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WO2000036195A1 - Spandex stabilise - Google Patents

Spandex stabilise Download PDF

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Publication number
WO2000036195A1
WO2000036195A1 PCT/US1999/029707 US9929707W WO0036195A1 WO 2000036195 A1 WO2000036195 A1 WO 2000036195A1 US 9929707 W US9929707 W US 9929707W WO 0036195 A1 WO0036195 A1 WO 0036195A1
Authority
WO
WIPO (PCT)
Prior art keywords
spandex
glycol
poly
mixture
huntite
Prior art date
Application number
PCT/US1999/029707
Other languages
English (en)
Inventor
Yuji Uemura
Original Assignee
Du Pont-Toray Company, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Du Pont-Toray Company, Ltd. filed Critical Du Pont-Toray Company, Ltd.
Priority to US09/857,523 priority Critical patent/US6372834B1/en
Priority to EP99966245A priority patent/EP1155173B1/fr
Publication of WO2000036195A1 publication Critical patent/WO2000036195A1/fr

Links

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
    • 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
    • D01F6/58—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

Definitions

  • the present invention relates to spandex containing a combination of additives and, more specifically, to spandex containing both an inorganic stabilizer and a polymeric hindered amine stabilizer.
  • United States Patent 2,999,839 discloses the use of poly (N,N-diethyl-2-aminoethyl methacrylate) , alone or in combination with specific inorganic additives, as an additive in spandex.
  • this additive is not particularly effective at preventing yellowing when the spandex is exposed to the chlorine agents present in swimming pools and laundries.
  • Various inorganic compounds such as zinc oxide and a mixture of huntite and hydromagnesite are disclosed as spandex additives in United States Patents 4,340,527 and 5,626,960, respectively. These additives offer chlorine resistance to spandex but may not be able to prevent yellowing of the spandex on exposure to nitrogen oxides or UV light.
  • the present invention is spandex containing a stabilizing composition of
  • spandex containing both poly (N,N-diethyl-2-aminoethyl methacrylate) and a mixture of huntite and hydromagnesite has high resistance to yellowing and high mechanical resistance to chlorine.
  • Spandex means a manufactured fiber in which the fiber- forming substance is a long chain synthetic elastomer comprised of at least 85% by weight of a segmented polyurethane .
  • Spandex is typically prepared by either melt- spinning a polyurethane or dry- or wet -spinning a polyurethane or polyurethaneurea solution either into a column filled with a hot inert gas such as air, nitrogen or steam or into an aqueous bath to remove the solvent followed by winding up the fiber.
  • the polyurethane is generally made by reacting a polymeric glycol with a diisocyanate to form a capped glycol, a mixture of isocyanate-terminated glycol and unreacted diisocyanate. If a polyurethane without urea moieties is desired, the capped glycol can be reacted with a diol chain extender and optionally a monofunctional chain terminator either in the melt or after being dissolved in a solvent. If a polyurethaneurea is desired, the capped glycol can be dissolved in a solvent before being reacted with a diamine chain extender and optional monofunctional chain terminator.
  • Polymeric glycols used to prepare polyurethanes for spandex include polyethers such as poly (tetramethylene- ether) glycol, poly (3 -methyl -1 , 5-pentamethyleneether) glycol, and poly (tetramethyleneether-co-2-methyltetra- methyleneether) glycol; polyesters such as the polycondensation products of diols such as ethylene glycol, 1,4 -butane diol, and 2 , 2-dimethyl-1 , 3 -propane diol with diacids such as adipic acid, succinic acid, dodecanedioic acid, and copoly ⁇ ners thereof; and polycarbonates such as poly (pentane-1 , 5-carbonate) diol and poly (hexane-1, 6-carbonate) diol.
  • polyethers such as poly (tetramethylene- ether) glycol, poly (3 -methyl -1 , 5-pentamethyleneether) glycol, and poly
  • Useful diisocyanates include 1 , 1 ' -methylenebis (4- isocyanatobenzene) ("MDI"), 1, 1 ' -methylenebis (4- isocyanatocyclohexane) , 4 -methyl -1 , 3-phenylene diisocyanate, 5-isocyanato-l- (isocyanatomethyl) -1,3,3- trimethylcyclohexane, 1, 6-hexamethylene diisocyanate, and mixtures thereof .
  • MDI 1 , 1 ' -methylenebis (4- isocyanatobenzene)
  • MDI 1, 1 ' -methylenebis (4- isocyanatocyclohexane)
  • 4 -methyl -1 4-phenylene diisocyanate
  • 5-isocyanato-l- (isocyanatomethyl) -1,3,3- trimethylcyclohexane 1, 6-hexamethylene diisocyanate, and mixtures thereof .
  • Useful chain extenders for making polyurethanes include ethylene glycol, trimethylene glycol, 1,4- butanediol, neopentyl glycol, 1 , 2-propylene glycol, 1,4- cyclohexane dimethylol, 1 , 4-cyclohexane diol, 1,4 -bis (2- hydroxyethoxy) benzene, bis (2-hydroxyethyl) terephthalate, paraxylylene diol, and mixtures thereof.
  • Useful chain extenders for making polyurethaneureas include ethylene diamine, 1, 3 -cyclohexane diamine, 1 , 4-cyclohexane diamine, 1,3- diaminopropane, 1 , 2-diaminopropane, 1 , 3-diaminopentane, 2 -methyl -1, 5-pentanediamine, and mixtures thereof.
  • Chain terminators optionally used to control molecular weight can include diethylamine, cyclohexylamine, butylamine, hexanol , and butanol .
  • the concentration of the polyurethane (urea) in the spinning solution is in the range of about 30-40 weight percent, based on the total weight of the solution.
  • Suitable solvents for the spinning solution include dimethylacetamide (“DMAc”), N-methylpyrrolidone, and dimethylformamide .
