[go: up one dir, main page]

KR20030000045A - Method producing cellulosic fibers by means of continuous alkali treating - Google Patents

Method producing cellulosic fibers by means of continuous alkali treating Download PDF

Info

Publication number
KR20030000045A
KR20030000045A KR1020010035659A KR20010035659A KR20030000045A KR 20030000045 A KR20030000045 A KR 20030000045A KR 1020010035659 A KR1020010035659 A KR 1020010035659A KR 20010035659 A KR20010035659 A KR 20010035659A KR 20030000045 A KR20030000045 A KR 20030000045A
Authority
KR
South Korea
Prior art keywords
cellulose
treatment
fibers
alkali
alkali treatment
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.)
Granted
Application number
KR1020010035659A
Other languages
Korean (ko)
Other versions
KR100472384B1 (en
Inventor
김익수
안종수
김병학
노재규
Original Assignee
에스케이케미칼주식회사
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 에스케이케미칼주식회사 filed Critical 에스케이케미칼주식회사
Priority to KR10-2001-0035659A priority Critical patent/KR100472384B1/en
Priority to PCT/KR2001/002038 priority patent/WO2003000967A1/en
Priority to US10/035,322 priority patent/US20030019047A1/en
Publication of KR20030000045A publication Critical patent/KR20030000045A/en
Application granted granted Critical
Publication of KR100472384B1 publication Critical patent/KR100472384B1/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

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
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • 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
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

본 발명은 저온에서 연속적 알칼리 처리 공정을 포함하는 것을 특징으로 하는 셀룰로오스 아세테이트 섬유로부터 셀룰로오스 섬유를 제조하는 방법에 관한 것으로, 본 발명에 의하면 간단한 제조공정, 낮은 생산원가 및 안전한 조업 조건에서 셀룰로오스 섬유를 제조할 수 있으며, 본 발명에 의해 제조된 셀룰로오스 섬유는 비스코스 레이온 섬유와 유사한 특성을 가져 의류용도로 매우 적합하고 샤리감이 우수한 레이온 섬유를 공급할 수 있게 된다.The present invention relates to a method for producing cellulose fibers from cellulose acetate fibers, characterized in that it comprises a continuous alkali treatment process at low temperature. According to the present invention, cellulose fibers are produced under a simple manufacturing process, low production cost, and safe operating conditions. In addition, the cellulose fibers prepared by the present invention have properties similar to those of viscose rayon fibers, which makes it possible to supply rayon fibers which are very suitable for clothing use and have excellent shariness.

Description

연속적 알칼리 처리에 의한 셀룰로오스 섬유의 제조방법{Method producing cellulosic fibers by means of continuous alkali treating }Method for producing cellulosic fibers by means of continuous alkali treating

본 발명은 셀룰로오스 아세테이트로부터 연속적 알칼리 처리에 의하여 셀룰로오스 섬유를 제조하는 방법에 관한 것이다.The present invention relates to a process for producing cellulose fibers by continuous alkali treatment from cellulose acetate.

종래, 셀룰로오스 아세테이트로부터 셀룰로오스 섬유를 제조하기 위한 알칼리 처리 방법으로는 액류 염색기에 일정량의 원단을 투입하여 처리하는 배치(Batch)방식이 있다.Conventionally, an alkali treatment method for producing cellulose fibers from cellulose acetate has a batch method in which a certain amount of fabric is added and treated in a liquid dyeing machine.

그러나, 위와 같은 불연속적인 배치방식은 셀룰로오스 아세테이트를 셀룰로오스 섬유로 전환시키는 반응시간이 길고 배치(Batch)당 투입량이 한정되어 있어 제조 원가가 상승하는 문제점이 발생한다.However, the discontinuous batch method as described above has a long reaction time for converting cellulose acetate into cellulose fibers and a limited input amount per batch, resulting in an increase in manufacturing cost.

또한 종래의 알칼리 처리 방법으로는 연속감량기를 사용하는 연속적 알칼리 처리 방법이 있다. 이 방법은 폴리에스테르 직물 감량에 주로 사용하는데, 높은 온도와 고농도의 알칼리 조건을 요한다. 폴리에스테르 직물의 감량에 사용되는 연속감량기를 사용하여 셀룰로오스 아세테이트로부터 셀룰로오스 섬유를 제조하는 경우에는 균일한 반응을 일으키지 못해 우수한 품질의 셀룰로오스 섬유를 제조하는 데에는 부적합하다.In addition, a conventional alkali treatment method includes a continuous alkali treatment method using a continuous reducer. This method is mainly used for weight loss of polyester fabrics, requiring high temperature and high alkalinity conditions. The production of cellulose fibers from cellulose acetate using a continuous reducer used to reduce polyester fabrics is not suitable for producing good quality cellulose fibers because they do not cause uniform reactions.

