KR20230060241A - Polyetherimide and polyphenylene sulfide conjugate multi filament, and manufacturing method thereof - Google Patents

Abstract

The present invention relates to polyetherimide and polyphenylene sulfide composite multifilament which, in a sheath-core type polyetherimide and polyphenylene sulfide composite multifilament formed of a sheath portion and a core portion, the sheath portion is formed of polyetherimide resin, and the core portion is polyphenylene sulfide.

Description

Polyetherimide and polyphenylene sulfide composite multifilament and manufacturing method thereof

The present invention relates to a polyetherimide and polyphenylene sulfide composite multifilament composite multifilament, to a polyetherimide and polyphenylene sulfide composite multifilament excellent in flame retardancy and heat resistance, and a method for producing the same.

Polyphenylene sulfide fibers have a variety of markets, including not only the industrial fields of battery separators, dust collector filters, and interior materials for automobiles, but also the interior fields of wallpaper, curtains, sofas, and bedding, and the protective clothing fields of industrial protective clothing and protective gloves. In recent years, as the demand for chemical resistance and flame retardancy has increased, its use has been increasing.

In particular, it is a filter material used for filters in filter cloth dust collectors. It is generally made of polyphenylene sulfide fibers, unlike non-woven fabrics made of glass fiber (Glass), meta aramid (MA), teflon (PTFE), polyimide (PI), etc. The prepared non-woven fabric is attracting attention as a heat-resistant filter material due to excellent heat resistance, chemical resistance, low absorption characteristics, and shape stability of polyphenylene sulfide fibers.

Meanwhile, polyphenylene sulfide fibers are manufactured through a melt spinning process. Specifically, melting and supplying PPS; Extruding the melt through a spinneret having a plurality of spinnerets to form a filament bundle having a plurality of filaments, cooling and solidifying the melt, and then introducing the melt into a plurality of cans; And, the step of multi-stage stretching the filament bundles in these multiple cans; it can be manufactured through.

However, since these polyphenylene sulfide fibers have disadvantages such as high polymer price, cutting due to poor solidification during the spinning process, and poor crimp expression in the drawing process, the yield can be improved by improving the processability of PPS fibers. There is a need for technology.

As a technology for improving the processability of polyphenylene sulfide fibers, German Patent DE No. 4006397 relates to a technology for producing polyphenylene sulfide multifilaments by applying high-temperature air or inert gas under a spinneret and then going through a drawing process. Japanese Unexamined Patent Publication No. 1991-168750, which relates to a technique of blowing an air current of 45 ° C. or higher into spun polyphenylene sulfide fibers, cooling them, and passing them through a heated region to heat-stretch them, and polyphenylene sulfide resins from 310 to 310 It is melted at a temperature of 340 ° C. and continuously spun through a hole with a diameter of 0.1 to 0.5 mm in a spinneret to produce multifilaments, which are passed through a high-temperature atmosphere sealed by an insulating tube or a heating tube, and then 100 ° C. There is Japanese Unexamined Patent Publication No. 1990-219475 relating to a technique of cooling with the following warm air flow or cold air flow.

In addition, patents related to polyphenylene sulfide fibers used as filter materials include European Patent No. 386,975, which uses polyphenylene sulfide fibers for filtration of high-temperature gas, and polyphenylene sulfide and acrylic fibers. PCT-US2007-019827 relates to a phenylene sulfide bag filter.

The above technologies have the significance of improving the filter characteristics by introducing polyphenylene sulfide fibers into dust collection filters that require heat resistance, but the spinning defects that occur during the cooling and solidification process when the molten polymer is continuously passed through the spinneret have the same problem

Due to the above-described poor spinning, most polyphenylene sulfide fibers use a polyphenylene sulfide resin in the sheath for spinning, and a composite that uses a polyester resin, a polyamide resin, or a polyolefin resin in the core part. After being made of fiber, it has been cut to a certain length to make it into short fibers, and then made into spun yarn and used.

