WO2020045769A1 - Polyurethaneurea elastic fiber having improved dyeability and manufacturing method therefor - Google Patents

Abstract

The present invention relates to a polyurethaneurea elastic fiber comprising a polyethylene glycol with a molecular weight of 500 to 4000 and improved in dyeability to acidic dye and reactive dye and to a manufacturing method therefor.

Description

Polyurethane urea elastic yarn with improved dyeability and manufacturing method thereof

The present invention relates to a polyurethaneurea elastic yarn with improved dyeability, and more particularly, when the polyurethaneurea elastic yarn is knitted with a counterpart yarn such as nylon and cotton, a reaction site that can be combined with a dye in the spandex due to the hydrophobic property of the spandex. Even if there is a dye is difficult to approach the polyurethane urea elastic yarn solved the problem of not showing a satisfactory dyeability.

Polyurethane fibers having elastic properties are widely used in the textile industry. 'Spandex' fiber is used as a general term for such an elastic fiber, and usually refers to a synthetic fiber having a polyurethane bond of 85% or more of the structure forming the fiber.

Such polyurethane fibers generally react with a polyol which is 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 the prepolymer in an appropriate solvent. After dissolution, the solution is prepared by a secondary polymerization reaction in which a diamine-based or diol-based chain extender is added and reacted.

Polyurethane fibers may be used in combination with various other fibers such as acrylic, wool, cotton, silk, etc., depending on the application, and have been commonly used for the purpose of requiring elasticity such as underwear, swimwear, and stockings.

Due to the inherent characteristics of such elasticity, polyurethane fibers are actively used for various purposes, 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, there is an increasing demand for polyurethane fibers having high heat setability and polyurethane fibers having improved dyeability.

Polyurethane fibers generally have a problem of poor dyeing, and a general technique for improving dyeing of acid dyes is 1) a method of introducing a tertiary nitrogen atom into a polyurethane polymer chain (Japanese Patent Publication No. 62 -23097), 2) A method of introducing a salt of an organic or inorganic acid and a tertiary amine into a polyurethane polymer chain (Japanese Patent Publication No. 50-17520), 3) A tertiary or A method of introducing a quaternary nitrogen atom (Japanese Patent Publication No. 44-16386), and 4) a method of using a low molecular diamine as a chain extender (Japanese Patent Publication No. 59-108021).

However, Method 1) and Method 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, Korean Patent Publication Nos. 10-2009-0118997 and 10-2005-0070652 disclose dyeing properties by dyeing with a specific blue acid dye containing a polymer having a maleimide structure composed of maleimide units or by adding a talc compound. To improve, but there was a limit to sufficiently improve the dyeability of the polyurethane.

In the present invention, when the polyurethane urea elastic yarn yarn is knitted with a fabric together with the other nylon, cotton, etc., the dye is made through a chemical bond between the dye and the fiber, polyurethane polyurethane due to the hydrophobic characteristics Even if the urea elastic yarn has a reaction site that can be combined with the dye, it is a problem to provide a polyurethane urea elastic yarn with improved dyeability that can solve the problem that the dye is difficult to access due to the problem of not showing satisfactory dyeability.

As a means for solving the above problem,

Polyurethane urea elastic yarn with improved dyeability of the present invention (a) a polyol comprising a first polyol and a second polyol; (b) at least one diisocyanate; (c) at least one diamine chain extender; And (d) a product obtained by reacting at least one amine chain terminator, wherein the second polyol is polyethylene glycol, the first polyol and the second polyol are different materials, and the weight of polyethylene glycol The average molecular weight is characterized in that 500 to 4000.

In addition, the polyethylene glycol is characterized by mixing 5.0 to 30.0 mol% relative to the total polyol.

In addition, the amine terminal number of the polyurethane urea elastic yarn is characterized in that 20.0 to 45.0 meq / kg.

