KR960005963B1 - Preparation process of polyester fiber comprising ceramic - Google Patents

Preparation process of polyester fiber comprising ceramic Download PDF

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KR960005963B1
KR960005963B1 KR1019930032154A KR930032154A KR960005963B1 KR 960005963 B1 KR960005963 B1 KR 960005963B1 KR 1019930032154 A KR1019930032154 A KR 1019930032154A KR 930032154 A KR930032154 A KR 930032154A KR 960005963 B1 KR960005963 B1 KR 960005963B1
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South Korea
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formula
polyester fiber
barium sulfate
alkyl group
phosphorus compound
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KR1019930032154A
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Korean (ko)
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KR950018737A (en
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권혁상
원제랑
한광석
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주식회사선경인더스트리
김준웅
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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
    • 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
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • 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
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • 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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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Artificial Filaments (AREA)

Abstract

The polyester fiber containing ceramic is prepared by adding 3-10wt.% of barium sulfate slurry, which consists of 0.01-1.05wt.% of dispersant of formula(I) and ethylene glycol, to terephthalic acid before transesterification, and polycondensing the mixture by adding 0.5-3.0M% of phosphorous compd. of formula (II) and metal compn. of 0.5-2.5 times the moles of used phosphorous compn into esterified cpd. In the formula (I), R1 is alkyl group of C1-C8; R2 is alkyl group of C5-C15; m is 1-4; n is 1-3. In (II), R3 and R4 are H or organic group with one valance; X is -OH, -OR, -OM; M is alkali metal with one valence or alkali earth metal with 1/2 valence; R is alkyl group of C1-C3.

Description

세라믹 함유 폴리에스테르 섬유의 제조방법Manufacturing method of ceramic-containing polyester fiber

본 발명은 세라믹 함유 폴리에스테르 섬유의 제조방법에 관한 것으로서, 더욱 상세하게는 폴리에스테르 합성시 분산제를 함유한 황산바륨 슬러리와 인화합물을 첨가하므로써, 레이온섬유와 같이 독특한 광택을 유지하면서 색상이 선명하고 드레이프성이 우수하며, 제사, 준비, 제직공정중에 있어 각종 가이드류의 마모성이 적고 동시에 염색, 가공 등 후가공성이 우수한 세라믹 함유 폴리에스테르 섬유를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a ceramic-containing polyester fiber, and more particularly, by adding a barium sulfate slurry and a phosphorus compound containing a dispersant during the synthesis of polyester, the color is vivid while maintaining a unique luster like rayon fibers The present invention relates to a method for producing a ceramic-containing polyester fiber having excellent drape property, less wear resistance of various guides during the weaving, preparation, and weaving process, and excellent post-processing properties such as dyeing and processing.

일반적으로 폴리에스테르 섬유는 물리, 화학적 성질이 우수하여 범용합성섬유로서 많이 사용되고 있는데 아세테이트, 비스코스레이온, 양모, 견, 아크릴 등의 섬유에 비해 염색하였을 때 심색성이 떨어질 뿐 아니라 특유의 광택을 발현하는데 미흡한 단점이 있으며, 특히 비중이 높아 직물상에서 드레이프성이나 고유 광택을 발현하면서 심색성을 갖는 비스코스레이온섬유와 같은 폴리에스테르 섬유의 제조는 곤란하였다.In general, polyester fiber is widely used as a general purpose synthetic fiber because of its excellent physical and chemical properties, and it is not only deep in color when dyed compared to fibers such as acetate, viscose rayon, wool, silk, acrylic, etc. There are inadequate disadvantages, and in particular, it is difficult to produce polyester fibers such as viscose rayon fibers having deep colorability while expressing drape or intrinsic luster on a fabric due to their high specific gravity.

이러한 결점들을 해소하기 위해 우선 폴리에스테르 섬유에 심색성을 부여하는 방법으로서는 (A) 폴리에스테르 섬유표면의 저굴절율을 위한 수지코팅방법, (B) 직·편물 표면에 플라즈마 조사에 의한 미세요철 부여방법, (C) 실리카졸과 같은 미세한 크기의 무기미립자를 0.1~10중량% 첨가한 후 폴리에스테르 섬유를 알칼리 감량처리하여 섬유표면에 무수히 많은 미세요철을 형성시키는 방법들이 제안되고 있다.In order to solve these drawbacks, first of all, the method of imparting color depth to the polyester fibers includes (A) a resin coating method for low refractive index of the polyester fiber surface, and (B) a method of imparting fine roughness by plasma irradiation on the surface of the woven or knitted fabric. , (C) The addition of 0.1 to 10% by weight of fine particles of inorganic fine particles such as silica sol and alkali reduction of the polyester fiber has been proposed to form a myriad of fine iron on the surface of the fiber.