따라서, 본 발명은 상기한 바와 같은 선행기술의 문제점이 없이 저온 조건에서 연속적 알칼리 처리 방법에 의해 셀룰로오스 아세테이트로부터 셀룰로오스 섬유를 제조하는 새로운 방법을 제공하는 것을 목적으로 한다.It is therefore an object of the present invention to provide a new method for producing cellulose fibers from cellulose acetate by a continuous alkali treatment method at low temperature conditions without the problems of the prior art as described above.

상기한 목적을 달성한 본 발명에 의하면 치환도 2.0~2.75(초산화도 45~59.5%)의 셀룰로오스 디아세테이트를 적어도 일부 함유하는 섬유 또는 섬유제품을 저온에서 연속적 알칼리 처리 방법에 의해 셀룰로오스 아세테이트 섬유를 셀룰로오스 섬유로 전환시키는 공정을 포함하는 것을 특징으로 하는 셀룰로오스 섬유의 제조 방법이 제공된다.According to the present invention which achieves the above object, a cellulose acetate fiber is prepared by continuous alkali treatment at a low temperature for a fiber or a textile product containing at least a portion of cellulose diacetate having a degree of substitution of 2.0 to 2.75 (superoxidation degree of 45 to 59.5%). There is provided a process for producing cellulose fibers, comprising the step of converting them to cellulose fibers.

이하, 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.

셀룰로오스 디아세테이트를 알칼리 처리하면 아세틸기가 히드록시기로 전환되는 검화가 일어나게 되는데 이때 무정형으로 존재하던 디아세테이트 섬유의 분자쇄들의 폴딩(folding)과 패킹(packing) 등의 재배열로 결정화가 일어난다. 일반적으로 천연의 셀룰로오스는 셀룰로오스Ⅰ의 결정구조를 가지게 되며 재생 셀룰로오스 섬유의 경우는 셀룰로오스Ⅱ의 구조를 가지는 데 반해 셀룰로오스 디아세테이트의 검화에 의해 제조된 셀룰로오스 섬유는 셀룰로오스Ⅱ와 Ⅵ가 혼합된 결정구조를 가지게 되며, 결정화도(비중법) 14~34%, 복굴절율 0.012~0.024이다.Alkali treatment of cellulose diacetate results in saponification in which acetyl groups are converted to hydroxy groups. Crystallization occurs due to rearrangement of folding and packing of molecular chains of diacetate fibers that were amorphous. In general, natural cellulose has a crystalline structure of cellulose I. In the case of regenerated cellulose fibers, cellulose II has a structure of cellulose, whereas cellulose fibers prepared by saponification of cellulose diacetate have a crystal structure of cellulose II and VI. Crystallinity (specific gravity method) 14-34%, birefringence 0.012 ~ 0.024.

셀룰로오스 디아세테이트 섬유의 검화에 의해 얻어지는 셀룰로오스 섬유도 일종의 레이온 섬유이다. 이러한 셀룰로오스 섬유의 물성은 비중이 1.48~1.51gm/cm3, 인장강도 1.2~2.5gf/de, 신도 20~50%, 표준상태 수분율 12~16%로 일반 레이온과 유사한 성능을 보인다.The cellulose fiber obtained by saponification of a cellulose diacetate fiber is also a kind of rayon fiber. The specific properties of these cellulose fibers are 1.48 ~ 1.51gm / cm 3 , tensile strength 1.2 ~ 2.5gf / de, elongation 20 ~ 50%, standard moisture content 12 ~ 16%.

본 발명에서 검화 혹은 알칼리 처리에는 강알칼리 단독 처리 또는 강알칼리와 약알칼리의 동욕처리 또는 이욕처리 방법을 이용할 수 있다.In the present invention, for saponification or alkali treatment, strong alkali alone treatment or copper bath treatment or strong bath treatment method of strong alkali and weak alkali can be used.

검화 과정에서 사용될 수 있는 알칼리화합물의 예로는 수산화나트륨 등과 같은 알칼리금속수산화물, 수산화칼슘 등과 같은 알칼리토금속류수산화물, 탄산나트륨 등과 같은 알칼리 금속탄산염 등이 있다. 이러한 알칼리 화합물은 단독으로 사용할 수도 있고, 또는 반응 속도 조절제를 병용하여 사용할 수도 있다. 반응속도조절제로는 포스포늄계 반응 속도 조절제와 4급암모늄계 반응 속도 조절제가 잘 알려져 있다. 반응 속도 조절제의 시중 구입 가능한 예로는 포스포늄계인 네오레이트 엔씨비(NEORATE NCB : 한국정밀제품) ; 제4급암모늄계인 케이에프 네오레이트 엔에이-40(KF NEORATE NA-40 : 한국정밀제품), 디와이케이-1125[DYK-1125 : 일본의 일방사(一方社)제품], 카세린PES, 카세린 PEL, 카세린 PEF[이상 일본의 명성화학(明成化學)제품], 스노겐 피디에스(SNOGEN PDS : 한국의 대영 화학제품)등을 들 수 있다.Examples of alkali compounds that can be used in the saponification process include alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate, and the like. These alkali compounds may be used alone or in combination with a reaction rate regulator. As the reaction rate regulator, phosphonium-based reaction rate regulators and quaternary ammonium-based reaction rate regulators are well known. Commercially available examples of reaction rate regulators include phosphonium-based neorate NCB (NEORATE NCB); KF NEORATE NA-40 (KF NEORATE NA-40: Korea Precision Products), DYK-1125 [Japan's one-sided yarn], Casein PES, Car And serine PEL, casein PEF (above Japan's famous chemical products), and SNOGEN PDS (Korean British Chemicals).

