KR100775756B1 - Acid resistante polyurethane fiber - Google Patents
Acid resistante polyurethane fiber Download PDFInfo
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- KR100775756B1 KR100775756B1 KR1020060130550A KR20060130550A KR100775756B1 KR 100775756 B1 KR100775756 B1 KR 100775756B1 KR 1020060130550 A KR1020060130550 A KR 1020060130550A KR 20060130550 A KR20060130550 A KR 20060130550A KR 100775756 B1 KR100775756 B1 KR 100775756B1
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- polyurethane
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- 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
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- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
본 발명은 폴리우레탄우레아 폴리머에 실란커플링제를 첨가시켜 제조한 폴리우레탄 섬유(스판덱스 섬유)에 관한 것으로서, 면, 레이온계 등과 같은 천연섬유 및 폴리에스테르 섬유를 함께 사용하여 제편한 편직물을 산성 번아웃 공정을 적용하여 처리하였을 때 폴리우레탄 섬유의 취화 현상이 개선되도록 한 것이다.The present invention relates to a polyurethane fiber (spandex fiber) prepared by adding a silane coupling agent to a polyurethane urea polymer, wherein the knitted fabric knitted using natural fibers such as cotton and rayon and polyester fibers together with the acid burnout When the process is applied to the treatment to improve the embrittlement of the polyurethane fiber.
일반적으로 편직포지에 무늬를 형성하는 방법으로는 스크린 인쇄방식과 디지털 날염 방식 등이 있으며, 1차원의 방식이 아닌 입체적인 무늬 효과를 위해서는 번 아웃(burn-out)이라는 공정이 있다. In general, there are screen printing and digital printing methods for forming patterns on knitted fabrics, and there is a process called burn-out for a three-dimensional pattern effect rather than a one-dimensional method.
번 아웃 공정은 다시 산성 번아웃과 알칼리 번 아웃으로 나뉘어진다. The burnout process is further divided into acid burnout and alkali burnout.
산성 번 아웃은 일반적으로 천연섬유와 폴리에스테르로 이루어진 편직물을 강한 산성 약품으로 처리함으로써 천연섬유는 녹고 폴리에스테르는 녹지 않는 성질을 이용하여 무늬를 형성하는 방법이다. Acid burnout is a method of forming a pattern using the property of melting natural fibers and not polyester by treating a knitted fabric composed of natural fibers and polyester with a strong acid chemical.
그러나 상기 언급한 산성 번 아웃 공정은 고농도의 산 조건과 열처리를 요구하므로 폴리우레탄 섬유에 적용하면 폴리우레탄 섬유의 취화로 인하여 편직물의 신축성 및 물성이 저하되는 문제점이 있다.However, the acid burnout process mentioned above requires a high concentration of acid conditions and heat treatment, so when applied to polyurethane fibers, there is a problem in that elasticity and physical properties of knitted fabrics are degraded due to embrittlement of polyurethane fibers.
미국특허 6329452호 및 대한민국 공개특허 2003-0099507호에서는 이러한 문제점을 개선하기 위하여 방사유제 내에 숙시네이트염 혹은 아미노 실란 등을 첨가하여 원단의 물성 저하를 개선하려고 하고 있다. In US Patent 6329452 and Korean Patent Laid-Open Publication No. 2003-0099507, in order to improve such a problem, succinate salt or amino silane is added to the spinning oil to improve the physical properties of the fabric.
하지만 상기 방법들은 숙시네이트 염과 유제의 주성분인 폴리디메틸실록산과의 비혼화성에 의한 층분리 현상이나 두 성분간의 불균일한 용해를 일으킬 염려가 있으며, 또 방사시에 고습도 환경에서 유제가 적용되기 때문에 수분에 의한 겔 생성이나 침전 등을 유발시키는 문제점들이 있다.However, the above methods may cause delamination due to incompatibility between succinate salt and polydimethylsiloxane, which is the main component of the emulsion, or uneven dissolution between the two components. There are problems that cause gel generation or precipitation by.
본 발명은 상기한 바와 같은 종래 기술의 문제점을 일으키지 않으면서 산성 번아웃 처리시에 산에 의한 폴리우레탄 섬유의 취화를 개선하는데 기술적 과제를 둔 것이다. The present invention is directed to improving the embrittlement of polyurethane fibers by acid during acid burnout treatment without causing the problems of the prior art as described above.
