KR100810865B1 - Method of Preparing Polyketone Fibers and the Polyketone Fibers Prepared by the Method - Google Patents

Method of Preparing Polyketone Fibers and the Polyketone Fibers Prepared by the Method Download PDF

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KR100810865B1
KR100810865B1 KR1020040112772A KR20040112772A KR100810865B1 KR 100810865 B1 KR100810865 B1 KR 100810865B1 KR 1020040112772 A KR1020040112772 A KR 1020040112772A KR 20040112772 A KR20040112772 A KR 20040112772A KR 100810865 B1 KR100810865 B1 KR 100810865B1
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polyketone
solution
method
resorcinol
fiber
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Korean (ko)
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KR20060074131A (en
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김명우
박성호
이기환
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주식회사 효성
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    • 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
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/06Wet spinning methods
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/063Load-responsive characteristics high strength

Abstract

The present invention relates to a method for producing a high strength polyketone fiber and a polyketone fiber produced by the method, more specifically (A) by adding 0.1 to 10% by weight of a salt to the aqueous solution of resorcinol Preparing a solution; (B) preparing a polyketone solution by dissolving the polyketone containing 90 to 100 mol% of ketone units in repeating units in the resorcinol solution; (C) extruding the polyketone solution through a spinneret and then passing through an air layer to reach a coagulation bath to solidify it to obtain a multifilament; And (D) relates to a method for producing a polyketone fiber comprising the step of stretching by washing, drying and emulsion treatment of the multifilament. According to the present invention, by adding a salt to the aqueous solution of resorcinol and using a mixed coagulation bath of water and methanol, it is possible to prepare a high homogeneous polyketone spinning solution, improve the desolvent rate, and the microfibrils in the fiber axis Orientation well in the direction of the polyketone multifilament as a whole not only a very high strength, but also a low shrinkage at high temperatures can be produced a high strength polyketone fiber excellent in shape stability.
Polyketone Fiber, Resorcinol, Water, Salt, Methanol, Wet Spinning

Description

Method of Preparing Polyketone Fibers and Polyketone Fibers Prepared by the Method

1 is a process schematic diagram illustrating a spinning process for producing a polyketone fiber of the present invention.

The present invention relates to a method for producing high-strength polyketone fibers and to polyketone fibers produced by the method, and more specifically, to a solution containing lesosinol, adding a salt and dissolving the polyketone in the solution. After spinning, it relates to a method for producing a high strength polyketone fiber comprising the step of stretching by stretching in a mixed solvent of water and methanol.

It is known that polyketones in which carbon monoxide and olefins are interchanged are obtained by polymerizing carbon monoxide with olefins such as ethylene and propylene using a transition metal complex such as palladium or nickel as a catalyst. The aliphatic polyketone is a polymer compound made from olefins such as ethylene and carbon monoxide as raw materials. The aliphatic polyketone is suitable for general purpose high-performance plastics, and is particularly excellent in impact resistance and chemical resistance at low temperatures. In addition, it has the strength of para-aramid fiber level and has the advantage of excellent affinity with rubber. Due to the characteristics of these polyketones, it is expected that para-amide fibers may be used for tire cords or rubber materials currently used exclusively.

Melting high molecular weight polyketones results in thermal crosslinking reactions, resulting in inadequate melt spinning. In general, wet spinning is preferred when fiberizing high molecular weight polyketones. JP-A 2-112413, JP-A 4-228613, and JP-A-7-508317 disclose the use of organic solvents such as hexafluoroisopropanol and m-cresol during polyketone wet spinning. However, in this case, there is a problem in toxicity or flammability, and the fiber obtained by the wet spinning using the solvent is easy to be divided, and has a disadvantage of insufficient fatigue resistance and processability for use as an industrial yarn.

In addition, WO 99/18143 and US Pat. No. 5,955,019 used aqueous solutions of metal salts such as zinc chloride, zinc bromide, lithium bromide, lithium iodide, and lithium thiocyanate as solvents. It has a disadvantage that it is difficult to prepare a spinning solution. In addition, the fiber prepared using such a solvent can remove the solvent contained on the fiber using water, alcohol or acetone as a coagulation liquid in the coagulation step, but at this time, the difference in the coagulation speed between the fiber surface and the center is large. The core structure has a problem that it is difficult to produce a polyketone fiber having a uniform and dense structure.

