KR102183246B1 - Polyphenylene Sulfide conjugate multi filament, AND MANUFACTURING METHOD THEREOF - Google Patents

Abstract

The present invention provides a sheath-core type polyphenylene sulfide composite multifilament formed of a sheath portion and a core portion. The sheath portion is formed of a polyphenylene sulfide resin, and the core portion is formed of a polyester-based resin having an intrinsic viscosity of 0.80 to 1.20 dl/g. Provided are the polyphenylene sulfide composite multifilament and a manufacturing method thereof.

Description

Polyphenylene sulfide conjugate multi filament, AND MANUFACTURING METHOD THEREOF}

The present invention relates to a polyphenylene sulfide composite multifilament and a method for producing the same, and to a polyphenylene sulfide composite multifilament having excellent heat resistance and chemical resistance as a composite multifilament in which a polyphenylene sulfide resin forms a sheath portion and a method for producing the same. will be.

Polyphenylene sulfide fiber has a variety of markets, including not only the industrial field of battery separators, dust collector filters, and interior materials for automobiles, but also the interior field of wallpaper, curtains, sofas, and bedding, industrial protective clothing, and protective clothing of protective gloves. In recent years, as the demand for chemical resistance and flame retardant function increases, the usage is increasing.

In particular, as a filter material used for filters in filter cloth dust collectors, unlike non-woven fabric made of glass fiber (Glass), meta aramid (MA), Teflon (PTFE), polyimide (PI), etc., it is made from polyphenylene sulfide fiber. The prepared nonwoven fabric is attracting attention as a heat-resistant filter material due to excellent heat resistance, chemical resistance, low absorption characteristics, and morphological 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 bundle of filaments having a plurality of filaments, cooling and solidifying, and then putting them into a plurality of cans; And, the step of multi-stage stretching the filament bundles in the plurality of cans; to be manufactured through.

However, since these polyphenylene sulfide fibers have disadvantages such as high cost of polymer and poor crimp expression in the stretching process and cutting due to poor solidification during the spinning process, the yield can be improved by improving the fairness of the PPS fiber. It is a situation that requires skills that are available.

As a technology for improving the fairness of polyphenylene sulfide fibers, German Patent DE 4006397 related to a technology for manufacturing polyphenylene sulfide multifilaments by applying hot air or inert gas under a spinneret and then performing a stretching process. , Japanese Laid-Open Patent Publication No. 1991-168750, and a polyphenylene sulfide resin related to a technology of thermally stretching the spun polyphenylene sulfide fiber by blowing an air stream of 45° C. or higher and passing it through a heated area. It is melted at a temperature of 340°C and continuously spun through a hole having a diameter of 0.1 to 0.5 mm of a spinneret to produce a multifilament, which is passed through a high-temperature atmosphere sealed by an insulating tube or a heating tube, and then 100°C. There is Japanese Laid-Open Patent Publication No. 1990-219475 related to a technique of cooling by the following hot air flow or cold air flow.

In addition, patents related to polyphenylene sulfide fibers used as filter materials include European Patent No. 386,975 using polyphenylene sulfide fibers for filtration of hot gases, and polyphenylene sulfide and acrylic fibers. There is PCT-US2007-019827 for a phenylene sulfide bag filter.

The above technologies introduce polyphenylene sulfide fiber into a dust collecting filter that requires heat resistance, which has the significance of improving the filter characteristics, but spinning defects that occur during the cooling and solidification process when the molten polymer is continuously passed through a spinneret. I have the problem as it is.

Due to the above-described poor spinning, most polyphenylene sulfide fibers are composites using polyphenylene sulfide resin in the sheath part and polyester resin, polyamide resin, and polyolefin resin in the core part for spinning property. After being made of fiber, it has been cut to a certain length to produce short fibers, and then made of spun yarn and used.

However, in the polyphenylene sulfide composite fiber used in the form of a spun yarn as described above, the resin of the core portion is exposed at both ends of the short fiber, resulting in a problem of lowering heat resistance and chemical resistance.