이러한 방법 중 상기(A)의 방법은 섬유표면에 반사되는 백색광의 분말을 줄여주므로서 색상의 개선효과는 인정되나 표면에 코팅된 저굴절율을 수지가 세척등에 의해 쉽게 탈락하게 되므로 내구성이 불량하다는 단점이 있으며, (B)의 방법은 플라즈마 방진설비가 고가이기 때문에 원가상승의 원인이 될 수 있고, 심색성 향상효과도 충분하지 못할 뿐 아니라 플라즈마 조사 이면에 있는 섬유표면에는 충분한 미세요철 부여가 어려워 공업적으로 생산하기는 아직도 많은 문제점을 지니고 있다.Among the above methods, the method of (A) reduces the white light powder reflected on the fiber surface, thereby improving the color. However, the low refractive index coated on the surface is easily eliminated by washing, so the durability is poor. In the method of (B), since the plasma dustproof equipment is expensive, it may cause a cost increase, not only the effect of improving color depth is sufficient, but also it is difficult to give sufficient fine roughness to the fiber surface behind the plasma irradiation. Production as an enemy still has many problems.

한편, (C)의 방법에 의해 제조된 섬유는 심새효과가 충분하지 못하며 섬유표면에 요철이 불규칙적으로 분포되어 염색, 가공시의 마찰 등 외력에 의해 요철부분이 파손되기 쉽기 때문에 파손된 부분이 색반을 일으킬 수 있는 결점을 내포하게 된다.On the other hand, the fiber produced by the method of (C) does not have enough core effect, and irregularities are irregularly distributed on the fiber surface, so the irregularities are easily damaged by external forces such as friction during dyeing and processing. It may contain defects that can cause it.

또한 폴리에스테르 섬유의 비중을 높여 직물상에 우수한 드레이프성을 부여하는 방법으로는, (1) 섬유 심부분에 고비중 물질(예를 들면 아연과 같은 고비중 금속 또는 고비중 금속화합물)을 넣는 방법, (2) 고비중 수지 섬유(예를 들면 염화비닐리덴 섬유)와 복합화하는 방법, (3) 폴리에스테르 섬유중에 고비중의 미립자(예를 들면 산화티탄, 황산바륨)를 첨가하는 방법등이 제안되고 있는데 이러한 방법 중 상기 (1), (2)의 방법은 현실적으로 생산성 및 기본적인 폴리에스테르 섬유의 물리, 화학적 성질발현이 곤란하여 현실적 적용성이 떨어지고, 상기 (3)의 방법은 폴리에스테르 섬유자체의 비중은 향상시킬 수 있으나, 비중을 높이기 위해 폴리에스테르 섬유중에 고비중 미립자의 과량 혼입으로 인한 고분자 내에서의 분산성 불량으로 인해 후가공성, 특히 제사, 준비, 제직공정에서의 각종 가이드류의 마모 및 염색가공 공정중에서의 염색이상 등으로 인해 제품의 질을 떨어뜨리는 단점이 있다.In addition, as a method of increasing the specific gravity of the polyester fiber to give excellent draping property on the fabric, (1) a method of placing a high specific gravity material (for example, a high specific metal such as zinc or a high specific metal compound) in the core of the fiber. (2) A method of complexing with a high specific gravity resin fiber (e.g. vinylidene chloride fiber), (3) A method of adding a high specific gravity particle (e.g. titanium oxide, barium sulfate) to polyester fiber, etc. Among these methods, the methods of (1) and (2) are difficult to express the physical and chemical properties of the basic polyester fiber in terms of productivity and practical applicability, and the method of (3) is a method of polyester fiber itself. Specific gravity can be improved, but post-processability, especially due to poor dispersibility in the polymer due to excessive incorporation of high specific gravity particles in the polyester fiber to increase the specific gravity There is a disadvantage in that the quality of the product is deteriorated due to the wear of various guides in the weaving, preparation, weaving process and dyeing abnormality during the dyeing process.

