WO2009084815A1

WO2009084815A1 - Easily dyeable polyurethaneurea spandex yarn and method of preparing the same

Info

Publication number: WO2009084815A1
Application number: PCT/KR2008/006883
Authority: WO
Inventors: Yoon Suk Chung; Tae Heon Kim; Yeon Soo Kang
Original assignee: Hyosung Corp
Current assignee: Hyosung Corp
Priority date: 2007-12-31
Filing date: 2008-11-21
Publication date: 2009-07-09
Anticipated expiration: 2010-06-30
Also published as: KR100973987B1; KR20090073749A

Abstract

The present invention relates to an easily dyeable polyurethaneurea spandex yarn containing polyimine or polyamine for maintaining specific characteristics of spandex yarn and improving dyeability of spandex yarn, and more particularly, to an easily dyeable polyurethaneurea spandex yarn and a method of preparing the same that improves light fastness and wash fastness by uniformly dispersing polyimine or polyamine in the polyurethaneurea spandex yarn and dyeing the polyurethaneurea spandex yarn with an acid dye or a disperse dye.

Description

EASILY DYEABLE POLYURETHANEUREA SPANDEX YARN AND METHOD OF PREPARING THE SAME

Technical Field

[1] The present invention relates to an easily dyeable polyurethaneurea spandex yarn containing polyimine or polyamine for maintaining specific characteristics of spandex yarn and improving dyeability of spandex yarn, and more particularly, to an easily dyeable polyurethaneurea spandex yarn and a method of preparing the same that improves light fastness and wash fastness by uniformly dispersing polyimine or polyamine in the polyurethaneurea spandex yarn and dyeing the polyurethaneurea spandex yarn with an acid dye or a disperse dye. Background Art

[2] A polyurethaneurea spandex yarn is a highly elastic polyurethane fiber containing more than 85 wt% (weight percent) urethane bond in its molecular structure, and generally used for manufacturing sports wears and women's foundations, such as a swimming suite and a stocking. The demand of polyurethane spandex yarn is gradually increasing.

[3] A conventional polyurethaneurea spandex yarn is generally prepared by mixing ether glycol with an isocyanate compound, forming a primary polymer through primary polymerization, forming at least one chain extender selected from a group consisting of ethylene diamine and diaminopropane, forming a secondary polymer through mixing and secondary polymerization of the primary polymer, the chain extender, and dimethylacetamide, and finally dry spinning with the secondary polymer.

[4] The polyurethaneurea spandex yarn prepared by the above method has disadvantages that dyeability of spandex yarn is decreased when using a disperse dye or an acid dye, and color fastnesses, in particular, light and wash fastness of the spandex yarn become very poor.

[5] In more detail, when a union cloth is manufactured by using the conventional polyurethaneurea spandex yarn together with a polyester yarn or a polyamide yarn and dyed with a disperse dye or an acid dye, dyeability and color fastness of the spandex yarn decrease greatly. In the case that the union cloth is dyed with a disperse dye, dyeability of the union fabric is high, because the disperse dye has a high affinity to the polyurethaneurea spandex yarn. However, wash fastness of the union fabric decreases. In the case that the union cloth is dyed with an acid dye, both dyeability and wash fastness of the union fabric decrease, because the acid dye has a low affinity to the polyurethaneurea spandex yarn. [6] Accordingly, in order to solve such a problem, research and development are actively being carried out for providing an easily dyeable polyurethaneurea spandex yarn that can easily be dyed with an acid dye or a disperse dye and can improve the light fastness and wash fastness.

[7] For example, U.S. Patent No. 0,165,200Al discloses an elastic polyurethaneurea fiber containing primary amine prepared by mixing diisocyanate 4,4-methylenediisocyanate with 2,4-methylenediisocyanate and reacting with glycol, diluting an isocyanate end isolating product with a solvent, and chain extending with diamine. The polyurethaneurea spandex yarn showed a good result, such as a high affinity to an acid dye and a reactive dye, and a high fastness of 4.5 - 5. However, the polyurethane spandex yarn has a low dyeability, which reduces the excellence of fastness. Further, the polyurethaneurea spandex has disadvantages of low modulus and elastic recovery due to the usage of 2,4-methylenediisocyanate.