In order to solve the above problems, Korean Patent No. 1783335 developed a polyphenylene sulfide composite fiber manufactured by adding a hydrolysis resistant agent to the core part, but the production cost was increased due to the hydrolysis resistant agent contained in the core part. There is a problem in that fairness and physical properties of the polyphenylene sulfide composite fiber are deteriorated due to the inclusion of a hydrolysis resistant agent.

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

In addition, an object of the present invention is to provide a polyphenylene sulfide composite multifilament having excellent heat resistance and chemical resistance by cutting a polyphenylene sulfide composite multifilament into a predetermined length and using it as a long fiber rather than a short fiber.

In addition, it is an object of the present invention to provide a manufacturing method capable of manufacturing a polyphenylene sulfide composite multifilament having excellent physical properties by improving spinning and stretching properties of the polyphenylene sulfide composite multifilament.

In order to solve the above problems, the present invention in the cis-core type polyphenylene sulfide composite multifilament formed of a sheath portion and a core portion, the sheath portion is formed of a polyphenylene sulfide resin, the The core portion provides a polyphenylene sulfide composite multifilament, characterized in that it is formed of a polyester resin having an intrinsic viscosity of 0.80 to 1.20 dl/g.

In addition, the sheath portion and the core portion provides a polyphenylene sulfide composite multifilament, characterized in that formed in an area ratio of 7:3 to 5:5.

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

In addition, the present invention in the cis-core type polyphenylene sulfide composite multifilament manufacturing method formed of a cis portion and a core portion, the sheath portion polyphenylene sulfide (Polyphenylene sulfide) resin, the core portion has an intrinsic viscosity of 0.80 ~ Spinning step of composite spinning in a cis-core form using a polyester-based resin of 1.20 dl/g; A cooling step of cooling the spun composite multifilament below 20°C; The first winding step of manufacturing undrawn yarn by winding the cooled composite multifilament at 1500-2500m/min; A drawing step of drawing the wound undrawn yarn at a speed of 300 to 500 m/min using two or more rollers; A contraction step of contracting the stretched composite multifilament to an over feed of 0.8 to 0.95; And, it provides a polyphenylene sulfide composite multifilament manufacturing method comprising a secondary winding step of winding the contracted composite multifilament.

In addition, it provides a polyphenylene sulfide composite multifilament manufacturing method, characterized in that the temperature of the first stretching roller in the stretching step is 70 ~ 90 ℃ and the temperature of the last stretching roller is 180 ~ 250 ℃.

In addition, it provides a method for producing a polyphenylene sulfide composite multifilament, characterized in that stretching at a draw ratio of 2.0 to 2.5 times in the stretching step.

In addition, the shrinking step provides a method for producing a polyphenylene sulfide composite multifilament, characterized in that it is carried out between the last stretching roller of the stretching step and the next roller.

In addition, it provides a polyphenylene sulfide composite multifilament manufacturing method, characterized in that the temperature of the first roller in the stretching step is 70 ~ 100 ℃ and the temperature of the last roller is 180 ~ 250 ℃.

As described above, the polyphenylene sulfide composite multifilament according to the present invention uses a polyphenylene sulfide resin in the sheath part and a polyester resin of high viscosity in the core part, so it has excellent spinnability and can be used as a multifilament. have.

In addition, the polyphenylene sulfide composite multifilament of the present invention is cut to a certain length and used as long fibers rather than short fibers, thereby having excellent heat resistance and chemical resistance.

In addition, the method of manufacturing a polyphenylene sulfide composite multifilament of the present invention has excellent processability by optimizing the spinning and stretching steps.

1 is a view showing a process chart of a method for manufacturing a polyphenylene sulfide composite multifilament according to the present invention.
2 is a schematic view showing a second process of the method for manufacturing a 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 represent the same reference numerals as possible. 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.

FIG. 1 is a view showing a process chart of a method for producing a polyphenylene sulfide composite multifilament according to the present invention, and FIG. 2 is a view schematically showing a second process of a method for producing a polyphenylene sulfide composite multifilament according to the present invention.

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

When the polyphenylene sulfide resin is single-spinned to form fibers, a cutting problem due to poor solidification and a problem of poor crimp expression during the stretching process may occur.Therefore, the present invention provides a poly(polyphenylene sulfide) resin using a polyester resin in the core. It is a phenylene sulfide complex multifilament.