본 발명은 이러한 종래 기술의 문제점을 해결한 것으로, 본 발명의 목적은 섬유중에 미립자를 첨가하므로써, 레이온 섬유와 같은 독특한 광택을 유지하면서 심색효과가 더욱 개선되고, 또한 사의 비중이 커져 직물에 훌륭한 드레이프성을 부여하며, 제사, 준비, 제직공정중에 있어 각종 가이드류의 마모성이 작고, 동시에 염색, 가공 등 후가공성이 우수한 폴리에스테르 섬유의 제조방법을 제공하는 데에 있다.The present invention solves these problems of the prior art, and an object of the present invention is to improve the deep color effect while maintaining a unique luster like rayon fiber by adding fine particles in the fiber, and also increase the specific gravity of the yarn, which is excellent drape for the fabric The present invention provides a method for producing a polyester fiber that provides the properties and has low abrasion property of various guides during the weaving, preparation, and weaving process, and at the same time, excellent post-processing properties such as dyeing and processing.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명은 테레프탈산을 주성분으로 하는 이염기산과 알킬렌글리콜로부터 폴리에스테르 섬유를 제조함에 있어서, 에스테르교환 반응전에 다음식 (I)로 표시되는 분산제가 황산바륨에 대하여 0.01~1.05중량%로 함유된 황산바륨 슬러리를 첨가하되 황산바륨의 첨가량이 이염기산에 대하여 3~10중량%가 되도록 하고, 중축합 반응식 다음 식 (II)로 표시되는 인화합물을 이염기산에 대하여 0.5~3.0mol% 첨가하고 금속화합물을 식 (II)로 표시되는 인화합물에 대하여 0.5~2.5mol배 첨가하는 것을 특징으로 하는 세라믹 함유 폴리에스테르 섬유의 제조방법이다.The present invention is a sulfuric acid containing 0.01 to 1.05% by weight of the dispersant represented by the following formula (I) to the barium sulfate before the transesterification reaction in the production of polyester fibers from dibasic acid and alkylene glycol mainly composed of terephthalic acid Add the barium slurry, but add the amount of barium sulfate to 3 to 10% by weight based on the dibasic acid, add 0.5 to 3.0 mol% of the phosphorus compound represented by the following formula (II) to the dibasic acid It is the manufacturing method of the ceramic containing polyester fiber characterized by adding 0.5-2.5 mol times with respect to the phosphorus compound represented by Formula (II).

상기 식(I)에서 R1은 탄소수 1~8의 알킬기이고, R2는 탄소수 5~15의 알킬기이며, m은 1~4의 정수이고, n은 1~3의 정수임.In said formula (I), R <1> is a C1-C8 alkyl group, R <2> is a C5-C15 alkyl group, m is an integer of 1-4, n is an integer of 1-3.

상기 식(II)에서 R3, R4는 각각 수소 또는 1가의 유기기, X는 -OH, -OR, -OM, 또는 1가의 유기기로서, 이때 M은 알칼리금속 또는 알칼리토금속이며, 알칼리금속일 경우에는 1가, 알칼리토금속일 경우에는 1/2가 이고, R은 탄소수 1~3의 알킬기임.In formula (II), R 3 , R 4 are each hydrogen or monovalent organic group, X is -OH, -OR, -OM, or monovalent organic group, wherein M is alkali metal or alkaline earth metal, and alkali metal In case of monovalent, in case of alkaline earth metal, 1/2 is and R is an alkyl group having 1 to 3 carbon atoms.

이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

일반, 폴리에스테르 섬유의 비중은 1.38~1.40g/㎠ 정도로서 레이온섬유의 비중(1.5)과 비교하면 많은 차이가 있는데 비중을 높여 주기 위해서는 비중 2.0 이상의 고비중 미립자를 폴리에스테르 섬유를 형성하는 수지중에 혼입할 필요가 있는데 이러한 미립자중에 가장 많이 사용되는 것이 산화티탄(비중 3.9)과 황산바륨(비중 4.4)등이 있으며, 이러한 것 중 산화티탄은 굴절율이 높아 폴리머중에 1% 이상 함유되게 되면 염색 후 파스텔조와 같은 희뿌연 색상을 나타내게 되며 선명한 심색성이 요구되는 용도에는 사용이 제한된다.In general, the specific gravity of polyester fiber is about 1.38 ~ 1.40g / ㎠ and there are many differences compared to the specific gravity of rayon fiber (1.5) .In order to increase the specific gravity, high specific gravity particles with specific gravity of 2.0 or more are mixed in resin forming polyester fiber. Among the fine particles, titanium oxide (specific gravity 3.9) and barium sulfate (specific gravity 4.4) are most commonly used. Among these, titanium oxide has a high refractive index and contains 1% or more of the polymer, so that after dyeing, The same rare color is used, and its use is limited to applications requiring vivid color depth.

