WO2008016255A1 - A polyurethane elastic fiber with high heat settable property - Google Patents
A polyurethane elastic fiber with high heat settable property Download PDFInfo
- Publication number
- WO2008016255A1 WO2008016255A1 PCT/KR2007/003689 KR2007003689W WO2008016255A1 WO 2008016255 A1 WO2008016255 A1 WO 2008016255A1 KR 2007003689 W KR2007003689 W KR 2007003689W WO 2008016255 A1 WO2008016255 A1 WO 2008016255A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyurethane elastic
- elastic yarns
- polyurethane
- chain extender
- heat
- Prior art date
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 39
- 239000004814 polyurethane Substances 0.000 title claims abstract description 39
- 210000004177 elastic tissue Anatomy 0.000 title description 3
- 239000004744 fabric Substances 0.000 claims abstract description 39
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004970 Chain extender Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims abstract description 6
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005700 Putrescine Substances 0.000 claims abstract description 3
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims abstract description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 description 11
- 239000004677 Nylon Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000835 fiber Substances 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229920006306 polyurethane fiber Polymers 0.000 description 6
- 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 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 238000009998 heat setting Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 229920002334 Spandex Polymers 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000009940 knitting Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 3
- 239000002964 rayon Substances 0.000 description 3
- 239000004759 spandex Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 1
- CYHYIIFODCKQNP-UHFFFAOYSA-N 5,7-ditert-butyl-3-(3,4-dimethylphenyl)-3h-1-benzofuran-2-one Chemical compound C1=C(C)C(C)=CC=C1C1C(C=C(C=C2C(C)(C)C)C(C)(C)C)=C2OC1=O CYHYIIFODCKQNP-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S528/906—Fiber or elastomer prepared from an isocyanate reactant
Definitions
- the present invention relates to a process for preparing polyurethane and an elastic fabric comprising polyurethane elastic yarns made therefrom and, particularly, to polyurethane prepared by adding diamine of chain extender at a predetermined rate and polyurethane elastic yarns made therefrom having excellent heat settable property.
- the present invention relates to a knitted fabric consisting of the elastic fabric having excellent heat settable property at low temperature and a heat- sensitive fiber such as nylon, silk, wool, polypropylene, rayon and polytrimethylene terephthalate.
- the knitted fabric may be heat-set at low temperature to prevent heat degradation of the heat- sensitive fiber and edge curling of the knitted fabric.
- Polyurethane is customarily prepared by reacting a polyol with an excessive amount of diisocyanate to prepare a prepolymer, dissolving the prepolymer in an organic solvent and then adding diamine or diol of chain extender to the resulting solution and reacting with chain terminator such as mono-alcohol and monoamine to form a polyurethane spinning solution which is then dry- or wet-spun to make the polyurethane elastic fiber.
- chain terminator such as mono-alcohol and monoamine
- the polyurethane fiber is characterized by its high elasticity and widely used in a variety of areas. As its usage has expanded, there is a growing demand for developing extra features of polyurethane fibers.
- polyurethane fibers is heat-set at high temperature during a post-process after knitting and the high temperature causes heat degradation of heat- sensitive fibers such as nylon, cotton, silk, wool, polypropylene, rayon and polytrimethylene terephthalate.
- heat-sensitive fibers such as nylon, cotton, silk, wool, polypropylene, rayon and polytrimethylene terephthalate.
- 5,948,875 disclose processes for improving the heat settable property of polyurethane elastic yarns. Due to the lack of heat settable property at a low temperature, however, heat-sensitive fibers have not been applicable to the processes disclosed in the prior arts. Disclosure of Invention Technical Problem
- the object of the present invention is to prepare polyurethane elastic yarns having excellent heat settable property with appropriate amine.
- the polyurethane elastic yarns are knitted with a heat-sensitive fiber such as nylon, cotton, silk, wool, polypropylene, rayon and polytrimethylene terephthalate.
