by mixing.

It is used by mixing the ratio of 0.3 ~ 1.0 wt% of acrylic dye enhancer and 0.5 ~ 2.0 wt% of urethane dye enhancer. If the acrylic dye enhancer is less than 0.5% by weight can not be expected to improve the dyeability, if the content exceeds 1.0% by weight there is a problem that can be released to the surface of the yarn during the lowering of the physical properties of the yarn and knitting fabric.

Acrylic dye enhancers include poly (acrylamide), poly (2-diethylamino) ethyl methacrylate, poly (N, N-diethylacrylamide) [ Poly (N, N-diethylacrylamide)], poly (N-isopropylacrylamide), poly (Nn-propylacrylamide), poly (N, N- Dimethacrylamide) [Poly (N, N-dimethylacrylamide)], (N-poly (N-sec-butylacrylamide)) [(N-Poly (N-sec-butylacrylamide))], poly (4-acryl Amide salicylate [(Poly (4-acrylamidesalicylicacid))], poly (N-vinylformamide) [Poly (N-vinylformamide)], poly (N-vinylacetamide) [Poly (N-vinylacetamide)] Use an acrylic dye enhancer that is used by dissolving at least one of the dimethyl acetamide in a solid content of 35% to 50%.

Urethane-based dye enhancers include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,5-naphthalene diisocyanate (NDI), One kind of diisocinate compound, N-methyl ethanolamine, N-propyl ethanolamine, N- in paraphenylene diisocyanate (PPDI) N-substituted one of N-methyl diethanolamine, N, N-dimethyl ethanolamine and N, N-diethyl ethanolamine Ethanolamine, Monoethylamine, Diethylamine, Triethyl triamine, Diethylene amine, Triethylene diamine, Monoethanol amine , Diethanol amine, triethanol amine Termination of one of amine), N-butylamine, dimethyl hydrazine, dimethyl hydrazine, N-methyl hydrazine and Nt-butyldiethanol amine Uritan-based dye enhancer is used to dissolve the synthesized material in a solvent (DMAc) so that the solid content is 35% to 50%.

Polyurethane urea elastic yarn polymerizes an ether glycol and an isocyanate compound to form a primary polymer, and mixes ethylene diamine and diaminopropane to form a chain extender, and the primary polymer, a chain extender and dimethylacetamide And a second polymerization to form a polyurethane urea liquid polymer, and is formed by dry spinning the polyurethane urea liquid polymer, in the present invention, rather than dry spinning the polyurethane urea liquid polymer as it is, the polyurethane urea liquid The liquid polymer composition formed by mixing a predetermined amount of an acrylic dye enhancer and a urethane dye enhancer in the polymer is dry-spun to form a dichroic polyurethaneurea elastic yarn according to the present invention.

 Example 1

Capping ratio (CR) 1.70 and polyol were prepared using polytetramethylene ether glycol (PTMG, molecular weight 1800) and prepared using 4,4'-diphenylmethane diisocyanate. Ethylenediamine and 1,2-diamino propane were used as the chain extender at a ratio of 80 mol% and 20 mol%, and diethylamine was used as the chain terminator. The ratio of the chain extender to the chain terminator was 10: 1, and the amine used was prepared at a total concentration of 7 mol%, and dimethylacetamide was used as the solvent. Ethylene bis (oxyethylene) bis- (3- (5- t -butyl-4-hydroxy- m -toyl) -propionate) 1.5% by weight, 5,7-di- t as an additive relative to the solid content of the polymer -Butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one 0.5% by weight, 1,1,1'1'-tetramethyl-4,4 '-(methylene-di- p- 1 weight% of phenylene) dimicarbazide, 1 weight% of poly (N, N-diethyl-2-aminoethyl methacrylate), and 0.1 weight% of titanium dioxide were added and mixed, and the polyurethaneurea spinning stock solution was obtained.

That is, 455.2 g of 4,4'-diphenylmethane diisocyanate and 1926 g of polytetramethylene ether glycol (molecular weight 1800) are reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream to form a polyurethaneurea having an isocyanate at the sock end. Prepared. After cooling the prepolymer to room temperature, 4485.3 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. 36.0 g (0.6 mole) of ethylenediamine, 11.1 g (0.15 mole) of 1,2-dioanopropane, and 4.4 g of diethylamine were dissolved in 684 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower. To obtain a polyurethaneurea solution. 0.5% of acrylic dye enhancer and 1.0% urethane-based dye enhancer were added to the solution and mixed at 45 ° C. for 60 minutes.

The spinning stock solution obtained as described above was spun at a speed of 900 m / min by dry spinning (spinning temperature: 260 ^° C.) to prepare a polyurethaneurea elastic yarn of 40 denia 3 filaments.