본 발명에 있어서, 폴리우레탄 제조시에 사용하는 세그먼트 폴리우레탄은 통상의 유기 디이소시아네이트와 고분자 디올을 반응시켜서 폴리우레탄 전구체를 제조한 다음, 이를 유기 용매에 용해한 후 디아민 및 모노아민과 반응시킴으로써 제조한 것이다.In the present invention, the segmented polyurethane used in the production of polyurethane is prepared by reacting a conventional organic diisocyanate with a polymer diol to prepare a polyurethane precursor, and then dissolving it in an organic solvent and then reacting with a diamine and a monoamine. will be.
본 발명에 사용되는 상기 유기 디이소시아네이트는 4,4′-디페닐메탄디이소시아네이트, 1,5′-나프탈렌디이소시아네이트, 1,4′-페닐렌디이소시아네이트, The organic diisocyanate used in the present invention is 4,4'-diphenylmethane diisocyanate, 1,5'- naphthalene diisocyanate, 1,4'-phenylene diisocyanate,
헥사메틸렌디이소시아네이트, 1,4′-시클로헥산디이소시아네이트, Hexamethylene diisocyanate, 1,4′-cyclohexanediisocyanate,
4,4′-디시클로헥실메탄디이소시아네이트, 이소프론디이소시아네이트와 같은 유기 디이소시아네이트의 1종 또는 이들의 2종 이상의 혼합물이다. One, or a mixture of two or more of organic diisocyanates such as 4,4'-dicyclohexyl methane diisocyanate and isopron diisocyanate.
또 상기 고분자 디올은 폴리테트라메틸렌에테르글리콜, 폴리프로필렌글리콜, 폴리카보네이트디올 등에서 선택한 것이다. The polymer diol is selected from polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol and the like.
또 상기 디아민류는 사슬연장제로 사용되며, 그 예로는 에틸렌디아민, In addition, the diamines are used as a chain extender, for example, ethylenediamine,
1,2′-프로필렌디아민, 헥사메틸렌디아민, 크실렌디아민, 4,4′-디페닐메탄디아민, 하이드라진 등의 1종 또는 이들의 2종 이상의 혼합물이다. It is 1 type, or 2 or more types of these, such as 1,2'-propylenediamine, hexamethylenediamine, xylenediamine, 4,4'- diphenylmethanediamine, and hydrazine.
그 외 충전제로서 UV 안정제, 산화방지제, NOx가스 황변방지제, 점착방지제, 염착증진제, 내염소제, 소광제 등이 사용될 수 있으며, 이는 아트리션보올밀, 샌드그라인더 등의 분산기로 분산시켜서 입자크기가 균일한 것으로 만들어서 사용한다. Other fillers may include UV stabilizers, antioxidants, NOx gas anti-yellowing agents, anti-sticking agents, dyeing enhancers, chlorine resistant agents, matting agents, etc., which are dispersed in dispersers such as attrition bowl mills and sand grinders Make it uniform and use it.
폴리우레탄의 용매로서는 N,N'-디메틸포름아미드, N,N'-디메틸아세트아미드, 테트라메틸요소, 헥사메틸포스포노아미드 등을 들 수 있다.Examples of the solvent for the polyurethane include N, N'-dimethylformamide, N, N'-dimethylacetamide, tetramethylurea and hexamethylphosphonoamide.
일반적으로 실란커플링제는 X3SiY(X: 무기작용기, Y: 유기 작용기)와 같이 두 개의 작용기, 즉 유기 작용기와 무기 작용기를 가지고 있기 때문에 복합재료 등에서 많이 사용되고 있다. In general, the silane coupling agent is widely used in composite materials because it has two functional groups such as X 3 SiY (X: inorganic functional group, Y: organic functional group), that is, organic functional group and inorganic functional group.
뿐만 아니라 이는 폴리머 등과 같은 수지에 사용될 경우, 점도 감소, 촉매 효과 그리고 실란 분자들의 가교나 상호확산을 촉진시킴으로 내약품성 및 내화학성 에서 뛰어난 효과를 나타낼 수 있다. In addition, when used in a resin such as a polymer, it can exhibit excellent effects in chemical resistance and chemical resistance by promoting viscosity reduction, catalytic effect and crosslinking or interdiffusion of silane molecules.
실란커플링제에는 메톡시(Methoxy)계, 에톡시(Ethoxy)계, 아미노(Amino)계, 에폭시(Epoxy)계 등 여러 가지가 있으며, 이 중에서 아미노 실란계 실란커플링제의 경우는 높은 반응성에 의해 뛰어난 내약품성을 나타낼 수 있다.There are various kinds of silane coupling agents such as methoxy, ethoxy, amino, epoxy, and the like. It can exhibit excellent chemical resistance.
