KR830001091B1 - High concentration colored polyester granules manufacturing method - Google Patents
High concentration colored polyester granules manufacturing method Download PDFInfo
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- KR830001091B1 KR830001091B1 KR1019810005110A KR810005110A KR830001091B1 KR 830001091 B1 KR830001091 B1 KR 830001091B1 KR 1019810005110 A KR1019810005110 A KR 1019810005110A KR 810005110 A KR810005110 A KR 810005110A KR 830001091 B1 KR830001091 B1 KR 830001091B1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
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Description
본 발명은 고농도 착색 폴리에스터 입상물의 제조방법에 관한 것으로, 방향족 선상폴리에스터의 폴리머에 불용성의 안료, 특히 카본불랙을 첨가혼합하여 고농도 상태에서 착색시키는 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing highly colored pigmented polyester granules, and to a method of coloring an insoluble pigment, in particular carbon black, by adding and mixing an insoluble pigment to a polymer of an aromatic linear polyester.
선상폴리에스터는 분자구조가 치밀하고 소수성이므로 폴리에스터성유의 활성화에너지가 타섬유에 비하여 크므로, 고온에서 염색하여야만 일정한 염착량을 얻을수 있는 것이다.Since the linear polyester has a dense molecular structure and hydrophobicity, the activation energy of the polyester oil is larger than that of other fibers, so that a constant dyeing amount can be obtained only by dyeing at a high temperature.
따라서 폴리에스터의 연속 중합공정에서 안료를 첨가 혼합하여 착색 상태로 방사되는 섬유를 얻는 방법이 오래전부터 착색비 절감의 한 방법으로 연구되어 왔으나, 폴리에스터는 용융방사 온도가 높으므로 사용 착색제의 제한이 따르고 색상의 다양화를 기할수 없는 결점이 있었다.Therefore, the method of obtaining fibers which are spun in a colored state by adding and mixing pigments in a continuous polymerization process of polyester has been studied as a way of reducing the color ratio for a long time, but polyester has a high melt spinning temperature, so the limitation of the colorant used There was a flaw that could not be followed and diversified colors.
착색 폴리에스터 입상물 제조 방법으로서는 영국 특허 제610,137, 일본특허 특공소 43-13475호, 일본특허 특공소 47-10861호 등과 같이 폴리에스터의 중합공정에서 안료를 에칠렌글리클에 분산시켜 첨가하는 방법이 있으나, 안료는 슬라리(Slurry)의 분산성 문제로 분산의 균일성을 기하기 어려워, 방사시 큰 입자를 제거하기 위하여 폴리머 여과를 실시하여야되며, 안료의 분산성 저하로 여과제의 교환빈도가 높고 폴리머의 수율을 저하시켜 생산원가의 상승을 초래케되며, 큰 입자가 섬유중에 포함되어 있으면 사절 현상이 발생하고, 제품 착색도에 얼룩현상이 생겨 상품 가치를 저하시키는 결점이 있었다.As a method for producing colored polyester granules, a method of dispersing a pigment in ethylene glycol in a polymerization process of polyester such as British Patent No. 610,137, Japanese Patent Application No. 43-13475, Japanese Patent Application No. 47-10861, etc. However, the pigment is difficult to achieve uniformity of dispersion due to the dispersibility of the slurry (Slurry), the polymer filtration must be carried out to remove the large particles during spinning, the exchange frequency of the filter agent due to the decrease in the dispersibility of the pigment It is high and lowers the yield of the polymer, which leads to an increase in the production cost. If large particles are included in the fiber, trimming occurs, and staining occurs in the coloration of the product.
또한 종래에 안료로써 카본불렉을 중합관에 투입하여 흑색 폴리에스터를 제조하는 방법은 반응물의 오염 그리고 반응 제어면에서 어려움이 따랐다.In addition, conventionally, a method of preparing black polyester by adding carbon bullet to a polymerization tube as a pigment has been difficult in terms of contamination of reactants and reaction control.