[8] U.S. Patent No. 6,468,652B 1 discloses a method for producing an elastic polyurethaneurea fiber by reacting compounds including a bifunctional amine group having a primary amine group and a secondary amine group, a nitrogen-containing compound having a tertiary nitrogen group and a heterocyclic nitrogen group (in particular, N-(2-aminoethyl)piperzine and organic diisocyanate), and an organic monoisocyanate, and adding a specific urea compound into the polyurethaneurea polymer. According to this method, the elastic polyurethane fiber has a high setting property and a high elastic recovery, and can be dyed with an acid dye, because 1 - 15 wt% urea compound containing additives is added based on the solid content of the polymer. However, the urea compound has a low thermal stability, and thereby spinning properties are decreased and fastness of the fiber becomes unsatisfactory.

[9]

Disclosure of Invention Technical Problem

[10] An object of the present invention is to provide an easily dyeable polyurethaneurea spandex yarn and a method of preparing the same that improves light fastness and wash fastness of spandex yarn by uniformly dispersing polyimine or polyamine in the polyurethaneurea spandex yarn and dyeing the polyurethaneurea spandex yarn with an acid dye or a disperse dye. Technical Solution

[11] In order to solve the above problems, the present invention provides an easily dyeable polyurethaneurea spandex yarn prepared by dry spinning with a polymer composition formed by mixing a secondary polymer with a predetermined amount of polyimine or polyamine. [12] Further, the present invention provides a method of preparing an easily dyeable polyurethaneurea spandex yarn including: forming a polymer composition by mixing secondary polymer with a predertemined amount of polyimine or polyamine; and dry spinning with the polymer composition.

Advantageous Effects

[13] The easily dyeable polyurethaneurea spandex yarn prepared according to the present invention improves light fastness and wash fastness greatly, because the polyimine or the polyamine is uniformly dispersed in the polyurethaneurea spandex yarn which can easily be dyed with an acid dye or a disperse dye maintaining specific characteristics of the poyurethaneurea spandex yarn. Best Mode for Carrying Out the Invention

[14] An easily dyeable polyurethaneurea spandex yarn according to the present invention is prepared not by dry spinning only with secondary polymer, but by dry spinning with a polymer composition containing the secondary polymer and a predetermined amount of polyimine or polyamine.

[15] Hereinafter, the easily dyeable polyurethaneurea spandex yarn is described in more detail referring to exemplary embodiments of the present invention.

[16] A polyurethaneurea spandex yarn is generally prepared by mixing ether glycol with an isocyanate compound, forming a primary polymer through primary polymerization, forming at least one chain extender selected from a group consisting of ethylene diamine and diaminopropane, forming a secondary polymer through mixing and secondary polymerization with the primary polymer, a chain extender, and dimethy- lacetamide, and finally dry spinning with the secondary polymer. However, the easily dyeable polyurethaneurea spandex yarn according to the present invention is prepared not by dry spinning only with the secondary polymer, but by dry spinning with a polymer composition containing the secondary polymer and a predetermined amount of polyimine or polyamine.

[17] The easily dyeable polyurethaneurea spandex yarn prepared according to the present invention provides uniform dispersion of polyimine or polyamine and uniform ionic bond with an acid dye, and thereby dyeability of the easily dyeable polyurethaneurea spandex yarn is improved. At the same time, the polyimine or polyamine having a high molecular weight is complicatedly entangled in the polyurethaneurea spandex yarn, and thereby wash and light fastness of the easily dyeable polyurethaneurea spandex yarn is improved.

[18] In order to provide easy dyeabilty to the polyurethaneurea spandex yarn, at least one polyimine mixed with the secondary polymer is selected from a group consisting of polyethyleneimine, poly(C2-6 alkyleneimine), polyarylimine, poly(propyleneimine) dendrimer, and poly(imidoamine)dendrimer, and at least one polyamine mixed with the secondary polymer is selected from a group consisting of poly(N-alkyl)arylamine, polyamidoamine, and polytetrahydrofuranamine. That is, the above imine compound and amine compound may be used solely or as a mixture of more than one compound to mix with the secondary polymer.

[19] For this, a polymer composition is formed by mixing the secondary polymer with 0.1

- 30 wt% polyimine or polyamine based on the weight of the secondary polymer, and the easily dyeable polyurethaneurea spandex yarn is produced by dry spinning with the polymer composition.

[20] If the content of polyimine or polyamine based on the weight of the secondary polymer is less than 0.1 wt% in forming a polymer composition, dyeabilty of the polyurethaneurea spandex yarn produced by dry spinning with the polymer composition decreases. If the content of polyimine or polyamine based on the weight of the secondary polymer is greater than 30 wt% in forming a polymer composition, viscosity of the polymer composition increases excessively for dry spinning, and thereby decreasing spinning properties of the polymer composition.

[21] In forming the polymer composition, polyimine or polyamine having an average molecular weight 100 ~ 100,000 is used.

