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WO2017010692A1 - Fibre spandex ayant une excellente résistance au chlore - Google Patents

Fibre spandex ayant une excellente résistance au chlore Download PDF

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Publication number
WO2017010692A1
WO2017010692A1 PCT/KR2016/006425 KR2016006425W WO2017010692A1 WO 2017010692 A1 WO2017010692 A1 WO 2017010692A1 KR 2016006425 W KR2016006425 W KR 2016006425W WO 2017010692 A1 WO2017010692 A1 WO 2017010692A1
Authority
WO
WIPO (PCT)
Prior art keywords
chlorine
weight
spandex fiber
compound
chlorine resistance
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2016/006425
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English (en)
Korean (ko)
Inventor
홍지혜
강연수
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hyosung Corp
Original Assignee
Hyosung Corp
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 Hyosung Corp filed Critical Hyosung Corp
Priority to CN201680040533.XA priority Critical patent/CN107849747B/zh
Publication of WO2017010692A1 publication Critical patent/WO2017010692A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/10—Filtering or de-aerating the spinning solution or melt
    • 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
    • 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

  • Spandex fibers are widely used in underwear, socks, sports clothes, and the like because they are excellent in physical properties such as tensile stress and recoverability while maintaining high rubber elasticity.
  • the polyurethane part which is the main component of spandex fiber, is significantly degraded in physical properties when washing with chlorine bleach, and even in swimwear made by alternating spandex fiber and polyamide fiber, the amount of chlorine in the pool (active chlorine concentration 0.5 to 3.5 ppm) degrades the physical properties of the spandex fibers.
  • U.S. Patent No. 4,340,527 uses zinc oxide and U.S. Patent No. 5,626,960.
  • No. 6-81215 describes a mixture of huntite and hydromagnesite, Korean Patent Publication No. 92-3250, calcium carbonate and barium carbonate, and Japanese Laid-Open Patent Publication No. Hei 6-81215 disclose a solid solution of MgO / ZnO.
  • Japanese Patent Laid-Open No. 59-133248 discloses magnesium oxide, magnesium hydroxide or hydrotalcite
  • Japanese Patent Laid-Open No. 3-292364 disclose hydrotalcite treated with higher fatty acid and silane coupling agent, respectively.
  • U.S. Patent No. 5,447,969 uses hydrotalcite having crystal water and C 10 to C 30 fatty acid attached thereto, thereby improving the dispersibility of hydrotalcite and preventing agglomeration of hydrotalcite during the manufacturing process of spandex fiber. It prevents, improves the discharge pressure and yarn breakage during the spinning process, and it is disclosed that even when treated with tannin solution, the spandex fibers do not brown and swell even when chlorine water is immersed.
  • U.S. Patent No. 6,692,828 discloses hydrotalcite coated with melamine-based compounds having excellent heat resistance as a chlorine resistant agent of spandex fiber, but even when using such hydrotalcite, the degree is less than that of U.S. Patent No. 5,447,969. However, the phenomenon of discoloration of the spandex during dry spinning in hot air at 250 ° C. still remained.
  • European Patent Publication No. 1 262 499 A1 is intended to improve the chlorine resistance of spandex fibers using milling hydrotalcite as the chlorine resistant agent and having an average particle diameter of 1 micron or less.
  • Korean Patent Laid-Open Publication No. 2006-5814 manufactures spandex having excellent discoloration and chlorine resistance by using hydrotalcite coated with melamine-based compound and decrystallized water.
  • the removed hydrotalcite is highly hygroscopic and easy to return to the hydrotalcite having the same number of crystals as its original state, so that great care must be taken in handling.
  • hydrotalcite absorbs moisture contained in the slurry or polymer during the slurry manufacturing process or the mixing process of the slurry and the polymer in the process of manufacturing spandex to hydrotalcite having crystal water. Since it changed, the yarn discolored when the spandex polymer disclosed by this patent publication was spun at 250 degreeC or more.
  • Korean Laid-Open Patent Publication No. 2006-66689 manufactures spandex having excellent discoloration resistance and chlorine resistance using partially dehydrated hydrotalcite, which is superior to that of Korean Laid-Open Patent Publication No. 2006-5814. It showed discoloration resistance and chlorine resistance.
  • the conventional chlorine-resistant spandex-related patents basically apply the inorganic chlorine-resistant agent, and confirm the effect by applying an organic additive to improve the durability of the chlorine-resistant.
  • these chlorine-resistant spandex fibers are often a decrease in strength after treatment in chlorine water.
  • the present inventors have realized that the strength of the fiber is maintained even after the treatment with chlorine water to improve the chlorine resistance, thereby completing the present invention. It is an object of the invention to improve the firing.