또한 황산바륨의 경우는 그 자체 비중이 높고, 굴절율이 폴리에스테르수지와 유사하나 염색후 선명한 색상을 유지할 수 있어 레이온섬유와 같은 광택을 갖는데 유리하나, 폴리에스테르의 비중을 1.4 이상으로 유지하기 위해서는 폴리에스테르 수지속에 3% 이상의 황산바륨을 과량으로 혼입하여 사용해야 하므로 고분자내의 입자 분산 불균일로 인한 마모 및 후가공성을 크게 떨어뜨리게 된다.In the case of barium sulfate, its specific gravity is high and its refractive index is similar to that of polyester resin, but it is advantageous to have the same gloss as rayon fiber because it can maintain vivid color after dyeing, but in order to maintain the specific gravity of polyester above 1.4 Since excess barium sulfate must be used in an excessive amount of 3% in the ester resin, wear and post-processability due to particle dispersion unevenness in the polymer are greatly reduced.

본 발명에서는 이러한 문제점을 해결하기 위해 에틸렌글리콜에 분산하는 황산바륨 슬러리를 제조할 때 황산바륨의 1차 입자크기가 1.0㎛ 이하인 것을 사용하여 슬러리중에 상기 식 (I)과 같은 형태의 분산제를 선택하여 슬러리 중에서의 입자응집에 의한 거대입자를 줄여 분산 안정화 효과를 극대화함과 동시에 테레프탈산을 주성분으로 하고 그의 에스테르형성성 유도체와 1종 이상의 알킬렌글리콜을 반응시켜 폴리에스테르 고분자를 합성할때, 해당 제조반응이 완결되는 임의의 시점에서 식 (I)과 같은 분산제를 사용한 황산바륨 슬러리중 황산바륨이 테레프탈산 성분에 대하여 3~10중량%를 첨가하여 폴리에스테르 섬유의 비중을 1.4~1.5정도가 되도록 하였다.In order to solve this problem, in the present invention, when preparing a barium sulfate slurry dispersed in ethylene glycol, a dispersant of the same type as formula (I) is selected in the slurry by using a barium sulfate having a primary particle size of 1.0 μm or less. Maximize dispersion stabilization effect by reducing the large particles by particle agglomeration in the slurry and at the same time, when the polyester polymer is synthesized by terephthalic acid as its main component and the ester-forming derivative and one or more alkylene glycols At this point in time, the barium sulfate was added in an amount of 3 to 10% by weight based on the terephthalic acid component in the barium sulfate slurry using a dispersant such as formula (I) so that the specific gravity of the polyester fiber was about 1.4 to 1.5.

또한 폴리에스테르 섬유의 심색성을 향상시키기 위해 해당 이염기산에 대하여 0.5~3.0mol%의 상기 식(II)로 표시되는 티오포스포릴(thiophosphoryl)기를 함유하고 있는 5가의 인화합물과 금속화합물을 투입하되 금속화합물의 투입량은 상기 인화합물에 대하여 전체 사용된 당량수와의 합계량이 식 (II)에 나타난 인화합물의 몰수에 대하여 0.5~2.5배가 되도록 하여 이들 해당 인화합물과 금속화합물을 미리 반응시키지 않고 첨가한 후 계속하여 폴리에스테르 섬유의 합성을 완결시켜 얻어진 칩을 통상의 건조 조건으로 수분율을 0.003% 이하로 관리하고 일반적인 제사조건으로 섬유를 형성시킨 후 알칼리 화합물의 수용액으로 처리하여 폴리에스테르 섬유를 제조하였다.In addition, in order to improve the deep color of the polyester fiber, pentavalent phosphorus and metal compounds containing 0.5 to 3.0 mol% of thiophosphoryl group represented by the formula (II) to the dibasic acid are added. The input amount of the metal compound is 0.5 to 2.5 times the total number of equivalents used for the phosphorus compound to the number of moles of the phosphorus compound shown in Equation (II), so that these phosphorus compounds and the metal compound are added without reacting in advance. After the synthesis of the polyester fiber was continued to manage the chip obtained by controlling the moisture content to 0.003% or less under normal drying conditions, and the fiber was formed under the general spinning conditions, and then treated with an aqueous solution of an alkali compound to prepare a polyester fiber. .

