KR20120071814A - Polyketone fiber with improved wearing property and method for preparing the same - Google Patents

Abstract

PURPOSE: A method for fabricating a polyketone fiber with reduced abradability is provided to minimize splitting and to fabricate industrial fibers for a tire cord, belt, horse, and rope. CONSTITUTION: A method for fabricating a polyketone fiber comprises: a step of melting polyketone containing 90 mole% of more of repeat units in a resorcinol solution to prepare a polyketone solution; a step of extruding/spinning the polyketone solution through a spinning nozzle and solidifying to prepare a multifilament(S2); and a step of washing and drying the multifilament and processing the multifilament with a finishing agent(S4,S5). The finishing agent is polyether, composite polyester, or polybutene.

Description

Polyketone Fiber with Improved Wearing Property and Method for Preparing the Same}

The present invention relates to a polyketone fiber with improved wear and high strength and a method for producing the same, and more particularly, to a manufacturing method for improving physical properties, particularly wearability, of a polyketone fiber by using a finishing agent.

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 based on olefins such as ethylene and carbon monoxide. The aliphatic polyketone is not only suitable for general purpose high-performance plastics but also excellent at low temperature impact resistance and chemical resistance, and has the same strength as para-aramid fibers. In addition to having, it has the advantage of having good affinity with rubber. Due to the characteristics of these polyketones, it is expected that para-aramid fibers may be used for tire cords or rubber materials currently used exclusively.

When the high molecular weight polyketone is melted, thermal crosslinking reactions occur, so that melt spinning is inadequate. In general, wet spinning is preferable when the high molecular weight polyketone is fibrous. In the case of wet spinning polyketone, conventional organic solvents such as hexafluoroisopropanol and m-cresol have problems in toxicity and flammability, and fibers obtained by wet spinning using the solvent are liable to be divided, It is disadvantageous in that fatigue resistance and processability are insufficient for use as an industrial yarn.

According to the present invention, after preparing a polyketone containing 90 mol% or more of ketone units as a repeating unit in an aqueous solution containing resorcinol, a finishing agent is applied to the surface of the fiber to improve anti-static property and to reduce cutting of lint or single yarn. To provide polyketone fibers.

According to a preferred embodiment of the present invention to achieve the above object, the step of dissolving a polyketone containing at least 90 mol% ketone units in repeating units in an aqueous solution of lesosinol to prepare a polyketone solution; Extruding the polyketone solution through a spinning nozzle, and then passing through an air layer to reach a coagulation bath, thereby solidifying the polyketone solution to obtain a multifilament; And then solidifying it to obtain a multifilament; And treating the finishing agent after washing and drying the multifilament obtained above, wherein the finishing agent comprises at least one selected from the group consisting of polyether, composite polyester, and polybutene. It provides a method for producing a polyketone.

According to another suitable embodiment of the present invention, the polyether has a molecular weight of 10,000 to 20,000, the composite polyester has a molecular weight of 7,000 to 15,000, and the polybutene has a molecular weight of 4,000 to 8,000.

According to another suitable embodiment of the present invention, the stretching comprises at least two temperature raising steps.

Polyketone fibers produced according to the present invention can minimize the single yarn cracking even in post-processing due to the excellent wear and stable static friction coefficient. Therefore, it is possible to produce industrial fibers, such as tire cords, belts, hoses, ropes with excellent strength through these polyketone fibers.

1 schematically illustrates a spinning process for producing a polyketone fiber according to the present invention.

Hereinafter, the present invention will be described in detail by using the presented embodiments, and well-known or obvious items in the description of the embodiments are omitted or briefly described. However, such things should not be understood as being excluded from the scope of the present invention.

Hereinafter, with reference to the accompanying drawings will be described in detail the present invention.

1 schematically illustrates a spinning process for producing a polyketone fiber 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 continuously solidifies 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 (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 interlace nozzle was passed in order to improve flatness and improve focusability. The air pressure for the interlaced nozzle 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 7-13%.

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

The stretching process in the polyketone fibers of the present invention produced through the above manufacturing process 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 hot air heating is more preferable for the production of high strength polyketone fibers because the filament is in contact with the roller surface and the fiber surface is easily damaged. In the case of using the hot air heating type, heating is possible at a temperature of 140 to 270 ° C, but preferably 160 to 260 ° C. If the heating temperature is below 140 ° C, the molecular chain is not sufficiently behaved, so high magnification thermal stretching is impossible.

In the present invention, it is characterized in that the finishing agent that can improve the wear property to be suitable for use as industrial fibers, such as tire cords, belts, hoses, ropes. By applying the finishing agent, single yarn cracking was minimized even in post processing because of excellent wearability and stable static friction coefficient. The finishing agent used in the present invention contains at least one selected from the group consisting of polyethers having a molecular weight of 10,000 to 20,000, composite polyesters having a molecular weight of 7,000 to 15,000, and polybutenes having a molecular weight of 4,000 to 8,000 as essential components.

The essential ingredients are preferably from 60 to 90% by weight of the finish, and contains a residual amount of water. By providing a finishing agent in such a polyketone fiber manufacturing process, an oil film is formed on a polyketone fiber, and this oil film can control abrasion of a fiber. In addition, by using a compound having a high molecular weight, the oil film strength can be improved to improve the bundle concentration of the yarn, and the finish agent can be prevented from penetrating into the yarn.

