EP1660706B1 - Process for preparing elastic fiber having high modulus, alkali-resistance and heat-resistance - Google Patents

Process for preparing elastic fiber having high modulus, alkali-resistance and heat-resistance Download PDF

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Publication number
EP1660706B1
EP1660706B1 EP04774308A EP04774308A EP1660706B1 EP 1660706 B1 EP1660706 B1 EP 1660706B1 EP 04774308 A EP04774308 A EP 04774308A EP 04774308 A EP04774308 A EP 04774308A EP 1660706 B1 EP1660706 B1 EP 1660706B1
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EP
European Patent Office
Prior art keywords
solution
elastic fiber
polyurethane
polyurethaneurea
process according
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EP04774308A
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German (de)
English (en)
French (fr)
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EP1660706A1 (en
EP1660706A4 (en
Inventor
Yeon Soo Kang
Joong Seong Jin
Seung Won Seo
Ik Hyeon Kwon
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Hyosung Corp
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Hyosung Corp
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Publication of EP1660706A4 publication Critical patent/EP1660706A4/en
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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber

Definitions

  • the present invention relates to a process for preparing an elastic fiber having a high modulus and superior resistance to alkali and heat. More specifically, the present invention relates to a process for preparing a high modulus and highly alkali and heat resistant elastic fiber by adding 1 ⁇ 20% by weight of a cellulose acetate to a polyurethane or polyurethaneurea solution, based on the total weight of the polyurethane or polyurethaneurea, to obtain a spinning solution, and ripening and spinning the solution. According to the process, a high modulus and highly heat resistant elastic fiber can be prepared without a sudden change in conditions for preparation of the polymer.
  • an elastic fiber is used in a wide variety of applications.
  • the elastic fiber acts to tightly hold a polyester yarn of a 3-way warp knitted velvet fabric, together with a polyester fiber.
  • the elastic fiber is required to have a modulus high enough to form and maintain a good raised state, and at the same time, to have heat resistance sufficient to endure dyeing and setting treatments at high temperature in subsequent post-processing steps of a polyester velvet fabric.
  • An embossing technique has been recently in the spotlight as a technique for increasing the added value of a velvet fabric. For embossing of various patterns, raised yarns of the velvet fabric must undergo burning-out and printing into a desired color. For the processes, superior alkali resistance is inevitably necessary for the elastic fiber.
  • a high concentration alkaline solution e.g., mainly caustic soda solution
  • a printing solution is applied thereto, followed by high temperature treatment for dye fixing, the elastic fiber is required to have superior alkali resistance in order to prevent it from being degraded by alkaline solution remaining on the fabric at high temperatures.
  • elastic fibers have alkali resistance to some extent due to their inherent characteristics, but are likely to easily degrade when caustic soda at a high concentration of about 25% to about 30% is applied at a temperature as high as 160°C ⁇ 180°C. Accordingly, burning-out and printing processes have been separately carried out. No technique has been established that can simultaneously proceed burning-out and printing processes to date.
  • Japanese Patent Laid-open No. 2000-303259 issued to Fujibo discloses a polyurethane elastic fiber having improved moisture-absorbing properties and biodegradability.
  • the polyurethane elastic fiber is prepared by adding a cellulose acetate to a polyurethane or polyurethaneurea solution, homogeneously stirring the mixture to obtain a spinning solution, spinning the solution to prepare an acetylcellulose-containing elastic fiber, and treating the acetylcellulose-containing elastic fiber with an alkali.
  • the publication does not mention the alkali or heat resistance of the elastic fiber.
  • the modulus of the elastic fiber is far too low to solve the above-mentioned problems.
  • the present inventors have earnestly and intensively conducted research to solve the above-mentioned problems, and as a result, have found that when 1 ⁇ 20% by weight of a cellulose acetate (diacetate or triacetate) having a degree of acetylation of about 28% to about 72% is added to a polymer solution, based on the solid content (i.e., polymeric components) of the polymer solution, homogeneously stirring the mixture to obtain a spinning solution, ripening the solution for a predetermined period of time, and spinning the ripened solution, an elastic fiber having a high modulus and superior resistance to heat and alkali can be easily prepared without a sudden change in polymerization viscosity or non-uniform physical properties of the fibrous product.
  • the present invention is based on this finding.
  • a process for preparing an elastic fiber comprising the steps of: adding 1 ⁇ 20% by weight of a cellulose acetate to a polyurethane or polyurethaneurea solution, based on the total weight of the polyurethane or polyurethaneurea, to obtain a spinning solution; ripening the solution for a predetermined period of time; and spinning the ripened solution.