본 발명에 있어서 폴리에스테르 섬유로서는 테레프탈산 및 에틸렌글리콜로부터 합성된 폴리에틸렌테레프탈레이트가 적당하며, 구성성분의 30mol%를 넘지 않는 범위내에서 다른 디카르복실산 성분, 글리콜성분 및 옥시카르본산 성분이 공중합되어도 좋다.In the present invention, polyethylene terephthalate synthesized from terephthalic acid and ethylene glycol is suitable as the polyester fiber, and other dicarboxylic acid component, glycol component and oxycarboxylic acid component may be copolymerized within the range not exceeding 30 mol% of the component. good.

이러한 산 분위기에서 섬유의 비중 및 드레이프성을 향상시킬 목적으로 사용되는 황산바륨의 양은 사용된 테레프탈산에 대하여 3~10%가 적당하다. 만약 3% 미만일 경우에는 섬유의 비중이 1.4 이하로서 드레이프성의 향상을 크게 하는 효과가 반감되고, 10%를 초과할 경우에는 사 제조 공정성 악화로 소기의 목적을 달성하기 곤란하다.The amount of barium sulfate used for the purpose of improving the specific gravity and drape of the fiber in this acid atmosphere is 3 to 10% relative to the terephthalic acid used. If it is less than 3%, the specific gravity of the fiber is 1.4 or less, and the effect of increasing the drape property is halved. If it exceeds 10%, it is difficult to achieve the intended purpose due to deterioration of yarn manufacturing processability.

또한 황산바륨 슬러리 제조공정은 우선 황산바륨을 에틸렌글리콜 중에 20~30중량%로 분산시켜 저속교반기가 달린 반응기에서 예비혼합한 후 침지조를 거쳐 습식 밑에서 고속 교반에 의해 황산바륨을 최종적으로 분산시킨 후 농도보정을 통하여 중합 제조공정중에 투입하는데 본 발명에서는 예비혼합 공정에서 식 (I)의 분산제를 사용하여 황산바륨에 대하여 0.01~1.00중량%를 첨가하는 것이 가장 우수한 분산 안정성을 보였고, 0.01중량% 미만에서는 분산 안정성 효과가 떨어지며, 1.0중량% 초과 사용시는 분산 안정성의 효과가 더 이상 증대되지 않았다.In addition, the barium sulfate slurry manufacturing process first disperses barium sulfate at 20-30% by weight in ethylene glycol, premixes in a reactor equipped with a low speed stirrer, and finally disperses barium sulfate by high-speed stirring under wet through a immersion tank. In the present invention, the concentration of the mixture is added to the polymerization manufacturing process. In the present invention, the dispersing agent of formula (I) was used to add 0.01 to 1.00% by weight of barium sulfate in the pre-mixing process, and the dispersion stability was less than 0.01% by weight. In the dispersion stability effect is lowered, and when used more than 1.0% by weight the effect of dispersion stability is no longer increased.

이러한 분산제가 첨가된 황산바륨 슬러리를 중합공정 중에 첨가하여 통상적인 방법으로 중합 및 제사를 행하여 후가공성을 평가하였는데, 후가공성의 평가는 사제조공정중 팩압 상승율과 동선에 대한 내마모도 평가방법을 사용하였다.The barium sulfate slurry to which such a dispersant was added was added during the polymerization process, and polymerization and sacrifice were carried out in a conventional manner to evaluate post-processability. The post-processability was evaluated using a pack pressure increase rate and abrasion resistance evaluation method during the prefabrication process.

그리고 본 발명에서 사용하는 특정한 인화합물(식 (II))의 첨가량이 테레프탈산 성분에 대해 0.5mol% 미만일 경우에는 얻어지는 폴레이스테르섬유의 심색효가와 선명성이 불충분하고 반대로 3mol%를 초과할 경우에는 거대 응집입자의 석출로 인한 심색효과 부족 및 내마찰 내구성이 저하된다.When the addition amount of the specific phosphorus compound (formula (II)) used in the present invention is less than 0.5 mol% with respect to the terephthalic acid component, the deep color efficiency and sharpness of the obtained polyester fiber are insufficient, and on the contrary, when the content exceeds 3 mol%, Insufficient deep color effect and frictional durability due to precipitation of aggregated particles are reduced.