Hereinafter, the configuration and effects of the present invention will be described in detail with 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) measuring the number of actual friction cuts

The number of thread friction cuts is the number of times the thread is rubbed until the cut occurs, and the greater the number, the better the wear property.

(c) strength (g / d)

After drying at 107 ° C. for 2 hours, a twist of 80Tpm (80 twists / m) was added using a low-strength tensile tester of Instron, and then measured at a sample length of 250 mm and a tensile speed of 300 m / min.

Example 1

12.0 wt% of a polyketone polymer (POK) having an intrinsic viscosity (IV) of 5.1 dl / g was added to an aqueous solution containing 75 wt% of resorcinol, followed by mixing under reduced pressure at 30 ° C. to 100 torr for 30 minutes to remove bubbles. When the bubble in the aqueous solution was completely removed, the resultant was sealed under reduced pressure, heated to 80 ° C., and stirred for 3 hours to obtain a transparent polyketone spinning solution. After passing the obtained polyketone spinning solution through a filter, the resultant was extruded at a rate of 20 m / min at 80 ° C. through a trench extruder through a nozzle (N / Z) having a diameter of 0.2 mm, L / D 2.0, and 200 holes. After extrusion, the air gap having a length of 10 mm was passed through the air gap, so that solidification occurred in the coagulation bath. The coagulation bath was used as a mixed solution of methanol and water in a 9: 1 (weight ratio). After passing through the coagulation bath, the fiber was dried by passing through a hot air dryer at 200 ° C. The polyketone was then wound up with 30% by weight of polyoxyethylene (molecular weight 12,000), 25% by weight cater-wax (molecular weight 8,000), 30% by weight polybutene (molecular weight 5,000) and the remaining amount of water. After the obtained fiber was subjected to three-stage stretching while gradually raising the temperature at 220 ° C, 230 ° C, and 240 ° C, the final filament fineness was adjusted to 1,000 denier. The physical properties of the fibers are shown in Table 1. The filament drawn yarn was evaluated for physical properties using an Instron's low-speed stretching type tester. The wear resistance of the fiber was good.

[Example 2]

The same method as in Example 1, except that 20% by weight polyoxyethylene (molecular weight 8,000), 25% by weight cater-wax (molecular weight 8,000), 30% by weight polybutene (molecular weight 5,0000) and the remaining amount of water were used. Polyketone fibers were prepared. The physical properties of the fiber are shown in Table 1. The wear resistance of the fiber was good.

Comparative Example 1

Except for using a finishing agent consisting of 30% by weight of bisphenol A ester (molecular weight 2000), 25% by weight of sorbitan trioleate ester (molecular weight 1,000), 30% by weight of polybutene (molecular weight 5,000) and residual water Fibers were prepared in the same manner as in 1. Physical properties of the produced fiber are shown in Table 1. Abrasion resistance was lowered because the condition of the finish was outside the stated components.

Comparative Example 2

A fiber was prepared in the same manner as in Example 1 except that no finishing agent was used. Physical properties of the produced fiber are shown in Table 1. Since no finishing agent was used, the wearability was significantly reduced.

division
Example 1 Example 2 Comparative Example 1 Comparative Example 2 Resorcinol / H ₂ O = 3: 1 Resorcinol / H ₂ O = 3: 1 Resorcinol / H ₂ O = 3: 1 Resorcinol / H ₂ O = 3: 1 The furtherance costs of coagulation bath
(Weight ratio) Methanol: Water
9: 1 Methanol: Water
9: 1 Methanol: Water
9: 1 Methanol: Water
9: 1 Polyketone Viscosity (dl / g) 5.1 5.1 5.1 5.1 Measurement of the number of thread friction cuts 410 times 570 times 240 times 80 times Strength (g / d) 16.3 15.7 14.1 12.4 Shinto (%) 5.3 4.1 3.9 3.5

Referring to Table 1, the polyketone fibers of Examples 1 and 2 using the finishing agent of the present invention was superior in the strength and wearability of the drawn yarn compared to the polyketone fibers of Comparative Examples 1 and 2.

In the above, the method for producing the polyketone fibers according to the present invention has been described in detail using the examples. It will be apparent to those skilled in the art that the presented embodiments are merely exemplary, and that modification inventions or modifications can be easily made from the presented embodiments. The scope of the present invention is not limited by the above modified or modified inventions, but only by the following claims.

Claims (3)

Preparing a polyketone solution by dissolving a polyketone containing 90 mol% or more of ketone units as a repeating unit in an aqueous solution of lesosinol;
Extruding the polyketone solution through a spinning nozzle, and then passing through an air layer to reach a coagulation bath, thereby solidifying the polyketone solution to obtain a multifilament; And
Solidifying it to obtain a multifilament; And
And treating the finishing agent after washing and drying the multifilament obtained above,
Wherein the finishing agent is a method of producing a polyketone, characterized in that it comprises at least one selected from the group consisting of polyether, composite polyester and polybutene. The method of claim 1, wherein the polyether has a molecular weight of 10,000 to 20,000, the composite polyester has a molecular weight of 7,000 to 15,000, and the polybutene has a molecular weight of 4,000 to 8,000. The method of claim 1, wherein the stretching comprises at least two temperature raising steps.

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