The present invention is to solve the above problems, by adding a salt to the aqueous solution containing resorcinol, by using a water and methanol mixed coagulation bath, it is possible to produce a homogeneous polyketone solution, desolvent rate Is uniform, the microfibrils are well oriented in the fiber axis, and the purpose of the present invention is to provide a high-strength polyketone fiber having excellent morphological stability with low shrinkage at high temperature as well as very high strength of the entire polyketone multifilament.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a method for producing a polyketone fiber comprising the following steps.

(A) adding 0.1 to 10% by weight of a salt to the aqueous solution of resorcinol to prepare a resorcinol solution;

(B) preparing a polyketone solution by dissolving the polyketone containing 90 to 100 mol% of ketone units in repeating units in the resorcinol solution;

(C) extruding the polyketone solution through a spinning nozzle, passing through an air layer to reach a mixed coagulation bath, and coagulating the polyketone solution to obtain a multifilament; And                     

(D) stretching the multifilament by washing, drying and emulsion treatment.

This will be described step by step.

First, step (A) is a step of preparing a solution to which the salt is added, in the present invention, an aqueous solution of resorcinol is used as a solvent for dissolving polyketone. The concentration of lesosinol in the aqueous solution of resorcinol is preferably 35 to 95% by weight. This is because when the concentration of the resorcinol is less than 35% by weight solubility is inferior, when the concentration of the resorcinol is more than 95% crystallization of the resorcinol is difficult to produce a uniform spinning solution. Water, methanol, ethanol, and the like may be used as a solvent for dissolving the resorcinol, but in particular, water is used in the present invention because it is advantageous in terms of economics and solvent recovery.

Core composition in the present invention is the aqueous solution of resorcinol Salt addition will be. The total weight of the salt added at this time is preferably 0.1 to 10% by weight relative to the aqueous solution of resorcinol. If the total weight of the salt is less than 0.1% by weight, it does not contribute to the improvement of physical properties such as strength, elasticity, and shrinkage of the polyketone fiber. If the total weight is more than 10% by weight, the fibril peeling phenomenon caused by the salt becomes serious, and It causes nonuniformity of solvent rate, resulting in lower fiber properties.

In the present invention, the salt added to the aqueous solution of resorcinol is preferably calcium chloride, calcium bromide, lithium chloride, lithium bromide or the like.

Step (B) is a step of preparing a polyketone solution by dissolving the polyketone in the resorcinol solution, the polyketone used in the present invention is represented by -CH2CH2-CO- as 90 to 100 mol% as the main repeating unit Contains ketone units. In addition, according to the present invention, repeating units other than the ethylene, for example, propylene, butylene, and 1-phenylethylene repeating unit may be contained in an amount of 0 to 10 mol% based on the total repeating units.

However, since the strength, elastic modulus, dimensional stability, and heat resistance of polyketone fibers decreases when the amount of repeating units such as propylene other than the repeating units of ethylene increases, the amount of the ketone units is preferably 95 to all the repeating units. 100%, more preferably from 98 to 100% by mole or moles, it is most preferred in the present invention, the polyketone fiber containing only a ketone unit represented by -CH 2 CH 2 -CO-.

The intrinsic viscosity [IV] of the polyketone of the present invention is 1 to 20 dl / g, preferably 3 to 10 dl / g. If the intrinsic viscosity is less than 1㎗ / g, the strength and fatigue resistance of the polyketone fiber is not sufficient, and if the intrinsic viscosity exceeds 20㎗ / g, it is economically time-consuming and expensive, and uniformly dissolving it It is difficult.