  • the present invention is selected from the group of compounds comprising an inorganic chlorine agent, a mono-hindered hydroxyphenyl group in a polyurethaneurea polymer, an additive comprising a dimicarbazide system and a dialkyl sulfosuccinate corresponding to the following formula (1): It is characterized in that the spandex fiber with excellent chlorine resistance improved strength produced by dry spinning a polyurethane urea spinning stock solution containing 0.01 to 10% by weight of nate.
  • R 1 and R 2 are each independently the same or different and are hydrogen or an alkyl group having 1 to 30 carbon atoms
  • M + represents H + , Li + , Na + , K + or NH 4 + series of cations .
  • the present invention may bring an effect of improving the chlorine resistance by improving the strength by adding an additive having a strength improving function to the existing chlorine resistant fiber.
  • the additive may improve the workability by improving the adhesion between the filaments to prevent the filament convergence due to the friction in the knitting machine using the spandex fiber to prevent trimming or stripping of the fabric.
  • polyurethane refers to an artificial fiber that is a long chain synthetic elastomer consisting of at least 85% by weight of fiber forming material.
  • Polyurethanes are prepared from a mixture of polyether glycols, diisocyanates and chain extenders and then melt spun and dry spun as described above to form fibers.
  • Polyurethane prepolymer solution used in the preparation of the spandex fiber of the present invention is prepared by reacting organic diisocyanate and polymer diol to prepare a polyurethane prepolymer as is known in the art, and then dissolved in an organic solvent, for example dimethylacetamide By reacting diamine with monoamine.
  • organic diisocyanate used in the present invention 4,4'-diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated P, P-methylene diisocyanate And the like, and the polymer diol may be polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, or the like.
  • the diamines are used as chain extenders, and examples thereof include ethylenediamine, propylenediamine, hydrazine, 1,2-diaminopropane, and the like. In the present invention, especially 80 mol of ethylenediamine and 1,2-diaminopropane are used. Mixtures of% and 20 mol% may be used. Monoamines are also used as chain terminators, for example diethylamine, monoethanolamine, dimethylamine and the like.
  • a polyurethaneurea radiation source solution may be prepared by adding a light-resisting agent, an antioxidant, an inorganic chlorine-resistant agent and a strength improving additive. Can be.
  • the resulting polyurethaneurea solution may be dry spun to form the spandex.
  • the light resistant agent includes titanium dioxide or magnesium stearate, and its use ranges from 0.1 to 1.0% by weight, preferably 0.3 to 0.6% by weight, based on the solid content of the polyurethaneurea polymer. Is added.
  • a urethane-based additive including a tertiary butyl group serving as an antioxidant for example, a compound obtained by copolymerizing t-butyldiethanolamine and 4,4'-methylenebis (cyclohexylisocyanate) It can mix and add in the range of weight%.
  • the inorganic chlorinating agent it is possible to use a hydrotalcite compound, a mixed mineral of a futite and hydromagnesite or a hydromagnesite compound.
  • Dihydro as hydrotalcite compounds include, for example, Mg 4 Al 2 (OH) 12 CO 3 ⁇ 3H 2 O, Mg 4 .5Al 2 (OH) 13 CO 3 ⁇ 3.5H 2 O, Mg 6 Al 2 (OH) 16 CO 3 H 2 O, Mg 8 Al 2 (OH) 20 CO 3 H 2 O, Mg 4 Al 2 (OH) 12 CO 3 H 2 O, Mg 4 .
  • Hydrotalcite has a feature of absorbing moisture, and when it is added to a polyurethane polymer without coating, gel generation and aggregation may occur and cause trimming in the spinning process. Hydrotalcite can be coated and used to prevent water absorption and improve dispersibility of hydrotalcite to improve the release pressure and trimming during the spinning process. Even in the case of using uncoated hydrotalcite, when the sand grinding or milling is performed, the same radioactivity can be obtained as in the case of using the coated hydrotalcite.
  • melamine compound 1 to 10% by weight of hydrotalcite coated with 1 to 3% by weight of stearic acid and 0.5 to 2% by weight of melamine compound is added to the polymer of the polyurethane solution.
  • the melamine-based compound is best used by selecting melamine polyphosphate.
  • Huntite compounds are represented by the formula Mg 3 Ca (CO 3 ) 4 , and examples of hydromagnesite compounds include Mg 5 (CO 3 ) 4 (OH) 2 .4H 2 O, Mg 4 (CO 3 ) 4 .Mg ( OH) 2 ⁇ H 2 O, Mg 3 (CO 3) 3 ⁇ Mg (OH) 2 ⁇ 3H 2 O, Mg 4 (CO 3) 4 ⁇ Mg (OH) 2, and Mg 3 (CO 3) 3 ⁇ Mg (OH) 2 , MgCO 3 , and the like.
  • the mixing ratio of the mixed minerals of the huntite and the hydromagnesite may be 90:10, 80:20, 70:30, 60:40 or 40:60, etc., and the ratio of 60:40 is most preferable. .