Polyphenylene sulfide resin forming the sheath 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 the application include electric/electronic parts, automobile parts, and mechanical parts.

In addition, the polyphenylene sulfide resin may be a linear, crosslinked, or semi-crosslinked polymer, but it is preferably linear, and the weight average molecular weight (Mw) is 2,000 to 8,000, and the melt flow index is 20 to 150g/10min can be used.

In addition, in order to use the mechanical and chemical durability of polyphenylene sulfide as a car interior material, black color is required. Can be excellent. It is preferable to use the fusion process mainly when expressing the basic colors such as black, indigo, and brown.

The core portion is formed of a polyester resin, and various polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polytrimethylene terephthalate resin may be used.

It is preferable to use a polyester-based resin having an intrinsic viscosity of 0.80 to 1.20 dl/g in order to improve the spinning processability and the strength of the composite multifilament produced for the polyester-based resin of the core part.

It is preferable that the sheath portion and the core portion are formed in an area ratio of 7:3 to 5:5.

When the cross-sectional area of the core portion exceeds 50%, eccentricity in which the core portion is biased toward one side from the fiber or a phenomenon in which the core portion protrudes to the fiber surface during the spinning process (or post-process) occurs, so that the heat resistance of the fiber and Chemical resistance may be deteriorated, and if the cross-sectional area of the core portion is less than 30%, it is difficult to position the core portion on the central axis of the fiber during spinning, and accordingly, the spinning processability and manufacturing cost reduction effect may be deteriorated.

The polyphenylene sulfide composite multifilament may adjust the fineness and the number of filaments according to the purpose of use, but it is preferable that the polyphenylene sulfide composite multifilament is formed with a fineness of 250 to 500 denier and 70 to 150 filaments for manufacturing processability.

In addition, if the single yarn fineness of the polyphenylene sulfide composite multifilament is less than 2 denier, the spinning and stretching processability may be deteriorated, so it is preferable that the single yarn fineness of the polyphenylene sulfide composite multifilament is 2 denier or more.

As described above, the polyphenylene sulfide composite multifilament according to the present invention includes a spinning step, a cooling step, a first winding step, a stretching step, a shrinking step, and a second winding step, as shown in FIG. A filament can be manufactured, and as shown in FIG. 1, undrawn yarn through the first process of manufacturing undrawn yarn (POY) through the spinning step, the cooling step, and the first winding step, and the drawing step, the shrinking step, and the second winding step. The manufacturing processability and the physical properties of the polyphenylene sulfide composite multifilament may be improved by manufacturing it in a two-step process of the second process of manufacturing a drawn yarn (FDY).

The first process is a process of manufacturing undrawn yarn (POY) through a spinning step, a cooling step, and a first winding step.The sheath part of the spinning step is a polyphenylene sulfide resin, and the core part has an intrinsic viscosity of 0.80. This is the step of forming fibers by composite spinning in a sheath-core form using a polyester resin of ~1.20 dl/g. Using a general composite spinning device, the spinning temperature will be about 270~350℃.

The cooling step is a step of cooling the spun composite multifilament at 20°C or less. The cooling temperature is a step before the first winding step at the discharge port, and the temperature in the cooling step is 20°C or less to increase crystallization of the polyphenylene sulfide resin. It is preferable, and more preferably, it is 10-20 degreeC.

In the cooling step, if the cooling temperature is too low or exceeds 20°C, the crystallinity of the spun composite multifilament decreases, and thus spinning processability and physical properties of the composite multifilament may be deteriorated.

The first winding step is a step of manufacturing an undrawn yarn by winding the cooled composite multifilament at 1500-2500m/min.

If the winding speed in the first winding step is too low, the elongation rate is too low, and then trimming may occur in the second step, thereby reducing fairness. If the winding speed is too fast, the elongation in the first step becomes too large and the cooling step Because cooling is not smooth at, the properties of the composite multifilament may deteriorate.

The second process is a process of manufacturing undrawn yarn into drawn yarn (FDY) through a stretching step, a shrinking step, and a second winding step, and is carried out through a plurality of rollers.