또한 T.P.A를 원료로하는 폴리에스터 제조 공법에서는 카본 블랙을 에틸렌글리클에 충분히 분산시킨 상태로 반응관에 주입하여도 카본블랙이 재응집하여 방사, 연신등의 제공정에서 작업성이 크게 떨어지게되는 결점이 있었다.In addition, in the polyester manufacturing method using TPA as a raw material, even if carbon black is sufficiently dispersed in ethylene glycol and injected into the reaction tube, carbon black reaggregates and workability is greatly reduced in providing wells such as spinning and drawing. There was this.
본 발명은 상기 종래 제조 방법을 개선하기 위하여 폴리에스터 용융상에서의 카본블랙의 분산정도를 실험한 결과 폴리에스터 용융시 폴리에스터의 물성에 큰 영향을 주지 않는 일정수준의 분해가 일어나면 말단관능기가 증가하여 카본블랙의 재옹집을 억제하고, 카본블랙의 종류, 특히 입경 및 표면 산화물의 양에 따라 분산상태가 크게 달라짐을 알 수 있었다.The present invention is to test the dispersion of carbon black in the polyester melt phase to improve the conventional manufacturing method, the terminal functional group is increased when a certain level of decomposition does not significantly affect the physical properties of the polyester when melting the polyester It was found that the re-agglomeration of the carbon black was suppressed, and the dispersion state greatly changed depending on the kind of the carbon black, especially the particle diameter and the amount of the surface oxide.
따라서 사용하는 폴리에스터칩의 크기 및 형상을 변경시켜, 카본블랙과의 혼화성을 높히고 혼련기내에서 초기전단력을 크게하여 일정수준의 카본블랙의 분산도를 얻는 기간을 최대한 짧게하여 처리중 폴리에스터의 열화를 방지하고, 폴리에스터에 쉽게 습윤, 분산되는 카본블랙을 선택하면 고농도 착색 폴리에스터의 입상물을 손쉽게 제조할 수 있다.Therefore, by changing the size and shape of the polyester chip used to increase the miscibility with carbon black, increase the initial shear strength in the kneader to obtain a certain degree of dispersion of the carbon black in the kneader as short as possible, Preventing deterioration and selecting carbon black, which is easily wetted and dispersed in polyester, makes it possible to easily prepare granules of highly concentrated colored polyester.
즉, 본 발명에서의 폴리에스터는 폴리에틸렌테레프탈레이트(PET)가 주대상이지만 그 산성분 및 또는 글리콜의 일부 또는 전부가 이소프탈산, 디페닐디카본산, 디페닐 설폰카본산과 같은 방향족산, 아디핀산, 수산등과 같은 지방족산, 테트라 메틸렌글리클, 헥사 메틸렌 글리클과 같은 지방족글리클로 되어 있어도 관계없으며, 용도로는 섬유, 병, 필름 등의 제조에도 사용할 수 있다.That is, the polyester in the present invention is mainly polyethylene terephthalate (PET), but some or all of its acid components and or glycols are aromatic acids such as isophthalic acid, diphenyldicarboxylic acid, diphenyl sulfonic carboxylic acid, adipic acid Aliphatic acids, such as, for example, oxalic acid, tetramethylene glycol, and aliphatic glycols, such as hexamethylene glycol, may be used, and it can be used also for manufacture of a fiber, a bottle, a film, etc. as a use.
본 발명에서의 폴리에스터칩 형상변경후의 크기는 입경이 적어도 700μ이하가 되어야하며 카본블랙의 농도 15-20% 중량을 폴리에스터와 충분히 섞기 위해서는 1-2mm정도의 크기가 적당하다.The size after changing the shape of the polyester chip in the present invention should be at least 700μ particle diameter and 1-2mm size is appropriate to sufficiently mix 15-20% weight of carbon black with polyester.