본 발명에서는 셀룰로오스 섬유를 제조하기 위한 원료로서 치환도 2.0~2.75의 셀룰로오스 디아세테이트를 적어도 일부 함유하는 섬유 또는 섬유제품을 사용한다.In the present invention, a fiber or a textile product containing at least a part of cellulose diacetate having a degree of substitution of 2.0 to 2.75 is used as a raw material for producing cellulose fibers.

또한, 본 발명에서는 상기와 같은 섬유로부터 셀룰로오스 섬유를 전환하는데 있어서, 저온에서 연속적 처리 방법에 의해 알칼리 처리하는 공정을 포함하는 것을 특징으로 하는데, 반응조건과 공정과정의 일예는 다음과 같다.In addition, the present invention is characterized in that in the conversion of cellulose fibers from the fibers as described above, comprising a step of alkali treatment by a continuous treatment method at a low temperature, an example of the reaction conditions and process is as follows.

콜드 패드 배치(Cold-Pad-Batch) 감량기의 패딩(Padding)조에 20~53%의 알칼리 수용액을 준비하고, 준비된 알칼리 수용액에 정련 건조한 셀룰로오스 디아세테이트 섬유를 일부 함유하는 섬유 또는 섬유제품을 침지하여 50~100% 웨트 픽업(Wet Pick-up)시킨다. 웨트 픽업시킨 섬유를 저장 롤(Roll)에 권취하고, 권취한 섬유를 20oC 이상 70oC 이하에서 1~48시간 동안 처리한 후 수세하여 셀룰로오스 섬유를 제조한다.Prepare 20-53% aqueous alkali solution in the padding tank of cold-pad batch reducer, and immerse the fibrous or fibrous product containing some refined dried cellulose diacetate fibers in the prepared aqueous alkali solution. ~ 100% Wet Pick-up. The wet-picked fibers are wound on a storage roll, and the wound fibers are treated at 20 ° C. or higher and 70 ° C. or lower for 1 to 48 hours and washed with water to prepare cellulose fibers.

상기 알칼리 수용액의 농도는 20~53% 범위내로 하는 것이 바람직하다. 이는 20% 미만에서는 반응이 불충분하며, 53% 초과시에는 알칼리 수용액이 수산화나트륨(NaOH)의 포화상태가 되어 용액을 제조하는 것이 불가능하기 때문이다.It is preferable to make the density | concentration of the said alkali aqueous solution into 20 to 53% of range. This is because the reaction is insufficient at less than 20%, and when it is above 53%, the aqueous alkali solution becomes saturated with sodium hydroxide (NaOH), making it impossible to prepare a solution.

또한, 본 발명의 공정중 알칼리 처리하는데 있어서 알칼리 처리 온도는 20oC 이상 70oC 이하가 바람직한데, 20oC 미만에서는 반응이 불충분하며, 70oC을 초과하는경우에는 불균일 반응과 분자쇄 절단이 일어나게 되어 본 발명에 부적합하게 된다.Further, according to an alkali treatment in the process of the present invention the alkaline processing temperature together is 20 o or more C 70 o C or less preferably, 20 o C less than the and the reaction is insufficient, 70 o, if it exceeds the C is non-uniform reaction, and the molecular chain Cleavage will occur which makes it unsuitable for the present invention.

상기한 바와 같은 본 발명의 특징 및 기타의 장점은 후술되는 실시예로부터 보다 명백하게 될 것이다. 단, 본 발명이 하기 실시예로 제한되는 것은 아니다.Features and other advantages of the present invention as described above will become more apparent from the following examples. However, the present invention is not limited to the following examples.

하기 실시예에서 셀룰로오스 아세테이트의 감량율과 기타 물성 등은 다음과 같은 방법으로 측정한 것이다.In the following examples, the loss ratio and other physical properties of cellulose acetate are measured by the following method.