실란커플링제의 수평균 분자량은 2000 이하인 것이 좋으며, 특히 수평균 분자량 200-1000의 것이 혼화성 및 분산성 면에서 바람직하다. It is preferable that the number average molecular weight of a silane coupling agent is 2000 or less, and the number average molecular weight 200-1000 is especially preferable at the point of miscibility and dispersibility.
수평균 분자량이 2000을 초과하는 경우 높은 분자량에 의해 폴리우레탄 폴리머와 혼합시 반응이 촉진되어 폴러머의 점도를 상승시키거나 폴리우레탄 탄성사의 물성을 저하시킬 수 있다When the number average molecular weight exceeds 2000, the reaction may be accelerated when mixed with the polyurethane polymer due to the high molecular weight, thereby increasing the viscosity of the polymer or decreasing the physical properties of the polyurethane elastic yarn.
본 발명에 의한 내산성 폴리우레탄 섬유는 상기 방법에 의해 제조된 폴리우레탄우레아 중합물에 실란커플링제를 단독 또는 두 종 이상 혼합하여 최종 폴리머 고형분 대비 0.03 ~ 10wt%가 되도록 첨가한 후 방사하여 제조한 것이다. Acid-resistant polyurethane fiber according to the present invention is prepared by spinning after the addition of a silane coupling agent alone or two or more to the polyurethane urea polymer prepared by the above method to 0.03 ~ 10wt% relative to the final polymer solids.
본 발명에 있어서, 방사방법은 특별히 제한되지 않으며, 화학방사를 제외한 건식방사, 습식방사, 용융방사법이 이용될 수 있으며, 특히 건식방사법이 바람직하다.In the present invention, the spinning method is not particularly limited, and dry spinning, wet spinning, and melt spinning methods other than chemical spinning may be used, and dry spinning is particularly preferable.
본 발명에 있어서, 실란커플링제의 사용량은 그 종류, 용도 등에 따라 다르지만, 최종 폴리머 고형분 대비 0.03wt% 내지 10wt%가 바람직하다. In this invention, although the usage-amount of a silane coupling agent changes with the kind, use, etc., 0.03 wt%-10 wt% are preferable with respect to final polymer solid content.
0.03wt% 미만인 경우에는 내산성의 효과 저하 및 원사내 혼합 불균일을 초래할 수 있고, 10wt%를 초과하는 경우에는 탄성섬유로서의 성능 상실, 고반응성에 의한 겔 생성 등의 결점을 야기시킬 수 있다. If it is less than 0.03wt%, it may cause the effect of acid resistance and non-uniform mixing of yarn, and if it exceeds 10wt%, it may cause defects such as loss of performance as an elastic fiber, gel formation due to high reactivity.
이하 본 발명을 실시예 및 비교예를 들어 설명하고자 하며, 실시예는 본 발명의 보호 범위를 제한하는 것은 아니다. Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, which do not limit the protection scope of the present invention.
< 실시예 1> <Example 1>
내산성 폴리우레탄 섬유를 제조하기 위해서 아미노 실란계 실란커플링제 (다미폴리켐, 제품명:LD5601, H2N(CH2)3Si(OC2H5)3)를 폴리우레탄 우레아에 혼합시키되, 최종 폴리머 고형분 중량 대비 0.1wt% 가 되도록 하였다. To prepare an acid resistant polyurethane fiber, an amino silane-based silane coupling agent (Damipolychem, product name: LD5601, H 2 N (CH 2 ) 3 Si (OC 2 H 5 ) 3 ) was mixed with polyurethane urea, but the final polymer It was made to be 0.1 wt% with respect to the solid content weight.
상기 폴리우레탄 폴리머의 혼합물을 교반하여 점도 4000 포아즈의 중합물을 얻는다. The mixture of polyurethane polymers is stirred to obtain a polymer of viscosity 4000 poise.
이 중합물을 통상의 건식방사법을 이용하여 방사함으로써 40 데니아 내산성 폴리우레탄 섬유를 제조한다. 40 denia acid-resistant polyurethane fiber is manufactured by spinning this superposition | polymerization using normal dry spinning method.
<실시예 2> <Example 2>
아미노 실란계 실란커플링제를 최종 폴리머 고형분 대비 0.3wt%로 하여 내산성 폴리우레탄 섬유를 제조한 것을 제외하고는 실시예 1과 동일하다. It is the same as Example 1 except the acid-resistant polyurethane fiber was made with the amino silane coupling agent as 0.3 wt% with respect to the final polymer solid content.