  • the stabilizing composition can be introduced into the spandex of this invention by first preparing a slurry of the composition, and optionally other additives and/or a viscosity enhancer (for example some of the polyurethane from which the spandex is to be made) , in DMAc and then mixing the slurry into the spinning solution just before spinning. Separate slurries can be used for the various additives, but it is not necessary to do so. In order to obtain a uniformly mixed slurry with very finely divided particle sizes, the slurry is mixed at high shear, for example, by milling or otherwise grinding.
  • the spandex of this invention contains 0.5%-5% by weight of pol (N,N-diethyl-2-aminoethyl methacrylate).
  • the inorganic material of the stabilizing composition can be a mixture of huntite [ (Mg 3 Ca (C0 3 ) 4) ] and hydromagnesite (basic magnesium carbonate) , generally represented as Mg 4 (C0 3 ) • Mg (OH) • 4H 2 0 or zinc oxide.
  • huntite (Mg 3 Ca (C0 3 ) 4)
  • hydromagnesite basic magnesium carbonate
  • Beneficial effects have been observed when the mixture of huntite and hydromagnesite is incorporated into the spandex in an amount of at least about 0.25% by weight.
  • the inorganic material is present as 1.5-5% by weight, based on the weight of the spandex.
  • T b tenacity-at break
  • Total isocyanate moiety content (“%NCO) in the capped glycol was measured by the method of S. Siggia,
  • a solution of polyurethaneurea was prepared by the following conventional method. MDI and poly (tetramethyleneether) glycol (Terathane® 1800, a registered trademark of E. I. du Pont de Nemours and
  • capped glycol having 2.22% NCO.
  • a 250-g quantity of the capped glycol was diluted with 440 g of DMAc (36wt% solids) .
  • 30 g DMAc, 4 g ethylene diamine chain extender and 0.2 g diethylamine chain terminator were mixed and the resulting solution was added to the capped glycol solution and very rapidly mixed at room temperature using a commercial high speed stirrer (model B200G, Tokyo Rikakikai Co., Ltd.) .
  • the resulting solution was 35wt% in polyurethane and had a viscosity of 2000-3000 poise, measured in accordance with the general method of ASTM D1343 -69 using a Model DV-8 Falling Ball Viscometer (Duratech Corp., Waynesboro, VA.), operated at 40°C.
  • a slurry was prepared from a mixture of huntite and hydromagnesite (50/50 weight ratio) (Ultracarb U3 , having a median particle size of about 3.6 microns, manufactured by Microfine Minerals Ltd.), a condensation polymer of p-cresol and divinyl benzene (Methacrol ® 2390 D, a registered trademark of E. I. du Pont de Nemours and Company), poly (N,N-diethyl-2-aminoethyl methacrylate) ("FHM", manufactured by Sanyo Kasei Kogyo KK) , DMAc, and a small amount of the polyurethaneurea to be used as the spandex.
  • huntite and hydromagnesite 50/50 weight ratio
  • U3 huntite and hydromagnesite
  • Methodhacrol ® 2390 D a registered trademark of E. I. du Pont de Nemours and Company
  • FHM N,N-diethyl-2-aminoeth
  • the slurry was milled with glass beads using a Dyno® Mill Type KDL-special (Shimaru Enterprise Corp.) to a final median particle size of about 0.4 micron.
  • the slurry was thoroughly mixed into the polyurethane solution to give a spinning solution.
  • the proportions in the slurry and the amount mixed into the polyurethane solution were such that the spinning solution contained 4wt% of the huntite/hydromagnesite mixture, 1.5wt% Methacrol ® 2390D, and 0.58wt% poly(N,N- diethyl-2-aminoethyl methacrylate) , all based on polymer solids.
  • the spinning solution was dry spun by conventional means to form a spandex of 4 coalesced filaments totalling 40 denier (44 decitex) . Results of tests performed on the spandex are given in the Table.
  • Example 1 To a polyurethane solution, prepared as in Example 1 was added a slurry as in Example 1 except that, instead of huntite/hydromagnesite, zinc oxide was utilized (Kadox-15, New Jersey Zinc Company) so that the spinning solution contained 3% by weight of zinc oxide of the polymer solids.
  • the slurry containing ZnO was milled in a transverse mill, filled with glass beads, until the average particle size was 0.1-1 ⁇ m.
  • the spinning solution was dry-spun as in Example 1 to afford spandex filaments as in Example 1. The results are tabulated in the Table.
  • Spandex was prepared in substantially the same way as described in Example 2 but without adding any poly (N,N-diethyl-2-aminoethyl methacrylate). Test results are given in the Table.
  • Spandex was prepared in substantially the same way as described in Example 1 but without adding the mixture of huntite and hydromagnesite. Test results are also given in the Table.
  • Spandex was prepared in substantially the same way as described in Example 1 but without adding either the mixture of huntite and hydromagnesite or the poly(N,N- diethyl-2-aminoethyl methacrylate) . Test results are also given in the the Table where "Comp.” denotes a Comparison Example and “Broke” means the spandex broke during treatment or during measurement so that determination of a value was not possible.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne un spandex stabilisé, contenant une composition de stabilisation à base d'un mélange d'amine polymère entravée et de matériau inorganique.
PCT/US1999/029707 1998-12-16 1999-12-15 Spandex stabilise WO2000036195A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US09/857,523 US6372834B1 (en) 1999-12-15 1999-12-15 Stabilized spandex
EP99966245A EP1155173B1 (fr) 1998-12-16 1999-12-15 Spandex stabilise