* 탈아세틸화 : 적외선 분광 분석기(MAGNA 750, Nicolet, 미국)를 사용하여 적외선 분광 분석에 의해 탈아세틸화를 확인하였다. 이 때 탈아세틸화는 1760cm-1에서 나타나는 아세틸기의 카르보닐 밴드의 유무로 확인하였다.Deacetylation: Deacetylation was confirmed by infrared spectroscopy using an infrared spectrometer (MAGNA 750, Nicolet, USA). At this time, deacetylation was confirmed by the presence or absence of the carbonyl band of the acetyl group which appears at 1760 cm <-1> .

* 감량율 : 알칼리 처리전/후의 시료의 중량변화를 측정하여 다음 식으로 구하였다.* Reduction rate: The weight change of the sample before and after alkali treatment was measured and obtained by the following equation.

(처리전 시료중량 - 처리후 시료중량)(Sample weight before treatment-sample weight after treatment)

감량율(%)=--------------------- ×100Reduction ratio (%) = --------------------- × 100

(처리전 시료중량)(Sample weight before treatment)

* 섬유의 절단강도 및 절단시도 : 만능시험기(Universal Testing Machine : ZWICK 1425, 독일)를 사용하여 시료길이 50mm, 인장속도 200m/min으로 인장 시켜 측정하였다.* Cutting strength and tryability of the fiber: using a universal testing machine (Universal Testing Machine: ZWICK 1425, Germany) was measured by stretching the sample length 50mm, tensile speed 200m / min.

* 염색성 : 직접염료인 C.I. Direct Blue 200(일본화약제 Kayarus Supra Blue 4BL)을 0.5%owf 농도로 100oC에서 30분 염색한 후 상법으로 70oC 에서 소핑(Soaping)과 린싱(Rinsing)을 실시하여 염색을 완료하였다. 얻어진 염색물을 분광광도계(Color-Eye 7000A, Machbeth,미국)를 사용하여 반사율(R:Reflectance)을 측정한 후 이를 식 K/S=(1-R)2/2R에 대입하여 K/S값을 구하고 이 값으로 염색성을 평가하였다.* Dyeing: Dyeing CI Direct Blue 200 (Kayarus Supra Blue 4BL) with 0.5% owf concentration at 100 o C for 30 minutes and then soaping and rinsing at 70 o C The dyeing was completed. Measure the reflectance (R: Reflectance) by using a spectrophotometer (Color-Eye 7000A, Machbeth, USA), and substitute this into the equation K / S = (1-R) 2 / 2R to determine the K / S value. Was obtained and the dyeability was evaluated using this value.

[실시예 1]Example 1

아세틸 치환도 2.55(초산화도 56.9%)의 셀룰로오스 디아세테이트 섬유로 구성된 평직물(경사 75d/20f, 위사 120d/33f, 위밀도 75본/inch,SK케미칼産, 韓國) 을 정련 건조한 후 콜드 패드 배치(Cold-Pad-Batch) 감량기의 패딩(Padding)조에 가성소다 53% 용액이 되도록 가성소다를 투입하여 용해시킨 후 반응속도조절제 1g/L를 넣어 다시 용해시켰다. 준비된 셀룰로오스 디아세테이트 정련지를 침지시켜 가성소다 용액의 웨트 픽업(Wet Pick-up)이 70%가 되도록 알칼리 처리하였다. 알칼리 처리된 셀룰로오스 디아세테이트를 저장 로올(Roll)에 권취한 후 20oC에서 24시간 동안 검화시켰다. 검화된 섬유를 수세조에서 수세하여 잔류 알칼리를 제거하고 섬유를 건조시켰다. 이러한 검화 공정을 통해 초기 셀룰로오스 디아세테이트 섬유 중량대비 감량율이 40%인 셀룰로오스 섬유를 얻었다.Cold pads made of cellulose diacetate fibers with an acetyl substitution degree of 2.55 (56.9% superoxide), followed by scouring and drying of plain fabrics (inclined 75d / 20f, weft 120d / 33f, gas density 75 bones / inch, SK Chemicals, etc.) Caustic soda was added to dissolve the caustic soda in a padding tank of a Cold-Pad-Batch reducer so as to be 53% solution. Then, 1 g / L of a reaction rate regulator was added to dissolve again. The prepared cellulose diacetate scouring paper was immersed in alkali treatment so that the wet pick-up of the caustic soda solution was 70%. Alkali-treated cellulose diacetate was wound in a storage roll and then saponified at 20 ° C. for 24 hours. The saponified fiber was washed in a water bath to remove residual alkali and to dry the fiber. Through this saponification process, a cellulose fiber having a reduction ratio of 40% based on the weight of the initial cellulose diacetate fiber was obtained.