The content of polyketone in the polyketone solution is such that the concentration is 5 to 30% by weight, more preferably 7 to 20% by weight, based on the degree of polymerization of the polyketone polymer. This is because when the content of the polyketone polymer is less than 5% by weight, it does not have physical properties as a fiber. On the other hand, when the content of the polyketone polymer is more than 30% by weight, it is difficult to dissolve it in an aqueous solution such as resorcinol and thus a homogeneous solution cannot be obtained.

On the other hand, as a method for producing a polyketone solution, specifically degassing the aqueous solution of the resorcinol dissolved in the salt maintained at 40 to 80 ℃ at 200torr or less, and then the polyketone polymer is 0.5 to 5 in a vacuum state of 200torr or less It is dissolved by stirring for a while.

In the present invention, the polyketone polymer may be used by mixing other polymer materials or additives. Examples of the polymer include polyvinyl alcohol, carboxymethyl polyketone, polyethylene glycol, and the like, and as an additive, an antioxidant, a radical inhibitor, a UV absorber, a flame retardant, a viscosity enhancer, titanium dioxide, silica dioxide, carbon, and ammonium chloride may be used. Can be.

Step (C) and (D) is a step of producing a polyketone fiber by extruding and solidifying the polyketone solution to obtain a multifilament, followed by washing, drying and stretching, which will be described in more detail with reference to the accompanying drawings. .

1 is a process schematic diagram illustrating a spinning process for producing a polyketone filament according to the present invention. Referring to FIG. 1, the solution extruded from the spinning nozzle passes through an air gap in a vertical direction (S1) and is solidified in a coagulation bath (S2). The air gap is formed such that spinning is performed within a range of about 1 to 300 mm in order to obtain a dense and uniform fiber and to impart a smooth cooling effect.

The filament passed through the coagulation bath (S2) is passed through the washing tank I (S3). The temperature of the coagulation bath and the washing tank I is controlled by using a mixed solvent of methanol and water to prevent a sudden desolvent. After passing through the water bath (S4) to remove the residual resorcinol after the step (S3), it is passed through the dryer (S5). In addition, the tanning agent undergoes a process (S6) of containing an emulsion and an additive.

In addition, the interlaced nozzles were passed to improve flatness and improve focusability. The air pressure for the interlaced nozzles was supplied to be 0.5-4.0 kg / cm 2 and the number of entanglements per meter of filament was 2-40 times.

Thereafter, the filament yarn passing through the interlace nozzle is dried again using a drying apparatus (S7). The drying temperature and drying method have a great influence on the post-processing and physical properties of the filament. According to the present invention, the drying temperature was adjusted so that the process water content could be about 7 to 13%.

Finally, the filament passed through the drying apparatus is finally wound up in the winder through the secondary emulsion treatment apparatus (S8).

The spinning nozzle is provided with a plurality of orifices having a diameter of 100 to 500 µm and a length of 100 to 1500 µm, the ratio (L / D) of the diameter and length of the orifice is 1 to 3 to 8, and the interval between the orifices is 1.0 To 5.0 mm. Spinning stock solution is extrusion spinning through the spinning nozzle, the spinning fibrous spinning stock solution reaches the spinning bath through the air layer. Solidification of the reached spinning stock solution in a mixed coagulation bath yields a multifilament.

The shape of the spinning nozzle used can generally be circular, and the nozzle diameter is 50 to 200 mm, preferably 80 to 130 mm. If the nozzle diameter is less than 50 mm, the distance between the orifices may be too short, so that adhesion may occur before the discharged solution is solidified. Because it is disadvantageous. In addition, the diameter of the nozzle orifice is preferably 100 to 500 µm. If the diameter of the nozzle orifice is less than 100 µm, a large number of trimmings occur during spinning, which adversely affects radioactivity. The coagulation rate of the solution is slow, and the desolvent and water washing of the aqueous solution of lesosinol are difficult.

In view of the application, especially for tire cords, and considering the orifice spacing for uniform cooling of the solution, the number of orifices is 100 to 2,200, more preferably 300 to 1,400.