[22] If the average molecular weight of the polyimine or polyamine is less than 100, fastness of the polyurethaneurea spandex yarn produced by dry spinning with the polymer composition decreases. If the average molecular weight of the polyimine or polyamine is greater than 100,000, viscosity of the polymer composition for dry spinning increases excessively.

[23] The easily dyeable polyurethaneurea spandex yarn produced by the above method showed an excellent dyeability with an acid dye and an excellent fastness of class 5.

[24] Hereinafter, a method of preparing an easily dyeable polyurethaneurea spandex yarn is described in more detail referring to exemplary embodiments of the present invention.

[25] A polyurethaneurea spandex yarn is generally prepared by mixing ether glycol with an isocyanate compound, forming a primary polymer through primary polymerization, forming at least one chain extender selected from a group consisting of ethylene diamine and diaminopropane, forming a secondary polymer through mixing and secondary polymerization with the primary polymer, a chain extender, and dimethy- lacetamide, and finally dry spinning with the secondary polymer. However, the easily dyeable polyurethaneurea spandex yarn according to the present invention is prepared not by dry spinning only with the secondary polymer, but by dry spinning with a polymer composition containing the secondary polymer and a predetermined amount of polyimine or polyamine. [26] In preparation of the polyurethaneurea spandex yarn, ethylene diamine or di- aminopropane is solely used as a chain extender for secondary polymerization, or a mixture of ethylene diamine and diaminopropane is used as a chain extender for secondary polymerization. The polymer composition formed by mixing the secondary polymer with a predetermined amount of polyimine or polyamine provides uniform dispersion of the polyimine or polyamine in the polyurethaneurea spandex yarn and easy dyeability to the polyurethaneurea spandex yarn, through dry spinning.

[27] The easily dyeable polyurethaneurea spandex yarn prepared by the above method is used for production of a union cloth by mixing with a polyester yarn or polyamide yarn, and the produced union cloth is dyed with a disperse dye or an acid dye. Mode for the Invention

[28] Easily dyeable polyurethaneurea spandex yarns were prepared according to the exemplary embodiments of the present invention, and the properties of the easily dyeable polyurethaneurea spandex yarns were evaluated by using comparative examples. However, the exemplary embodiments are provided for the purpose of description, and the present invention is not limited thereto.

[29] <Exemplary embodiment 1>

[30] 1. A primary polymer was formed by mixing 540 kg polytetramethyleneglycol having an average molecular weight 1,800 with 123.9 kg

4,4'-diphenylmethanediisocyanate at 45⁰C with a homogenizer to yield an end group mole ratio 1.65, and primarily polymerized for 90 min at 95⁰C in a pipe reactor (Step SlO).

[31] 2. A polymer mixture solution was formed by cooling the primary polymer to 4O⁰C, conditioning for 12 hrs, and mixing the primary polymer with N,N'-dimethylacetamide to yield the content of the primary polymer 44 wt% (Step S20).

[32] 3. A chain extender was formed by mixing and agitating 11.4 kg ethylene diamine,

2.0 kg diaminopropane, and 190.8 kg N,N'-dimethylacetamide (Step S30).

[33] 4. A secondary polymer was formed by cooling the polymer mixture solution prepared at Step S20 to 5⁰C for chain extending reaction, and polymerizing the polymer mixture solution while agitating at 200 rpm and adding the chain extender prepared at Step S30. Here, the initial viscosity of the secondary polymer was 2550 poise at 40 ⁰C (Step S40).

[34] 5. A polymer composition was formed by feeding the secondary polymer into a reactor, and adding and agitating 5 wt% polyethyleneimine having a molecular weight 25,000 for improvement of dyeabilty, 4.5 wt% titanium oxide as an anti-discoloring agent, 3 wt% CYANOX 1790(product of Cynamid, USA) as an antioxidant, and 6 wt% hydrotalcite as an anti-chlorine agent, based on the weight of the secondary polymer (Step S50).

[35] 6. 40 denier / 4 filaments polyurethaneurea spandex yarn was produced by spinning with a conventional dry spinning method (Step S60).

[36] 7. A union cloth (content of spandex yarn: 30 wt%) was produced by weaving with the polyurethaneurea spandex yarn and a polyamide yarn, and dyeing with an acid dye (CI. Acid Blue 40) (Step S70).

[37] <Exemplary embodiment 2>

[38] An easily dyeable polyurethaneurea spandex yarn was prepared in the same method as Exemplary embodiment 1 except that 5 wt% polyethyleneimine having a molecular weight 2,000 based on the weight of the secondary polymer was added instead of polyethyleneimine having a molecular weight 25,000 at Step S50 of forming a polymer composition.

