KR101262775B1 - A polyurethaneurea fibers with stabilization of inorganic materials - Google Patents

Abstract

In the present invention, the reaction molar ratio of glycol: diisocyanate is 1: 1.5 to 1.8 to react with stirring at 40 to 50 ° C. using a homogeneous mixer to prepare a primary polymer, and 90 to 99.9 mole% of ethylene diamine, 0.1 To 10 mole% of a mixture of 1,2-diaminopropane is used as a chain extender, characterized in that it is polymerized to 35% by weight or more of the primary polymer and the solid content. It relates to the production of polyurethane urea elastic yarn excellent in inorganic stabilization through dry spinning by mixing the polymer and the additive containing a low molecular weight polyurethane.

Polyurethane urea elastic yarn having excellent inorganic stabilization prepared according to the present invention has an excellent effect on stabilization of inorganic materials, especially titanium dioxide to increase additive dispersibility and viscosity stability in high concentration polymer, reducing the occurrence of wave yarn, polyester fiber and It is very suitable as a relative elastic yarn of teaching and circular knitting.

    Additive, Polyurethane Urea Elastic Yarn, Polyurethane, Polymer, Primary Polymerization, Secondary Polymerization

Description

 A polyurethaneurea fibers with stabilization of inorganic materials

The present invention provides a method for producing a polyurethane urea elastic yarn that can significantly reduce the breakage of wave yarns and elastic yarns by increasing the dispersion stability of inorganic materials, especially titanium dioxide and high viscosity polymers while maintaining the inherent physical properties of elastic fibers It is about.

 More specifically, the reaction molar ratio of diisocyanate to glycol is 1: 1.5 to 1.8 to react with stirring to prepare an isocyanate end-block polymer, 90 to 99.9 mol% of ethylene diamine, 0.1 to 10 mol% of 1,2 A mixture of diaminopropane is used as the chain extender, which is polymerized with the primary polymer to prepare a polyurethaneurea polymer. Subsequently, the present invention relates to a polyurethane urea elastic yarn prepared by preparing an inorganic dispersion of an organic solvent containing a low molecular weight polyurethane having a molecular weight of about 4,000 to 10,000, and then mixing the inorganic dispersion with the polyurethane urea polymer. The addition amount is characterized in that 5 to 30% by weight based on the polyurethane urea polymer.

Spandex fibers are well known in the art as highly stretchable polyurethane based fibers having at least 85% by weight of urethane bonds.

Polyurethane urea elastic yarn is a polyurethane urea elastic fiber in which the molecular chain having a urethane bond occupies more than 85% of the chemical structure constituting the fiber, and is used for the manufacture of sports clothes such as stockings, swimwear, and women's foundation. Demand is increasing.

Generally known elastic fiber manufacturing method is as follows.

React polyether glycol with diisocyanates such as methylene-bis (4-phenylisocyanate), 2,4-toluene diisocyanate, hexamethylene diisocyanate and the like, dilute the isocyanate endblocking product with a solvent and then chain extend with diamine It is made by spinning.

Important in this manufacturing process is excellent quality and economical efficiency, in terms of quality, uniform mixing of the inorganic compound and the inorganic material is important, and in terms of economics to increase the concentration of the final polymer. Uneven mixing of the polymer and the inorganic material adversely affects the post-processability and the quality of the processed paper due to the splitting of the trimmer and the filament due to the aggregation of the inorganic material. have.

Therefore, it is essential to consider the quality and productivity in developing the manufacturing method of the elastic fiber, various studies have been made on the manufacturing method of the elastic fiber excellent in inorganic dispersibility, high concentration polymer spinning.