원료 섬유와 검화에 의해 감량된 섬유를 각각 적외선 분광 스펙트럼으로 분석한 결과, 원료로 사용된 디아세테이트 섬유는 1760cm-1근처에서 아세틸기의 카르보닐 밴드가 크게 나타나는 반면 실시예 1에서 감량율이 40%인 셀룰로오스 섬유는 1760cm-1근처에서의 카르보닐 밴드가 완전히 사라지고 3400cm-1의 히드록시기 스트레칭(Hydroxy Stretching)이 증가하여 모든 아세틸기가 히드록시기로 치환되었음을 알 수 있었다.Infrared spectroscopy analysis of the raw fiber and the fiber reduced by saponification showed that the diacetate fiber used as the raw material showed a large carbonyl band of acetyl group near 1760 cm -1 , while the loss ratio was 40 in Example 1. % of cellulose fibers, it was found that all of the acetyl group is substituted with a hydroxy group to a carbonyl band completely disappears and increase the stretching of the hydroxyl groups 3400cm -1 (hydroxy stretching) in the vicinity of 1760cm -1.

상기 실시예에서의 얻어진 섬유의 물성 측정 결과는 표 1에 제시된다.The measurement results of the physical properties of the fibers obtained in the above examples are shown in Table 1.

[실시예 2]Example 2

25%의 가성소다 용액을 사용하고, 가성소다 용액을 셀룰로오스 디아세테이의 웨트 픽업(Wet Pick-up) 70%가 되도록 하고, 알칼리 처리시의 온도를 70oC가 되도록한 것을 제외하고는 실시예 1과 동일한 절차를 반복하였다.25% caustic soda solution was used, caustic soda solution was made to be 70% wet pick-up of cellulose diacetate, and the temperature during alkali treatment was adjusted to 70 ° C. The same procedure as in Example 1 was repeated.

상기 실시예의 검화 공정을 통해 초기 셀룰로오스 디아세테이트 섬유 중량대비 감량율이 39.5%인 셀룰로오스 섬유를 얻었다.Through the saponification process of the above embodiment, a cellulose fiber having a weight loss ratio of 39.5% based on the weight of the initial cellulose diacetate fiber was obtained.

실시예 1과 마찬가지로 적외선 분광 스펙드럼 분석을 통하여 아세틸기가 완전히 히드록시기로 치환되었음을 알 수 있었다.As in Example 1, it was found that the acetyl group was completely substituted with a hydroxy group through infrared spectroscopic spectrometry.

실시예 2에서 얻어진 섬유의 물성 측정 결과도 표 1에 제시된다.The measurement results of the physical properties of the fibers obtained in Example 2 are also shown in Table 1.

[비교예 1]Comparative Example 1

아세틸 치환도 2.55(초산화도 56.9%)의 셀룰로오스 디아세테이트 섬유로 구성된 평직물(경사 75d/20f, 위사 120d/33f, 위밀도 75본/inch,SK케미칼産, 韓國) 을 정련 건조한 후 액류염색기에 디아세테이트 섬유 중량 대비 15배의 물을 넣고 가성소다 2.7% 수용액이 되도록 가성소다를 투입한 후 반응속도 조절제 1g/l를 첨가하여 용해시켰다.Liquid dyeing machine after scouring and drying plain fabrics (inclined 75d / 20f, weft 120d / 33f, gas density 75 bones / inch, SK chemicals) Water was added 15 times the weight of diacetate fiber, caustic soda was added so as to be 2.7% aqueous solution of caustic, and then dissolved by adding 1 g / l reaction rate regulator.

준비된 디아세테이트 섬유 정련지를 액류 염색기에 투입한 후 30oC에서 2oC/min로 승온하여 98oC에서 30분간 처리한 뒤 30oC까지 2oC/min로 냉각시키고 배액하였다. 상온의 물을 넣고 수세하여 잔류 알칼리를 제거하고 섬유를 건조시켰다. 이러한 검화공정을 통해 초기 디아세테이트 섬유중량대비 감량율이 40%인 섬유를 얻었다.The prepared diacetate fiber scouring paper was added to a liquid dyeing machine, and then heated to 30 ° C. at 2 ° C / min, treated at 98 ° C. for 30 minutes, cooled to 30 ° C. at 2 ° C / min, and drained. Water was added at room temperature and washed with water to remove residual alkali and dried the fibers. Through this saponification process, a fiber having a loss ratio of 40% relative to the initial diacetate fiber weight was obtained.

실시예 1과 마찬가지로 적외선 분광 스펙트럼 분석을 통하여 아세틸기가 히드록시기로 완전히 치환되었음을 확인하였다.As in Example 1, it was confirmed that the acetyl group was completely substituted with a hydroxy group through infrared spectroscopic analysis.

