KR20080096814A - Process for the production of acrylic fibre for fabrics with a low pilling formation and acrylic fibres thus obtained - Google Patents
Process for the production of acrylic fibre for fabrics with a low pilling formation and acrylic fibres thus obtained Download PDFInfo
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- D—TEXTILES; PAPER
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- 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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- 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
- D01D1/02—Preparation of spinning solutions
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- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
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- 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
- D01D5/06—Wet spinning methods
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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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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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
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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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
- D10B2401/00—Physical properties
- D10B2401/14—Dyeability
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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
- D10B2501/00—Wearing apparel
- D10B2501/02—Underwear
- D10B2501/021—Hosiery; Panti-hose
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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
- D10B2505/00—Industrial
- D10B2505/18—Outdoor fabrics, e.g. tents, tarpaulins
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3065—Including strand which is of specific structural definition
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- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Woven Fabrics (AREA)
Abstract
Description
본원 발명은 낮은 필링(pilling) 형성의 직물을 위한 아크릴섬유의 생산 공정에 관한다.The present invention relates to the production process of acrylic fibers for low pilling fabrics.
더욱 특정하게는, 본원 발명은 낮은 필링 형성의 직물을 위한 아크릴섬유의 생산 공정 및 그로부터 수득되는 아크릴섬유에 관한다.More particularly, the present invention relates to the production process of acrylic fibers for low peel forming fabrics and to acrylic fibers obtained therefrom.
공지된 바와 같이, 아크릴섬유는 모 및 면과 같은 천연섬유를 모조하고 아주 흔하게 그들을 능가하는 특성으로 인하여, 합성섬유 및 인조섬유 중에서 강한 입지를 확립해왔다.As is known, acrylic fibers have established a strong position among synthetic and man-made fibers due to their characteristics of imitating and very often exceeding natural fibers such as wool and cotton.
면 또는 모 방적기 상에서 아크릴섬유의 가공성은 의심의 여지 없이 탁월하고 상기 언급된 천연섬유보다 훨씬 더 높다. 동시에, 오랜 시간동안 내광성(light-fast)이고 밝은 색상으로 아크릴섬유를 쉽게 염색할 수 있는 가능성으로 천연의 경쟁 상대에 대하여 아크릴섬유의 성능이 매우 뛰어나다.The processability of acrylic fibers on cotton or woolen yarns is undoubtedly excellent and much higher than the above mentioned natural fibers. At the same time, the ability of acrylic fibers to be easily dyed in light-fast and bright colors for a long time makes the acrylic fibers extremely superior to their natural competitors.
또한 아크릴섬유는 무수히 많은 최종 용도에 채택될 수 있고, 이에 대하여 니트 의류, 양말류, 운동복, 가구, 천막, 시멘트 보강재 등과 같은 분야에서 흔히 가치가 인정되고 천연섬유보다 선호된다.Acrylic fibers can also be employed in a myriad of end uses, which are often valued and preferred over natural fibers in areas such as knitwear, hosiery, sportswear, furniture, tents, cement reinforcement, and the like.
아크릴섬유 이용의 주된 분야는, 단독으로 또는 모와 배합하여, 의심의 여지없이 니트 의류이다. 그러나 이러한 타입의 최종 제품은 사용함에 따라 미관을 해치고 사용과 시간에 따라 증가하는 필(pill)의 출현에 의하여 나타나는 성가신 문제를 야기한다.The main field of acrylic fiber use, alone or in combination with wool, is undoubtedly knitted garments. However, this type of end product compromises aesthetics with use and causes annoying problems manifested by the appearance of pills that increase with use and time.