In US Pat. No. 3,111,369, paint-milling is used to disperse titanium dioxide in a polyester resin having a molecular weight of 2100, followed by p, p'-di, which is twice the polyester resin in molar ratio. Phenylmethane diisocyanate is reacted with 10% titanium dioxide containing polyester at 120 ° C. to produce a prepolymer terminated with isocyanate groups. However, in such a case, since the polymerization reaction may be affected by the additive by adding the additive before the polymerization reaction, additives that have hydroxyl groups and are reactive with the terminal isocyanate groups cannot be added. In addition, since the viscosity of the polyol in which the additive is mixed is not good dispersion, there is a disadvantage that an expensive milling machine (milling m / c) must be used.

In Korean Patent Laid-Open Publication No. 2002-0081605 (Preparation Method of Polyurethane-Based Elastic Fiber), which contains triamine in an additive to prevent inorganic aggregation, the chain extender is 60 to 75 mol% of ethylenediamine and 24.9 to 1,2-diaminopropane. A method for producing a polyurethane-based elastic fiber is described, which is a N, N'-dimethylacetamide solution composed of 39 mol% and 0.1-1 mol% of diethylenetriamine.

In the above production method, the content of the triamine-based compound contained in the additive is added to 0.1 to 0.3% by weight based on the polymer solids to improve the viscosity stability of the polymer and to significantly reduce the generation of the weave yarn. Due to the reduced physical properties, there is a disadvantage that it is not suitable as a relative elastic yarn when knitting circular knitted fabrics.

U.S. Pat.No.56,440,45 uses a mixture of 74 to 80 moles of ethylenediamine, 19 to 25 moles of 1,2-propylenediamine and 0.2 to 0.8 moles of diethylenetriamine as a chain extender to achieve 32-35% solids concentration. A method for preparing a phosphorus polymer is described.

Since the manufacturing method uses triamine together as a chain extender, the thermosetability is somewhat improved, and the physical properties can be prevented from being lowered after the thermoset. However, the triamine content is low so that a high concentration of polymer cannot be prepared. have. In addition, the production method has a problem in that the reaction process for preparing the prepolymer proceeds at a temperature of about 95 ° C., so that a large amount of side reactants are generated and contained, thereby decreasing radioactivity.

The present invention is to solve the problems of the prior art, while maintaining the viscosity stability of the high concentration polyurethane urea polymer of 35% by weight or more, while uniformly mixing the inorganic and final polymers such as titanium dioxide, hydrotalcite, wave company And it is to provide a polyurethane urea elastic yarn excellent in inorganic stabilization that can significantly reduce the occurrence of trimming of elastic yarn.

The present invention is to prepare a first polymer by reacting a glycol: diisocyanate with a reaction molar ratio of 1: 1.5 to 1.8 with stirring at 40 to 50 ° C. using a homogeneous mixer, 90 to 99.9 mole% of ethylene diamine, It is characterized in that a mixture of 0.1 to 10 mole% of 1,2-diaminopropane is used as the chain extender to polymerize it to 35 to 40% by weight of the primary polymer and the solid content. It relates to the production of polyurethaneurea elastic yarn through dry spinning by mixing the polymer and an additive (inorganic dispersion) containing a low molecular weight polyurethane of about 4,000 to 10,000 molecular weight.

Organic diisocyanates used in the present invention include methylene-bis (4-phenylisocyanate), 2,4-toluene diisocyanate, hexamethylene diisocyanate, and the like, and methylene-bis (4-phenylisocyanate) is particularly preferably used. Can be. In addition, polytetramethylene glycol, polypropylene glycol, polycarbonate diol, and the like may be used as the polymer diol, and polytetramethylene glycol is particularly preferable.

The low molecular weight polyurethane used in the present invention is a reaction molar ratio of glycol: diisocyanate 1: 1.5 to 2.0 and reacted with stirring using a reaction vessel at 70 to 100 ℃ to prepare a primary polymer, 100 mol% Propanol, butanol, hexanol and the like as a chain terminator, characterized in that the polymerization of low molecular weight polyurethane with a molecular weight of 4,000 to 10,000 of the primary polymer and the solid content of 30 to 50% by weight.