  • a high modulus and highly alkali and heat resistant elastic fiber which is prepared by the process.
  • the polyurethane or polyurethaneurea solution for use in the present invention is obtained by procedures known in the art. For example, an organic diisocyanate is reacted with a polymeric diol to form a polyurethane precursor. After the polyurethane precursor is dissolved in an organic solvent, the resulting precursor solution is reacted with a diamine for chain extension. The chain extension reaction is terminated by using a monoamine to obtain the polyurethane or polyurethaneurea solution.
  • organic diisocyanates usable in the present invention include diphenylmethane-4,4'-diisocyanate, hexamethylenediisocyanate, toluenediisocyanate, buthylenediisocyanate, hydrogenated p,p-methylenediisocyanate, and the like.
  • the polymeric diol there may be used, for example, polytetramethyleneether glycol, polypropyleneglycol, or polycarbonatediol, all of which preferably have a number-average molecular weight of 1,750 to 2,050.
  • the diamine employed as a chain extender may be ethylenediamine, propylenediamine, hydrazine, or the like
  • the monoamine employed as a chain terminator may be diethylamine, monoethanolamine, dimethylamine, or the like.
  • suitable organic solvents that can be used to obtain the polymer solution include, but are not particularly limited to, N,N' -dimethylformamide, N,N'-dimethylacetamide, dimethylsulfoxide, and the like.
  • the polyurethane or polyurethaneurea solution may further contain at least one additive selected from dulling agents, UV stabilizers, antioxidants, NO x gas anti-yellowing agents, anti-adhesion agents, dyeing promoters, and anti-chlorine agents.
  • cellulose acetate 1 ⁇ 20% by weight of the cellulose acetate is added to the polyurethane or polyurethaneurea solution, based on the total weight of the polymer, and the mixture is homogeneously stirred to obtain a spinning solution. If the amount of the cellulose acetate added is below 1% by weight, the addition effect is negligible. On the other hand, if the amount of the cellulose acetate exceeds 20% by weight, homogeneous mixing is difficult.
  • the cellulose acetate may be cellulose diacetate or cellulose triacetate, and preferably has a degree of acetylation of about 28% to about 72%.
  • the spinning solution is ripened by allowing it to stand at 30°C ⁇ 70°C for 28-38 hours, and is then spun to prepare the final elastic fiber having a high modulus and superior resistance to heat and alkali.
  • the steps have a direct influence on the increase of the modulus and improvement in the resistance to alkali and heat of the electric yarn. Accordingly, it is important to set optimized conditions for the steps.
  • the cellulose acetate is dissolved in the same organic solvent as that used to obtain the polymer solution, the resulting solution is homogeneously stirred for 7 ⁇ 8 hours, and then the homogeneous solution is added to the polymer solution. Thereafter, the resulting mixture is homogeneously stirred for at least 2 hours. At this time, the stirring time is extended by 30 minutes with increasing percentage of the cellulose acetate added. After stirring, the mixture of the cellulose acetate and the polymer solution is ripened for about 28 ⁇ 38 hours, and is then spun through a spinning nozzle to prepare the final elastic fiber.
  • polyurethane precursor 518g of diphenylmethane-4,4'-diisocyanate, and 2,328g of polytetramethyleneetherglycol having a number-average molecular weight of 1,800 were reacted with each other at 85°C for 90 minutes with stirring to form a polyurethane precursor containing isocyanate groups at both terminal positions.
  • the polyurethane precursor was allowed to cool to room temperature, and was then dissolved in 4,643g of N,N'-dimethylacetamide to obtain a polyurethane precursor solution.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that a solution of 5% by weight of cellulose diacetate (degree of acetylation: 45%) in N,N'-dimethylacetamide was added to the polymer solution, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 4 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that a solution of 10% by weight of cellulose diacetate (degree of acetylation: 45%) in N,N'-dimethylacetamide was added to the polymer solution, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 6.5 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that a solution of 15% by weight of cellulose diacetate (degree of acetylation: 45%) in N,N'-dimethylacetamide was added to the polymer solution, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 9.5 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as is Example 1, except that a solution of 20% by weight of cellulose diacetate (degree of acetylation: 45%) in N,N'-dimethylacetamide was added to the polymer solution, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 12 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that cellulose triacetate (degree of acetylation: 65%) was dissolved in N,N'-dimethylacetamide at 110°C for 30 minutes and then the resulting solution was added to the polymer solution so that the amount of the cellulose triacetate was 1% by weight, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 