If the number of orifices is less than 100, sufficient strength is not secured as an industrial company, and the fineness of each filament is thickened, so that the solvent cannot be sufficiently released within a short time, so that solidification and washing are not completed. If the number of orifices is more than 2,200, the filaments and affixes close to the filament are likely to occur in the air layer section, and the stability of each filament decreases after spinning, rather than the deterioration of physical properties. Can cause.

When the fibrous spinning stock solution passed through the spinning nozzle is solidified in the upper coagulating solution, the larger the diameter of the fluid, the greater the difference in the coagulation rate between the surface and the inside, thus making it difficult to obtain a dense and uniform fiber. Therefore, when spinning the polyketone solution, it is advantageous to allow the spun fibers to be obtained into the coagulating liquid with a smaller diameter while maintaining the proper air layer even with the same discharge amount. The air layer is preferably 5 to 50 mm, more preferably 10 to 20 mm. Too short air gap distances increase the rate of micropores generated during rapid surface layer solidification and desolvation, which impedes the increase of elongation ratio. It is difficult to maintain process stability as it receives a lot.

As another key technical matter in the present invention, the composition ratio of water and methanol in the mixed coagulation bath is an important factor. For example, when water is used alone as a coagulation bath, adhesion between the filaments occurs, resulting in poor process stability. When methanol is used alone, the difference in the solidification speed between the fiber surface and the center is large due to the skin-core structure. There is a problem that it is difficult to produce polyketone fibers having a uniform and dense structure. Therefore, in the present invention, a mixed coagulation bath of methanol and water is used, and the composition of methanol and water is 9: 1 to 5: 5. The ratio is weight percent. At this time, the coagulation bath temperature is -20 ~ 20 ℃ and more preferably maintained at -10 ~ 10 ℃.

In the present invention, the dryer temperature is 100 ℃ or more, preferably 150 ℃ or more and impart an emulsion, heat-resistant agent, antioxidant or stabilizer to the fiber passed through the dryer.

In addition, the stretching process in the polyketone fibers of the present invention is very important for high strength and hot water resistance improvement. The heating method of the stretching process is hot air heating and roller heating, but in the case of the roller heating, the hot air heating is suitable for the production of high-strength polyketone fibers because the filament is easily in contact with the roller surface. In the case of the hot air heating type, heating is possible at a temperature of 140 to 260 ° C, but preferably 160 to 240 ° C. If the heating temperature is less than 140 ℃ high molecular stretching is not possible because the molecular chain does not behave sufficiently, and above 260 ℃ polyketone is easy to decompose physical properties are degraded.                     

The stretching is carried out in one or two or more stages of multistage for stretching the polyketone fibers. In addition, when performing multistage stretching, it is preferable that the temperature-stretching at which the stretching temperature gradually increases as the draw ratio is increased. As conditions of specific temperature extending | stretching, 1st stage is 180-200 degreeC, 2nd stage is 200-220 degreeC, and 3rd stage is 220-240 degreeC. The draw ratio of the present invention has a total draw ratio of 5 to 40 times, preferably 10 to 30 times.

On the other hand, the present invention relates to a polyketone fiber produced according to the above method. The multifilaments produced by the process of the present invention are polyketone multifilaments having a total denier range of 500 to 3,000 and a cutting load of 6.0 to 40.0 kg. The multifilament is composed of 100 to 2200 individual filaments having a fineness of 0.5 to 8.0 denier. The strength of the multifilament is 15.0 to 30g / d, elongation is 2 to 10%, shrinkage of 0.5 to 1.8%, it can be advantageously used as a tire cord for passenger cars.

Hereinafter, the structure and effect of the present invention will be described in more detail with reference to specific examples and comparative examples, but the above examples are not intended to limit the scope of the present invention. In Examples and Comparative Examples, properties of the tire cord and the like were evaluated in the following manner.

(a) intrinsic viscosity

The intrinsic viscosity [IV] of the dissolved polyketone was measured using a Uberod viscometer in 0.5M hexafluoroisopropanol solution according to ASTM D539-51T at a temperature of 25 ± 0.01 ° C and a concentration range of 0.1 to 0.6 g / dl. . Intrinsic viscosity is obtained by extrapolating specific viscosity according to concentration.