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/375804 1998-12-16
JP37580498 1998-12-16

Publications (1)

Publication Number Publication Date
WO2000036195A1 true WO2000036195A1 (fr) 2000-06-22

Family

ID=18506092

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/029707 WO2000036195A1 (fr) 1998-12-16 1999-12-15 Spandex stabilise

Country Status (3)

Country Link
EP (1) EP1155173B1 (fr)
KR (1) KR100580407B1 (fr)
WO (1) WO2000036195A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009008600A1 (fr) * 2007-07-10 2009-01-15 Hyosung Corporation Fibres d'élasthanne contenant de l'hydromagnésite

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100780395B1 (ko) * 2006-09-04 2007-11-29 태광산업주식회사 항염소성을 갖는 폴리우레탄우레아 탄성섬유 및 그의제조방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2999839A (en) * 1958-01-17 1961-09-12 Du Pont Stabilization of elastomers containing ureylene groups
GB929257A (en) * 1960-08-05 1963-06-19 Geigy Ag J R 2-imino-1, 3-di-n-heterocyclic compounds, their production and use
US4340527A (en) * 1980-06-20 1982-07-20 E. I. Du Pont De Nemours And Company Chlorine-resistant spandex fibers
WO1997009473A1 (fr) * 1995-09-07 1997-03-13 E.I Du Pont De Nemours And Company Spandex contenant un additif a base de huntite et d'hydromagnesite

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3428711A (en) 1966-02-01 1969-02-18 Du Pont Hindered polymeric tertiary amines as stabilizers for polyurethanes
US3553290A (en) 1968-04-10 1971-01-05 Du Pont Spandex fibers stabilized with condensates of substituted phenols and divinyl benzenes
GB2126812B (en) 1982-08-30 1986-05-08 Rca Corp Television sound detection system using a phase-locked loop

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2999839A (en) * 1958-01-17 1961-09-12 Du Pont Stabilization of elastomers containing ureylene groups
GB929257A (en) * 1960-08-05 1963-06-19 Geigy Ag J R 2-imino-1, 3-di-n-heterocyclic compounds, their production and use
US4340527A (en) * 1980-06-20 1982-07-20 E. I. Du Pont De Nemours And Company Chlorine-resistant spandex fibers
WO1997009473A1 (fr) * 1995-09-07 1997-03-13 E.I Du Pont De Nemours And Company Spandex contenant un additif a base de huntite et d'hydromagnesite
US5626960A (en) * 1995-09-07 1997-05-06 E. I. Du Pont De Nemours And Company Spandex containing a huntite and hydromagnesite additive

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1155173A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009008600A1 (fr) * 2007-07-10 2009-01-15 Hyosung Corporation Fibres d'élasthanne contenant de l'hydromagnésite

Also Published As

Publication number Publication date
EP1155173A1 (fr) 2001-11-21
EP1155173B1 (fr) 2004-03-24
KR20010101230A (ko) 2001-11-14
KR100580407B1 (ko) 2006-05-16

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