WO2017086658A1 - Élasthanne à propriété de déroulage améliorée et sans apparition de mousse et son procédé de fabrication - Google Patents

Élasthanne à propriété de déroulage améliorée et sans apparition de mousse et son procédé de fabrication Download PDF

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Publication number
WO2017086658A1
WO2017086658A1 PCT/KR2016/012927 KR2016012927W WO2017086658A1 WO 2017086658 A1 WO2017086658 A1 WO 2017086658A1 KR 2016012927 W KR2016012927 W KR 2016012927W WO 2017086658 A1 WO2017086658 A1 WO 2017086658A1
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WIPO (PCT)
Prior art keywords
spandex
scum
polyethylene glycol
properties
glycol polymer
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PCT/KR2016/012927
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English (en)
Korean (ko)
Inventor
정현기
조주현
정용대
강연수
Original Assignee
주식회사 효성
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Priority claimed from KR1020160148455A external-priority patent/KR101913416B1/ko
Application filed by 주식회사 효성 filed Critical 주식회사 효성
Publication of WO2017086658A1 publication Critical patent/WO2017086658A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • 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
    • D01F6/58—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 without improving the unwinding property and the occurrence of scum, and to a method of manufacturing the same, more particularly, a polyethylene having a number average molecular weight of more than 3,000 to 11,000 in a polyurethaneurea solution, a spinning solution.
  • a polyethylene having a number average molecular weight of more than 3,000 to 11,000 in a polyurethaneurea solution, a spinning solution By preparing spandex by injecting glycol, it is possible not only to effectively improve irregular ballooning and tension spike during dissolving spandex, but also to improve other physical properties such as adhesive properties with hot melt.
  • the present invention relates to a spandex and a method for manufacturing the same, which have improved maritime properties and no scum, which can improve scum problems that may occur in rollers and guides during the diaper manufacturing process without a negative effect. .
  • Spandex maintains a high degree of rubber elasticity and is excellent in physical properties such as tensile stress and recoverability. Therefore, spandex is widely used in underwear, socks and sports clothing.
  • spandex is now being used as a functional fiber as its use is further expanded, and is being used for special purposes such as infants and elderly diapers or medical fibers.
  • Conventional medical spandex fiber has a higher interlaminar adhesion between fiber yarn and fiber yarn than general medical fiber, so it has poor maritime properties, resulting in many trimming and post-static processes in post-processing such as covering, canon and knitting work. There is a disadvantage that the tension of the non-uniform.
  • additives such as inorganic (Mg-st or Ca-st, Zn-st) compounds, which are conventionally used as anti-sticking agents, are not dissolved in the polymer solution and are dispersed, so that the material is evenly distributed on the dead surface.
  • Mg-st or Ca-st, Zn-st inorganic compounds
  • KR 2011-0128884 A conventionally proposes an elastic fiber comprising polyurethane or polyurethaneurea and about 0.5% to 25% by weight of a soluble anti-sticking composition.
  • cellulose CAB
  • an anti-sticking agent CAB
  • JP 2001-509847 A relates to spandex having low viscosity and a method for producing the same, and it is proposed to use an amide system such as ethylene bis-oleylamide / stearylamide containing nitrogen as an anti-sticking agent, and CN 001291079 C uses an antimicrobial agent such as zirconium phosphate, glass or zeolite as an anti-sticking agent for spantex.
  • an amide system such as ethylene bis-oleylamide / stearylamide containing nitrogen
  • CN 001291079 C uses an antimicrobial agent such as zirconium phosphate, glass or zeolite as an anti-sticking agent for spantex.
  • the anti-sticking agent applied to the existing spandex manufacturing prevents the adhesion between the fiber yarns, irregular ballooning and tension during the process of dissolving the spandex yarn during the diaper manufacturing process according to the addition of the inorganic material of the anti-sticking agent Tension spikes are not improving properly.
  • the organic anti-sticking agent even if the organic anti-sticking agent, the above problems are still not solved due to the drooping phenomenon, deterioration in adhesion with the hot melt and compatibility problems with the spandex polymer.