- the knitted fabric may be heat- set at low temperature to prevent fabric degradation of the heat-sensitive fiber which in turn improves fabric hand value and to provide the knitted fabric without edge curling.
- a process for preparing polyurethane elastic yarns having excellent heat settable property and an elastic fabric made therefrom are produced by reacting polyols with an excessive amount of diisocyanate to prepare a prepolymer, dissolving the prepolymer in an organic solvent and reacting the resulting solution with a chain extender in order to prepare polyurethane elastic yarns, wherein an amount of 1,3-diaminopropane contained in the chain extender is 40 mol% or more based on the total chain extender.
- a process for preparing polyurethane elastic yarns wherein the chain extender further comprises at least one selected from a group consisting of ethylene diamine, 1,2- di- aminopropane, 1,4-diaminobutane, 2,3-butanediamine, 1,5-pentanediamine, 1,6-hexandiamine and 1,4-cyclohexanediamine.
- a process for preparing polyurethane elastic yarns wherein the prepolymer contains 1.56 wt% to 4.29 wt% of isocyanate based on the total prepolymer.
- a knitted fabric may be heat-set at lower temperature after knitting compared to the prior arts. Hence, heat degradation of the heat-sensitive fiber may be prevented which in turn improves fabric hand value. It also prevents edge curling of the knitted fabric. Best Mode for Carrying Out the Invention
- Segmented polyurethane used in the present invention is made by reacting organic diisocyanate with polymer diol to prepare a prepolymer, dissolving the prepolymer in an organic solvent and then reacting with diamine and monoamine.
- Examples of organic diisocyanate used in the present invention may include at least one selected from a group consisting of diphenylmethane-4,4-diisocyanate, 1 ,5-naphthalenediisocyanate, 1 ,4-phenylenediisocyanate, hexamethylenediisocyanate, 1,4-cyclohexanediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophorone diisocyanate.
- Examples of polymer diol used in the present invention may include polyte- tramethylen-etherglycol, polypropylene-etherglycol and polycarbonatediol.
- Diamine may be used as chain extender from at least one selected from a group consisting of ethylenediamine, 1,2-diaminopropane, 1,6-hexamethylendiamine and 1,3-diaminopropane.
- the content of 1,3-diaminopropane based on the total chain extender should be 40 mol% or more preferably. If it is less than 40 mol %, the heat settable property of polyurethane elastic yarn considerably deteriorates.
- Examples of amine having one functional group used in the present invention to control molecule weight of polyurethaneurea may include diethyl amine, mo- noethanolamine, dimethyleamine and so on.
- sterically hindered phenolic compounds benzofuran-on compounds, semicarbazide compounds, benzotriazole compounds and polymeric tertiary amine stabilizer may be added in combination into a spinning solution.
- the polyurethane elastic yarns in the present invention may further include additives such as titanium dioxide and magnesium stearate.
- additives such as titanium dioxide and magnesium stearate.
- Heat settable property(%) ⁇ (heat-set length - original length) ⁇ / (stretched length - original length) ⁇ x 100
- Edge curling(%) (the area of triangle being curled/ the initial area of the triangle) x
- the solid additives to the solution may include 1.5 wt% of ethylenebis(oxyethylene)bis-(3-(5-ter-butyl-4-hydroxy-m-toyl)-propionate), 0.5 wt% of 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, 1 wt% of l,l,r,l'-tetramethyl-4,4'-(methylene-di-p-phenylene)disemicarbazide, 1 wt% of poly(N,N-diethyl-2-aminoethyl methacrylate) and 0.1 wt% of titanium dioxide to produce a polyurethane spinning solution.
- a circular-knitted fabric was made using a circular-knitting machine(Mayer Co.) with 38 inches cylinder diameter, 28 gauge and 120 feeder.
- the nylon used in preparing the knitted fabric is 70 denier nylon and knitted with 40 denier of elastic yarns produced by the process, and the content of the elastic yarns is 8 wt% based on the total fabric weight.