  • a compound containing a mono-hindered hydroxyphenyl group as an additive for improving chlorine resistance for example, 1,1,3-tris (2'-methyl-4'-hydroxy-5'-t-butyl Phenyl) butane may be used, with a range of 0.1 to 3.0% by weight relative to solids of the polyurethaneurea polymer being preferred.
  • the additive including a dimicarbazide system having heat resistance and radical scavenger function is 1,1,1 ', 1'-tetramethyl-4,4'-(methylene-di-) which is a hindered amine compound.
  • p-phenylene) disemicarbazide or 1,6-hexamethylene bis (N, N-dimethyl disemicarbazide) is preferably added and mixed with 0.1 to 3.0% by weight, preferably 0.3 to 1.2% by weight. .
  • the strength enhancing additive it is preferable to use 0.01 to 10% by weight of the dialkyl sulfosuccinate corresponding to the following general formula (1).
  • R 1 and R 2 are each independently the same or different and are hydrogen or an alkyl group having 1 to 30 carbon atoms
  • M + represents H + , Li + , Na + , K + or NH 4 + series of cations .
  • dialkyl sulfosuccinate of formula (1) examples include sodium diisobutyl sulfosuccinate, sodium dioctyl succinate, sodium dihexyl sulfosuccinate, sodium diamyl sulfosuccinate and sodium dicyclohexyl sulfo. Succinate. More particularly preferred dialkyl sulfosuccinates are sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate.
  • a step of dissolving in a solvent is required, and when the mixture is mixed with the slurry, the slurry dispersibility is improved and the yarn uniformity can be improved.
  • the strength according to the present invention is increased. It is possible to produce a spantex fiber with excellent chlorine resistance.
  • the spandex fiber having excellent strength and chlorine resistance with improved strength according to the present invention is different from the conventional art of preparing spandex with improved chlorine resistance by applying inorganic additives and organic additives to maximize the effect of improving chlorine resistance by applying dialkyl sulfoxinate. It is characterized by. Chlorine resistance is evaluated by the power retention rate of the spandex yarn before and after chlorine water treatment, and the higher the strength of the spandex yarn, the better the properties. It can be seen that not only the strength of the yarn is improved through the application of the dialkyl sulfoxinate but also the length of time that the strength retention rate after the chlorine water treatment is high increases, thereby improving the chlorine resistance improving effect compared to the conventional technology.
  • the spinning temperature was 260 ° C. in the dry spinning process, and the winding speed was wound at 900 m / min to prepare 3 filament 40 denier spandex yarn, and its yarn properties and chlorine resistance were evaluated and shown in Table 1 below. .
  • Table 1 In order to evaluate the chlorine resistance of the obtained spandex yarn, strong retention in chlorine water was evaluated by the following method.
  • the measurement is made at a sample length of 10 cm and a tensile velocity of 100 cm / min. At this time, the strength and elongation at break are measured, and the load (200% modulus) on the yarn when the yarn is stretched 200% is also measured.
  • the spandex yarn was treated for 1 hour in water at 99-100 ° C. under 50% elongation, dried and cooled at room temperature, immersed in chlorine water at 3.5 ppm of active chlorine at pH 7.6 for 120 hours at room temperature, and then subjected to the following formula. The retention rate was calculated.
  • a MEL instrument was used for the strong evaluation, and the sample length was 10 cm and measured at a cross head speed of 1000 mm / min using a cell of 32 kg f .
  • Example 1 the spinning stock solution obtained by adding and mixing 1.0% by weight of dialkyl sulfosuccinate was spun at a speed of 900 m / min by dry spinning yarn to prepare 40 denier 3 filament polyurethaneurea elastic yarn. And the physical properties thereof are shown in Table 1.
  • Example 2 In the same manner as in Example 1, a spinning stock solution obtained by adding and mixing 2.0 wt% of dialkyl sulfosuccinate was spun at a speed of 900 m / min by dry spinning to prepare 40 denier 3 filament polyurethaneurea elastic yarn. The physical properties were evaluated and shown in Table 1.
  • a 40-denia 3 filament polyurethaneurea elastic yarn was prepared by preparing a spinning stock solution in the same manner as in Example 1 except for not adding a dialkyl sulfosuccinate and spinning at a speed of 900 m / min by dry spinning.
  • the physical properties were evaluated and shown in Table 1.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une fibre spandex ayant une résistance mécanique améliorée et une excellente résistance au chlore, comprenant un sulfosuccinate de dialkyle correspondant à la formule suivante (1), où R1 et R2 sont indépendants l'un de l'autre, sont identiques ou différents, et sont de l'hydrogène ou un groupe alkyle avec 1 à 30 atomes de carbone ; et M+ représente un cation à base de H+, Li+, Na+, K+ ou NH4+.
PCT/KR2016/006425 2015-07-10 2016-06-16 Fibre spandex ayant une excellente résistance au chlore Ceased WO2017010692A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201680040533.XA CN107849747B (zh) 2015-07-10 2016-06-16 具有良好的耐氯性的氨纶纤维