  • KR 2016-0080822 A which was previously filed by the present applicant, did not affect the adhesion properties and physical properties of hot melt when polyethylene glycol having a molecular weight of 100 to 3,000 was used for the purpose of improving sealife properties.
  • Polyethylene glycol with molecular weight of 100-3,000 exists in unstable form in which liquid and solid such as semi-solid, cream or soft wax coexist at room temperature. There is a problem of burying and scum.
  • Patent Document 1 KR 2011-0128884 A
  • Patent Document 2 JP 2001-509847 A
  • Patent Document 3 CN 001291079 C
  • Patent Document 4 KR 2016-0080822 A
  • the present invention efficiently improves irregular ballooning phenomenon and tension spike phenomenon appearing in the process of dissolving the spandex by using a new anti-sticking agent, diaper production without problems of other physical properties It is an object of the present invention to provide a spandex and a method of manufacturing the same, which does not generate scum in rollers and guides.
  • the improvement in the dissolvability and the generation of scum according to the present invention is characterized in that it comprises a polyethylene glycol polymer represented by the following formula (1).
  • the polyethylene glycol polymer of Formula 1 has a number average molecular weight of more than 3,000 to less than 11,000.
  • the method for producing a spandex without improving the sea resolution and the occurrence of scum according to the present invention is a method for producing a spandex comprising a polyurethane prepolymer solution, polyurethane solution, polyurethane urea spinning solution, polyurethaneurea room Characterized in that it comprises a polyethylene glycol polymer represented by the following formula (1) as a slurry in the use solution in the form of a slurry.
  • the polyethylene glycol polymer of Formula 1 has a number average molecular weight of more than 3,000 to less than 11,000.
  • the present invention is a polyethylene glycol polymer having a number average molecular weight of more than 3,000 to less than 11,000 in the form of a slurry in a spandex fiber spinning stock solution as an anti-sticking agent, conventionally added inorganic anti-sticking agents (Mg-st, Ca-st, Zn-st)
  • Mg-st, Ca-st, Zn-st conventionally added inorganic anti-sticking agents
  • Figure 3 is a photograph showing the structure diagram and scum occurrence position of the OETO maritime device in Experimental Example 4 according to the present invention.
  • 5 (a) and 5 (b) are photographs showing when scum did not occur in the OETO maritime apparatus in Experimental Example 4 according to the present invention.
  • Spandex without disintegration improvement and scum generation of the present invention includes a polyethylene glycol polymer represented by the following Formula 1 as an anti-sticking agent.
  • the polyethylene glycol polymer of Formula 1 preferably has a number average molecular weight of more than 3,000 to less than 11,000.
  • the polyethylen glycol polymer is preferably included in 0.1 to 20% by weight based on the weight of the polyurethane urea solution solids.
  • a method for preparing a spandex without improving the disintegration property and generating a scum is a method for preparing a spandex, which comprises preparing a conventional polyurethane prepolymer solution, a polyurethane solution, and a polyurethaneurea spinning solution, wherein the spinning source is poly
  • a polyethylene glycol polymer represented by the following formula (1) is used as an anti-sticking agent.
  • the polyethylene glycol polymer of Formula 1 has a number average molecular weight of more than 3,000 to 11,000.
  • a polyethylene glycol polymer having a number average molecular weight of more than 3,000 to less than 11,000 represented by Formula 1 above is added to a polyurethane urea solution used as a spinning stock solution in the preparation of spandex in the form of a slurry. Problems such as irregular ballooning and tension spike phenomenon do not occur.
  • the number average molecular weight of the polyethylene glycol polymer is 3,000 or less, it exists in an unstable form in which a liquid and a solid such as semi-solid, cream or soft wax coexist at room temperature. Scum appears in the roller or guide due to the manufacturing process, and if the number average molecular weight exceeds 11,000, it does not dissolve uniformly in the solvent when preparing the slurry. You may not.
  • the polyethylene glycol polymer is added in the form of slurry in the spinning stock solution, since the polyurethane urea spinning is caused because it causes a change in the basic physical properties of the polymer when it is added during the polymerization of the polyurethane prepolymer solution to obtain the polyurethane solution. It is intended to express only the anti-sticking properties by adding the slurry in the form of a stock solution.