필의 출현에 관한 이 현상은 공지되어 있고, 필이 형성되고 증가되는 메커니즘 역시 그러하다. 과거에 본 출원인은, 예를 들어 단섬유(single fibre)의 방적사로부터 적출을 지연시키는 높은 표면 주름 및 필을 최종 제품에 결속시키는 필라멘트(filament)의 절단에 유리한, 섬유의 낮은 강인성(toughness)을 가지는 Leacril NP의 이름으로 하에 시장에 알려진 아크릴섬유의 제안에 따른, 필의 형성, 성장 및 감퇴의 역학 모델을 가지는 필의 형성을 연구했다(Doria G., Trevisan E. "Textile Asia", 64, 1989).This phenomenon with regard to the appearance of the fill is known, as is the mechanism by which the fill is formed and increased. In the past, Applicants have demonstrated the low toughness of the fibers, which is advantageous for the cutting of the filaments, which binds the fill to the final product and high surface pleats, for example, delaying extraction from single-fiber yarns. Eggplants studied the formation of pill with a dynamic model of pill formation, growth and decay, in accordance with the proposal of acrylic fiber known on the market under the name of Leacril NP (Doria G., Trevisan E. "Textile Asia", 64, 1989).
다른 생산자들이 본 출원인에 의하여 개발된 상기 모델에 따른 "필링이 없는(No Pilling)" 버전의 아크릴섬유, 즉, 낮은 강도 및 길이방향과 노트(knot)에서도 낮은 신도(elongation)를 가지는 섬유를 제안하였다.Other producers have proposed a "no pilling" version of acrylic fiber according to the model developed by the applicant, ie a fiber with low strength and length and low elongation even in knots. It was.
이들 상용의 섬유의 일부는 필링이 형성되지 않거나 적게 형성되는 섬유를 "자발적으로" 생산하는 공정으로부터 수득된다. 이들 중에서, 수용성 용매를 사용하는 공정이 존재하고, 이 때 방사(spinning) 용액에서의 낮은 중합체(polymer) 농도로 인하여, 섬유를 약하게 하는 대량의 잠재적 "스페이스(space)"를 가지는 섬유가 수득된다. 반면에 대부분의 습식방사(wet spinning) 및 건식방사(dry spinning) 공 정은, 가압된 포화 증기의 오토클레이브(autoclave)에서보다 조업 중에 섬유를 느슨해지게 하고 따라서 낮은 노트 특성을 가지는 섬유의 자발적인 생산이 유리해진다.Some of these commercial fibers are obtained from a process that "voluntarily" produces fibers with little or no peeling. Among them, there is a process using a water-soluble solvent, whereby due to the low polymer concentration in the spinning solution, fibers with a large amount of potential "space" of weakening fibers are obtained. . On the other hand, most wet spinning and dry spinning processes loosen the fibers during operation than in the autoclave of pressurized saturated steam and thus spontaneous production of fibers with low knot properties. Is advantageous.
시장에 현존하는 모든 상용의 섬유는, 비록 필링이 없고 Leacril NP을 비롯한 전통적인 아크릴섬유에 대하여 개선된 버전일지라도, 최종 제품 상에 미관을 해치는 필이 출현하는 문제를 완전히 해결하지는 못한다.All of the commercially available fibers on the market, even without peeling and an improved version of traditional acrylic fibers, including Leacril NP, do not completely solve the problem of the appearance of peels on the final product.
모든 상용의 아크릴섬유는 사실, 중합체의 조성과 관련된 "물리-화학적" 한계, 즉 습열(wet heat) 하에서 낮은 치수안정성으로 어려움을 겪는다. 습열에 대한 상용의 아크릴섬유의 이러한 불안정성의 원인은 중합체의 용해도 및 가공성을 향상시키기 위하여, 특히 낮은 용매 능력(capacity)을 가지는 용매를 사용하여 큰 분자 장애를 가지고 이온적으로 중성인 공단량체(comonomer), 예를 들어 비닐아세테이트 또는 메틸아크릴레이트의 중합체 사슬로의 도입으로 CN기를 "희박화"하는 필요성에 있다.All commercially available acrylic fibers, in fact, suffer from the "physical-chemical" limitations associated with the composition of the polymer, ie low dimensional stability under wet heat. The cause of this instability of commercially available acrylic fibers against moist heat is a comonomer which is largely molecularly disturbed and ionically neutral, especially using solvents with low solvent capacity to improve the solubility and processability of the polymer. ), Eg the introduction of vinylacetate or methylacrylate into the polymer chain, to "thin" the CN group.
