WO2009084815A1 - Easily dyeable polyurethaneurea spandex yarn and method of preparing the same - Google Patents
Easily dyeable polyurethaneurea spandex yarn and method of preparing the same Download PDFInfo
- Publication number
- WO2009084815A1 WO2009084815A1 PCT/KR2008/006883 KR2008006883W WO2009084815A1 WO 2009084815 A1 WO2009084815 A1 WO 2009084815A1 KR 2008006883 W KR2008006883 W KR 2008006883W WO 2009084815 A1 WO2009084815 A1 WO 2009084815A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- spandex yarn
- polymer
- polyurethaneurea
- easily dyeable
- polyimine
- Prior art date
Links
- 229920002334 Spandex Polymers 0.000 title claims abstract description 75
- 239000004759 spandex Substances 0.000 title claims abstract description 75
- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920000768 polyamine Polymers 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims description 82
- 239000000203 mixture Substances 0.000 claims description 31
- 238000000578 dry spinning Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- 239000004970 Chain extender Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- -1 isocyanate compound Chemical class 0.000 claims description 10
- 229920002873 Polyethylenimine Polymers 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000000412 dendrimer Substances 0.000 claims description 2
- 229920000736 dendritic polymer Polymers 0.000 claims description 2
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 2
- 229920000333 poly(propyleneimine) Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000980 acid dye Substances 0.000 abstract description 15
- 239000000986 disperse dye Substances 0.000 abstract description 10
- 238000004043 dyeing Methods 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229940113088 dimethylacetamide Drugs 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002959 polymer blend Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920006306 polyurethane fiber Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- NTOOJLUHUFUGQI-UHFFFAOYSA-M sodium;4-(4-acetamidoanilino)-1-amino-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].C1=CC(NC(=O)C)=CC=C1NC1=CC(S([O-])(=O)=O)=C(N)C2=C1C(=O)C1=CC=CC=C1C2=O NTOOJLUHUFUGQI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/14—Dyeability
Definitions
- 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.
- 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.
- 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.
- 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.
- 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.
- the polyurethane spandex yarn has a low dyeability, which reduces the excellence of fastness.
- the polyurethaneurea spandex has disadvantages of low modulus and elastic recovery due to the usage of 2,4-methylenediisocyanate.
- 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.
- 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.
- 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.
- the urea compound has a low thermal stability, and thereby spinning properties are decreased and fastness of the fiber becomes unsatisfactory.
- 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.
- 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.
- 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.
- 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
- 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.
- 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.
- 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.
- 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.
- 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.
- 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
- 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.
- a polymer composition is formed by mixing the secondary polymer with 0.1
- the easily dyeable polyurethaneurea spandex yarn is produced by dry spinning with the polymer composition.
- polyimine or polyamine having an average molecular weight 100 ⁇ 100,000 is used.
- 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.
- 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.
- 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.
- a primary polymer was formed by mixing 540 kg polytetramethyleneglycol having an average molecular weight 1,800 with 123.9 kg
- a polymer mixture solution was formed by cooling the primary polymer to 4O 0 C, 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).
- a chain extender was formed by mixing and agitating 11.4 kg ethylene diamine,
- a secondary polymer was formed by cooling the polymer mixture solution prepared at Step S20 to 5 0 C for chain extending reaction, and polymerizing the polymer mixture solution while agitating at 200 rpm and adding the chain extender prepared at Step S30.
- the initial viscosity of the secondary polymer was 2550 poise at 40 0 C (Step S40).
- 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).
- 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).
- 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.
- 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.
- 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.
- 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.
- 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.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Mechanical Engineering (AREA)
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
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 ]
[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.
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| KR10-2007-0141784 | 2007-12-31 | ||
| KR20070141784A KR100973987B1 (en) | 2007-12-31 | 2007-12-31 | Easily dyeable polyurethaneurea spandex yarn and method for preparing the same |
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| WO2009084815A1 true WO2009084815A1 (en) | 2009-07-09 |
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| PCT/KR2008/006883 WO2009084815A1 (en) | 2007-12-31 | 2008-11-21 | Easily dyeable polyurethaneurea spandex yarn and method of preparing the same |
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| WO (1) | WO2009084815A1 (en) |
Cited By (7)
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| CN104372441A (en) * | 2014-11-19 | 2015-02-25 | 浙江华峰氨纶股份有限公司 | Spandex fiber with air purification function and preparation method of spandex fiber |
| JP2015038261A (en) * | 2013-07-19 | 2015-02-26 | 東レ・オペロンテックス株式会社 | Polyurethane elastic yarn and method of producing the same |
| CN109881291A (en) * | 2019-02-18 | 2019-06-14 | 华峰重庆氨纶有限公司 | A kind of acid dyes is easily painted the preparation method of spandex |
| WO2020102044A1 (en) | 2018-11-12 | 2020-05-22 | The Lycra Company Llc | Spandex fiber with reduced visibility |
| CN113710838A (en) * | 2019-04-01 | 2021-11-26 | 美津浓株式会社 | Swimming suit |
| CN114892303A (en) * | 2022-05-26 | 2022-08-12 | 华峰重庆氨纶有限公司 | Preparation method of macromolecular amine modified multifunctional spandex |
| EP3951037A4 (en) * | 2019-04-01 | 2023-01-18 | Toray Industries, Inc. | Fibrous structure containing elastic polyurethane yarn |
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| CN104153033B (en) * | 2014-08-13 | 2016-05-04 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of porous easy dyeing spandex |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020102044A1 (en) | 2018-11-12 | 2020-05-22 | The Lycra Company Llc | Spandex fiber with reduced visibility |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100973987B1 (en) | 2010-08-05 |
| KR20090073749A (en) | 2009-07-03 |
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