  • the slurry state may be prepared and used in a solution state dissolved in DMAc.
  • the polyethylene glycol polymer used as an anti-sticking agent may be added in an amount of 0.1 to 20% by weight based on the weight of the solid content of the polyurethaneurea spinning solution.
  • the present invention is a spandex having a new maritime properties prepared as described above, is very suitable for application as a medical or hygine spandex.
  • the adhesive property is excellent but also the sea tension is uniform, thus preventing irregular ballooning phenomenon and improving the tension spike phenomenon and preventing the occurrence of scum.
  • ethylenediamine, 1,2-propyldiamine, and 13.4 g of diethylamine were dissolved in 829 g of dimethylacetamide and added to the prepolymer solution at 9 ° C. or lower to obtain a polyurethane solution.
  • 1% by weight of antioxidant triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate as an additive to the solid content of the polymer, and 1% by weight titanium dioxide as a light-resistant agent % was added and the spinning stock solution was obtained.
  • the spinning stock solution was prepared using 2 wt% of polyethylene glycol (number average molecular weight 4,000) as an anti-sticking agent in the form of a slurry in the spinning stock solution.
  • the spinning temperature was set at 260 ° C. or higher and the winding speed was wound at 500 m / min.
  • Spandex fibers were prepared in the same manner as in Example 1, except that 5 wt% of a polyethylene glycol polymer (number average molecular weight 4,000) as an anti-sticking agent was added to the spinning dope.
  • a polyethylene glycol polymer number average molecular weight 4,000
  • Spandex fibers were prepared in the same manner as in Example 1, except that 10 wt% of a polyethylene glycol polymer (number average molecular weight 4,000) as an anti-sticking agent was added to the spinning dope.
  • a polyethylene glycol polymer number average molecular weight 4,000
  • Spandex fibers were prepared in the same manner as in Example 1, except that 20 wt% of a polyethylene glycol polymer (number average molecular weight 4,000) as an anti-sticking agent was added to the spinning dope.
  • 20 wt% of a polyethylene glycol polymer (number average molecular weight 4,000) as an anti-sticking agent was added to the spinning dope.
  • Spandex fibers were prepared in the same manner as in Example 1, except that 2 wt% of a polyethylene glycol polymer (number average molecular weight 3,500) as an anti-sticking agent was added to the spinning dope.
  • Spandex fibers were prepared in the same manner as in Example 1, except that 2 wt% of a polyethylene glycol polymer (number average molecular weight 10,000) as an anti-sticking agent was added to the spinning dope.
  • Spandex fibers were prepared in the same manner as in Example 1, except that 25 wt% of a polyethylene glycol polymer (number average molecular weight 4,000) as an anti-sticking agent was added to the spinning dope.
  • a polyethylene glycol polymer number average molecular weight 4,000
  • Spandex fibers were prepared in the same manner as in Example 1, except that 2 wt% of a polyethylene glycol polymer (number average molecular weight 2,500) as an anti-sticking agent was added to the spinning stock solution.
  • a polyethylene glycol polymer number average molecular weight 2,500
  • Spandex fibers were prepared in the same manner as in Example 1, except that 2 wt% of a polyethylene glycol polymer (number average molecular weight 2,800) as an anti-sticking agent was added to the spinning stock solution.
  • a polyethylene glycol polymer number average molecular weight 2,800
  • Spandex fibers were prepared in the same manner as in Example 1, except that 2 wt% of a polyethylene glycol polymer (number average molecular weight 12,000) as an anti-sticking agent was added to the spinning dope.
  • Spandex fibers were prepared in the same manner as in Example 1, except that 1% by weight of magnesium stearate was added instead of 2% by weight of the polyethylene glycol polymer (number average molecular weight 4,000) as an anti-sticking agent in the spinning solution.
  • Spandex fibers were prepared in the same manner as in Example 1, except that 0.5 wt% of the silicone emulsion in the spinning stock was added without adding the anti-sticking additive in the spinning stock.
  • Spandex fibers were prepared in the same manner as in Example 1, except that 0.5 wt% of the silicone emulsion was applied to the solids of the yarn without adding an anti-tack additive in the spinning stock solution.