The low molecular weight polyurethane is introduced into an organic solvent in which inorganic substances such as titanium dioxide are dispersed, and then the inorganic dispersion is added to the polyurethane urea polymer, wherein the content of the low molecular weight polyurethane is higher than that of the polyurethane urea polymer. Add to 5-30% by weight. Low molecular weight polyurethane deagglomerates the minerals through three-dimensional stabilization of the minerals and gives the same charge to the inorganics, causing electro-repulsion between the inorganics to prevent precipitation due to reaggregation of the inorganics, and improving the viscosity stability of the high concentration polymer. And a high concentration of the polymer serves to uniformly mix. At this time, the uniform mixing of the additive and the final polymer is important, and if the mixing of the additive and the final polymer is uneven, wave yarn is generated in the elastic fiber spun by the additive component that is not uniformly dispersed and mixed, which causes trimming during spinning. . In addition, the bonding force between each filament is lowered, causing problems such as cracking of the filament during post-processing, which adversely affects the workability and the quality of the processed paper.

Although the said inorganic substance is not specifically limited, Representative examples thereof include titanium dioxide, hydrotalcite, magnesium stearate and the like.

When the amount of the low molecular weight polyurethane added in the present invention is less than 5% by weight based on the polyurethane urea polymer solid content, the dispersibility effect intended by the present invention cannot be obtained, whereas the amount of the low molecular weight polyurethane is more than 30% by weight compared to the polyurethane urea polymer. In this case, excessive viscosity decrease of the polymer is caused, which is not preferable. In addition, if the molecular weight of the low molecular weight polyurethane is less than 4,000, the dispersibility effect intended by the present invention cannot be obtained, whereas if the molecular weight is more than 10,000, it leads to excessive viscosity decrease of the polymer, which is not preferable. Therefore, the addition amount and molecular weight of the low molecular weight polyurethane added to the inorganic dispersion liquid of an organic solvent in this invention are essential to be in the said range.

Examples of the organic solvent that can be used include N, N'-dimethylformamide, N, N'-dimethylacetamide, tetramethylurea and hexamethylphosphonoamide, and dimethylacetamide can be preferably used.

Spandex yarn is easily degraded by heat or light (ultraviolet rays) compared to fibers such as nylon or polyester yarn, and is easily discolored by nitrogen dioxide in the air. Therefore, various additives may be added to the inorganic dispersion of the organic solvent of the present invention to prevent this. Examples of such additives include antioxidants, dye enhancers, ultraviolet absorbers, light emitting agents, antibacterial agents and the like.

When preparing the semi-dull spandex yarn using the inorganic dispersion liquid of the organic solvent of the present invention, for example, a polymer dispersion and an inorganic dispersion liquid such as titanium dioxide and hydrotalcite on dimethylacetamide containing additives are spun through a spinning nozzle. Discharge into. At this time, when the heated hot gas is introduced through the upper part of the spinning tube to evaporate and diffuse the solvent in the discharged polymer solution, the filament is solidified and fined. The filament is then combusted by a combustor, passed through a gode controller and an emulsion feeder and then wound up in a winder.

High concentration spinning dope prepared by the present invention has a low gel content, and the additives are uniformly mixed / dispersed, which results in excellent spinning properties during spinning and also significantly reduces the occurrence of wave yarns. In addition, the polyurethane urea elastic yarn excellent in stabilizing the inorganic material of the present invention prepared by the spinning dope has the advantage of improving the uniformity, spinning workability and productivity of the yarn is excellent in viscosity stability even at high concentrations.

 <Evaluation method of physical property>

1. Polymer viscosity stability: The viscosity of the polymer was measured at 40 ° C with a DV-III (Model No.) viscometer from Brookfield, and the viscosity measured immediately after polymerization was referred to as initial viscosity, and 45 rpm at 40 ° C. After stirring at low speed for 4 hours and standing for 48 hours, the viscosity measured immediately before spinning is called final viscosity.