However, the polyphenylene sulfide composite fiber used in the form of spun yarn as described above has a problem in that heat resistance and chemical resistance are lowered because the resin of the core portion is exposed at both ends of the single fiber.

In order to solve the above problems, Korean Patent Registration No. 2183246 proposes a composite multifilament in which a high-viscosity polyester resin is used for the core part and polyphenylene sulfide resin is used for the sheath part, but the polyester resin for the core part Compared to the multifilament formed only of polyphenylene sulfide resin using a polyphenylene sulfide resin, there was a problem of lower hydrolysis resistance.

The present invention was invented to solve the problems of the prior art as described above, and an object of the present invention is to provide a polyetherimide and polyphenylene sulfide composite multifilament that can be used as a composite multifilament rather than a single fiber.

In addition, to provide a polyetherimide and polyphenylene sulfide composite multifilament having excellent flame retardancy and heat resistance by cutting the polyetherimide and polyphenylene sulfide composite multifilament to a certain length and using it as a long fiber rather than a short fiber. The purpose.

Another object of the present invention is to provide a manufacturing method capable of producing polyetherimide and polyphenylene sulfide composite multifilament having excellent physical properties by improving spinning and stretching properties of the polyetherimide and polyphenylene sulfide composite multifilament.

In order to solve the above problems, the present invention is a sheath-core type polyetherimide and polyphenylene sulfide composite multifilament formed of a sheath part and a core part, wherein the sheath part is formed of polyetherimide resin , The core portion provides a polyetherimide and polyphenylene sulfide composite multifilament, characterized in that formed of a polyphenylene sulfide (Polyphenylene sulfide) resin.

In addition, the sheath part and the core part provide a polyetherimide and polyphenylene sulfide composite multifilament, characterized in that formed in an area ratio of 7:3 to 3:7.

In addition, the composite multifilament provides a polyetherimide and polyphenylene sulfide composite multifilament characterized in that the fineness of 250 to 500 denier, the number of filaments is 70 to 150, and the single yarn fineness is 2 denier or more.

In addition, the present invention is a method for manufacturing a sheath-core type composite multifilament formed of a sheath part and a core part, wherein the sheath part uses polyetherimide resin and the core part uses polyphenylene sulfide resin a spinning step of complex spinning in the form of a sheath-core; A first winding step of manufacturing an undrawn yarn by winding the spun composite multifilament at 1000 to 2500 m/min; A drawing step of drawing the wound unstretched yarn at a speed of 300 to 600 m/min using two or more rollers; It provides a polyetherimide and polyphenylene sulfide composite multifilament manufacturing method comprising a secondary winding step of winding the composite multifilament.

In addition, the temperature of the first elongation roller in the elongation step is 70 ~ 100 ℃, the temperature of the last elongation roller is 150 ~ 250 ℃, characterized in that it provides a polyetherimide and polyphenylene sulfide composite multifilament manufacturing method.

In addition, it provides a polyetherimide and polyphenylene sulfide composite multifilament manufacturing method characterized in that the stretching at a stretching ratio of 2.0 to 4.0 times in the stretching step.

As described above, the polyetherimide and polyphenylene sulfide composite multifilament according to the present invention uses a polyetherimide resin in the sheath part and a polyphenylene sulfide resin in the core part, so that it has excellent spinnability and can be used as a multifilament It works.

In addition, the polyetherimide and polyphenylene sulfide composite multifilament of the present invention is cut to a certain length and used as a long fiber rather than a short fiber, so that flame retardancy and heat resistance are excellent.

In addition, the polyetherimide and polyphenylene sulfide composite multifilament manufacturing method of the present invention has an effect of excellent processability by optimizing the spinning and drawing steps.

1 is a view briefly showing a second step of a method for manufacturing a polyetherimide and polyphenylene sulfide composite multifilament according to the present invention.

Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. First of all, it should be noted that in the drawings, the same components or parts are denoted by the same reference numerals as much as possible. In describing the present invention, detailed descriptions of related known functions or configurations are omitted in order not to obscure the gist of the present invention.

As used herein, the terms 'about', 'substantially', and the like are used in a sense at or approximating that number when manufacturing and material tolerances inherent in the stated meaning are given, and are intended to convey an understanding of the present invention. Accurate or absolute figures are used to help prevent exploitation by unscrupulous infringers of the disclosed disclosure.

1 is a view briefly showing a second step of a method for manufacturing a polyetherimide and polyphenylene sulfide composite multifilament according to the present invention.

The present invention relates to a sheath-core polyetherimide and polyphenylene sulfide composite multifilament formed of a sheath part and a core part.

When the polyphenylene sulfide resin is spun alone to make fibers, cutting problems due to poor solidification and poor crimp expression during the stretching process may occur. and a polyetherimide and polyphenylene sulfide composite multifilament using a polyphenylene sulfide resin in the core portion.

[Formula 1]

The polyetherimide resin forming the sheath portion is a polymer resin having a chemical structure as shown in Chemical Formula 1, and has a higher melting point and a higher limiting oxygen index than polyphenylene sulfide resin, thereby exhibiting excellent flame retardancy and heat deflection temperature. is 200 ℃, it has better thermal stability and chemical resistance than polyphenylene sulfide resin, which has a heat distortion temperature of 110 ~ 120 ℃.

In addition, the polyetherimide resin is a resin having a lower smoke amount than general polymer resins during combustion, and when used as a sheath part of a composite multifilament, it has excellent dimensional stability at high temperatures and excellent smoke amount when a fire occurs, so it has properties suitable for high-temperature work can be granted

It is preferable to use the polyetherimide resin having a melt flow index of 10 to 50 g/10 min at 337° C. and a load of 6.6 kg.

The polyphenylene sulfide resin forming the core part is a crystalline engineering plastic having a relative viscosity of 0.1 to 10, and has high heat resistance and excellent mechanical properties, chemical resistance, electrical properties, and dimensional stability. Examples of applications include electric/electronic parts, automobile parts, mechanical parts, and the like.

In addition, the polyphenylene sulfide resin may be a linear, cross-linked, or semi-cross-linked polymer, but it is preferably linear, has a weight average molecular weight (Mw) of 2,000 to 8,000, and melts at 300 ° C and a load of 2.16 kg. A melt flow index of 20 to 150 g/10 min may be used, and a melt flow index of 30 to 100 g/10 min may be preferable.

Preferably, the sheath part and the core part are formed in an area ratio of 7:3 to 3:7.

When the cross-sectional area of the core portion exceeds 70%, eccentricity of the core portion on one side of the fiber occurs or a phenomenon in which the core portion protrudes to the surface of the fiber during the spinning process (or post-process) occurs, resulting in heat resistance and Chemical resistance may be lowered, and if the cross-sectional area of the core part is less than 30%, it is difficult for the core part to be positioned on the central axis of the fiber during spinning, and accordingly, spinning processability and manufacturing cost reduction effect may be reduced.

Although the fineness and number of filaments of the polyetherimide and polyphenylene sulfide composite multifilament can be adjusted according to the purpose of use, it is preferable to have a fineness of 250 to 700 denier and a filament number of 70 to 200 for manufacturing processability. will be.

In addition, if the single yarn fineness of the polyetherimide and polyphenylene sulfide composite multifilament is less than 2 denier, the spinning and drawing processability may be deteriorated.

As described above, the polyetherimide and polyphenylene sulfide composite multifilament according to the present invention can be manufactured by including a spinning step, a cooling step, a first winding step, a drawing step, and a second winding step, and the 2 steps of the first process of manufacturing undrawn yarn (POY) through the spinning step and the first winding step and the second process of manufacturing the undrawn yarn into the drawn yarn (FDY) through the drawing step and the second winding step. ) process, it will be possible to improve the manufacturing processability and physical properties of the composite multifilament.