실제 폴리에스터의 크기는 작을수록 좋으나, 폴리에스터는 타합성수지와 마찬가지로 점착성을 가져 칩 형상변경이 어려우므로 공업적 생산을 위한 크기는 15-25% 중량 카본블랙의 농도에는 1.5-2mm의 크기가 가장 바람직하다.Actually, the smaller the size of polyester is, the better, but polyester has the same adhesiveness as other synthetic resins, making it difficult to change the chip shape. Therefore, the size for industrial production is 1.5-25mm at the concentration of 15-25% by weight carbon black. desirable.
폴리에스터 칩의 형상을 변경시키는 목적은 분말성의 안료(카본블랙)과 충분히 섞고, 또 카본블랙과 폴리에스터의 접촉면을 크게하여 용융 훈련시 초기 전단력을 크게하여, 카본블랙의 분산 시간을 짧게하기 위하여서다.The purpose of changing the shape of the polyester chip is to sufficiently mix with the powdery pigment (carbon black), to increase the contact surface between the carbon black and the polyester to increase the initial shear force during the melt training, and to shorten the dispersion time of the carbon black. stand.
본 발명은 고농도로 착색된 폴리에스터 입상물을 제조하는 방법에 관한 것으로 이 입상물을 미착색 폴리에스터의 일정비율로 섞어, 통상의 엑스트루머(Extruder)에서 용융, 방사하여 일정농도의 폴리에스터 착색물을 얻는 수단을 제공하는 것으로 특히 착색제로 분산이 어려운 카본블랙을 사용 흑색폴리에스터를 제조하는데 있어 색감이 뛰어나고 방사, 연신 등의 제공정에서 통상의 폴리에스터 섬유 제조시와 같은 수준의 작업성을 갖게끔, 고농도의 흑색폴리에스터 입상물을 제조하는 것이다.The present invention relates to a method for producing a highly colored polyester granular material, which is mixed with a certain ratio of uncolored polyester, melted and spun in a conventional extruder to produce a polyester of a certain concentration. It provides a means to obtain colored materials, especially carbon black, which is difficult to disperse as a colorant. It has excellent color in producing black polyester and provides the same level of workability as that of ordinary polyester fibers in providing tablets such as spinning and drawing. In order to have a high concentration of black polyester granules.
선상폴리에스터는 연화점이 높고 특히 연화영역이 좁으며 유동성이 나쁘고, 가공중 열분해, 가수분해가 일어나기 쉽다.The linear polyester has a high softening point, in particular a narrow softening area, poor fluidity, and is susceptible to pyrolysis and hydrolysis during processing.
따라서 종래에는 폴리에스터착색용 고농도 착색 입상물(이를 마스타 배치라 일컬음)을 만들때는 비교적 가공이 용이하고 폴리에스터와 상용성이 좋은 변성폴리에스터, 왁스 등에 착색제를 고농도로 섞어 용융상에서 착색제를 분산, 입상화하여 왔으나 이 고농도착색입상물을 사용, 착색폴리에스터섬유를 제조시에는 방사, 연신등에서의 작업성이 나쁘고 섬유의 품질 저하가 일어난다. 또 폴리에스터 및 착색제를 녹이지 않는 유기용제에 안료를 고속의 혼합기에서 분산시킨 다음 이 분산액을 폴리에스터의 분말 또는 용융액에 넣어, 교반하여 안료를 폴리에스터 혼합 또는 부착시키고, 유기용제를 제거하여 폴리에스터의 분산상의 안료와의 혼합상을 얻는 방법이 있으나 이러한 방법은 폴리에스터에 친화성이 큰 유기용제의 선택 및 회수의 문제가 있으며 필요에 따라 안료의 폴리에스터에로의 이행을 돕기 위하여 조제를 사용하여야하므로 용융시폴리에스터 물성변화의 우려가 있으며, 고농도(15-25% 중량)의 폴리에스터 안료 혼합상을 얻기 힘들다.Therefore, conventionally, when making high-density colored granules for polyester coloring (referred to as master batches), the coloring agent is dispersed in a molten phase by mixing a high concentration of a coloring agent in a modified polyester or wax which is relatively easy to process and compatible with polyester. Although it has been granulated, when using this highly concentrated colored granular material to produce colored polyester fibers, workability in spinning and stretching is poor and the quality of the fiber is degraded. In addition, the pigment is dispersed in a high speed mixer in an organic solvent which does not dissolve the polyester and the colorant, and then the dispersion is added to a powder or a melt of the polyester and stirred to mix or attach the pigment to the polyester and remove the organic solvent to remove the poly There is a method of obtaining a mixed phase with the pigment of the dispersed phase of the ester, but this method has a problem of selecting and recovering an organic solvent having a high affinity for polyester, and preparing a preparation to assist the transition of the pigment to the polyester if necessary. As it should be used, there is a possibility of changing polyester properties during melting, and it is difficult to obtain a polyester pigment mixed phase of high concentration (15-25% by weight).