폴리아크릴로니트릴 단일중합체(homopolymer)는 중합체를 용해하기 어렵고 섬유로 변형시키기 어렵게 만드는 CN기 간의 쌍극자-쌍극자 유형의 강한 상호작용으로 인하여 사실상 뜨거운 물과 증기에 민감하지 않은 매우 밀집된 구조를 가진다. 실제로 본 출원인에 의한, 기술적 용도에 채택되는 Ricem을 제외하고 폴리아크릴로니트릴 단일중합체 섬유가 존재하지 않는다.Polyacrylonitrile homopolymers have a very dense structure that is virtually insensitive to hot water and steam due to the strong interaction of the dipole-dipole type between CN groups, making the polymer difficult to dissolve and difficult to transform into fibers. Indeed there is no polyacrylonitrile homopolymer fiber, except Ricem, which is adopted by the applicant for technical use.
비닐아세테이트, 메타크릴레이트 타입 등의 공단량체를 5-10% 범위 이내의 백분율로 채택하는, 방적 용도를 위한 전통적인 아크릴섬유에서, 물 분자는 섬유를 투과하는 데에 성공하여, CN기를 "용매화"할 수 있어 섬유의 취성(fragility)을 감소시키는 실제적인 가소제(plasticizer)로서 작용하고, 낮은 분자 배향(신장(stretch)) 및 낮은 어닐링(annealing)을 가지도록 구성되어, 섬유 자체를 더욱 연성이 있도록 하여 필의 형성을 지연시킨다.In traditional acrylic fibers for spinning applications, which employ comonomers such as vinyl acetate, methacrylate type, in percentages within the range of 5-10%, water molecules have successfully penetrated the fibers, thus "solvating" CN groups. "Can act as a practical plasticizer that reduces the fragility of the fibers, and is configured to have low molecular orientation (stretch) and low annealing, making the fibers themselves more ductile. To delay the formation of the fill.
물 분자에 의한 아크릴섬유의 용매화는 100℃와 같거나 그보다 더 높은 온도의 물에서 섬유를 염색하는 단계에서 또는 사용하는 동안 인체의 습기를 통하여 일어난다.Solvation of acrylic fibers by water molecules occurs through the moisture of the human body during or during the dyeing of the fibers in water at a temperature equal to or higher than 100 ° C.
상기 기술된 것들에 대한의 해법이 문헌에 제안되었다. 예를 들어, 고령토, 실리카 또는 TiO2와 같은 불활성 물질의 입자의 도입(일본 특허 3,174,012), 필라멘트 상의 표면 절개(incision) 유발(미국 특허 3,928,528), 불규칙한 표면을 가지는 두 판 사이의 최종 제품 압착(pressing)(미국 특허 3,894,318) 또는 20% 이하의 중합체 농도로 방사 용액을 유지시키면서, 강도와 노트 신도를 곱한 값을 2.0 g/den 이하로 감소시켜(일본 특허 출원 4057909) 섬유를 약화시키는 것이다.Solutions to those described above have been proposed in the literature. For example, introduction of particles of inert material such as kaolin, silica or TiO 2 (Japanese Patent 3,174,012), causing surface incision on the filament (US Patent 3,928,528), and final product compression between two plates with irregular surfaces ( pressing (US Pat. No. 3,894,318) or while maintaining the spinning solution at a polymer concentration of 20% or less, the product of strength and note elongation is reduced to 2.0 g / den or less (Japanese Patent Application 4057909) to weaken the fiber.
제안된 모든 이들 해법들은 공중합체(copolymer)로부터 낮은 신장(stretch) 값을 가지는 섬유를 생산할 때 비효율적이거나, 최종 제품의 외관 및 방사 공정에서 품질 저하가 나타나는 것으로 알려졌다. 특히 낮은 신축의 섬유는 섬유의 생산 시스템의 잠재성에 부정적인 영향을 미친다는 것이 기억되어야 한다.All of these proposed solutions are known to be inefficient when producing fibers with low stretch values from copolymers, or to degrade quality in the appearance and spinning process of the final product. It should be remembered that especially low stretch fibers negatively affect the potential of the fiber's production system.