The method for preparing a polyurethaneurea elastic yarn having improved dyeability of the present invention comprises the steps of: (a) preparing a polyurethane prepolymer by contacting a polyol comprising a first polyol and a second polyol with at least one diisocyanate; (b) adding a solvent to the prepolymer of step (a); (c) contacting the product of step (b) with at least one diamine chain extender and at least one amine chain terminator; (d) spinning the product of step (c) to produce a polyurethaneurea elastic yarn, wherein the second polyol is polyethylene glycol, the first polyol and the second polyol are different materials, and The weight average molecular weight is characterized in that 500 to 4000.

In addition, the second polyol is characterized in that the mixture of 5.0 to 30.0 mol% relative to the total polyol.

In addition, the amine terminal number of the polyurethane urea elastic yarn is characterized in that 20.0 to 45.0 meq / kg.

The present invention can improve the dyeability of the acidic and reactive dyes of polyurethaneurea elastic yarn by improving the hydrophilicity of the polyurethaneurea elastic yarn to improve the dyeing, deepening of the fabric containing spandex and grin-through ( Fabric stretch (stretch) when the spandex is not dyed dyeing phenomenon that can prevent the appearance).

Hereinafter, the polyurethaneurea elastic yarn with improved dyeability of the present invention and a manufacturing method thereof will be described in more detail.

The present invention (a) a polyol comprising a first polyol and a second polyol; (b) at least one diisocyanate; (c) at least one diamine chain extender; And (d) a product obtained by reacting at least one amine chain terminator, wherein the second polyol is polyethylene glycol, the first polyol and the second polyol are different materials, and the weight of polyethylene glycol The average molecular weight relates to polyurethaneurea elastic yarns with improved dyeability to acid dyes and reactive dyes of 500 to 4000.

In addition, the present invention comprises the steps of (a) contacting a polyol comprising a first polyol and a second polyol with at least one diisocyanate to prepare a polyurethane prepolymer; (b) adding a solvent to the prepolymer of step (a); (c) contacting the product of step (b) with at least one diamine chain extender and at least one amine chain terminator; (d) spinning the product of step (c) to produce a polyurethaneurea elastic yarn, wherein the second polyol is polyethylene glycol, the first polyol and the second polyol are different materials, and The weight average molecular weight relates to a method for producing a polyurethaneurea elastic yarn improved dyeing properties for acid dyes and reactive dyes, characterized in that 500 to 4000.

In the present invention, the polyol includes a first polyol and a second polyol. That is, the first polyol and the second polyol are mixed and used as a polyol, and the first polyol and the second polyol are different materials.

In the present invention, the first polyol may be polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, or the like.

In the present invention, the second polyol is polyethylene glycol. Polyethyleneglycol has excellent hydrophilicity, so that the mixed application at the stage of preparing the polyurethane prepolymer improves the hydrophilicity of the polyurethaneurea elastic yarn, thereby improving the accessibility of the acid dye and the reactive dye to the polyurethaneurea elastic yarn, It is possible to improve the dyeability of polyurethaneurea elastic yarns for dyes and reactive dyes.

In the present invention, the polyethylene glycol is preferably mixed 5.0 to 30.0 mol% relative to the total polyol. When polyethylene glycol is applied at less than 5.0 mol%, it is difficult to expect hydrophilicity improvement effect, and when it is applied at more than 30.0 mol%, it is difficult to apply the process due to poor spinning workability and lower yarn properties due to lower heat resistance. .

In the present invention, as the diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated P, P-methylene diisocyanate and the like can be used. The above can be used.

The polyol and diisocyanate are contacted to prepare a polyurethane prepolymer, to which a solvent is added. At this time, the solvent is preferably dimethylacetamide. Thereafter, the polyurethaneurea solution is prepared by contact with at least one chain extender and at least one chain terminator. Polyurethane urea elastic yarn is prepared through a fiber spinning process such as dry spinning or melt spinning of the prepared product polyurethaneurea solution.