  • Spandex fibers were prepared in the same manner as in Example 1, except that the anti-tack agent was not added to the spinning dope.
  • laminates were prepared using nonwoven fabric and spandex fibers.
  • Nonwoven fabrics 1 and 2 are fed and spandex yarns are fed side by side in the center.
  • the production speed of the sample is 100 m / min.
  • the creep evaluation is carried out by the following procedure by the evaluation method of Japanese U company using the manufactured laminate.
  • the laminate part is stretched to the maximum and fixed to a plastic plate 30 cm wide and 50 cm long.
  • Example Comparative example Item One 2 3 4 5 6 One 2 3 4 5 6 7 8 Adhesive property (%) 78.5 76.1 75.9 74.9 78.3 80.5 63.4 70.1 69.8 80.9 77.3 56.3 54.3 81.5
  • Table 1 The results in Table 1 are obtained using the pilot coater of FIG. 1, and may be slightly different from the results during the diaper manufacturing process.
  • the pilot coater is slower than the actual diaper manufacturing process, and the adhesive method was also evaluated using a specific spray among various methods of the diaper manufacturing process.
  • the maritime characteristic evaluation method is evaluated by installing a guide to fix the yarn at a distance of 30 cm from the fixed bobbin holder, and installing a sensor for measuring tension and a winding device with adjustable speed.
  • the tension measuring apparatus used for this evaluation apparatus is measured using the electronic tension meter of ROTHSCHILD. Maximum, minimum, average, and deviation values were measured and the results are shown in Table 2 below.
  • Example Comparative example Item One 2 3 4 5 6 One 2 3 4 5 6 7 8 Max. (G) 2.58 2.14 2.31 2.09 2.44 2.69 0.69 2.89 2.29 4.45 8.15 2.34 2.89 60.88 Min. (G) 0.31 0.22 0.33 0.20 0.39 0.41 0.02 0.25 0.22 1.73 0.47 0.25 0.34 10.54 Ave. (g) 0.71 0.64 0.72 0.62 0.76 0.69 0.12 0.70 0.72 2.73 1.07 0.69 0.73 29.25 Dev. (G) 0.56 0.41 0.52 0.40 0.46 0.49 0.02 0.45 0.42 1.67 0.94 0.44 0.47 8.19
  • OETO Over-end-take-off
  • This OETO maritime assessment was conducted in the following way.
  • the Spandex fiber winding body When the Spandex fiber winding body is dismantled by OETO method, the following three types of sea sand are generated according to the magnitude of the force between the centrifugal force applied to the yarn and the adhesive force formed between the yarn and the yarn.
  • the reference numeral in FIG. 2 means the following state.
  • Reference numeral 1 denotes a fixed guide: the seal is moved by the OETO method and moves straight from this point.
  • Reference numeral 2 is the firing point of the winding body: the point where the thread is first dismissed from the winding body under tension.
  • Reference numeral 3 denotes an angle formed by a line connecting a fixed guide and a winding body center and a sea thread when in an ideal sea form.
  • Reference numeral 4 denotes an angle corresponding to 1/2 of the reference numeral 3 outside the ideal solution angle.
  • Reference numeral 5 denotes a type 1 nautical morphology: an ideal nautical state in which the yarn is linearly dismantled along the angle of reference numeral 3.
  • Reference numeral 6 denotes a type 2 nautical morphology: the yarn follows the trajectory formed by the angle of reference 3, but with slight shaking.
  • Reference numeral 7 indicates a level 3 nautical form: the fact that a weak ballooning has occurred due to the fact that the track deviates from the trajectory of the reference number 3, but the trajectory of the reference number 4 does not deviate, indicates that there is no possibility of connecting to the thread.
  • Reference No. 8 shows a grade 4 maritime form: the balloon balloon is larger, leaving the trajectory of reference No. 4, and more likely to be connected to the thread according to the surrounding situation.
  • Example according to the present invention exhibits excellent maritime characteristics compared to Comparative Examples (1 to 5, 8).
  • Comparative Examples 6 and 7 when 0.5 wt% of the silicone emulsion in the spinning stock solutions of Comparative Examples 6 and 7 were applied or 0.5 wt% of the solids of the yarn, it was judged that there was no problem in the OETO maritime characteristics.