석탄 발전소로부터의 뜨거운 매연(fume)의 여과 용도를 위한 폴리아크릴로니트릴 단일중합체 섬유의 생산자인 본 출원인은 특수하게 개질된 폴리아크릴로니트릴 단일중합체 섬유가 임의의 상용의 아크릴섬유와 비교될 수 없는 필링에 대한 예기치 않은 성질을 보임을 발견하였다. 개시된 청구범위에서 상세하게 기술되는 이 결과는 폴리아크릴로니트릴 단일중합체 섬유가 전통적인 방적 용도에 적합 않은 것으로 공지되어 있으므로 특히 놀랍고 예기치 않은 것이다. 본 출원인은 퍼설페이트-비설파이트 산화환원 촉매를 사용하여 통상적으로 수득된 것에 대하여 더욱 충분히 염색가능한 작용기를 도입하여 이 결점을 극복하였다.Applicants of polyacrylonitrile homopolymer fibers for filtration applications of hot fumes from coal power plants have found that the specially modified polyacrylonitrile homopolymer fibers cannot be compared with any commercially available acrylic fibers. It was found to exhibit unexpected properties for the peeling. These results, which are described in detail in the disclosed claims, are particularly surprising and unexpected because polyacrylonitrile homopolymer fibers are known to be unsuitable for traditional spinning applications. Applicants have overcome this drawback by introducing more fully dyeable functional groups to those conventionally obtained using a persulfate-bisulfite redox catalyst.
비닐아세테이트 또는 메틸아크릴레이트와 같은 공단량체를 6% 이상 함유하는 상용의 아크릴섬유를 위한, 산화환원 촉매에 의하여 생성된 설폰기 및 설페이트기는, 물과 증기의 가소성 효과로 인하여 염료가 모든 설폰기 및 설페이트기에 접근하면서 섬유를 쉽게 관통하므로, 보통 어두운 색상으로 섬유를 염색하기에도 또한 충분하다.For commercial acrylic fibers containing at least 6% of comonomers such as vinyl acetate or methyl acrylate, the sulfone groups and sulfate groups produced by the redox catalysts, due to the plasticity effects of water and steam, are not used for the dyeing of all sulfone groups and As it penetrates the fibers easily while approaching the sulfate group, it is also sufficient to dye the fibers in the usual dark colors.
폴리아크릴로니트릴 단일중합체 섬유의 경우, 소듐 메탈릴설포네이트와 같은 에틸렌성 불포화된 설포네이트화 공단량체의 첨가로 중합에 다량의 추가적인(산화환원 촉매로부터 유래한) 설폰기의 도입은 상용의 섬유를 위한 아크릴로니트릴에 기초한 공중합체에서 얻어진 결과와 유사한 결과를 얻기에 충분하였다.In the case of polyacrylonitrile homopolymer fibers, the introduction of large amounts of additional (derived from redox catalysts) sulfone groups into the polymerization by addition of ethylenically unsaturated sulfonated comonomers such as sodium metalylsulfonate is a common fiber. It was sufficient to obtain results similar to those obtained in copolymers based on acrylonitrile for.
최대 3.0 중량%까지, 예를 들어 0.01 내지 3.0 중량%, 바람직하게는 0.1 내지 3 중량%의 설포네이트화 공단량체의 도입으로, 습열 하에서 폴리아크릴로니트릴 단일중합체 섬유의 치수안정성은 변하지 않고, 이례적인 필링 성능을 가지는 섬유는 방사 공정에서 구축된 "취성"을 유지한다.With the introduction of sulfonated comonomers of up to 3.0% by weight, for example from 0.01 to 3.0% by weight, preferably from 0.1 to 3% by weight, the dimensional stability of the polyacrylonitrile homopolymer fibers under wet heat does not change, which is unusual Fibers with peeling capability retain the "brittleness" built up in the spinning process.