In the present invention, the chain extender is at least one diamine. Examples of diamines that can be used include hydrazine, ethylene diamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine (1,2-diaminobutane), 1,3-butanediamine (1,3 -Diaminobutane), 1,4-butanediamine (1,4-diaminobutane), 1,3-diamino-2,2-dimethylbutane, 4,4'-methylenebis-cyclohexylamine, 1- Amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 1,6-hexanediamine, 2,2-dimethyl-1,3-diaminopropane, 2,4-diamino-1-methylcyclohexane , N-methylaminobis (3-propylamine), 2-methyl-1,5-pentanediamine, 1,5-diaminopentane, 1,4-cyclohexanediamine, 1,3-diamino-4-methyl Cyclohexane, 1,3-cyclohexane-diamine, 1,1-methylene-bis (4,4'-diaminohexane), 3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3-pentane Diamine (1,3-diaminopentane), m-xylylenediamine, and mixtures thereof, but is not limited thereto. Ethylenediamine is preferred as the chain extender.

In the present invention, the chain terminator is at least one amine. Examples of the amines that can be used include, but are not limited to, diethylamine, cyclohexylamine, n-hexylamine and mixtures thereof. Diethylamine is preferred as chain terminator.

It is preferable that the polyurethane urea elastic yarn of this invention is 20.0-45.0 meq / kg of amine terminal number of yarns. The amine end of the yarn serves as a dyeing seat bondable with the dye. When the number of amine ends of the yarn is less than 20.0 meq / kg, insufficient dyeing improvement effect cannot be expected due to the lack of the dyeing seat. In addition, when the number of amine end of the yarn is more than 45.0 meq / kg, the dyeability is sufficient, but excessive increase in the number of amine end may cause a big problem in the storage stability of the polymer.

In addition, in the present invention, in order to prevent discoloration of the polyurethane urea and deterioration of physical properties due to ultraviolet rays, atmospheric smog and heat treatment process associated with spandex processing, a steric hindrance phenol compound, a benzofuran-one compound, and a semicarbazide Type compound, a benzo triazole type compound, a polymeric tertiary amine stabilizer, etc. can be added combining them suitably. In addition to the above components, the spandex fiber of the present invention may be added with a pigment or dye showing a blue complementary color of yellow to alleviate yellowish yarn.

Furthermore, the polyurethaneurea elastic yarn of the present invention may include additives such as titanium dioxide, magnesium stearate, and the like in addition to the above components.

Polyurethane urea elastic yarn of the present invention can be fabricated by knitting with nylon, PET, cotton, etc. as a counterpart, in particular, except the PET using a disperse dye that is dyed by physical bonding, through a chemical bond between the dye and fiber When weaving fabrics using nylon, cotton, etc., which are dyed, as a counterpart, the hydrophilicity of polyurethaneurea elastic yarns facilitates dye access to improve dyeability for not only acid dyes but also reactive dyes, and the grin-through phenomenon. It is excellent in dyeing deep color effect of fabric.

The polyethylene glycol contained in the polyurethaneurea elastic yarn of the present invention preferably has a weight average molecular weight of 500 to 4000. If the weight average molecular weight is less than 500, it is difficult to expect the effect of improving the dyeability by improving the hydrophilicity of the polyurethane urea elastic yarn, and if it is more than 4000, it is difficult to apply the process due to the problems of deterioration in physical properties and insufficient spinning processability of the polyurethane urea elastic yarn.

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, and these examples are only to illustrate the present invention and should not be construed as limiting the scope of the present invention.

Example  One

15.0 mol% of polyethylene glycol (molecular weight 2000) was mixed with 31.1 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), followed by adding 8.9 kg of 4,4'-diphenylmethane diisocyanate to 90 DEG C, The reaction was stirred for 120 minutes to prepare a polyurethane prepolymer having an isocyanate at the sock end. After cooling the prepolymer to room temperature, 67.0 kg of dimethylacetamide was added as a solvent to obtain a polyurethane prepolymer solution.

Subsequently, 1.1 kg of ethylenediamine as a chain extender and 0.1 kg of diethylamine as a chain terminator were dissolved in 15.9 kg of dimethylacetamide, and added to the prepolymer solution at 10 ° C. or lower, thereby obtaining 60 meq / of amine terminal number of the polyurethaneurea solution solid. A polyurethane urea solution of kg was obtained.