또한 금속화합물의 첨가량은 해당 금속화합물과 상기 인화합물의 금속 당량수 합계량이 인화합물의 몰수에 대하여 0.5배 보다 적은 양이면 석출입자가 폴리에스테르에 대하여 가용화 될 뿐만 아니라 석출 입자량도 적어지게 되어 얻어지는 폴리에스테르 섬유의 심색효과가 불충분할 뿐만 아니라 생성 폴리에스테르의 연화점이 저하될 우려가 있으며, 2.5배 보다 많은 경우에는 심색효과 부족 및 내마찰 내구성이 저하된다.The addition amount of the metal compound is obtained when the total amount of metal equivalents of the metal compound and the phosphorus compound is less than 0.5 times the number of moles of the phosphorus compound, so that not only the precipitated particles are solubilized to the polyester but also the amount of precipitated particles is reduced. Not only the deep color effect of the polyester fiber is insufficient, but also the softening point of the resultant polyester may be lowered, and when it is more than 2.5 times, the deep color effect is insufficient and the frictional durability is lowered.

이와같은 본 발명에 의해 제조된 세라믹 함유 폴리에스테르 섬유는 비스코스레이온 섬유같이 비중이 높아, 직물상에서 드레프성이 우수하며 독특한 광택을 유지하면서 색상이 선명한 장점이 있다.Such a ceramic-containing polyester fiber produced by the present invention has a high specific gravity, such as viscose rayon fiber, excellent in drape on the fabric and has the advantage of vivid color while maintaining a unique luster.

이하, 본 발명을 실시예를 통하여 더욱 상세히 설명하겠는 바, 본 발명이 실시에에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the Examples.

실시예에서 부는 중량부를 의미한다.In the examples, part means parts by weight.

각종 물성 측정방법은 다음과 같다.Various measurement methods are as follows.

◇입도 : 쿨터 LS 130 입도분석기를 사용하여 평균입경을 측정◇ Size: Measure average particle size using Coulter LS 130 particle size analyzer

◇5㎛ 이상 입자수◇ Number of particles more than 5㎛

*5㎛ 이상 입자수/mg=측정입자수/시료(mg)* 5 µm or more particles / mg = number of particles measured / sample (mg)

*측정방법 : 평량병에 에틸렌글리콜 20ml를 취해 세라믹 슬러리를 스테인레스봉(3mm) 3눈금까지 침적후 평량병에 떨어뜨려 혼합한 후 스테인레스봉으로 1눈금(16mm) 침적 후 토마 상부 중앙에 떨어뜨리고 커버글래스로 시료부분을 덮고 손으로 눌러 과성 에틸렌글리콜을 제거한 후 현미경에서 배율 200배로 측정.* Measurement method: Take 20ml of ethylene glycol in the basis weight bottle, immerse the ceramic slurry up to 3 scales of stainless rod, drop it into the basis weight bottle, mix it, and immerse 1 scale (16mm) with the stainless rod, and drop it in the center of the top of the toma. Cover the sample with glass and press it by hand to remove excess ethylene glycol, and measure at 200 times magnification under microscope.

◇동선 마모도 : 마찰계수측정기의 마찰봉에 붙인 직경 0.7mm의 동선을 150m/분의 주행속도로 주행하는 사와 30분간 접촉시켜 주해 전,후의 마모도(%)로 평가.◇ Wear wear: Copper wire with a diameter of 0.7mm attached to the friction bar of friction coefficient measuring device is contacted with a company running at 150m / min for 30 minutes and evaluated as the wear rate before and after casting.

마모도가 낮을 수록 입자분산성이 좋고, 사표면에 거대응집 입자 석출이 적음을 나타냄.The lower the degree of abrasion, the better the particle dispersibility and the less precipitation of coagulated particles on the dead surface.

◇심색효과 : 칼라측색기(Hunter lab scale)를 사용하여 칼라-L, a, b를 측정.◇ Deep color effect: Color-L, a, b is measured using a color lab (Hunter lab scale).

◇직물의 드레이프성 : JIS 규격의 강연도 측정법중 드레이프법을 사용해 드레이프(Drape)계수로 판정.◇ Drapery of fabric: It is determined by the Drape coefficient using the drape method among the stiffness measurement methods of JIS standard.