The second process includes, for example, a roller 100 in which undrawn yarn is wound and a stretching roller 210 and 230 for stretching, a shrink roller 250 for contracting by giving an opfeed, and a winding roller 300 for winding. You can do it.

The stretching step is a step of stretching the wound undrawn yarn using two or more rollers, and it will be preferable to stretch at a speed of 300 to 500 m/min in order to suppress the trimming phenomenon during stretching.

It is preferable that the temperature of the first drawing roller is 70 to 90°C and the temperature of the last drawing roller is 180 to 250°C, as it is possible to increase the fairness of the composite multifilament by controlling the drawing temperature in the drawing step.

That is, when manufacturing with the apparatus as shown in FIG. 2, the temperature of the first drawing roller 210 is 70 to 90°C, and the temperature of the last drawing roller 230 is preferably 180 to 250°C.

If the stretching temperature is too high when starting the stretching of the undrawn yarn, the crystallinity of the polyphenylene sulfide resin proceeds rapidly, and the orientation rate during stretching may decrease, thereby reducing the strength of the composite multifilament. Therefore, the temperature of the first stretching roller in the stretching step is It would be a very important factor.

The first stretching roller 210 in the stretching step starts stretching at a low temperature, and the last stretching roller 230 at which the stretching is completed provides a heat treatment effect of the composite multifilament stretched at a high temperature of 180 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 about 2.0 to 2.5 times.

The shrinking step is a step of shrinking the stretched composite multifilament with an over feed of 0.8 to 0.95, and is a step performed between the last stretching roller of the stretching step and the next roller. That is, in FIG. 2, this is a step between the last stretching roller 230 and the shrinking roller 250.

The shrinking step is a step carried out continuously with the stretching step, and the composite multifilament in a high temperature state is relaxed with an overfeed of 0.8 to 0.95 with the last stretching roller to cause the composite multifilament to shrink.

Through the shrinking step, the polyphenylene sulfide composite multifilament of the present invention has a low dry heat shrinkage.

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

The polyphenylene sulfide composite multifilament according to the present invention, which is produced by spinning as described above, in the first process of producing undrawn yarn (POY) and the second process of producing undrawn yarn into drawn yarn (FDY), is used in the cooling step. By controlling the cooling temperature and the stretching temperature in the stretching step, it is possible to manufacture a polyphenylene sulfide composite multifilament having excellent physical properties with high manufacturing processability.

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

Hereinafter, the present invention will be described through examples. The following examples are only for understanding the present invention more accurately, and do not limit the scope of the present invention.

Examples 1 and 2 and Comparative Examples 1 to 3

Using polyphenylene sulfide resin with a relative viscosity of 0.3 as the cis part and polyethylene terephthalate resin as the core part, the spinning temperature was mixed at 290°C, cooled, and first wound at a speed of 2,000 m/min to produce undrawn yarn. I did.

The prepared undrawn yarn was stretched at twice the draw ratio using the same device as in FIG. 2, the shrinking step was performed with an overfeed of 0.90, and a second winding was performed to prepare a polyphenylene sulfide composite multifilament of 330D/72F.

Table 1 shows the intrinsic viscosity of the core part, the cross-sectional area ratio of the sheath part to the core part, the cooling temperature, and the stretching roller temperature of the above examples and comparative examples.

◈ Evaluation of polyphenylene sulfide complex multifilament

The stretching processability, strength, heat resistance, and strength retention rate after the alkali resistance test of the polyphenylene sulfide composite multifilaments of Examples 1 and 2 and Comparative Examples 1 to 3 were measured, and are shown in Table 1.

* Relative viscosity is determined by dissolving the sample at a concentration of 0.5% in a solvent (a mixture of phenol and ethane tetrachloride in a weight ratio of 5:5) and using an Ubbelohde type viscometer set in a thermostat adjusted to a constant temperature. The flow time (sec) of is calculated, and the relative viscosity is obtained by the flow time (sec) of the same volume of solvent.

