KR20210001651A - Manufacturing Method Of Polyphenylene Sulfide Filament Fiber Excellent In Chemical Resistance - Google Patents

Abstract

The present invention, in a method for manufacturing polyphenylene sulfide filament fibers, relates to polyphenylene sulfide filament fibers having excellent chemical resistance, characterized in that the spinning speed is 2,000 to 3,000 m/min. The present invention provides polyphenylene sulfide filament fibers having excellent chemical resistance, in which a strength is 4.0 g/d or more and an elongation is 20% or more.

Description

Polyphenylene Sulfide Filament Fiber Excellent In Chemical Resistance {Manufacturing Method Of Polyphenylene Sulfide Filament Fiber Excellent In Chemical Resistance}

The present invention is a method for producing polyphenylene sulfide filament fibers having excellent chemical resistance, and in more detail, the strength is 4.0g/d or more and the elongation is 20% or more.

Polyphenylene sulfide resin is a semi-crystalline thermoplastic resin that belongs to the group of super engineering plastics that combines high heat resistance, chemical resistance, self-flammability and insulation properties, and its chemical structure is a rigid polymer in which sulfur atoms are attached to the para position of the benzene ring.

The characteristics of polyphenylene sulfide resin are heat deflection temperature of 260 ℃ or higher and UL standard long-term use temperature of 240 ℃, which has the highest level of heat resistance. Another characteristic of polyphenylene sulfide resin is that it has excellent chemical resistance, so no organic solvent that dissolves polyphenylene sulfide resin has been found below 200℃, and it has the next best chemical resistance after fluorine resin (PTFE).

As described above, polyphenylene sulfide resin is excellent in heat resistance, chemical resistance, electrical insulation, and mechanical strength and molding processability as described above, and is therefore widely used as a metal substitute material or as a material capable of withstanding extreme environments. Polyphenylene sulfide fibers are also proposed to be used in industrial materials such as filters, brush base materials, paper dryer canvas, electrical insulating paper, etc. using these properties.

Polyphenylene sulfide filaments can be obtained as monofilament yarns, multifilament yarns or staple fibers. Polyphenylene sulfide filaments are produced by a melt spinning process. They can be used at temperatures of 190° C. without showing serious damage or decomposition. Polyphenylene sulfide filaments are flame retardant and self-extinguishing, and have a melting point of about 285°C.

In recent years, in the use of filters used in manufacturing sites such as chemistry, electricity/electronics, automobiles, foods, precision equipment, medicines and medicines, studies of polyphenylene sulfide monofilament have been actively conducted as an alternative to SUS steel wires. For example, in recent years, in order to produce monofilaments in a high-productivity and inexpensive manner, a method of producing multifilaments once and then branching has been proposed.

However, in this method, since the entanglement treatment in the multifilament manufacturing process performs stretching and row setting in a state in which entanglements are interposed between the single yarns, the stretching or row set between the single yarns tends to become uneven, and the monofilament after powdering However, it is difficult to obtain a uniform monofilament due to unevenness in the fineness in the fiber axis direction.

In fact, polyphenylene sulfide resin having a small molecular weight was attempted to increase the molecular weight to use polyphenylene sulfide resin for fiber by inducing a crosslinking reaction between polyphenylene sulfide resins through aging after polymerization, but the crosslinking reaction is uneven. Due to non-uniformity of fiber properties, crosslinking reaction, weakening and cutting of polyphenylene sulfide branched chain due to excessive oxidation, and generation of a large amount of gel, it causes production problems such as frequent cutting of fiber yarn during fiber spinning. Improvement measures are being demanded.

An object of the present invention is to select appropriate spinning conditions to prepare polyphenylene sulfide fibers in a partially oriented yarn (POY) state, and then to produce polyphenylene sulfide fibers having excellent physical properties through stretching and heat treatment processes. It aims to provide a way to do it.

In order to solve the above problems, the present invention provides a method for producing polyphenylene sulfide filament fibers having excellent chemical resistance, characterized in that the spinning speed is 2,000 to 3,000 m/min. do.

In addition, the present invention provides a method for producing polyphenylene sulfide filament fibers having excellent chemical resistance, characterized in that the strength of a cooling wind flux is 4 to 10 mmAq in a method for producing polyphenylene sulfide fibers.

In addition, the present invention provides a method for producing polyphenylene sulfide filament fibers having excellent chemical resistance in which the temperature of the drawing roller is 70 to 200°C in the filament fiber manufacturing method.

In addition, the present invention provides a method for producing polyphenylene sulfide filament fibers having excellent chemical resistance with a stretching speed of 300 to 800 m/min in the filament fiber manufacturing method.