[실시예 1]Example 1

에틸렌글리콜에 황산바륨 분말을 30중량%로 하여 교반기가 달려 있는 반응기에서 300rpm으로 교반하면서 분산제 KR46B(미국, 켄리치사)를 황산바륨에 대하여 0.1중량% 첨가하여 30분간 교반한 후 침지조를 거쳐 습식분쇄기에서 3,000rpm으로 고속 교반시킨 후 에틸렌글리콜로 황산바륨 농도를 보정하여 미리 슬러리를 제조한 후 입도분석 및 5㎛ 이상 입자수를 측정하였다.30% by weight of barium sulfate powder to ethylene glycol was added at a speed of 300 rpm in a reactor equipped with a stirrer, followed by stirring for 30 minutes by adding 0.1 wt% of a dispersant KR46B (Kenrich, USA) to barium sulfate. After stirring at high speed at 3,000rpm in the mill, barium sulfate concentration was corrected with ethylene glycol to prepare a slurry in advance, and particle size analysis and particle number of 5 μm or more were measured.

고순도 테레프탈산(이하 TPA라 함), 1,000부에 대하여 슬러리중 황산바륨이 5중량%가 되도록 계량하여 에스테르 교환반응전에 미리 첨가하여 교반을 30분간 행하고, TPA 10,000부, 에틸렌글리콜 430부를 130분간에 걸쳐 첨가하고, 반응압력 1.2kg/㎠으로 에스테르교환반응을 30분간 행하면서 생성된 물을 유출시키고 상압하에서 15분간 에틸렌글리콜을 유출시켜 내었다.High purity terephthalic acid (hereinafter referred to as TPA) was weighed so that the barium sulfate in the slurry was 5% by weight, and added before the transesterification reaction, and stirred for 30 minutes, and 10,000 parts of TPA and 430 parts of ethylene glycol were added for 130 minutes. Water was added while the transesterification reaction was carried out at a reaction pressure of 1.2 kg / cm &lt; 2 &gt; for 30 minutes, and ethylene glycol was distilled out for 15 minutes at atmospheric pressure.

이후 코발트 아세테이트 0.04부를 첨가하고 반응내온을 250℃로 유지하면서 에스테르교환반응을 완결시켜 비스하이드록시에틸렌테레프탈레이트(BHET)를 얻었다. 얻어진 생성물에 리튬아세테이트 2부, 트리에틸포스포로티오에이트 35.8부를 첨가하고 중축합 촉매로서 산화안티몬(Sb2O3) 0.25부를 첨가하여 통상의 방법으로 중축합반응을 진행하였다.Thereafter, 0.04 parts of cobalt acetate was added, and the transesterification reaction was completed while maintaining the reaction temperature at 250 ° C to obtain bishydroxyethylene terephthalate (BHET). To the obtained product, 2 parts of lithium acetate and 35.8 parts of triethylphosphorothioate were added, and 0.25 parts of antimony oxide (Sb 2 O 3 ) was added as a polycondensation catalyst, and the polycondensation reaction was carried out in a conventional manner.

이렇게 하여 얻어진 칩의 극한점도는 0.634dlnm/g이었다.The ultimate viscosity of the chip thus obtained was 0.634 dlnm / g.

이 칩을 진공건조기에서 수분율이 0.003% 이하로 건조를 행해 50D/36F, 75D/36F로 원사를 제조하는 공정중 방사공정에서는 팩압 상승정도를, 연신공정에서는 랩율(%)을 확인하고 마모성을 평가하기 위해 동선마모도를 측정하였으며, 그 결과는 표 2에 나타내었다.The chip is dried in a vacuum dryer with a moisture content of 0.003% or less, and the yarn pressure is increased during the spinning process of 50D / 36F and 75D / 36F. In order to measure the copper wear, the results are shown in Table 2.

또한 이렇게 하여 제사된 원사를 경사로서 50D/36F(S연 150T/M)를, 위사로서는 75D/36F(Z연 120T/M)를 사용하여 사틴(Satin)조직으로 제직하여 생지로 한 후 통상의 방법으로 정련, 열고정(pre-setting)을 실시한 후 감량율이 20%가 되도록 5% 수산화나트륨 수용액으로 처리해 통상의 방법으로 블랙 고압염색을 실시하고 칼라측색기로 칼라-L, a, b를 측정하였으며, 직물의 드레이프성을 측정하여 그 결과를 표 2에 나타내었다.In addition, weaving the yarn thus obtained is made of 50D / 36F (S-lead 150T / M) as the warp yarn and 75D / 36F (Z-lead 120T / M) as the weft yarn to satin tissue to make the dough. After scouring and pre-setting by the method, the solution is treated with 5% aqueous sodium hydroxide solution so that the weight loss rate is 20%, and black high-pressure dyeing is carried out by the usual method, and color-L, a, and b are measured with a colorimeter. The drape of the fabric was measured and the results are shown in Table 2.