(b) strength (g / d), breaking elongation (%), modulus of elasticity (g / d) of multifilament

Using Instron's low speed extension type tensile tester, twist was added at 80 Tpm (80 twist / m) and measured at a sample length of 250 mm and a tensile speed of 300 m / min.

Modulus of elasticity is expressed as the slope of the load to produce a certain level of elongation, which is the slope of the elongation-load curve in the elongation test.

(c) fibril evaluation

Polyketone fibers produced in the present invention was evaluated for the fibrillation index (F.I.) using the following method. To force fibrils, put 50 10mm long multifilaments in a 250ml Erlenmeyer Flask (narrow neck) containing 25 ° C water, and use a magnetic stirrer (magnetic bar 40L × 10mmφ) with 10 5mm diameter stainless steel balls. It was rotated at 10rpm for 30 minutes and dried to evaluate the fibrillation index (FI) through an optical microscope.

Samples of the fibers were arranged corresponding to the increase in fibrillation.

From each sample, the reference fiber length is measured, the number of fibrils according to the reference field is counted, the length of each fibrils is measured, the average fibrillation length is calculated, and the value obtained by multiplying the number of fibrils is determined for each fiber. It was.

The fiber showing the highest value is the most fibrillated fiber, the fibrillation index is set to an arbitrary value, the fibrillation index is attached to the nonfibrillated fiber as a whole, and the remaining fibers are in the range of 1 to 10. Arranged random values in.

(d) Dry heat shrinkage (%, Shrinkage)

After leaving for 24 hours at 25 ° C. and 65% RH, the dry heat shrinkage ratio is shown using the ratio of the length (L 0) measured at 20 g of super load and the length (L 1) after treatment at 150 g for 20 minutes at a static load of 30 g.

S (%) = (L0-L1) / L0 × 100

Preparation Example: Preparation of Polyketone Polymer (POK)

First, the autoclave was filled with methanol, and the catalyst solution prepared by stirring palladium acetate, 1,3-bis (di (2-methoxyphenyl) phosphino) propane, and trifluoroacetic acid was added thereto. After the above process, the autoclave was charged with a mixed gas containing carbon monoxide and ethylene in a molar ratio of 1: 1, and the mixed gas was continuously added to maintain a pressure of 1 to 10 MPa while reacting at 50 to 100 ° C. for several hours. . After the completion of the reaction, the white polymer obtained by releasing the pressure was repeatedly washed with heated methanol, 1,3-pentanedione. The polyketone obtained through the above process was found to be poly (1-oxotrimethylene) by analysis of nuclear magnetic resonance spectra. In addition, it was found that the molecular weight distribution of the polyketone was 2.8, and the intrinsic viscosity was 5.0 kV / g.                     

Example 1

2 wt% of calcium chloride was added to an aqueous solution containing 75 wt% of resorcinol, and then 12.0 wt% of a polyketone polymer (POK) having an intrinsic viscosity [IV] of 5.0 dl / g obtained in the preparation example was added thereto and then 100torr at 60 ° C. The mixture was decompressed to 30 minutes to remove bubbles.

After the bubble in the aqueous solution was completely removed, the resultant was sealed under reduced pressure, and then heated to 80 ° C. and stirred for 3 hours to obtain a transparent POK spinning solution. After passing the obtained POK spinning solution through a filter, the resultant was extruded at a rate of 20 m / min at 80 ° C. as a trench type extruder through a nozzle (N / Z) having a diameter of 0.2 mm, L / D 2.0, and 200 holes. After the extrusion was passed through an air gap having a length of 10mm (Air Gap) to cause a solidification in the coagulation bath. In the coagulation bath, a 8.5: 1 mixed solution of methanol and water was used. The fiber passed through the coagulation bath was dried while passing through a hot air dryer at 200 ° C. after passing through a water washing bath. Thereafter, the fiber obtained by applying an oil agent, an antioxidant, and the like to the wound was subjected to three-stage stretching while gradually raising the temperature at 180 ° C, 210 ° C, and 225 ° C, and the final filament fineness was adjusted to 1,000 denier.