The first process is a process of manufacturing undrawn yarn (POY) through a spinning step and a first winding step. In the spinning step, the sheath part is polyetherimide resin, and the core part is polyphenylene sulfide resin In the step of composite spinning in the form of a sheath-core to make fibers, it will be possible to spin at a spinning temperature of about 270 to 350 ° C using a general composite spinning device.

The first winding step is a step of manufacturing an undrawn yarn by winding the spun composite multifilament at 1000 to 2500 m/min.

If the winding speed in the first winding step is too low, the elongation rate is too low, and a trimming phenomenon may occur in the second process afterwards, resulting in a decrease in fairness. properties may deteriorate.

The second process is a process of manufacturing undrawn yarn into drawn yarn (FDY) through a drawing step and a secondary winding step, and is performed through a plurality of rollers.

The second process may be performed by, for example, the roller 100 on which the unstretched yarn is wound, the drawing rollers 210 and 230 for stretching, and the take-up roller 300 for winding, as shown in FIG. 1 .

A shrinking step may be further performed by further forming a shrinking roller 250 between the stretching rollers 210 and 230 and the winding roller 300 .

The drawing step is a step of drawing the wound unstretched yarn using two or more rollers, and it is preferable to draw at a speed of 300 to 600 m/min to suppress thread breakage during drawing.

In the drawing step, the processability of the composite multifilament can be improved by controlling the drawing temperature, and it is preferable that the temperature of the first drawing roller is 70 to 100 ° C and the temperature of the last drawing roller is 180 to 250 ° C.

That is, when manufacturing with the apparatus as shown in FIG. 1, the temperature of the first elongating roller 210 is 70 to 100 ° C, and the temperature of the last elongating roller 230 is preferably 150 to 250 ° C.

If the drawing temperature is too high when the unstretched yarn is started to be drawn, the crystallinity of the polyetherimide resin and the polyphenylene sulfide resin rapidly progresses, and the orientation ratio is lowered during drawing, which may lower the strength of the composite multifilament. The temperature of the stretching roller is a very important factor.

The first elongation roller 210 in the elongation step begins elongation in a low temperature state, and the elongation roller 230, which is the last elongation finish, gives a heat treatment effect to the composite multifilament elongated at a high temperature of 150 to 250 ° C. to increase strength. can be maintained

In the stretching step, the stretching ratio may be adjusted in consideration of the stretching ratio in the first step, but if the stretching ratio is too large, the stretching processability may be deteriorated, so it is preferable to stretch the film by about 2.0 to 4.0 times.

It will be possible to further improve the manufacturing processability of the composite multifilament by further performing a shrinking step after the stretching step.

The shrinking step is a step of shrinking the stretched composite multifilament at an overfeed of 0.95 to less than 1.0, and is a step performed between the last drawing roller and the next roller in the drawing step. That is, in FIG. 2, it is a step between the last elongation roller 230 and the shrinking roller 250.

The shrinking step is a step performed continuously with the stretching step, and the manufacturing processability can be improved by causing the composite multifilament to shrink by relaxing the high-temperature composite multifilament with an overfeed of 0.95 to less than 1.0 with the last drawing roller.

The second winding step is a winding step of winding the contracted composite multifilament.

The polyetherimide and polyphenylene sulfide composite multifilament according to the present invention manufactured by the first process of spinning to produce undrawn yarn (POY) and the second process of manufacturing undrawn yarn into drawn yarn (FDY) as described above A polyetherimide and polyphenylene sulfide composite multifilament having excellent physical properties can be manufactured with high manufacturing processability through the control of the stretching temperature in the stretching step.

The polyetherimide and polyphenylene sulfide composite multifilament of the present invention can be used in the form of long fibers rather than short fibers, and has high flame retardancy, heat resistance and chemical resistance, so that it can be used in industrial fields such as battery separators, dust collector filters, and interior materials for automobiles. It can be used in various fields such as industrial protective clothing, protective clothing field of protective gloves, interior field of curtains, sofas, and bedding.