[실시예 2~3][Examples 2-3]

[비교예 1~4][Comparative Examples 1-4]

조건을 표 1과 같이 변경하여 실시한 것을 제외하고는 상기 실시예 1과 동일하게 실시하였고, 그 결과를 표 2에 나타내었다.The same process as in Example 1 was carried out except that the conditions were changed as in Table 1, and the results are shown in Table 2.

* TPT : 트리에틸포스포로티오에이트(Triethyl Phosphoro Thioate)* TPT: Triethyl Phosphoro Thioate

** LA : 리튬 아세테이트(Litium Acetate)** LA: Lithium Acetate

상기 표 2에서와 같이 본 발명의 실시예는 비교예에 비해 슬러지 중 거대입자(5㎛ 이상)수가 현저히 적게 나타나고 후가공에서의 동선마모도(%)가 월등히 낮아 내마찰 내구성이 높아짐을 알 수 있었다.As shown in Table 2, in the embodiment of the present invention, the number of the large particles (5 μm or more) in the sludge was significantly lower than that of the comparative example, and the copper wear resistance (%) in the post-processing was significantly lower, indicating that the frictional resistance was increased.

Claims (1)

테레프탈산을 주성분으로 하는 이염기산과 알킬렌글리콜로부터 폴리에스테르 섬유를 제조함에 있어서, 에스테르 교환반응 전에 다음 식 (I)로 표시되는 분산제가 황산바륨에 대하여 0.01~1.05중량% 함유된 황산바륨 슬러리를 첨가하되, 황산바륨의 첨가량이 이염기산에 대하여 3~10중량%가 되도록 하고, 중축합 반응시 다음 식 (II)로 표시되는 인화합물을 이염기산에 대하여 0.5~3.0몰% 첨가하고, 금속화합물은 상기 인화합물에 대하여 전체 사용된 당량수와의 합계량이 식 (II)에 나타난 인화합의 몰수에 대하여 0.5~2.5배 첨가하는 것을 특징으로 하는 세라믹 함유 폴리에스테르 섬유의 제조방법 :In preparing polyester fiber from dibasic acid and alkylene glycol mainly composed of terephthalic acid, a barium sulfate slurry containing 0.01 to 1.05% by weight of a dispersant represented by the following formula (I) relative to barium sulfate is added before the transesterification reaction. However, the addition amount of barium sulfate is 3 to 10% by weight relative to the dibasic acid, and 0.5 to 3.0 mol% of the phosphorus compound represented by the following formula (II) is added to the dibasic acid during the polycondensation reaction, and the metal compound A method for producing a ceramic-containing polyester fiber, characterized in that the total amount of the phosphorus compound and the total equivalent number of the phosphorus compound is added 0.5 to 2.5 times the number of moles of the phosphorus compound represented by the formula (II): 상기 식 (I)에서 R1은 탄소수 1~8의 알킬기이고, R2는 탄소수 5~15의 알킬기이며, m은 1~4의 정수이고, n은 1~3의 정수임.In said formula (I), R <1> is a C1-C8 alkyl group, R <2> is a C5-C15 alkyl group, m is an integer of 1-4, n is an integer of 1-3. 상기 식 (II)에서 R3, R4는 각각 수소 또는 1가의 유기기, X는 -OH, -OR, -OM, 또는 1가의 유기기로서, 이때 M은 알칼리금속 또는 알칼리토금속이며, 알칼리금속일 경우에는 1가, 알칼리토금속일 경우에는 1/2가 이고, R은 탄소수 1~3의 알킬기임.In formula (II), R 3 , R 4 are each hydrogen or a monovalent organic group, X is -OH, -OR, -OM, or a monovalent organic group, wherein M is an alkali metal or an alkaline earth metal, and an alkali metal In case of monovalent, in case of alkaline earth metal, 1/2 is and R is an alkyl group having 1 to 3 carbon atoms.
KR1019930032154A 1993-12-31 1993-12-31 Preparation process of polyester fiber comprising ceramic KR960005963B1 (en)

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