In addition, the present invention provides a polyphenylene sulfide filament fiber having excellent chemical resistance, characterized in that it is manufactured by any one of the above manufacturing methods and has a strength of 4.0 g/d or more and an elongation of 20% or more.

The present invention relates to a method for producing polyphenylene sulfide filament fibers and fibers thereof. The polyphenylene sulfide resin having an appropriate viscosity is selected, and by using the primary and secondary filtering and distribution plates inside the pack, it has excellent spinnability and high magnification. It has elongation characteristics.

Hereinafter, a preferred embodiment of the present invention will be described in detail. First, in describing the present invention, detailed descriptions of related known functions or configurations are omitted so as not to obscure the subject matter of the present invention.

The terms'about','substantially', etc. of the degree used in the present specification are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and are used in the sense of the present invention. To assist, accurate or absolute figures are used to prevent unfair use of the stated disclosure by unscrupulous infringers.

The term "filament" as used herein refers to fibers of practically infinite length. Therefore, yarn made of a plurality of filaments is called filament yarn.

The polyphenylene sulfide resin is a crystalline engineering plastic having the following chemical structure and has high heat resistance and excellent mechanical properties, chemical resistance, electrical properties, and dimensional stability. Examples of the application include electric/electronic parts, automobile parts, and mechanical parts.

In addition, polyphenylene sulfide resin may be a linear, crosslinked, or semi-crosslinked polymer, but it is preferably linear, has an intrinsic viscosity of 0.1-10 dl/g, and a weight average molecular weight (Mw) of 2,000 to 8,000. , Melt flow index (Melt Flow index) 20 ~ 150g / 10min can be used.

The present invention is characterized in that the spinning speed is 2000 to 3000 m/min, the strength of the cooling wind is melt-spun through 4 to 10 mmAq and then subjected to stretching heat treatment.

In addition, during the stretching process, the stretching speed is 300 to 800 m/min, and the temperature is 60 to 200°C.

Hereinafter, the present invention will be described in detail.

PPS in the present invention is a polymer composed of a phenylene sulfide unit such as a p-phenylene sulfide unit represented by the structural formula (1) as a main repeating unit and an m-phenylene sulfide unit.

In the production method of the present invention, drying of the PPS polymer before it is subjected to melt spinning is preferable in order to suppress foaming due to moisture incorporation and improve spinning performance. Moreover, since the low-boiling-point monomer remaining in the PPS polymer can be removed by vacuum drying, the spinning property can be further improved, which is more preferable. As drying conditions, vacuum drying for 8 to 24 hours at 100 to 200°C is usually used.

The extruded polymer is metered through a pipe by a known metering device such as a gear pump, passed through a filter for removing foreign matter, and then introduced into a nozzle. At this time, the temperature (radiation temperature) from the polymer piping to the nozzle is preferably set to be higher than the melting point of PPS, more preferably higher than the melting point of PPS +10° C. in order to increase fluidity. However, excessively high spinning temperature causes thermal deterioration of PPS, generation of decomposition gas, and deterioration of spinning performance, so it is preferable to set the temperature to 350°C or less, and more preferably 320°C or less. It is also possible to independently adjust the temperature from the polymer piping to the nozzle. In this case, discharging is stabilized by raising the temperature of the portion close to the nozzle higher than the temperature on the upstream side thereof.

For the nozzle used for discharging, it is preferable that the hole diameter D of the nozzle hole is 0.10 mm or more and 1.00 mm, and the land length L of the nozzle hole (the length of the straight pipe part equal to the hole diameter of the nozzle hole) is divided by the hole diameter. L/D defined as is preferably 1.0 or more and 5.0 or less.

In the spinning conditions of the present invention, when spinning polyphenylene sulfide POY, the spinning speed is preferably 2000 to 3000 m/min, and if the spinning speed is less than 2000 m/min, the strength rapidly decreases and affects the final drawn yarn. When is 3000m/min or more, the strength increases, but there is a problem in that fairness decreases due to an increase in the number of trimmings.

In addition, the strength of the cooling wind flux is preferably 4 to 10mmAq, and when the strength of the cooling wind speed is less than 4mmAq, the fiber is not completely solidified and the strength is reduced. There is a problem of this worsening.

In addition, in the stretching process, the temperature of the roller is preferably 60 to 200°C, and when the temperature of the stretching roller is lowered to less than 60°C, the stretching ratio is lowered so that the strength is not developed, and when the temperature is higher than 200°C, there is a problem of poor fairness. .

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited to these examples only.

<Measurement method>

1.Melt index Melt index ( M.I )

Measure the amount of resin flowing for 10 minutes by ASTM D1238 method under 300℃, 2.16kgf load condition.