2. The polymer gel content was evaluated using SBSS-C-16 (Model No.) manufactured by PAMAS.

3. Determination of wave yarn: A 10 cm long sample is stretched to 500% at a constant rate of 500% / 30 sec, left for 1 minute in the stretched state and then relaxed again. After the relaxation, the state of the thread is observed, and if there are two or more curved or tortuous nodes within a length of 10 cm, the yarn is judged as wave yarn. The incidence of wave yarn is a percentage of the number generated by examining 5,000 yarns.

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

5. Bonding force: In a polyurethaneurea-based elastic yarn composed of several filaments, one strand of monofilament is separated by about 5 cm, and each end of the monofilaments attached to each other without being separated Mount at a constant speed of 1,000% / min after mounting on an instron machine (instron m / c) equipped with a load cell of 1kg or less so that the contact point where the filament and the monofilaments that are not separated are located in the center of the 5cm cage The force is measured when the separated monofilament and the remaining monofilaments are separated by elongation. The resulting value is the average of the measured values obtained by measuring the average value of the bonding forces during elongation and three measurements per sample.

6. Evaluation of the degree of damage to circular knitted fabrics: Circular knitted fabrics of elastic yarns and polyester yarns which have been dyed are cut into 100 cm long fabrics and 100 cm wide fabrics, and 10 hours at 80 ° C. in a 10% by weight aqueous sodium hydroxide solution. The yarn is then immersed to remove the polyester yarn, and then the number of trimming yarns of the elastic yarn is obtained from the remaining elastic fabric.

Examples and comparative examples of the present invention will be described in detail below, but the present invention is not limited only to the following examples.

 &Lt; Example 1 >

540 kg of polytetramethylene glycol having an average molecular weight of 1,800 and 123.9 kg of 4,4'-diphenylmethane diisocyanate were mixed in a homogeneous mixer at 45 DEG C with a terminal molar ratio of 1.65 and then reacted in a pipe reactor at 95 DEG C for 90 minutes. Let's do it. The compound is cooled to 40 ° C., left for 12 hours and then dissolved completely with N, N′-dimethylacetamide to approximately 44% solids. The mixed solution was cooled to 5 ° C. for the chain extension reaction, and 11.4 kg of the chain extender ethylenediamine, 2.0 kg of the chain stopper diethyl amine, and N, N′-dimethylacetamide solution were mixed under high speed stirring (200 rpm). 190.8 kg was added. The synthesized polyurethane urea solution contained about 37% of solids and had an initial viscosity of 3,650 poise at 40 ° C. After stirring at 45 rpm for 48 hours, the final viscosity measured immediately before spinning was 4,500 poise.

Separately, 1,800 g of polytetramethylene glycol having a molecular weight of 1800 and 375 g of 4,4'-diphenylmethane diisocyanate were placed in a reaction vessel with a terminal molar ratio of 1.5 and reacted at 80 ° C for 2 hours, followed by N, N'- 519 g of N, N'-dimethylacetamide solution dissolved in 3,283 g of dimethylacetamide and containing 36 g of butanol was added to the solution in which the reactant was dissolved, so that the solid content of the polymer was 37% by weight of a molecular weight 6300 low molecular weight polyurethane solution. Was prepared.

4.5 wt% titanium oxide based on the solid content of the polyurethaneurea polymer and 3.5 wt% antioxidant "CYANOX 1,790" (product of Cynamid, USA) for improving the discoloration resistance and the dyeability of the low molecular weight polyurethane solution. , An inorganic dispersion was prepared by adding 5.5% by weight of hydrotalcite as a chlorine resistance enhancer and 0.01% by weight of a blue pigment (ultramarine blue). The low molecular weight polyurethane was 5% by weight relative to the polyurethaneurea polymer solids.

The polymer solution prepared as described above was allowed to stand for 40 hours, and dry spinning at a speed of 900 m / min at a spinning temperature of 250 ° C. to prepare a polyurethane urea elastic fiber of 4f / 40d. In the manufacturing process of the polyurethane urea elastic yarn, the viscosity stability of the final polymer, the dispersion of additives, the frequency of wave yarn occurrence, tensile strength, elongation and bonding strength of the prepared elastic yarn were evaluated, and the polyester yarn of 96f / 150d Knitting, refining and dyeing together into circular knits. The results of evaluation of the physical properties of the polymer, yarn and circular knitted fabric are shown in Table 1 below.