- Example 4 to 6 and Comparative Example 1 to 3 were carried out as in Example 1, except the changes in the weight percent (wt%) of isocyanate, the type and mol percent(mol%) of chain extender as shown in Table 1.
- Example 7 to 10 were carried out to produce a circular-knitted fabric with elastic yarns prepared in Example 1 and nylon, and Comparative Example 4 to 6 were carried out with elastic yarns prepared by Comparative Example 1 and nylon. They were then treated under the heat-setting conditions shown in Table 2. The edge curling(%) and fabric hand value of the resulting fabric are shown in Table 2.
- the polyurethane elastic yarns of the present invention show excellent heat settable property at low temperature. Therefore, the fabric comprising the elastic yarns prepared in the present invention do not cause edge curling with the heat-set process at low temperature, which resulted in excellent fabric hand value of the resulting knitted fabric available in various areas.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Knitting Of Fabric (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to a process for preparing polyurethane and polyurethane elastic yarns made therefrom, wherein an amount of 1,3-diaminopropane contained in a chain extender is 40 mol % or more based on the total chain extender and the chain extender further comprises at least one selected from a group consisting of ethylene diamine, 1,2- diaminopropane, 1,4-diaminobutane, 2,3-butanediamine, 1,5-pentanediamine, 1,6-hexandiamine and 1,4-cyclohexanediamine. The polyurethane elastic yarns show excellent heat settable property at low temperature and a fabric using the elastic yarns may be heat-set at low temperature to prevent edge curling and to improve fabric hand value of a knitted fabric.
Description
Description
A POLYURETHANE ELASTIC FIBER WITH HIGH HEAT
SETTABLE PROPERTY
Technical Field
[1] The present invention relates to a process for preparing polyurethane and an elastic fabric comprising polyurethane elastic yarns made therefrom and, particularly, to polyurethane prepared by adding diamine of chain extender at a predetermined rate and polyurethane elastic yarns made therefrom having excellent heat settable property.
[2] More particularly, the present invention relates to a knitted fabric consisting of the elastic fabric having excellent heat settable property at low temperature and a heat- sensitive fiber such as nylon, silk, wool, polypropylene, rayon and polytrimethylene terephthalate. The knitted fabric may be heat-set at low temperature to prevent heat degradation of the heat- sensitive fiber and edge curling of the knitted fabric. Background Art
[3] Polyurethane is customarily prepared by reacting a polyol with an excessive amount of diisocyanate to prepare a prepolymer, dissolving the prepolymer in an organic solvent and then adding diamine or diol of chain extender to the resulting solution and reacting with chain terminator such as mono-alcohol and monoamine to form a polyurethane spinning solution which is then dry- or wet-spun to make the polyurethane elastic fiber.
[4] The polyurethane fiber is characterized by its high elasticity and widely used in a variety of areas. As its usage has expanded, there is a growing demand for developing extra features of polyurethane fibers.
[5] Generally, polyurethane fibers is heat-set at high temperature during a post-process after knitting and the high temperature causes heat degradation of heat- sensitive fibers such as nylon, cotton, silk, wool, polypropylene, rayon and polytrimethylene terephthalate. In order to prevent heat degradation and improve fabric hand value, it is increasingly necessary to develop a polyurethane fiber to be heat-set at low temperature.
[6] In the related art, efforts to improve the heat settable property of polyurethane fibers have been continued. For examples, Japanese Patent Publication No. S63-53287, Japanese Patent Publication No. S63-53288, Japanese Patent Publication No. S43-639, Japanese Patent Publication No. H7-316922, Korean Patent Publication No. 2001-5854, Korean Patent Publication No. 2001-16788 disclose processes for improving heat settable property of polyurethane elastic yarns. Furthermore, U.S. Patent No. 6,472,494, U.S. Patent No. 6,403,682, U.S. Patent No. 6,376,071, U.S.