특히 카본블랙은 입자가 대단히 작으며 표면활성이 커서 혼합정도에 따라 재응집의 우려가 있다. 본 발명에서는 카본블랙은 폴리에스터의 습윤력이 좋고, 최종성형물 특히 섬유(스페이플, 필라멘트)의 색농도에 적합한 카본블랙량이 가능한한 적어 폴리에스터의 물성에 영향을 적게 주는 것이 바람직하다.In particular, carbon black has a very small particle and a large surface activity, which may cause reagglomeration depending on the degree of mixing. In the present invention, it is preferable that carbon black has good wetting power of polyester, and the amount of carbon black suitable for the color concentration of the final molded product, especially fibers (spaffles and filaments), is as small as possible, so that the physical properties of the polyester are less affected.
이는 카본블랙의 입경 및 표면 산화물의 양에 의하여 결정되며, 본 발명에서 즉, 카본블랙의 농도 15-25% 중량 이상의 고농도 착색폴리에스터 입상물의 제조시에는 분산처리중 폴리에스터는 약간의 열화가 일어나서 일단 관능기량이 증가하여 분산을 용이하게 하므로 입경이 15mμ-30mμ, 표면 산화물량이 20-70% 사이인 카본블랙이 적당하다.This is determined by the particle diameter of the carbon black and the amount of the surface oxide. In the present invention, in the production of highly colored pigmented polyester granules having a concentration of 15-25% by weight of carbon black, the polyester is slightly deteriorated during the dispersion treatment. Since the functional group amount is increased once to facilitate dispersion, carbon black having a particle size of 15 mμ-30 mμ and a surface oxide amount of 20-70% is suitable.
또 카본블랙은 분말형도 사용할 수 있으나 버드형이 더 바람직하다.In addition, carbon black may be used in powder form, but bird type is more preferable.
이하에 본 발명의 실시예를 들면서 구체적으로 설명한다.It demonstrates concretely, taking an Example of this invention below.
[실시예 1]Example 1
TPA와 에틸렌글리콜을 주원료로 하여 통상의 방법으로 축중합하여, 생성된 PET(Ⅳ : 0.66, SP=259℃-COOH량 48eq/106eq)를 평균 입도 1mm가 되게끔 형상 변경 후 (수율 약 97%), 동 PET 800그램과 카본블랙(입경 15mμ, 표면 산화물 2.4%) 200그램을 혼합기에서 섞었다.Condensation polymerization of TPA and ethylene glycol as the main raw materials in a conventional manner, the shape of the resulting PET (IV: 0.66, SP = 259 ℃-COOH amount 48eq / 10 6 eq) to an average particle size of 1mm (yield about 97 %), 800 grams of PET and 200 grams of carbon black (particle size 15 μm, surface oxide 2.4%) were mixed in a mixer.
이때 가능한 한 저속으로 운전하여 분말의 카본블랙이 재응집이 적게 일어나도록 하였다.At this time, it was operated as low speed as possible so that carbon black of powder had little reagglomeration.