Further, in the polyurethaneurea solution, 1.0% by weight of triethylene glycol-bis-3- (3-tertylbutyl-4-hydroxyphenyl) propionate as an antioxidant and 1 weight of melamine polyphosphate as an inorganic chlorine agent. 4% by weight of the hydrotalcite (Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · H ₂ O) coated with%, 0.5% by weight of titanium dioxide as a light-resistant agent was prepared to prepare a polyurethaneurea spinning stock solution.

The spinning stock solution obtained as described above was spun at a speed of 900 m / min by dry spinning to prepare a polyurethane urea elastic yarn having 40 denier 3 filaments and an amine terminal number of yarn of 33 meq / kg.

Example 2

In preparing the prepolymer of Example 1, 15.0 mol% of polyethylene glycol (molecular weight 4000) was mixed with 27.3 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), and then 4,4'-diphenylmethane di 8.3 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Example 3

During the preparation of the prepolymer of Example 1, after mixing 15.0 mol% of polyethylene glycol (molecular weight 500) with 34.9 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), 4,4'-diphenylmethanedi 9.5 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Example 4

During the preparation of the prepolymer of Example 1, after mixing 15.0 mol% of polyethylene glycol (molecular weight 1000) to 33.5 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), 4,4'-diphenylmethanedi 9.3 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Example 5

During the preparation of the prepolymer of Example 1, 15.0 mol% of polyethylene glycol (molecular weight 3000) was mixed with 29.1 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), and then 4,4'-diphenylmethane di 8.6 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Example 6

During the preparation of the prepolymer of Example 1, after mixing 30.0 mol% of polyethylene glycol (molecular weight 2000) in 25.4 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), 4,4'-diphenylmethanedi 8.9 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Example 7

During the preparation of the prepolymer of Example 1, after mixing 5.0 mol% of polyethylene glycol (molecular weight 2000) in 35.1 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), 4,4'-diphenylmethanedi 8.9 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Example 8

During the preparation of the prepolymer of Example 1, 10.0 mol% of polyethylene glycol (molecular weight 2000) was mixed with 33.1 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), and then 4,4'-diphenylmethane di 8.9 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Example 9

During the preparation of the prepolymer of Example 1, 20.0 mol% of polyethylene glycol (molecular weight 2000) was mixed with 29.2 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), and then 4,4'-diphenylmethane di 8.9 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Comparative Example 1

In preparing the prepolymer of Example 1, 9.0 kg of 4,4'-diphenylmethane diisocyanate was added without mixing polyethylene glycol to 37.1 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840). The reaction was stirred at 90 ° C. for 120 minutes in a gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Comparative example  2

During the preparation of the prepolymer of Example 1, after mixing 15.0 mol% of polyethylene glycol (molecular weight 300) to 35.4 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), 4,4'-diphenylmethanedi 9.6 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Comparative Example 3

In preparing the prepolymer of Example 1, 15.0 mol% of polyethylene glycol (molecular weight 4500) was mixed with 28.1 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), and then 4,4'-diphenylmethane di 8.4 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Comparative Example 4

During the preparation of the prepolymer of Example 1, after mixing 3.0 mol% of polyethylene glycol (molecular weight 2000) to 36.1 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), 4,4'-diphenylmethane di 9.0 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Comparative Example 5

During the preparation of the prepolymer of Example 1, 35.0 mol% of polyethylene glycol (molecular weight 2000) was mixed with 25.5 kg of polytetramethylene ether glycol (PTMG, molecular weight 1840), and then 4,4'-diphenylmethane di 9.3 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Experimental Example

The spandex prepared in Examples and Comparative Examples was dyed with an acid dye of black color, and after dyeing, the dyeability (darkness) was measured by lightness (L *) value.

The evaluation results are shown in comparison with Table 1 below.

The measuring method for the property of the elastic yarn shown in the Example and the comparative example is as follows.

(1) 200% M measurement method

It is measured by load cell 32cN, sample length 10cm, saddle speed 100cm / min using automatic elongation measuring device (MEL machine, Textechno company), and 200% M (modulus) load on yarn when 200% elongation of yarn .