2 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that cellulose triacetate (degree of acetylation: 65%) was dissolved in N,N'-dimethylacetamide at 110°C for 30 minutes and then the resulting solution was added to the polymer solution so that the amount of the cellulose triacetate was 5% by weight, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 2 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that cellulose triacetate (degree of acetylation: 65%) was dissolved in N,N'-dimethylacetamide at 110°C for 30 minutes and then the resulting solution was added to the polymer solution so that the amount of the cellulose triacetate was 10% by weight, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 2 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that cellulose triacetate (degree of acetylation: 65%) was dissolved in N,N'-dimethylacetamide at 110°C for 30 minutes and then the resulting solution was added to the polymer solution so that the amount of the cellulose triacetate was 15% by weight, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 2 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that cellulose triacetate (degree of acetylation: 65%) was dissolved in N,N'-dimethylacetamide at 110°C for 30 minutes and then the resulting solution was added to the polymer solution so that the amount of the cellulose triacetate was 20% by weight, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 2 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that a solution of 25% by weight of cellulose diacetate (degree of acetylation: 45%) in N,N'-dimethylacetamide was added to the polymer solution, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 9.5 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that cellulose triacetate (degree of acetylation: 65%) was dissolved in N,N'-dimethylacetamide at 110°C for 30 minutes and then the resulting solution was added to the polymer solution so that the amount of the cellulose triacetate was 25% by weight, based on the solid content of the polymer solution, and homogeneous stirring was carried out for 2 hours. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • a polyurethaneurea elastic fiber having a thickness of 40 deniers was prepared and wound in the same manner as in Example 1, except that cellulose diacetate was not added. Thereafter, a velvet fabric was manufactured in the same manner as in Example 1, and was then subjected to burning-out and printing. The properties of the velvet fabric were measured and evaluated, and the results are shown in Table 1.
  • Table 1 Exa. No. Evaluation of Yarns Evaluation of Fabrics Remarks Modulus (g) Heat resistance 1) Alkali resistance 2) Power retention 3) Raised state before burning-out 4) Occurrence of holes on fabric after burning-out 5) Ex. 1 5.4 47% 117 min. 39.7% ⁇ Occurred Ex. 2 6.2 65% 130 min. 47.3% O Few occurred Ex.
  • the heat resistance of the yarns was evaluated by the following procedure: A yam sample is stretched by 100%, and wet-heat treated at 130°C for 1 hour. The heat treatment is repeated five times (5 cylces). The heat resistance of the yarn sample is expressed as percentage of the difference between the length ("initial length") of the yam sample before the heat treatment and that ("download value") after the fifth cycle. 2) The alkali resistance of the yarns was evaluated by the following procedure: A yam sample is dipped in an 25% aqueous NaOH (25wt%) solution, and heated to 150°C.
  • the alkali resistance of the yam sample is expressed as the time taken for the yarn sample to decompose.
  • the power retention of the fabrics was measured by the following procedure: A finally processed fabric is cut into a fabric sample (1 inch x 30cm). The fabric sample is held by grips from Instron Co., so that the length of the fabric sample for measurement is 20cm. The holding is repeated five times (5 cycles). The power retention of the fabric sample is expressed as percentage of the difference between the length ("upload value") of the fabric sample after the first cycle and that ("download value”) after the fifth cycle. 4) The raised state before burning-out was evaluated by visually examining the degree of uprightness of raised yarns after the velvet fabrics were subjected to shearing and background dyeing.
  • the process of the present invention enables uniform management of polymerization and spinning viscosity, the elastic fibers show uniform physical properties, a high modulus, and improved resistance to heat and alkali. Accordingly, when the process of the present invention is applied to general velvet fabrics or special velvet fabrics requiring continuous burning-out and printing, it has advantages that no degradation of elastic fibers arises, and the state of raised yarns and fabrics is stably maintained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Woven Fabrics (AREA)
  • Knitting Of Fabric (AREA)
  • Inorganic Fibers (AREA)
EP04774308A 2003-09-01 2004-08-13 Process for preparing elastic fiber having high modulus, alkali-resistance and heat-resistance Active EP1660706B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2003-0060810A KR100524323B1 (ko) 2003-09-01 2003-09-01 높은 모듈러스, 내알칼리성 및 내열성을 가진 탄성사 제조방법
PCT/KR2004/002031 WO2005021847A1 (en) 2003-09-01 2004-08-13 Process for preparing elastic fiber having high modulus, alkali-resistance and heat-resistance