또한 표 1에 제시된 바와 같이 저온에서 연속적 처리방법에 의해 제조된 셀룰로오스 섬유의 물성 및 염색성이 비교예 1의 액류에서 제조된 셀룰로오스 섬유와 거의 유사한 성질을 나타내는 것을 확인할 수 있었다.In addition, as shown in Table 1, it was confirmed that the physical properties and dyeing properties of the cellulose fibers prepared by the continuous treatment method at low temperature showed almost similar properties to the cellulose fibers prepared in the liquid stream of Comparative Example 1.

구분division 실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 가성소다 농도(%)Caustic Sodium Concentration (%) 5353 2525 2.72.7 처리온도(oC)Treatment temperature ( o C) 2020 7070 9898 아세테이트 감량율(%)Acetate loss rate (%) 4040 39.539.5 4040 섬도(De)Fineness (De) 168.9168.9 170.4170.4 164.4164.4 절단강도(gf/de)Cutting strength (gf / de) 1.351.35 1.331.33 1.341.34 절단신도(%)Elongation at break (%) 42.542.5 43.043.0 42.042.0 염색성(K/S)Dyeability (K / S) 8.518.51 8.428.42 8.478.47

상기한 실험결과로부터 명백하게 되는 바와 같이, 본 발명에 의해 셀룰로오스 디아세테이트 섬유로부터 저온에서 연속적 처리방법에 의해 제조된 셀룰로오스 섬유는 기존의 비스코스 레이온 섬유와 화학적 구조 및 물리적 특성이 유사하며, 고온에서 액류처리에 의해 제조된 셀룰로오스 섬유와도 유사한 특성을 가짐으로 동일한 용도로 적용이 가능하며, 또한 저온에서 연속적 처리방법에 의해 제조함으로서 간단한 제조공정, 낮은 제조원가, 안전한 조업조건에서 제조할 수 있는 장점이 있는 것이다.As will be apparent from the above experimental results, the cellulose fiber prepared by the continuous treatment method at low temperature from the cellulose diacetate fiber according to the present invention is similar in chemical structure and physical properties to the existing viscose rayon fiber, and liquid-treated at high temperature. It has similar characteristics to the cellulose fibers produced by it, so it can be applied to the same use, and also by the continuous processing method at low temperature, it has the advantage of being manufactured in a simple manufacturing process, low manufacturing cost, and safe operating conditions. .

Claims (5)

치환도 2.0~2.75(초산화도 45~59.5%)의 셀룰로오스 디아세테이트를 적어도 일부 함유하는 섬유 또는 섬유제품을 20~70oC 범위의 저온에서 연속적 알칼리 처리 방법에 의해 셀룰로오스 아세테이트 섬유를 셀룰로오스 섬유로 전환시키는 공정을 포함하는 것을 특징으로 셀룰로오스 섬유의 제조방법.Fibrous or fibrous products containing at least a part of cellulose diacetate having a degree of substitution of 2.0 to 2.75 (45 to 59.5% superoxide) at a low temperature in the range of 20 to 70 ° C. A process for producing cellulose fibers, comprising the step of converting. 제 1 항에 있어서, 상기 저온, 연속적 알칼리 처리가 콜드 패드 배치(Cold-Pad-Batch) 감량기에서 수행하는 것을 포함하는 것을 특징으로 하는 셀룰로오스 섬유의 제조방법.The method of claim 1, wherein the low temperature, continuous alkali treatment is performed in a cold-pad batch reducer. 제 1 항에 있어서, 상기 알칼리 처리가 강알칼리 단독처리, 강알칼리와 약알칼리의 동욕처리, 또는 강알칼리와 약알칼리의 이욕처리에 의해 수행되는 것을 특징으로 하는 셀룰로오스 섬유의 제조방법.The method for producing a cellulose fiber according to claim 1, wherein the alkali treatment is performed by a strong alkali treatment, a copper bath treatment of strong alkalis and weak alkalis, or a bathing treatment of strong alkalis and weak alkalis. 제 1 항에 있어서, 알칼리 처리조건에 있어서 알칼리 처리농도를 20~53%하고, 처리시간 1~48시간으로 하는 것을 특징으로 하는 연속적 처리방법에 의한 셀룰로오스 섬유의 제조 방법.The method for producing a cellulose fiber according to the continuous treatment method according to claim 1, wherein the alkali treatment concentration is 20 to 53% under alkaline treatment conditions, and the treatment time is 1 to 48 hours. 제 1항에 있어서, 상기 알칼리 처리에 반응 속도 조절제로서 제4급암모니움염 및 또는 포스포늄염을 첨가하는 것으로 특징으로 하는 셀룰로오스 섬유의 제조방법.The method for producing cellulose fibers according to claim 1, wherein a quaternary ammonium salt and / or phosphonium salt are added to the alkali treatment as a reaction rate controlling agent.
KR10-2001-0035659A 2001-06-22 2001-06-22 Method producing cellulosic fibers by means of Cold-pad-batch Expired - Fee Related KR100472384B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR10-2001-0035659A KR100472384B1 (en) 2001-06-22 2001-06-22 Method producing cellulosic fibers by means of Cold-pad-batch
PCT/KR2001/002038 WO2003000967A1 (en) 2001-06-22 2001-11-27 Method of producing cellulose fibers by use of cold-pad-batch
US10/035,322 US20030019047A1 (en) 2001-06-22 2002-01-04 Method for producing cellulose fibers by use of cold-pad-batch