특히, 본원 발명의 목적은, 필수적으로 적어도 97 중량%의 아크릴로니트릴 및 메틸알릴설폰산이나 알릴설폰산 또는 그들의 소듐염과 같은, 설폰 타입의 강산기를 가지는, 다음의 일반식을 가지는 것에서 선택되는 3%까지의 양의 공단량체를 함유하는 공중합체의 습식방사에 의한 필링이 없는 아크릴섬유 생산에 관한다: In particular, the object of the present invention is selected from those having the following general formula having essentially sulfonic type strong acid groups, such as acrylonitrile and methylallylsulfonic acid or allylsulfonic acid or their sodium salts, which are essentially at least 97% by weight. Regardless of peeling acrylic fiber production by wet spinning of copolymers containing comonomers in amounts up to 3%:
CH2=C(R)-CH2SO3-MCH 2 = C (R) -CH 2 SO 3 -M
여기서 R은 수소 원자 또는 -CH3 라디칼을 나타내고, 반면 M은 수소 원자 또는 알칼리 금속을 나타낸다.Where R represents a hydrogen atom or a —CH 3 radical, while M represents a hydrogen atom or an alkali metal.
본원 발명에 따라, 아크릴섬유 제조에 사용되는 아크릴 공중합체는 또한 비닐 타입의 중성 공단량체, 예를 들어, 비닐아세테이트와 같은 C1-C4 산의 비닐에스테르 또는 메틸아크릴레이트나 메틸메타크릴레이트와 같은 아크릴산(메타크릴산)의 알킬 C1-C4 에스테르를 최대 1.5 중량%까지의 양으로 함유할 수 있지만 필수적인 것은 아니다.According to the invention, the acrylic copolymers used for the production of acrylic fibers can also be used with vinyl type neutral comonomers, for example vinyl esters of C 1 -C 4 acids such as vinyl acetate or methyl acrylate or methyl methacrylate. The alkyl C 1 -C 4 esters of the same acrylic acid (methacrylic acid) may be contained in amounts up to 1.5% by weight, but are not required.
본원 발명의 목적인 공정에서 사용되는 공중합체는 퍼설페이트-비설파이트 타입의 산화환원 촉매계를 사용하여 수용성 현탁액에서의 중합으로 수득되고, 통상의 방적 용도에서 최종-섬유의 탁월한 염색 가능성를 보증하는 다수의 염색 가능한 사슬-말단 위치를 가진다.The copolymer used in the process, which is the object of the present invention, is obtained by polymerization in an aqueous suspension using a redox catalyst system of the persulfate-bisulfite type, and a number of dyeings that guarantee excellent dyeability of the end-fibers in conventional spinning applications. It has a possible chain-end position.
도프(dope)에 의하여 17-23 중량% 범위 백분율의 고체로 응고조(coagulation bath)에서 수득된 섬유는 습윤 신축(wet stretching), 뜨거운 롤(role) 상에서 건조 및 증기에서 어닐링한 후, 26 cN/tex의 최소 파단강도(breaking tenacity) 및 18%의 최소 파단신도(breaking elongation)를 가진다. 상기 섬유로부터 시작하여 제조된 순수한 직물 및 혼방 직물의 안티-필링 시험(ICI 박스 시험 또는 마틴데일 시험)에 대하여 탁월한 반응을 예시하는 루프(loop) 기계적 특성의 기준값은 다음과 같다: 루프 강도 ≤ 4.0 cN/tex, 루프 신도 ≤ 1.5% 및 강도와 신도의 곱 또는 루프 일 ≤ 6 cN/tex. The fibers obtained in the coagulation bath by solids in the range of 17-23 wt% by dope were wet stretched, dried on hot rolls and annealed in steam, followed by 26 cN. It has a minimum breaking tenacity of / tex and a minimum breaking elongation of 18%. The reference values of the loop mechanical properties illustrating the excellent response to the anti-pilling test (ICI box test or Martindale test) of pure and blended fabrics made starting from the fibers are as follows: loop strength <4.0 cN / tex, loop elongation ≤ 1.5% and product of strength and elongation or loop work ≤ 6 cN / tex.
다음의 실시예들은 본원 발명의 비제한적 예시로서 제공된다.The following examples are provided as non-limiting examples of the invention.
이 실시예는 본원 발명의 목적인 아크릴섬유 습식방사에 의한 생산 공정을 기술한다.This example describes a production process by acrylic fiber wet spinning, which is the object of the present invention.