After preparing the fabric (elastic yarn content: 30% by weight) using the polyurethane urea elastic yarn and polyamide yarn, and dyed with acid dye (CI Acid Blue 40), daylight of the fabric using a polyamide woven cloth as a contaminated cloth And washing fastnesses were measured (step S70). The physical properties thereof are shown in Table 1 below.

[Example 2]

It is the same as Example 1 except adding 1.0% of an acrylic dye enhancer and 2.0% of a uritan dyeing enhancer.

[Comparative Example 1]

It is the same as Example 1 except not adding a dyeing promoter.

[Comparative Example 2]

It is the same as Example 1 except adding 0.5% of the acrylic dye enhancer.

[Comparative Example 3]

 It is the same as Example 1 except adding 1.0% of a urethane dyeing promoter.

<Evaluation Method>

1. Tensile strength and elongation of yarn were evaluated according to KSK 0219.

2. Elastic recovery rate: After repeating 300% elongation in instron five times, the ratio of the length of the sample to the initial length in the tensionless state is expressed as a percentage.

3. Wash fastness: measured by KSK 0430 AI method.

4. Daylight fastness: measured by AATCC 16E-1982 method.

5. L value (achromaticity), a * value and b * value in chromaticity coordinates: After reflectance of the yarn was measured using a spectrophotometer, it was calculated using the formula of CIE 76 CIE Lab color difference equation.

division Dyeing and Fastness Yarn Properties L level Daylight Fastness (Grade) Wash fastness (class) Elastic recovery rate (%) Tensile strength (g / d) Shinto (%) modulus Example 1 75.31 Class 3.5 Class 3.5 96.1 1.19 540 7.0 Example 2 84.30 Class 3.5 Level 3 95.0 1.14 570 6.7 Comparative Example 1 39.86 Level 3 Level 3 94.1 1.27 540 7.1 Comparative Example 2 49.43 Class 3.5 Class 3.5 94.2 1.17 520 6.9 Comparative Example 3 56.44 Class 3.5 Class 3.5 93.9 1.21 540 7.2

In Table 1, it was shown that the polyurethane urea elastic yarn prepared according to the examples greatly improves the dyeability while maintaining the inherent properties of the elastic yarn.

Claims (4)

A method for producing a polyurethane urea elastic yarn with improved dyeability, characterized by using a dyeing enhancer mixed in an amount of 0.3 to 1.0 wt% of an acrylic dye enhancer and 0.5 to 2.0 wt% of a urethane dye enhancer. The method of claim 1, wherein the acrylic dye enhancer is poly (acrylamide), poly (2-diethylamino) ethyl methacrylate [poly (2-diethylamino) ethylmethacrylate], poly (N, N Poly (N, N-diethylacrylamide), Poly (N-isopropylacrylamide), Poly (Nn-propylacrylamide) Poly (Nn-propylacrylamide) , Poly (N, N-dimethylacrylamide) [Poly (N, N-dimethylacrylamide)], (N-poly (N-sec-butylacrylamide)) ((N-Poly (N-sec-butylacrylamide)) ], Poly (4-acrylamidesalicylic acid) (Poly (4-acrylamidesalicylicacid)), poly (N-vinylformamide) [Poly (N-vinylformamide)], poly (N-vinylacetamide) [Poly (N -vinylacetamide)] at least one selected from the group consisting of dissolved in dimethylacetamide so that the solid content is 35% to 50% by weight of the dyeability is improved Method for producing polyurethane urea elastic yarn. The method of claim 1, wherein the urethane-based dye enhancer is hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,5-naphthalene diisosinate (1,5-naphthalene diisocyanate) N-methyl ethanolamine, N-propyl ethanolamine (N-diethanolamine) and one of diisocyanate-based compounds of Naphthalene diisocyanate (NDI) and paraphenylene diisocyanate (PPDI) -propyl ethanolamine), N-methyl diethanolamine, N, N-dimethyl ethanolamine, N, N-diethyl ethanolamine N-substituted ethanolamine, monoethylamine, diethylamine, triethyl triamine, diethylene amine, triethylene diamine, Monoethanol amine, diethanol amine, One of ethanol amine, N-butylamine, dimethyl hydrazine, dimethyl hydrazine, N-methyl hydrazine, and Nt-butyldiethanol amine Method for producing a polyurethane urea elastic yarn with improved dyeing properties, characterized in that the material synthesized using the reaction terminator of the dissolved in a solvent (DMAc) so that the solid content is 35% to 50% by weight. Polymerization of ether glycol and isocyanate compound to form a primary polymer, mixing the primary polymer, chain extender and dimethylacetamide and secondary polymerization to form a polyurethaneurea liquid polymer, the polyurethaneurea The liquid polymer may include 0.3 to 1.0% by weight of an acrylic dye enhancer and 0.5 to 2.0% by weight of a urethane dye enhancer, and a dye polymer with improved dyeability, characterized in that the liquid polymer mixed with the acrylic dye and the urethane dye enhancer is dry-spun. Method for producing urethane urea elastic yarn.