Publications (3)

Publication Number Publication Date
EP1660706A1 EP1660706A1 (en) 2006-05-31
EP1660706A4 EP1660706A4 (en) 2007-09-19
EP1660706B1 true EP1660706B1 (en) 2009-12-16

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Country Status (10)

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US (1) US20070059523A1 (pt)
EP (1) EP1660706B1 (pt)
JP (1) JP4527118B2 (pt)
KR (1) KR100524323B1 (pt)
CN (1) CN100406622C (pt)
AT (1) ATE452227T1 (pt)
BR (1) BRPI0413903B8 (pt)
DE (1) DE602004024688D1 (pt)
MX (1) MXPA06001760A (pt)
WO (1) WO2005021847A1 (pt)

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SG174277A1 (en) * 2009-03-23 2011-10-28 Invista Tech Sarl Elastic fiber containing an anti-tack additive
CN104831377A (zh) * 2009-06-25 2015-08-12 路博润高级材料公司 由薄规格恒定压缩弹性纤维构成的高强度织物
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KR101148583B1 (ko) * 2009-12-30 2012-05-23 주식회사 효성 우수한 파워 및 신도를 가진 탄성사의 제조 방법
KR101148302B1 (ko) * 2009-12-31 2012-05-25 주식회사 효성 고속방사용 폴리우레탄우레아 탄성사의 제조방법
EP2619359A4 (en) * 2010-09-21 2014-03-26 Invista Tech Sarl METHODS OF MAKING AND USING ELASTIC FIBER CONTAINING ANTI-STICKER ADDITIVE
KR101533912B1 (ko) * 2014-02-10 2015-07-03 주식회사 효성 친수성 폴리우레탄우레아 탄성사
KR20160079158A (ko) * 2014-12-25 2016-07-06 주식회사 효성 염색성이 향상된 스판덱스
CN106381560B (zh) * 2016-09-30 2019-06-18 宏杰内衣股份有限公司 一种薄棉裸氨面料
CN108048952B (zh) * 2017-12-15 2020-11-10 浙江华峰氨纶股份有限公司 一种高弹性易粘合聚氨酯脲纤维的制备方法
CN110577640A (zh) * 2019-08-31 2019-12-17 贵州大学 一种3,6-二叔丁基-4-羟基苄基丙烯酸酯与乙二胺共聚大分子抗氧剂及其应用
CN111548471B (zh) * 2020-05-29 2021-06-08 浙江恒泰源聚氨酯有限公司 一种高弹运动鞋底用聚氨酯原液及其制备方法
CN114717734B (zh) * 2022-05-05 2024-04-19 青岛全季服饰有限公司 一种防晒针织面料及其制备方法

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Publication number Publication date
BRPI0413903B8 (pt) 2016-09-13
US20070059523A1 (en) 2007-03-15
BRPI0413903B1 (pt) 2014-08-12
MXPA06001760A (es) 2006-05-12
EP1660706A1 (en) 2006-05-31
ATE452227T1 (de) 2010-01-15
WO2005021847A1 (en) 2005-03-10
EP1660706A4 (en) 2007-09-19
DE602004024688D1 (de) 2010-01-28
CN1846018A (zh) 2006-10-11
CN100406622C (zh) 2008-07-30
JP4527118B2 (ja) 2010-08-18
KR20050024720A (ko) 2005-03-11
JP2007504370A (ja) 2007-03-01
BRPI0413903A (pt) 2006-10-24
KR100524323B1 (ko) 2005-10-26

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