(2) How to measure L * value

 L * value of the degree of dyeability was measured by measuring the reflectance of the yarn using a spectrophotometer, and then it was calculated using the formula of CIE Lab color difference equation. The L * value of the L * a * b * color difference values is a value indicating brightness, and as the dye is stained with the same dye, the lower the L * value is.

division	PEG molecular weight	PEG content (mol%)	Strength (g / de)	Elongation (%)	200% M	L value	Radiation fairness
Example 1	2000	15	1.13	505	6.9	13.7	○
Example 2	4000	15	1.05	510	6.6	6.5	○
Example 3	500	15	1.25	490	7.2	24.3	○
Example 4	1000	15	1.17	500	7.1	17.6	○
Example 5	3000	15	1.08	510	6.8	9.3	○
Example 6	2000	30	1.08	515	6.6	6.2	○
Example 7	2000	5	1.21	495	7.2	21.1	○
Example 8	2000	10	1.15	500	7.0	15.3	○
Example 9	2000	20	1.11	510	6.8	11.1	○
Comparative Example 1	-	No addition	1.32	490	7.3	72.0	○
Comparative Example 2	300	15	1.28	490	7.3	48.5	○
Comparative Example 3	4500	15	0.89	520	5.1	5.8	△
Comparative Example 4	2000	3	1.25	490	7.2	42.4	○
Comparative Example 5	2000	35	0.82	530	4.9	5.6	X

※ Radiation Fairness: ○ (good), △ (not good), X (bad)

From the above experimental results, it can be confirmed that the case according to the present invention shows a remarkably excellent dyeability compared to the comparative example. In addition, it was confirmed that there is a critical significance for the molecular weight and the amount of polyethylene glycol according to the present invention.

In the case of Comparative Example 2, when the molecular weight of polyethylene glycol is less than 500, there is a problem that it is difficult to secure excellent dyeability due to the decrease of the hydrophilic effect.

In the case of Comparative Example 3 when the molecular weight of polyethylene glycol exceeds 4000, there is a problem that the strength and modulus of the yarn is lowered, the workability during spinning is insufficient and the process is difficult to apply.

In the case of Comparative Example 4 when the content of polyethylene glycol is less than 5mol%, there is a problem that it is difficult to secure excellent dyeability due to the decrease of the hydrophilic effect.

In the case of Comparative Example 5 when the content of polyethylene glycol is more than 30mol%, it is difficult to secure the spinning workability due to the lowered heat resistance, there is a problem that the process is difficult to apply.

Claims (6)

1. (a) a polyol comprising a first polyol and a second polyol; (b) at least one diisocyanate; (c) at least one diamine chain extender; And (d) a product obtained by reacting at least one amine chain terminator, a polyurethaneurea elastic yarn,

   The second polyol is polyethylene glycol, the first polyol and the second polyol are different materials,

   Polyurethane urea elastic yarn with improved dyeability to acid dyes and reactive dyes, characterized in that the weight average molecular weight of polyethylene glycol is 500 to 4000.
2. According to claim 1, Polyethylene glycol is a polyurethane urea elastic yarn with improved dyeability, characterized in that 5.0 to 30.0 mol% of the total polyol is mixed.
3. The polyurethane urea elastic yarn with improved dyeability according to claim 1, wherein the number of amine ends of the polyurethane urea elastic yarn is 20.0 to 45.0 meq / kg.
4. (a) contacting a polyol comprising a first polyol and a second polyol with at least one diisocyanate to produce a polyurethane prepolymer;

   (b) adding a solvent to the prepolymer of step (a);

   (c) contacting the product of step (b) with at least one diamine chain extender and at least one amine chain terminator;

   (d) spinning the product of step (c) to produce a polyurethaneurea elastic yarn,

   The second polyol is polyethylene glycol, the first polyol and the second polyol is a different material, the weight average molecular weight of the polyethylene glycol is 500 to 4000, characterized in that the dyeability to the acid dyes and reactive dyes improved polyurethane Method for producing urea elastic yarn.
5. The method of claim 4, wherein the second polyol is 5.0 to 30.0 mol% mixed with respect to the total polyol.
6. The method according to claim 4, wherein the number of amine ends of the polyurethaneurea elastic yarn is 20.0 to 45.0 meq / kg.