98%의 아크릴로니트릴 및 2%의 소듐 메틸알릴설포네이트를 함유하는 공중합체는, pH = 2.8-3.0 및 50℃의 온도에서, 촉매의 질량유속에 대하여 활성제의 질량유속으로서 표현되는 1.30-1.90의 비율로 공급되는, 포타슘 퍼설페이트 촉매 및 소듐 비설파이트 활성제를 가지는 수용성 현탁액에서의 연속적인 중합에 의하여 수득된다. 미-반응된 단량체의 제거, 펠렛의 여과 및 건조 후에 수득된 공중합체는, 디메틸아세트아마이드에 녹아 25℃의 온도에서 1 g/ℓ용액에서 측정되었을 때, 0.240-0.290의 범위 이내로 하락하는 비점도(specific viscosity)를 가진다. 공중합체는 실온의 용매/중합체 슬러리로부터 시작하여 1℃/min의 속도로 가열되며, 90±2℃의 온도에서 디메틸아세트아마이드에서의 최대 용해 피크(로토-점도계(roto-viscometer)로 측정된)를 가진다.Copolymers containing 98% acrylonitrile and 2% sodium methylallylsulfonate are 1.30-1.90 expressed as mass flow rate of the active agent relative to the mass flow rate of the catalyst at a temperature of pH = 2.8-3.0 and 50 ° C. Obtained by continuous polymerization in an aqueous suspension with potassium persulfate catalyst and sodium bisulfite activator, supplied in proportions. The copolymer obtained after removal of unreacted monomers, filtration and drying of pellets, has a specific viscosity that falls within the range of 0.240-0.290 when dissolved in dimethylacetamide and measured in a 1 g / l solution at a temperature of 25 ° C. (specific viscosity). The copolymer is heated at a rate of 1 ° C./min starting from the solvent / polymer slurry at room temperature and the maximum dissolution peak in dimethylacetamide (measured by roto-viscometer) at a temperature of 90 ± 2 ° C. Has
수득된 중합체는 용매에 대하여 18±2 중량%의 고체로 디메틸아세트아마이드 에 용해되고, 85℃의 온도에서 여과된 도프의 압출이 이어진다.The polymer obtained is dissolved in dimethylacetamide as a solid of 18 ± 2% by weight relative to the solvent, followed by extrusion of the filtered dope at a temperature of 85 ° C.
섬유의 최종 타이터(titer)는 2.2 dtex이다. 52 미크론(micron)의 모세관 지름을 가지는 다이(die)가 사용되었고, 물에서 45%의 농도를 가지는 디메틸아세트아마이드 용매의 응고조에 42℃에서 잠기었다.The final titer of the fiber is 2.2 dtex. A die having a capillary diameter of 52 microns was used and immersed at 42 ° C. in a coagulation bath of dimethylacetamide solvent having a concentration of 45% in water.
응고조를 떠나는 토우(tow)는 6x의 총 신장비(stretch ratio)로 신장되고 9.0 atm의 내부 증기압을 가지는 롤(roll) 상에서 붕괴된다. 고온 권축가공(crimping) 후에 토우는 2.0-3.0 atm의 압력에서 어닐러(annealer)에서의 증기의 직접적인 도입으로 안정화되고 1% 이하의 잔류 수축(residual shrinkage)을 유지한다.The tow leaving the coagulation bath expands to a total stretch ratio of 6x and collapses on a roll with an internal vapor pressure of 9.0 atm. After hot crimping the tow is stabilized by the direct introduction of steam in the annealer at a pressure of 2.0-3.0 atm and maintains residual shrinkage of less than 1%.
이렇게 획득된 섬유의 파단강도는 28 cN/tex이고 파단신도는 23%이다. 루프에서 측정된 강도는 2.2 cN/tex이고 루프 신도는 1%이며 강도와 신도의 곱(루프 일)은 2.2 cN/tex 임이 증명되었다.The breaking strength of the fiber thus obtained was 28 cN / tex and the breaking elongation was 23%. The strength measured in the loop proved to be 2.2 cN / tex, the loop elongation was 1%, and the product of strength and elongation (loop days) was 2.2 cN / tex.