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR10-2001-0035659A KR100472384B1 (en) 2001-06-22 2001-06-22 Method producing cellulosic fibers by means of Cold-pad-batch

Publications (2)

Publication Number Publication Date
KR20030000045A true KR20030000045A (en) 2003-01-06
KR100472384B1 KR100472384B1 (en) 2005-03-08

Family

ID=19711217

Family Applications (1)

Application Number Title Priority Date Filing Date
KR10-2001-0035659A Expired - Fee Related KR100472384B1 (en) 2001-06-22 2001-06-22 Method producing cellulosic fibers by means of Cold-pad-batch

Country Status (3)

Country Link
US (1) US20030019047A1 (en)
KR (1) KR100472384B1 (en)
WO (1) WO2003000967A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100472385B1 (en) * 2001-10-10 2005-03-07 에스케이케미칼주식회사 Method producing fabrics of rayon polyester/nylon ultrafine composite yarn
KR100483808B1 (en) * 2001-12-11 2005-04-20 에스케이케미칼주식회사 Method for producing cellulosic fibers by means of Cold-pad-batch

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI393807B (en) * 2010-03-26 2013-04-21 Taiwan Textile Res Inst Cellulose masterbatch with improved breaking elongation, application thereof and method for preparing the same
CN111705374B (en) * 2020-06-11 2021-07-16 台州恒彩纺织科技有限公司 Modified regenerated cellulose fiber, knitted fabric processed therefrom and dyeing process

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57117614A (en) * 1980-07-25 1982-07-22 Mitsubishi Rayon Co Ltd Preparation of cellulose acetate fibrous aggreagate
JPS5898411A (en) * 1981-11-30 1983-06-11 Teijin Ltd Hollow fiber membrane for blood treatment and its production
JP3065850B2 (en) * 1993-05-06 2000-07-17 三菱レイヨン株式会社 Method for modifying composite yarn
JP2844292B2 (en) * 1993-05-25 1999-01-06 三菱レイヨン株式会社 Method for producing novel woven or knitted material containing acetate fiber
JP2932337B2 (en) * 1993-10-12 1999-08-09 三菱レイヨン株式会社 Acetate conjugate fiber and method for producing the same
JPH07216651A (en) * 1994-01-19 1995-08-15 Mitsubishi Rayon Co Ltd Acetate fiber and method for producing the same
JP3108347B2 (en) * 1995-11-22 2000-11-13 三菱レイヨン株式会社 Cellulose acetate conjugate fiber and method for producing the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100472385B1 (en) * 2001-10-10 2005-03-07 에스케이케미칼주식회사 Method producing fabrics of rayon polyester/nylon ultrafine composite yarn
KR100483808B1 (en) * 2001-12-11 2005-04-20 에스케이케미칼주식회사 Method for producing cellulosic fibers by means of Cold-pad-batch

Also Published As

Publication number Publication date
WO2003000967A1 (en) 2003-01-03
US20030019047A1 (en) 2003-01-30
KR100472384B1 (en) 2005-03-08

Similar Documents

Publication Publication Date Title
US5403530A (en) Elongate member production method
US5417752A (en) Product containing silicon dioxide and a method for its preparation
Wilkes The viscose process
KR100503393B1 (en) The preparation of hollow-rayon fiber
KR100472384B1 (en) Method producing cellulosic fibers by means of Cold-pad-batch
KR100483808B1 (en) Method for producing cellulosic fibers by means of Cold-pad-batch
KR100472385B1 (en) Method producing fabrics of rayon polyester/nylon ultrafine composite yarn
KR100387972B1 (en) Rayon/polyester mixtured yarn and method of producing it
KR100472827B1 (en) Method for producing cellulous/cellulous triacetate fabric
KR100472386B1 (en) Method of producing cellulose fibers by use of consecutive Alkali treatment
US2068631A (en) Preparation of cellulose xanthate solutions
RU2104358C1 (en) Wool production process
RU2130515C1 (en) Method of treating flax fiber
KR100450529B1 (en) Method for producing fabric of rayon and fine fibers
KR100477469B1 (en) Rayon fabrics and method of production thereof
KR100406884B1 (en) Method for producing fabric of cellulose mixed fibers with different shrinkages
KR100473680B1 (en) The method for producing fabrics of Rayon/ultrafine composite yarn by use of Cold-pad-batch
US1831197A (en) Low viscosity cellulose fiber and process of making
JPS6130042B2 (en)
US2001621A (en) Treatment of artificial fibrous material
RU2129171C1 (en) Fiber manufacture process
JP3030316B2 (en) Processing of regenerated cellulose fiber products
KR100477466B1 (en) Method for producing rayon/silk composite fabrics
KR20020080828A (en) Y-shaped rayon fiber and method for producing it
EP4540452A1 (en) A method of treating regenerated cellulose fiber for textile and non-woven applications