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2015-0098433 2015-07-10
KR1020150098433A KR101684792B1 (ko) 2015-07-10 2015-07-10 내염소성이 우수한 스판덱스 섬유

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WO2017010692A1 true WO2017010692A1 (fr) 2017-01-19

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KR (1) KR101684792B1 (fr)
CN (1) CN107849747B (fr)
WO (1) WO2017010692A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101913354B1 (ko) * 2017-02-28 2018-10-30 태광산업주식회사 생산성 및 작업성이 우수한 폴리우레탄우레아 탄성섬유

Citations (5)

* Cited by examiner, † Cited by third party
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KR970006564A (ko) * 1995-07-11 1997-02-21 박홍기 폴리우레탄계 탄성섬유의 제조방법
KR20040007647A (ko) * 2001-06-05 2004-01-24 이 아이 듀폰 디 네모아 앤드 캄파니 페놀계 화합물의 혼합물을 함유하는 스판덱스
KR20120076268A (ko) * 2010-12-29 2012-07-09 주식회사 효성 멀티필라멘트 탄성섬유의 필라멘트간 접착력이 우수한 폴리우레탄 섬유 및 이의 제조방법
KR20120090120A (ko) * 2010-12-30 2012-08-17 주식회사 효성 내염소성과 내변색성이 향상된 스판덱스 섬유 및 이의 제조방법
KR20140054509A (ko) * 2012-10-29 2014-05-09 주식회사 효성 내염소성 및 내변색성이 우수한 스판덱스 섬유 및 그의 제조방법

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DE19805130A1 (de) * 1998-02-09 1999-08-12 Bayer Ag Antistatisch ausgerüstete Polyurethane und Elastan-Fasern
KR101130510B1 (ko) * 2009-09-30 2012-03-28 주식회사 효성 내염소성이 우수한 스판덱스 섬유 및 그의 제조방법
KR101238495B1 (ko) * 2010-12-30 2013-03-04 주식회사 효성 내염소성과 내변색성이 향상된 스판덱스 섬유 및 이의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR970006564A (ko) * 1995-07-11 1997-02-21 박홍기 폴리우레탄계 탄성섬유의 제조방법
KR20040007647A (ko) * 2001-06-05 2004-01-24 이 아이 듀폰 디 네모아 앤드 캄파니 페놀계 화합물의 혼합물을 함유하는 스판덱스
KR20120076268A (ko) * 2010-12-29 2012-07-09 주식회사 효성 멀티필라멘트 탄성섬유의 필라멘트간 접착력이 우수한 폴리우레탄 섬유 및 이의 제조방법
KR20120090120A (ko) * 2010-12-30 2012-08-17 주식회사 효성 내염소성과 내변색성이 향상된 스판덱스 섬유 및 이의 제조방법
KR20140054509A (ko) * 2012-10-29 2014-05-09 주식회사 효성 내염소성 및 내변색성이 우수한 스판덱스 섬유 및 그의 제조방법

Also Published As

Publication number Publication date
CN107849747B (zh) 2020-07-03
CN107849747A (zh) 2018-03-27
KR101684792B1 (ko) 2016-12-21

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