수득된 섬유의 최종 부분은 둥글다. 토우 형태에서 섬유는 찢겨졌고, 톱(top)으로 변형되어 (23 미크론) 타이터의 Nm 2/28- 꼬임 400 z- 240 s-의 100% 아크릴 방적사 및 50% 아크릴과 50% 모의 혼방 방적사를 수득하도록 방적되었다.The final part of the fiber obtained is round. In the toe form, the fibers were torn and deformed into tops (23 microns) to form 100% acrylic yarns of twisted yarns of Nm 2 / 28-twist 400 z-240 s- and 50% acrylic and 50% simulated blended yarns of titers. It was spun to obtain.
그 후에 두 가지의 편직물이 제조되었고, 염색 후에 편직물 상에서 표준 방법 BS-5811/86(ICI 박스 시험)에 따라 필링 저항 시험이 수행되었다. 형성된 필링 상에서 평가 척도는 1(불량) 내지 5(매우 우수) 범위였고, 14,400 사이클(cycle) 후에 할당된 점수는 상기 기술된 100% 아크릴섬유 함유하는 방적사로부터의 직물 및 또한 혼방 모직물 양쪽 모두에 대하여 4 및 5였다.Two knit fabrics were then prepared, and after staining, peeling resistance tests were performed on the knit fabric according to the standard method BS-5811 / 86 (ICI Box Test). The evaluation scales on the peeling formed ranged from 1 (poor) to 5 (very good), and the scores assigned after 14,400 cycles were for both fabrics and also blended wool from 100% acrylic fiber containing yarn described above. 4 and 5.
1.0 내지 5.6 dtex 범위 이내의 타이터를 가지는, 낮은 필링 형성의 직물을 위한 아크릴섬유 제조 공정, 이는 필수적으로 97 내지 99.99 중량% 범위의 양의 아크릴로니트릴 및 설폰 타입의 강산기를 가지는 0.01 내지 3 중량%까지의 양의 다음 일반식의 공단량체를 포함하는 공중합체의 용매에서의 습식방사를 포함:Acrylic fiber manufacturing process for low peel forming fabrics with titers in the range 1.0 to 5.6 dtex, which is essentially 0.01 to 3 weights having acrylonitrile and sulfone type strong acid groups in an amount in the range of 97 to 99.99% by weight. Wet spinning in a solvent of a copolymer comprising a comonomer of the following general formula in an amount up to%:
CH2=C(R)-CH2SO3-MCH 2 = C (R) -CH 2 SO 3 -M
여기서 R은 수소 원자 또는 -CH3 라디칼을 나타내고, 반면에 M은 수소 원자 또는 알칼리 금속을 나타냄.Where R represents a hydrogen atom or a —CH 3 radical, while M represents a hydrogen atom or an alkali metal.
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US11594732B2 (en) | 2018-03-01 | 2023-02-28 | Adeka Corporation | Organo sulfur-based electrode active material |
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CN106661771B (en) * | 2014-08-27 | 2020-05-19 | 三菱化学株式会社 | Gloss pilling-resistant acrylic fiber, process for producing the same, and yarn and knitted fabric comprising the same |
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GB911341A (en) * | 1960-06-08 | 1962-11-28 | Du Pont | Polyacrylonitrile fiber |
JP2908046B2 (en) * | 1991-02-21 | 1999-06-21 | 三菱レイヨン株式会社 | Anti-pilling acrylic fiber and method for producing the same |
JPH0559608A (en) * | 1991-08-30 | 1993-03-09 | Mitsubishi Rayon Co Ltd | Anti-pilling acrylic fiber and its production |
JP3656311B2 (en) * | 1996-03-14 | 2005-06-08 | 東レ株式会社 | Anti-pill ultrafine acrylic fiber and method for producing the same |
US6268450B1 (en) * | 1998-05-11 | 2001-07-31 | Solutia Inc. | Acrylic fiber polymer precursor and fiber |
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US11594732B2 (en) | 2018-03-01 | 2023-02-28 | Adeka Corporation | Organo sulfur-based electrode active material |
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JP2009528453A (en) | 2009-08-06 |
EP1991722A1 (en) | 2008-11-19 |
WO2007098796A1 (en) | 2007-09-07 |
CN101421445A (en) | 2009-04-29 |
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