Hereinafter, the present invention will be explained through examples. The following examples are only for a more accurate understanding of the present invention, but do not limit the protection scope of the present invention.

Example 1, 2

Polyetherimide resin with a melt flow index of 30g/10min is used as the sheath part, and polyphenylene sulfide resin with a melt flow index of 80g/10min is used as the core part. First winding was performed to prepare unstretched yarn.

The prepared unstretched yarn was drawn at a draw ratio of 3 times using the same device as in FIG. 2, a contraction step was performed at an overfeed of 0.99, and a second winding was performed to prepare 530D/144F polyetherimide and polyphenylene sulfide composite multifilaments. did

Table 1 shows the cross-sectional area ratio of the sheath part to the core part and the temperature of the drawing roller of the above embodiments.

Comparative Example 1

Polyphenylene sulfide resin with a melt flow index of 80g/10min is used as the sheath part, and polyetherimide resin with a melt flow index of 30g/10min is used as the core part, and the spinning temperature is 290℃. First winding was performed to prepare unstretched yarn.

The prepared unstretched yarn was drawn at twice the draw ratio using the same device as in FIG. 2, and a contraction step was performed with an overfeed of 0.99, followed by secondary winding to produce 530D/144F polyphenylene sulfide and polyethylene terephthalate composite multifilaments. did

Table 1 shows the cross-sectional area ratio of the sheath part to the core part and the temperature of the drawing roller in Comparative Example 1.

Comparative Example 2

Polyphenylene sulfide resin with a melt flow index of 80 g/10 min was used as the sheath part and polyethylene terephthalate resin with an intrinsic viscosity of 0.8 dl/g was used as the core part. The unstretched yarn was prepared by first winding at a speed of .

The prepared unstretched yarn was drawn at twice the draw ratio using the same device as in FIG. 2, and a contraction step was performed at an overfeed of 0.90, and a second winding was performed to prepare 530D/144F polyphenylene sulfide and polyethylene terephthalate composite multifilaments. did

Table 1 shows the cross-sectional area ratio of the sheath part to the core part and the temperature of the drawing roller in Comparative Example 2.

Comparative Example 3

A polyphenylene sulfide resin having a melt flow index of 80 g/10 min was individually spun at a spinning temperature of 290° C. and then primarily wound at a speed of 2,000 m/min to prepare an undrawn yarn.

The prepared unstretched yarn was drawn at a draw ratio of 2 times using the same device as in FIG. 2, a contraction step was performed at an overfeed of 0.90, and a second winding was performed to prepare 530D/144F polyphenylene sulfide multifilaments.

The temperature of the stretching roller of Comparative Example 3 is shown in Table 1.

◈ Evaluation of composite multifilament

The flame retardancy, smoke density, dry heat shrinkage, and strength retention after heat resistance and alkali resistance tests of the composite multifilaments of Examples 1 and 2 and Comparative Examples 1 to 3 were measured, and are shown in Table 1.

* Melt flow index: The amount of polyetherimide resin flowing for 10 minutes was measured by the ASTM D1238 method under the conditions of 337 ° C and 6.6 kgf load. The amount of polyphenylene sulfide resin flowing for 10 minutes was measured by the ASTM D1238 method under a load condition of 2.16 kgf at 300 °C.

* Flame retardancy: Evaluated by UL94 by UL (Underwriters Laboratories) method

* Smoke density: Measured in accordance with KS M ISO 5659-2 (Flamming Mode measurement). Using a burner with a flame length of 30 mm in the state of radiant heat of 25 kW/㎡ (measured by dividing it into 1.5 minutes and 4.0 minutes)

* Dry heat shrinkage rate: Change in length before and after 30 minutes of treatment in a dry heat hot air dryer at the set temperature

* Chemical resistance evaluation: Tensile strength was evaluated before and after treatment at 90 ° C for 72 hours in a 0.25 g / L Ca (OH) ₂ solution.