  • the scum generation phenomenon was evaluated using an OETO (Over-end-take-off) dissolving facility for the spandex fibers prepared according to the Examples and Comparative Examples.
  • the OETO maritime system is composed of the tension control roller and sensor part of BTSR, and the frame, roller and guide device manufactured by Hyosung Co., Ltd.
  • the spandex fiber winding body is dismantled using the OETO method, and the occurrence of scum on the tension control roller surface and the primary and secondary guides is evaluated.
  • reference numeral 1 denotes a roller for controlling the supply tension of spandex yarn during OETO maritime
  • reference numeral 2 denotes a first guide to be passed first
  • reference numeral 3 denotes a second guide to be passed second.
  • the sea speed was 250 m / min, the sea time was 6 hours, and the tension was 40 g.
  • the scum occurrence evaluation results are shown in Table 4.
  • Table 1 (1) is the tension control roller surface, (2) is the primary guide, (3) is the secondary guide, when scum occurs as shown in Fig. 4 ( ⁇ ), when scum does not occur as shown in FIG. It is written as (X).

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Abstract

La présente invention concerne un élasthanne présentant des propriétés de déroulage améliorées et sans apparition de mousse et son procédé de production. Plus particulièrement, la présente invention concerne un élasthanne qui est produit en ajoutant du polyéthylène glycol à une solution de polyuréthane-urée, qui est une solution de filage, améliorant ainsi efficacement un phénomène de gonflement irrégulier et un phénomène de tension transitoire lors du déroulage de l'élasthanne, ne présentant pas d'effet néfaste sur d'autres propriétés telles que des propriétés d'adhérence avec une matière thermofusible et présentant des propriétés de déroulage sans apparition de mousse, et son procédé de production.
PCT/KR2016/012927 2015-11-16 2016-11-10 Élasthanne à propriété de déroulage améliorée et sans apparition de mousse et son procédé de fabrication WO2017086658A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20150160719 2015-11-16
KR10-2015-0160719 2015-11-16
KR10-2016-0148455 2016-11-08
KR1020160148455A KR101913416B1 (ko) 2015-11-16 2016-11-08 해사성 개선 및 스컴 발생이 없는 스판덱스, 및 이의 제조방법

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100227005B1 (ko) * 1995-09-07 1999-10-15 미리암 디. 메코너헤이 헌티트 및 히드로마그네사이트 첨가제를 포함하는 스판덱스
KR20000070628A (ko) * 1997-01-31 2000-11-25 메리 이. 보울러 저점착성 스판덱스 및 그의 제조 방법
KR20110087031A (ko) * 2010-01-25 2011-08-02 한국화학연구원 분리 개섬이 가능한 나노 장섬유 또는 극세사의 제조방법
KR20130138241A (ko) * 2010-09-21 2013-12-18 인비스타 테크놀러지스 에스.에이.알.엘. 점착 방지 첨가제를 함유하는 탄성 섬유의 제조 및 사용 방법
KR20140096923A (ko) * 2013-01-29 2014-08-06 주식회사 효성 점착 특성 및 해사성이 향상된 스판덱스 섬유 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100227005B1 (ko) * 1995-09-07 1999-10-15 미리암 디. 메코너헤이 헌티트 및 히드로마그네사이트 첨가제를 포함하는 스판덱스
KR20000070628A (ko) * 1997-01-31 2000-11-25 메리 이. 보울러 저점착성 스판덱스 및 그의 제조 방법
KR20110087031A (ko) * 2010-01-25 2011-08-02 한국화학연구원 분리 개섬이 가능한 나노 장섬유 또는 극세사의 제조방법
KR20130138241A (ko) * 2010-09-21 2013-12-18 인비스타 테크놀러지스 에스.에이.알.엘. 점착 방지 첨가제를 함유하는 탄성 섬유의 제조 및 사용 방법
KR20140096923A (ko) * 2013-01-29 2014-08-06 주식회사 효성 점착 특성 및 해사성이 향상된 스판덱스 섬유 제조방법

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