Legal Events

Date Code Title Description
PA0109 Patent application

St.27 status event code: A-0-1-A10-A12-nap-PA0109

E13-X000 Pre-grant limitation requested

St.27 status event code: A-2-3-E10-E13-lim-X000

P11-X000 Amendment of application requested

St.27 status event code: A-2-2-P10-P11-nap-X000

P13-X000 Application amended

St.27 status event code: A-2-2-P10-P13-nap-X000

E13-X000 Pre-grant limitation requested

St.27 status event code: A-2-3-E10-E13-lim-X000

P11-X000 Amendment of application requested

St.27 status event code: A-2-2-P10-P11-nap-X000

P13-X000 Application amended

St.27 status event code: A-2-2-P10-P13-nap-X000

P11-X000 Amendment of application requested

St.27 status event code: A-2-2-P10-P11-nap-X000

P13-X000 Application amended

St.27 status event code: A-2-2-P10-P13-nap-X000

A201 Request for examination
PA0201 Request for examination

St.27 status event code: A-1-2-D10-D11-exm-PA0201

PG1501 Laying open of application

St.27 status event code: A-1-1-Q10-Q12-nap-PG1501

D13-X000 Search requested

St.27 status event code: A-1-2-D10-D13-srh-X000

D14-X000 Search report completed

St.27 status event code: A-1-2-D10-D14-srh-X000

E701 Decision to grant or registration of patent right
PE0701 Decision of registration

St.27 status event code: A-1-2-D10-D22-exm-PE0701

GRNT Written decision to grant
PR0701 Registration of establishment

St.27 status event code: A-2-4-F10-F11-exm-PR0701

PR1002 Payment of registration fee

St.27 status event code: A-2-2-U10-U11-oth-PR1002

Fee payment year number: 1

PG1601 Publication of registration

St.27 status event code: A-4-4-Q10-Q13-nap-PG1601

R18-X000 Changes to party contact information recorded

St.27 status event code: A-5-5-R10-R18-oth-X000

R18-X000 Changes to party contact information recorded

St.27 status event code: A-5-5-R10-R18-oth-X000

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 4

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 5

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 6

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 7

R18-X000 Changes to party contact information recorded

St.27 status event code: A-5-5-R10-R18-oth-X000

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 8

FPAY Annual fee payment

Payment date: 20130121

Year of fee payment: 9

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 9

PN2301 Change of applicant

St.27 status event code: A-5-5-R10-R13-asn-PN2301

St.27 status event code: A-5-5-R10-R11-asn-PN2301

FPAY Annual fee payment

Payment date: 20140121

Year of fee payment: 10

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 10

FPAY Annual fee payment

Payment date: 20150126

Year of fee payment: 11

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 11

R18-X000 Changes to party contact information recorded

St.27 status event code: A-5-5-R10-R18-oth-X000

FPAY Annual fee payment

Payment date: 20160120

Year of fee payment: 12

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 12

FPAY Annual fee payment

Payment date: 20170119

Year of fee payment: 13

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 13

R18-X000 Changes to party contact information recorded

St.27 status event code: A-5-5-R10-R18-oth-X000

FPAY Annual fee payment

Payment date: 20180126

Year of fee payment: 14

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 14

PN2301 Change of applicant

St.27 status event code: A-5-5-R10-R11-asn-PN2301

PN2301 Change of applicant

St.27 status event code: A-5-5-R10-R14-asn-PN2301

FPAY Annual fee payment

Payment date: 20190129

Year of fee payment: 15

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 15

FPAY Annual fee payment

Payment date: 20200129

Year of fee payment: 16

PR1001 Payment of annual fee

St.27 status event code: A-4-4-U10-U11-oth-PR1001

Fee payment year number: 16

PC1903 Unpaid annual fee

St.27 status event code: A-4-4-U10-U13-oth-PC1903

Not in force date: 20210206

Payment event data comment text: Termination Category : DEFAULT_OF_REGISTRATION_FEE

PC1903 Unpaid annual fee

St.27 status event code: N-4-6-H10-H13-oth-PC1903

Ip right cessation event data comment text: Termination Category : DEFAULT_OF_REGISTRATION_FEE

Not in force date: 20210206