Patent No. 6,063,892, U.S. Patent No. 5,981,686, U.S. Patent No. 5,948,875 disclose processes for improving the heat settable property of polyurethane elastic yarns. Due to the lack of heat settable property at a low temperature, however, heat-sensitive fibers have not been applicable to the processes disclosed in the prior arts. Disclosure of Invention Technical Problem
[7] The object of the present invention is to prepare polyurethane elastic yarns having excellent heat settable property with appropriate amine. According to the present invention, the polyurethane elastic yarns are knitted with a heat-sensitive fiber such as nylon, cotton, silk, wool, polypropylene, rayon and polytrimethylene terephthalate. The knitted fabric may be heat- set at low temperature to prevent fabric degradation of the heat-sensitive fiber which in turn improves fabric hand value and to provide the knitted fabric without edge curling. Technical Solution
[8] According to a preferred embodiment of the present invention, a process for preparing polyurethane elastic yarns having excellent heat settable property and an elastic fabric made therefrom are produced by reacting polyols with an excessive amount of diisocyanate to prepare a prepolymer, dissolving the prepolymer in an organic solvent and reacting the resulting solution with a chain extender in order to prepare polyurethane elastic yarns, wherein an amount of 1,3-diaminopropane contained in the chain extender is 40 mol% or more based on the total chain extender.
[9] According to another preferred embodiment of the present invention, a process for preparing polyurethane elastic yarns is provided wherein the chain extender further comprises at least one selected from a group consisting of ethylene diamine, 1,2- di- aminopropane, 1,4-diaminobutane, 2,3-butanediamine, 1,5-pentanediamine, 1,6-hexandiamine and 1,4-cyclohexanediamine.
[10] According to another preferred embodiment of the present invention, a process for preparing polyurethane elastic yarns is provided wherein the prepolymer contains 1.56 wt% to 4.29 wt% of isocyanate based on the total prepolymer.
Advantageous Effects
[11] By using the polyurethane elastic yarns produced in accordance with the present invention, a knitted fabric may be heat-set at lower temperature after knitting compared to the prior arts. Hence, heat degradation of the heat-sensitive fiber may be prevented which in turn improves fabric hand value. It also prevents edge curling of the knitted fabric. Best Mode for Carrying Out the Invention
[12] Hereinafter, polyurethane elastic yarns having excellent heat settable property
according to the present invention will be described.
[13] Segmented polyurethane used in the present invention is made by reacting organic diisocyanate with polymer diol to prepare a prepolymer, dissolving the prepolymer in an organic solvent and then reacting with diamine and monoamine.
[14] Examples of organic diisocyanate used in the present invention may include at least one selected from a group consisting of diphenylmethane-4,4-diisocyanate, 1 ,5-naphthalenediisocyanate, 1 ,4-phenylenediisocyanate, hexamethylenediisocyanate, 1,4-cyclohexanediisocyanate, 4,4'-dicyclohexylmethanediisocyanate and isophorone diisocyanate.
[15] Examples of polymer diol used in the present invention may include polyte- tramethylen-etherglycol, polypropylene-etherglycol and polycarbonatediol. Diamine may be used as chain extender from at least one selected from a group consisting of ethylenediamine, 1,2-diaminopropane, 1,6-hexamethylendiamine and 1,3-diaminopropane. The content of 1,3-diaminopropane based on the total chain extender should be 40 mol% or more preferably. If it is less than 40 mol %, the heat settable property of polyurethane elastic yarn considerably deteriorates.
[16] Examples of amine having one functional group used in the present invention to control molecule weight of polyurethaneurea may include diethyl amine, mo- noethanolamine, dimethyleamine and so on.
[17] Furthermore, in order to prevent discoloration and deterioration of spandex under certain environmental conditions such as ultraviolet rays and smog and possibly in the heat-setting process, sterically hindered phenolic compounds, benzofuran-on compounds, semicarbazide compounds, benzotriazole compounds and polymeric tertiary amine stabilizer may be added in combination into a spinning solution.