2. Method of measuring the strength of yarn

After the yarn is left for 24 hours in a constant temperature and humidity room in a standard condition, that is, a temperature of 25°C and a relative humidity of 65%, the sample is measured through a tensile tester according to ASTM D-885.

3. Dry heat How to measure shrinkage

The yarn is left for 24 hours in a constant temperature and humidity room with a standard condition, that is, a temperature of 25℃ and a relative humidity of 65%. It is left in an oven at 180° C. for 5 minutes. The yarn is left in the standard condition for 24 hours. The shrinkage rate of the yarn is measured according to the following equation.

Equation: Shrinkage (%) = (L0-L1) / L0 ×100

In the above equation,

L0 is the length measured under super load (0.01g/d) after leaving the sample in standard condition for 24 hours, and L1 is the length of the sample reduced under super load (0.01g/d) after heating for a certain period of time.

* Example 1 and Comparative example 1~4

After vacuum drying the polyphenylene sulfide chip at 150° C. for 10 hours or more, a drawn yarn was manufactured through POY spinning and stretching process. The piping temperature was 290~320℃, and the closer to the nozzle, the spinning was performed under the condition corresponding to 320℃. The spinning temperature was set to 300 or higher, and the molten polymer was extruded and wound up through a 12-hole nozzle with a nozzle diameter of 0.4 mm at a discharge rate of 40 g per minute using a polymer gear pump.

<Example 1>

POY was prepared with a spinning speed of 2000m/min and a cooling wind speed of 6mmAq, and the drawing roller temperature was 80/180°C.

Polyphenylene sulfide fibers were manufactured using a conventional drawing equipment at a drawing speed of 300 m/min.

<Example 2>

POY was prepared with a spinning speed of 2500 m/min and a cooling wind speed of 6 mmAq, and the temperature of the drawing roller was 80/200.

Polyphenylene sulfide fibers were manufactured using a conventional drawing equipment at a drawing speed of 300 m/min.

<Comparative Example 1>

It was prepared in the same manner as in Example 1 except for a spinning speed of 1500 m/min.

<Comparative Example 2>

It was prepared in the same manner as in Example 1 except for a spinning speed of 3,500 m/min.

<Comparative Example 3>

It was prepared in the same manner as in Example 1 except for a cooling wind speed of 2 mmAq.

<Comparative Example 4>

The POY manufacturing method was the same as in Example 1, and was prepared after setting the drawing roller temperature to 60/180°C.

The conditions of Examples and Comparative Examples 1 to 4 are shown in Table 1, and the remaining conditions are the same as those of Example 1.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Spinning speed (m/mon) 2,000 2,500 1,500 3,500 2,000 2,000 Cooling wind speed (mmAq) 6 6 6 6 2 6 Drawing roller temperature (℃) 80/180 80/200 80/180 80/180 80/180 60/180 Strength (g/d) 4.1 4.6 3.4 4.7 3.7 Unwindable Elongation (%) 21 22 18 18 19 - Fairness Good Good Poor fairness Poor fairness Strength drop

As can be seen in Examples 1 to 2 of Table 1, there are appropriate conditions for preparing polyphenylene sulfide fibers. It can be seen that lowering or raising the room speed greatly affects the strength and elongation of the final fiber, and it can be seen that the processability and physical properties change according to the stretching temperature.

Depending on the POY state, the difference in physical properties and appearance of the final drawn yarn was markedly revealed, so it can be seen that it is important to secure the proper conditions for POY.

As can be seen in Comparative Examples 1 to 4, it can be confirmed that the spinning speed, the strength of the cooling wind speed, and the temperature of the drawing roller are important factors.

The present invention described above is not limited by the above-described embodiments and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope of the technical spirit of the present invention. It will be obvious to those who have the knowledge of.

Claims (5)

In the method for producing polyphenylene sulfide fibers, a method for producing polyphenylene sulfide filament fibers having excellent chemical resistance, characterized in that the spinning speed is 2,000 to 3,000 m/min.
In the method for producing polyphenylene sulfide fiber, a method for producing polyphenylene sulfide filament fiber having excellent chemical resistance, characterized in that the strength of a cooling wind flux is 4 to 10 mmAq.
The method of claim 1,
Polyphenylene sulfide filament fiber manufacturing method having excellent chemical resistance in which the temperature of the drawing roller is 70 to 200°C in the filament fiber manufacturing method.
The method of claim 1,
Polyphenylene sulfide filament fiber production method having excellent chemical resistance with a stretching speed of 300 to 800 m/min in the filament fiber production method.
A polyphenylene sulfide filament fiber having excellent chemical resistance, characterized in that it is prepared by any one of the manufacturing methods of claim 1 to 4, and has a strength of 4.0 g/d or more and an elongation of 20% or more.