* Heat resistance evaluation: Tensile strength was evaluated before and after 24 hr treatment in a hot air oven at 200 ° C.

* Strength retention rate: [strength before heat resistance (alkali resistance) treatment - strength after treatment] / strength before heat resistance (alkali resistance) treatment * 100 (%)

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 profit sheath PEI PEI PPS PPS PPS core part PPS PPS PEI PET - Sheath part: core part (weight ratio) 70:30 50:50 30:70 70:30 100:0 Temperature of the first drawing roll (℃) 80 80 90 90 90 Last drawing roller temperature (℃) 180 180 200 200 200 flame retardant UL94-0 UL94-0 UL94-0 UL94-2 UL94-0 smoke density 1.5min 5 7 5 38 12 4min 8 9 8 67 17 200℃ dry heat shrinkage (%) 2.80 3.10 5.1 6.5 5.2 220℃ dry heat shrinkage (%) 3.20 4.20 5.3 7.4 5.8 robbery
Retention rate (%) Alkali resistance (CaOH ₂ ) 99 98.9 97.8 90.6 97.2 Heat resistance (200℃) 98.7 98.4 98.1 89.5 95.7

As shown in Table 1, in the case of flame retardancy, it can be seen that all of them have excellent flame retardancy as UL94-0 except for Comparative Example 2 using a polyethylene terephthalate resin.

In the case of smoke density, it can be seen that the amount of smoke is small in Example 1 and Comparative Example 1, which have a high polyetherimide resin content, and Examples 1 and 2 have a higher smoke density than Comparative Examples 2 and 3, which do not use polyetherimide resin It can be seen that there is a low smoke amount during combustion.

The polyetherimide and polyphenylene sulfide composite multifilaments of Examples 1 and 2 prepared under the manufacturing conditions of the present invention have excellent dry heat shrinkage compared to Comparative Examples 1 to 3 because the sheath portion is formed of polyetherimide resin, and heat resistance And it can be seen that the alkali resistance is also better.

Claims (6)

In a sheath-core type polyetherimide and polyphenylene sulfide composite multifilament formed of a sheath part and a core part,
The sheath part is formed of polyetherimide resin,
The polyetherimide and polyphenylene sulfide composite multifilament, characterized in that the core portion is formed of polyphenylene sulfide resin. According to claim 1,
The sheath part and the core part are formed in an area ratio of 7: 3 to 3: 7, characterized in that polyetherimide and polyphenylene sulfide composite multifilament. According to claim 1,
The composite multifilament is a polyetherimide and polyphenylene sulfide composite multifilament, characterized in that the fineness of 250 to 500 denier, the number of filaments is 70 to 150, and the single yarn fineness is 2 denier or more. In the sheath-core type composite multifilament manufacturing method formed of the sheath part and the core part,
a spinning step of composite spinning in a sheath-core form by using polyetherimide resin for the sheath part and polyphenylene sulfide resin for the core part;
A first winding step of manufacturing an undrawn yarn by winding the spun composite multifilament at 1000 to 2500 m/min;
A drawing step of drawing the wound unstretched yarn at a speed of 300 to 600 m/min using two or more rollers;
A method for manufacturing polyetherimide and polyphenylene sulfide composite multifilament comprising a second winding step of winding the composite multifilament. According to claim 4,
Polyetherimide and polyphenylene sulfide composite multifilament manufacturing method, characterized in that the temperature of the first elongation roller in the elongation step is 70 ~ 100 ℃ and the temperature of the last elongation roller is 150 ~ 250 ℃. According to claim 4,
Polyetherimide and polyphenylene sulfide composite multifilament manufacturing method, characterized in that in the stretching step, stretching at a stretching ratio of 2.0 to 4.0 times.

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