[18] The polyurethane elastic yarns in the present invention may further include additives such as titanium dioxide and magnesium stearate. Mode for the Invention
[19] A better understanding of the present invention may be obtained in light of the following Examples which are set forth to illustrate, but are not to be construed to limit the present invention.
[20] As described below in the Examples and Comparative Examples, the heat settable property of polyurethane yarns and the edge curling of polyurethane fibers were measured using the following methods.
[21]
[22] Evaluation of heat settable property of polvurethane yarns
[23] After being stretched to 100% (from 125 mm to 250 mm) in the air, the produced yarns was dry -heated at 17O0C for one minute and then the yarns were cooled to room
temperature. The length of the yarns was measured, and heat settable property was calculated according to the following formula:
[24]
[25] Heat settable property(%)= {(heat-set length - original length)}/ (stretched length - original length)} x 100
[26]
[27] Evaluation of edge curling
[28] Spandex heat-set at low temperature were knitted with nylon to prepare a circular- knitted fabric. After drawing a regular triangle whose side is 5 cm long on the knitted fabric, two sides of the triangle were cut it out with scissor, and water-sprayed on it and dried. After drying, the edge curling the knitted fabric was calculated according to the following formula.
[29]
[30] Edge curling(%)= (the area of triangle being curled/ the initial area of the triangle) x
100
[31]
[32] [Example 1]
[33] 550g of diphenylmethane-4,4-diisocyanate and 2328g of polytetramethylene etherglycol(the molecular average weight was 1800) were reacted with agitation in a nitrogen gas atmosphere at 8O0C for 90 minutes to produce a polyurethane prepolymer having isocyanate at both ends thereof. The prepolymer was cooled to room temperature, and 4122g of dimethylacetamide was added and dissolved to produce a polyurethane prepolymer solution. Subsequently, 46.08g(0.622 mol) of 1,3-diaminopropane, 16.01g(0.266 mol) of ethylenediamine and 5.2g of diethylamine were dissolved in 894g of dimethylacetamide, and added to the prepolymer solution below 1O0C to produce a polyurethane solution.
[34] The solid additives to the solution may include 1.5 wt% of ethylenebis(oxyethylene)bis-(3-(5-ter-butyl-4-hydroxy-m-toyl)-propionate), 0.5 wt% of 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, 1 wt% of l,l,r,l'-tetramethyl-4,4'-(methylene-di-p-phenylene)disemicarbazide, 1 wt% of poly(N,N-diethyl-2-aminoethyl methacrylate) and 0.1 wt% of titanium dioxide to produce a polyurethane spinning solution.
[35] The solution was then dry-spun at 25O0C to produce polyurethane elastic yarns of
40 denier.
[36] Using the resulting polyurethane elastic yarns whose heat-set temperature is low and nylon fibers, a circular-knitted fabric was made using a circular-knitting machine(Mayer Co.) with 38 inches cylinder diameter, 28 gauge and 120 feeder. The nylon used in preparing the knitted fabric is 70 denier nylon and knitted with 40 denier
of elastic yarns produced by the process, and the content of the elastic yarns is 8 wt% based on the total fabric weight.
[37]
[38] [Example 2]
[39] 550.2g of diphenylmethane-4,4-diisocyanate and 2328g of polytetramethylene etherglycol(the molecular average weight was 1800) were reacted with agitation in a nitrogen gas atmosphere at 8O0C for 90 minutes to produce a polyurethane prepolymer having isocyanate at both ends thereof. The prepolymer was cooled to room temperature, and 4122g of dimethylacetamide was added and dissolved to produce a polyurethane prepolymer solution. Subsequently, 32.92g(0.444 mol) of 1,3-diaminopropane, 16.01g(0.2664 mol) of ethylenediamine, 13.17g(0.1776 mol) of 1,2-diaminopropane and 5.2g of diethylamine were dissolved in 894g of dimethylacetamide, and added to the prepolymer solution below 1O0C to produce a polyurethane solution. Additives having the same composition as those of Example 1 were added and the process for preparing yarns and fabric was carried out as in Example 1.