The filament drawn yarn was evaluated for physical properties using an Instron's low-speed stretching type tester.

Example 2-3

A stretch yarn and a treatment cord were prepared by performing experiments in the same manner as in Example 1 while changing the calcium chloride weight% added to the aqueous solution of resorcinol as shown in Table 1 below. The physical properties of the drawn yarn thus obtained are evaluated and shown in Table 1 below.

Comparative Example 1

In Example 1, an aqueous solution of resorcinol to which no salt was added was used, and a subsequent process was performed in the same manner to prepare a stretched yarn.

Comparative Example 2

In Example 1 zinc chloride 75wt% was used as a solvent instead of an aqueous solution of resorcinol, and the process was carried out in the same manner to prepare a stretched yarn. The physical properties of the drawn yarn thus obtained were evaluated and shown in Table 1 below.

Table 1

Figure 112004061538214-pat00001

* Salt addition ratio in Table 1 means the weight percent.

According to the present invention, by adding 0.1 to 10% by weight of a salt to an aqueous solution containing resorcinol, it is possible to prepare a high homogeneous polyketone spinning solution, to improve the desolvent rate in the manufacture of fibers, microfibrils It is well oriented in the direction of the fiber axis, and not only has a very high strength of the entire polyketone multifilament, but also has low shrinkage at high temperatures, which is excellent in form stability, and thus is suitable for use in industrial textile fields such as tire cords, belts, hoses, and ropes.

Claims (6)

  1.  (A) adding 0.1 to 10% by weight of salt to the aqueous solution of resorcinol to prepare a resorcinol solution;
     (B) preparing a polyketone solution by dissolving the polyketone containing 90 to 100 mol% of ketone units in repeating units in the resorcinol solution;
     (C) extruding the polyketone solution through a spinning nozzle, passing through an air layer to reach a mixed coagulation bath, and coagulating the polyketone solution to obtain a multifilament; And
     (D) a method for producing a polyketone fiber, characterized in that it is produced by a method comprising the step of stretching by washing, drying and emulsion treatment of the multifilament.
  2. The method of claim 1, wherein the salt is selected from the group consisting of calcium chloride, calcium bromide, lithium chloride and lithium bromide.
  3. The method of claim 1, wherein the ketone unit is represented by -CH 2 CH 2 -CO-.
  4. The method for producing polyketone fibers according to claim 1, wherein the diameter of the spinning nozzle is 50 to 200 mm, and the number of orifices of the spinning nozzle is 100 to 2200.
  5. The method of claim 1, wherein the mixed coagulation bath has a composition ratio of water and methanol of 9: 1 to 5: 5.
  6. It is prepared by the method of claim 1, having (1) strength of 15 to 30 g / d, (2) 500 to 3,000 denier of fineness, (3) 2 to 10% elongation, and (4) 0.5 to 1.8% of shrinkage. Polyketone fiber.
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Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04228613A (en) * 1990-05-09 1992-08-18 Akzo Nv Polyketone fiber and its production
US5714101A (en) 1992-06-26 1998-02-03 Akzo Nobel N.V. Process of making polyketon yarn
KR20030082609A (en) * 2001-02-27 2003-10-22 아사히 가세이 가부시키가이샤 Polyketone Fiber and Process for Producing the Same
KR100595990B1 (en) 2004-10-22 2006-07-03 주식회사 효성 Polyketone Fibers and A Process for Preparing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04228613A (en) * 1990-05-09 1992-08-18 Akzo Nv Polyketone fiber and its production
US5194210A (en) 1990-05-09 1993-03-16 Akzo Nv Process for making polyketone fibers
US5714101A (en) 1992-06-26 1998-02-03 Akzo Nobel N.V. Process of making polyketon yarn
KR20030082609A (en) * 2001-02-27 2003-10-22 아사히 가세이 가부시키가이샤 Polyketone Fiber and Process for Producing the Same
KR100595990B1 (en) 2004-10-22 2006-07-03 주식회사 효성 Polyketone Fibers and A Process for Preparing the same

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