<실시예 3><Example 3>
내산성 폴리우레탄 섬유를 제조하기 위해서 메타크릴계 실란커플링제 (다미폴리켐, 제품명:LD5720, HS(CH2)3Si(OCH3)3)를 폴리우레탄우레아에 혼합 시키되, 최종 폴리머 고형분 중량 대비 0.5wt% 가 되도록 하였다. Methacrylic silane coupling agent (Damipolychem, product name: LD5720, HS (CH 2 ) 3 Si (OCH 3 ) 3 ) is mixed with polyurethane urea to prepare acid resistant polyurethane fiber, but the weight of the final polymer solids is 0.5 wt%.
상기 폴리우레탄 폴리머의 혼합물을 교반하여 점도 4000 포아즈의 중합물을 얻는다. The mixture of polyurethane polymers is stirred to obtain a polymer of viscosity 4000 poise.
이 중합물을 통상의 건식방사법을 이용하여 방사함으로써 40 데니아 내산성 폴리우레탄 섬유를 제조한다. 40 denia acid-resistant polyurethane fiber is manufactured by spinning this superposition | polymerization using normal dry spinning method.
<실시예 4> <Example 4>
메톡시 실란계 실란커플링제(다미폴리켐, 제품명 LD5501, CH2=CHSi(OCH3)3)를 최종 폴리머 고형분 대비 1.0wt%로 하여 내산성 폴리우레탄 섬유를 제조한 것을 제외하고는 실시예 3과 동일하다. Example 3 except that the acid-resistant polyurethane fiber was prepared by using a methoxy silane-based silane coupling agent (Damipolychem, product name LD5501, CH 2 = CHSi (OCH 3 ) 3 ) to 1.0wt% of the final polymer solids. same.
<비교예 1> Comparative Example 1
실란커플링제를 첨가하지 않은 것을 제외하고는 실시예 1과 동일하게 시행한다. The same procedure as in Example 1 was conducted except that no silane coupling agent was added.
<비교예 2> Comparative Example 2
메톡시계 실란커플링제를 폴리머가 아닌 유제에 1.0 중량% 혼합하여 처리 한 것을 제외하고는 실시예 4와 동일하다. It is the same as Example 4 except the methoxy silane coupling agent was processed by mixing 1.0 weight% with the oil agent rather than a polymer.
상기 실시예 및 비교예에 따라 제조된 제품의 물성 평가 방법은 다음과 같이 실시하였으며, 그 결과는 <표 1>에 나타내었다. The physical property evaluation method of the product manufactured according to the said Example and the comparative example was performed as follows, The result is shown in <Table 1>.
산(acid) 처리 전/후 강력 유지율 평가Strong retention evaluation before and after acid treatment
각각의 원사를 100% 신장시킨 후, 염산 10% 농도의 용액에 2시간 동안 충분 히 침지시킨다. Each yarn is stretched 100% and then immersed sufficiently in a solution of 10% hydrochloric acid for 2 hours.
침지 후, 자연 상태에서 원사를 건조 시킨 후 처리 전/후에 따른 강력을 평 가한다.After immersion, the yarn is dried in its natural state and the strength is evaluated before and after treatment.
강력 측정은 UTM(Instron)을 이용하여 시료길이 50mm, 인장속도 500mm/min로 하여 측정한다. Robust measurement is performed using a UTM (Instron) with a sample length of 50 mm and a tensile speed of 500 mm / min.
<표 1>TABLE 1
본 발명에 의한 내산성 폴리우레탄 섬유는 산처리 후 높은 강력유지율을 나타낼 수 있다. Acid-resistant polyurethane fiber according to the present invention can exhibit a high strength retention after acid treatment.
그러므로 본 발명의 내산성 폴리우레탄 섬유를 면, 레이온 등의 천연 섬유 및 폴리에스테르와 혼용하여 편직한 후 산성 번아웃 처리를 하더라도 산에 의한 폴리우레탄 섬유의 손상을 방지할 수 있기 때문에 최종 원단의 강도와 신축성 저하를 개선할 수 있다.Therefore, even if the acid-resistant polyurethane fiber of the present invention is mixed with natural fibers such as cotton and rayon and polyester and knitted after the acid burnout treatment, damage to the polyurethane fiber by acid can be prevented, so Reduced elasticity can be improved.
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| CN105088402A (en) * | 2015-09-17 | 2015-11-25 | 无锡市长安曙光手套厂 | Anti-static fabric and preparation method thereof |
| CN109825895A (en) * | 2019-03-05 | 2019-05-31 | 浙江华峰氨纶股份有限公司 | A kind of alkaline-resisting spandex of high temperature resistant and preparation method thereof |
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