[39] <Exemplary embodiment 3>

[40] An easily dyeable polyurethaneurea spandex yarn was prepared in the same method as Exemplary embodiment 1 except that 5 wt% polytetrahydrofuranamine having a molecular weight 1,700 based on the weight of the secondary polymer was added instead of polyethyleneimine having a molecular weight 25,000 at Step S50 of forming a polymer composition.

[41] <Comparative example 1>

[42] An easily dyeable polyurethaneurea spandex yarn was prepared in the same method as Exemplary embodiment 1 except that polyethyleneimine having a molecular weight 25,000 was not used at Step S50 of forming a polymer composition.

[43] <Comparative example 2>

[44] An easily dyeable polyurethaneurea spandex yarns were prepared in the same method as Exemplary embodiment 1 except that 1 wt% Methacrol (product of Takemoto, Japan) based on the weight of the secondary polymer was added for improvement of dyeability instead of polyethyleneimine having a molecular weight 25,000 at Step S50 of forming a polymer composition.

[45] <Comparative example 3>

[46] An easily dyeable polyurethaneurea spandex yarn was prepared in the same method as Exemplary embodiment 1 except that 0.3wt% polyethyleneimine having a molecular weight 25,000 based on the weight of the secondary polymer was added at Step S50 of forming a polymer composition.

[47] Properties of yarns prepared according to the exemplary embodiments were compared with properties of yarns prepared according to the comparative examples by using the following evaluation method. The result of the evaluation is shown in Table 1.

[48] <Evaluation method> [49] 1. Tenacity and elongation: measured by KSK 0219 method.

[50] 2. Elastic recovery: after repeating 300% elongation test 5 times with Instron, the ratio of the length of the tested specimen to the initial length of the untested specimen in a tensionless state was calculated in a percentage. [51] 3. Wash fastness: measured by KSK 0430 AI method.

[52] 4. Light fastness: measured by AATCC 16E- 1982 method.

[53] 5. L* value (color strength), a* value, and b* value of chromaticity coordinates: calculated by using CIE 76 CIE Lab formulas after measuring a reflection rate of yarn with a spectrophotometer. [54] where, a polyamide woven fabric was used as a staining cloth for measurement of the light and wash fastness. [55] Table 1

[Table 1]

[Table ]

Industrial Applicability

[56] Referring to Table 1, the polyurethaneurea spandex yarns produced according to the exemplary embodiments of the present invention show much improved dyeability and fastness while maintaining specific characteristics of the spandex yarns.

[57] Although exemplary embodiments of the present invention have been described in detail hereinabove, it should be understood that many variations and modifications of the basic inventive concept herein described, which may appear to those skilled in the art, will still fall within the spirit and scope of the exemplary embodiments of the present invention as defined in the appended claims.

Claims

[1] An easily dyeable polyurethaneurea spandex yarn prepared by mixing ether glycol with an isocyanate compound, forming a primary polymer through primary polymerization, forming a secondary polymer through mixing and polymerizing the primary polymer, a chain extender, and dimethylacetamide, and dry spinning with the secondary polymer, wherein the easily dyeable polyurethaneurea spandex yarn is prepared by dry spinning with a polymer composition containing the secondary polymer mixed with a predetermined amount of polyimine or polyamine.

[2] The easily dyeable polyurethaneurea spandex yarn of claim 1, wherein the polyimine added to the secondary polymer is selected from a group consisting of polyethyleneimine, poly(C2-6 alkyleneimine), polyarylimine, poly(propyleneimine)dendrimer, and poly(imidoamine)dendrimer, and the polyamine added to the secondary polymer is selected from a group consisting of poly(N-alkyl)arylamine, polyamidoamine, and polytetrahydrofuranamine.

[3] The easily dyeable polyurethaneurea spandex yarn of claim 1, wherein the polymer composition is formed by adding a 0.1 - 30 wt% (weight percent) mixture of the polyimine and polyamine based on the weight of the secondary polymer.

[4] The easily dyeable polyurethaneurea spandex yarn of claim 1, wherein the average molecular weight of the polyimine or polyamine is 100 - 100,000.

[5] A method of preparing an easily dyeable polyurethaneurea spandex yarn comprising: forming a primary polymer through primary polymerization of a mixture of ether glycol and an isocyanate compound primary, forming a secondary polymer through secondary polymerization of the primary polymer, a chain extender, and dimethylacetamide, and dry spinning with the secondary polymer, further comprising: forming a polymer composition by adding a predetermined amount of polyimine or polyamine to the secondary polymer; and dry spinning with the polymer composition.