[40]
[41] [Example 3]
[42] 550.2g of diphenylmethane-4,4-diisocyanate and 2328g of polytetramethylene etherglycol(the number average molecular weight was 1800) were reacted with agitation in a nitrogen gas atmosphere at 8O0C for 90 minutes to produce a polyurethane prepolymer having isocyanate at both ends thereof. The prepolymer was cooled to room temperature, and 4122g of dimethylacetamide was added and dissolved to produce a polyurethane prepolymer solution. Subsequently, 65.83g(0.888 mol) of 1,3-diaminopropane and 5.2g of diethylamine were dissolved in 90Og of dimethylacetamide, and added to the prepolymer solution below 1O0C to produce a polyurethane solution.
[43] Additives having the same composition as those of Example 1 were added and the process for preparing yarns and fabric was carried out as in Example 1.
[44]
[45] [Example 4 to 6 and Comparative Example 1 to 3]
[46] Example 4 to 6 and Comparative Example 1 to 3 were carried out as in Example 1, except the changes in the weight percent (wt%) of isocyanate, the type and mol percent(mol%) of chain extender as shown in Table 1.
[47] Table 1
[48] [49] As shown in Table 1, the polyurethane elastic yarns prepared with 1,3-diaminopropane as chain extender at 40 mol% or more resulted in an increase of heat settable property.
[50] [51] [Example 7 to 10 and Comparative Example 4 to 6] [52] Example 7 to 10 were carried out to produce a circular-knitted fabric with elastic yarns prepared in Example 1 and nylon, and Comparative Example 4 to 6 were carried out with elastic yarns prepared by Comparative Example 1 and nylon. They were then treated under the heat-setting conditions shown in Table 2. The edge curling(%) and fabric hand value of the resulting fabric are shown in Table 2.
[53] [54] Table 2
[55] [56] As shown in Table 2, in the process of preparing circular-knitted nylon fabric, the fabric of Example 7 to 10 prepared with yarns in Example 1 do not cause edge curling even at 2O0C lower heat-setting temperature, compared to the fabric in Comparative Example 5 prepared with yarns in comparative Example 1. Meanwhile, no edge curling occurred in Comparative Example 5, but the fabric hand value was inferior because it was heat-set at high temperature. As shown in the Table, the fabric using spandex does not cause heat degradation of nylon with the heat- setting process at lower temperature and therefore the fabric may have excellent fabric hand value. Furthermore, as shown in Example 10, the process of pre-setting may be omitted.
[57] The present invention is specifically explained providing illustrative embodiments. It is to be appreciated that those skilled in the art may change or modify the embodiments without departing from the scope and sprit of the present invention. While the present invention has been described with reference to the particular illustrative embodiments, it is not to be restricted by the embodiments but only by the appended claims. Industrial Applicability
[58] The polyurethane elastic yarns of the present invention show excellent heat settable property at low temperature. Therefore, the fabric comprising the elastic yarns prepared in the present invention do not cause edge curling with the heat-set process at low temperature, which resulted in excellent fabric hand value of the resulting knitted fabric available in various areas.
[59]
Claims
[1] A process for preparing polyurethane elastic yarns having excellent heat settable property, comprising the steps of:
(a) reacting polyols with an excessive amount of diisocyanate to prepare a prepolymer, (b) dissolving the prepolymer in an organic solvent and (c) reacting the resulting solution with a chain extender in order to prepare polyurethane elastic yarns, wherein an amount of 1,3-diaminopropane contained in the chain extender is 40 mol% or more based on the total chain extender.