이 혼합물을 용융 훈련기에서 온도 270℃ 부근에서 30초간 처리하여 성형하고 카본블랙 농도 20%의 흑색폴리에스터 입상물 약 950그램을 얻었다. 이 입성물의 Ⅳ는 0.61이며, 카본블랙의 분산상태는 카본 블랙농도 1%로 희석시, 크기 10μ이상의 카본블랙의 응집체는 전혀 나타나지 않는 만족할만한 상태이었다.The mixture was processed by melting for 30 seconds at a temperature of about 270 ° C. in a melt trainer to obtain about 950 grams of black polyester granules having a carbon black concentration of 20%. IV of this granular material was 0.61, and the dispersion state of carbon black was a satisfactory state in which aggregates of carbon black having a size of 10 mu or more were not found at all when diluted to 1% of carbon black concentration.
입상물과 미착색 폴리에스터를 1:7의 비율로 섞어 통상의 엑스트루더(Extruder)에서 온도 285℃ 부근에서 용융, 방사하여 카본블랙 농도 2.5%의 검정 화이바를 얻었다.The granular material and the uncolored polyester were mixed at a ratio of 1: 7, and melted and spun at a temperature of around 285 ° C. in a conventional extruder to obtain a black fiber having a carbon black concentration of 2.5%.
[실시예 2]Example 2
DMT와 에틸렌글리콜을 주원료로 하여 통상의 방법으로 축중합하여, 칩 상태의 PET(Ⅳ : 0.65, SP=259℃-COOH량=36eq/106eq)를 얻는다.Condensation polymerization is carried out in a conventional manner using DMT and ethylene glycol as the main raw materials to obtain PET in the form of chips (IV: 0.65, SP = 259 ° C-COOH amount = 36 eq / 10 6 eq).
이 PET를 입도 1.5mm로 형상변경후(수율 약 95%)등 PET 400그램, 카본블랙(입경 23mμ, 표면 산화물량 2.8%) 50그램프탈로시아닌계의 녹색유기안료 50그램을 혼합기에서 가볍게 섞고, 이 분말상의 혼합물을 용융 훈견기에서 온도 265℃ 부근에서 약 1분간 처리하여 성형, 안료 농도 20%의 흑색폴리에스터입상물 약 480그램을 얻었다.After changing the shape of this PET to 1.5mm in particle size (yield about 95%), lightly mix 400 grams of PET, carbon black (particle size 23mμ, surface oxide amount 2.8%) and 50 grams of phthalocyanine-based green organic pigment in a mixer. The powdery mixture was treated for about 1 minute at a temperature of about 265 DEG C in a molten tube to obtain about 480 grams of black polyester granular material having a 20% pigment concentration.
이 입상물의 고유점도는 0.60점도이었다.The intrinsic viscosity of this granular material was 0.60 viscosity.
이 입상물을 미착색폴리에스터와 2 : 17의 비율로 섞어 통상의 엑스트루더(Extruder)에서 온도 285℃ 부근에서 용융방사하여, 붉은 색감이 적은 흑색 화이바를 얻었다.This granular material was mixed with the uncolored polyester in the ratio of 2:17, and melt-spun at the temperature of around 285 degreeC with the usual extruder, and the black fiber with little red color was obtained.
상기 실시예 1,2에서 연신의 작업성을 통상의 미착색폴리에스터와 거의 동일 수준이며 섬유의 강도도 거의 같음을 알수 있었다.In Examples 1 and 2, it was found that the workability of stretching was almost the same level as that of ordinary uncolored polyester, and the strength of the fibers was also almost the same.
Claims (3)
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KR1019810005110A KR830001091B1 (en) | 1981-12-23 | 1981-12-23 | High concentration colored polyester granules manufacturing method |
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KR1019810005110A KR830001091B1 (en) | 1981-12-23 | 1981-12-23 | High concentration colored polyester granules manufacturing method |
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KR830001091B1 true KR830001091B1 (en) | 1983-06-02 |
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1981
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