&Lt; Example 2 >

The content was carried out under the same conditions as in Example 1 except that the content of the low molecular weight polyurethane was 15% by weight relative to the solid content of the polyurethaneurea polymer.

<Example 3>

Except for changing the content of the low molecular weight polyurethane applied to the inorganic dispersion to 25% by weight was carried out under the same conditions as in Example 1.

<Comparative Example 1>

1800 g of polytetramethylene glycol having a molecular weight of 1800 and 626 g of 4,4'-diphenylmethane diisocyanate were placed in a reaction vessel with a terminal molar ratio of 2.5, and reacted at 80 DEG C for 2 hours, followed by 2868 g of N, N'-dimethylacetamide. 1557 g of N, N'-dimethylacetamide solution containing 109 g of butanol was added to the solution in which the reactant was dissolved, and then a solid content of the polymer produced a 37 weight% molecular weight 3500 low molecular weight polyurethane solution. It carried out on the same conditions as Example 1.

 <Comparative Example 2>

The same process as in Example 1 was conducted except that low molecular weight polyurethane was not added to the inorganic dispersion.

 <Comparative Example 3>

Solid content of the polyurethaneurea polymer was 34%, and it carried out on the conditions similar to Example 1 except not having added low molecular weight polyurethane to an inorganic dispersion liquid.

[Table 1]

evaluation Polymer Yarn Circular knitting Initial viscosity
(poise) Final viscosity
(poise) Gel content
(ppm) Wave
Incidence (%) The tensile strength
(g / d) Shindo
(%) Cohesion
(mgf) Number of cuts
(dog) Example 1 4650 4980 100 0.1% 1.34 540 183 2 Example 2 4540 4820 60 0.14% 1.39 570 175 One Example 3 4440 4640 70 0.08% 1.33 580 170 One Comparative Example 1 4560 7080 3000 0.42% 1.33 530 156 5 Comparative Example 2 4640 10000 2500 Elastic yarn cannot be manufactured - Comparative Example 3 3520 4360 1100 0.5% 1.47 540 141 4

 The high concentration of polyurethaneurea polymer prepared according to the present invention has good additive dispersibility and viscosity stability, and also has a low gel content, which greatly reduces the occurrence rate of wave yarn, and is very suitable as a relative elastic yarn of cross-woven fabric and circular knitting with polyester fiber. Do.

Claims (3)

Isocyanate primary polymers were prepared using a reaction molar ratio of diisocyanate to glycol 1: 1.5 to 1.8, and a mixture of 90 to 99.9 mole% ethylene diamine and 0.1 to 10 mole% 1,2-diaminopropane was chained. Inorganic material, characterized in that the polyurethane polymer prepared by polymerizing with a primary polymer using an extender, and then mixed with the polymer and the inorganic dispersion containing a low molecular weight polyurethane having a molecular weight of 4,000 to 10,000 after spinning Polyurethane urea elastic yarn with excellent stabilization. The method of claim 1, Polyurethane urea elastic yarn excellent in inorganic stabilization, characterized in that the low molecular weight polyurethane is contained 5% to 30% by weight of the polyurethane urea polymer. The method of claim 1, The low molecular weight polyurethane mixed in the additive is a reaction molar ratio of diisocyanate to glycol 1: 1.5 to 2.0 and reacted with stirring using a reaction vessel at 70 to 100 ℃ to prepare an isocyanate end-block polymer, 100 mol% Polyurethane urea elastic yarn excellent in inorganic stabilization, characterized in that a low molecular weight polyurethane having a molecular weight of 4,000 to 10,000 by polymerizing it with a primary polymer using a chain terminator selected from propanol, butanol, nucleic acid.