[2] The process for preparing polyurethane elastic yarns according to the claim 1, wherein the chain extender further comprises at least one selected from a group consisting of ethylene diamine, 1,2- diaminopropane, 1,4-diaminobutane, 2,3-butanediamine, 1,5-pentanediamine, 1,6-hexandiamine and 1 ,4-cyclohexanediamine.
[3] The process for preparing polyurethane elastic yarns according to the claim 1 or
2, wherein the prepolymer contains 1.56 wt% to 4.29 wt% of isocyanate based on the total prepolymer.
[4] An elastic fabric containing the polyurethane elastic yarns made by the process of claim 1.
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| CN2007800277099A CN101495683B (en) | 2006-07-31 | 2007-07-31 | A polyurethane elastic fiber with high heat settable property |
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| KR1020060071869A KR100711644B1 (en) | 2006-07-31 | 2006-07-31 | A polyurethane elastic fiber with high heat settable property |
| KR10-2006-0071869 | 2006-07-31 |
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| KR (1) | KR100711644B1 (en) |
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| MX2011003995A (en) * | 2008-10-17 | 2011-05-10 | Invista Tech Sarl | Fusible bicomponent spandex. |
| CN103255500B (en) * | 2013-05-30 | 2015-03-25 | 浙江华峰氨纶股份有限公司 | Preparation method of polyurethane elastic fiber suitable for low-temperature setting |
| CN103498209B (en) * | 2013-10-21 | 2015-10-28 | 浙江华峰氨纶股份有限公司 | There is the preparation method of high temperature resistant and alkaline-resisting polyurethane elastomeric fiber |
| CN105506777A (en) * | 2016-01-26 | 2016-04-20 | 浙江华峰氨纶股份有限公司 | Polyurethane elastic fiber easy to adhere and preparation method thereof |
| CN107663670B8 (en) * | 2017-08-16 | 2019-10-15 | 东华大学 | A kind of polyurethane elastomeric fiber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0219511A (en) * | 1988-05-26 | 1990-01-23 | E I Du Pont De Nemours & Co | Spuntex fiber having copolymer soft segment |
| US20020028901A1 (en) * | 1999-04-23 | 2002-03-07 | Elastomedic Pty Limited | Siloxane-containing polyurethane-urea compositions |
| KR20020095226A (en) * | 2000-04-26 | 2002-12-20 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Spandex with high heat-set efficiency |
| KR20050055740A (en) * | 2002-10-04 | 2005-06-13 | 인비스타 테크놀러지스 에스.에이.알.엘 | Spandex fiber using ethylene diamene/1,2-diaminopropane as chain extender and process for making same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5644015A (en) * | 1996-07-24 | 1997-07-01 | Hyosung T & C Co., Ltd. | Process of manufacturing improved polyurethane fiber polymer |
| US6468652B1 (en) * | 1999-03-19 | 2002-10-22 | Asahi Kasei Kabushiki Kaisha | Elastic polyurethane-urea fiber and method for producing the same |
-
2006
- 2006-07-31 KR KR1020060071869A patent/KR100711644B1/en active IP Right Grant
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2007
- 2007-07-31 CN CN2007800277099A patent/CN101495683B/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0219511A (en) * | 1988-05-26 | 1990-01-23 | E I Du Pont De Nemours & Co | Spuntex fiber having copolymer soft segment |
| US20020028901A1 (en) * | 1999-04-23 | 2002-03-07 | Elastomedic Pty Limited | Siloxane-containing polyurethane-urea compositions |
| KR20020095226A (en) * | 2000-04-26 | 2002-12-20 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Spandex with high heat-set efficiency |
| KR20050055740A (en) * | 2002-10-04 | 2005-06-13 | 인비스타 테크놀러지스 에스.에이.알.엘 | Spandex fiber using ethylene diamene/1,2-diaminopropane as chain extender and process for making same |
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|---|---|
| KR100711644B1 (en) | 2007-04-25 |
| CN101495683B (en) | 2011-09-14 |
| CN101495683A (en) | 2009-07-29 |
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