* Stretching processability evaluation: Grade 1 production/total production*100 = yield (based on weight)

* Strength: measured by the KS K 0860 method

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

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Suzy Sheath PPS PPS PPS PPS PPS Core part (intrinsic viscosity) PET(0.8) PET(0.8) PET(0.8) PET(0.6) PET(0.8) Sheath: Core (weight ratio) 50:50 70:30 50:50 50:50 70:30 Cooling step temperature (℃) 15 15 15 15 25 First drawing roll temperature (℃) 80 80 100 80 80 Last draw roller temperature (℃) 200 200 200 200 200 Stretch fairness (%) 95 91 92 53 70 Strength (g/d) 4.81 4.57 3.56 4.10 3.42 burglar
Retention rate
(%) Heat resistance (180℃) 91.9 95.8 90.7 88.5 87.7 Alkali resistance
(CaOH ₂ ) 90.6 96.7 87.2 89.6 86.4

As shown in Table 1, it can be seen that the polyphenylene sulfide composite multifilament of Examples 1 and 2 prepared under the manufacturing conditions of the present invention has superior strength and strength retention compared to Comparative Examples 1 to 3.

In addition, as in Comparative Example 1, when the temperature of the first drawing roller in the drawing step exceeds 90°C, the strength decreases, and as in Comparative Example 2, when the intrinsic viscosity of the polyester-based resin in the core portion is lower than 0.8 It can be seen that the strength is low, and the strength retention rate in heat resistance-alkali resistance is low, and as in Comparative Example 3, when the cooling temperature in the first process exceeds 20°C, the strength is low, and the strength retention rate in heat resistance-alkali resistance You can see that this is falling.

Therefore, in the polyphenylene sulfide composite multifilament of the present invention, it can be seen that the cooling temperature in the cooling step and the temperature of the first drawing roll in the drawing step are very important factors in manufacturing.

◈ Comparison of heat resistance and chemical resistance between Examples 1 and 2 and polyphenylene sulfide spun yarn

The heat resistance and chemical resistance of the spun yarn made of 100% polyphenylene sulfide short fiber and the polyphenylene sulfide composite multifilament of Example 1,2 were evaluated and shown in Tables 2 and 3.

* Heat resistance evaluation: The tensile strength before and after 24 hours treatment in a 180,200,220°C hot air oven was evaluated.

* Evaluation of chemical resistance: In 0.25g/L Ca(OH) ₂ solution, the tensile strength before and after treatment at 90° C. * 72 hours was evaluated.

division Before treatment After treatment 180℃ 200℃ 220℃ burglar
(g/d) cotton yarn 3.40 3.10 2.90 2.88 Example 1 4.81 4.42 4.10 4.10 Example 2 4.57 4.38 4.00 3.96 Strength reduction rate
(%) cotton yarn - 8.8 14.7 15.3 Example 1 - 8.1 14.8 14.8 Example 2 - 4.2 12.5 13.3

As shown in Table 2, in Examples 1 and 2 of the present invention, it can be seen that the strength reduction rate is lower than that of the spun yarn made of only short polyphenylene sulfide fibers in high-temperature hot air, and has heat resistance.

division Before treatment After treatment burglar
(g/d) cotton yarn 3.4 3.06 Example 1 4.81 4.36 Example 2 4.57 4.42 Strength reduction rate
(%) cotton yarn - 10 Example 1 - 9.4 Example 2 - 3.3

As shown in Table 3, in Examples 1 and 2 according to the present invention, it can be seen that the strength reduction rate in the treatment of CaOH ₂ was much lower than that of the spun yarn made of only short polyphenylene sulfide fibers, and thus, the chemical resistance was very excellent.

Claims (7)

delete delete delete In the method for producing a cis-core polyphenylene sulfide composite multifilament formed of a sheath portion and a core portion,
A spinning step of complex spinning in a cis-core form using a polyphenylene sulfide resin for the sheath portion and a polyester resin having an intrinsic viscosity of 0.80 to 1.20 dl/g for the core portion;
A cooling step of cooling the spun composite multifilament below 20°C;
The first winding step of producing undrawn yarn by winding the cooled composite multifilament at 2000m/min;
A drawing step of drawing the wound undrawn yarn at a speed of 300 to 500 m/min using two or more rollers;
A contraction step of contracting the stretched composite multifilament to an over feed of 0.8 to 0.95; And,
Polyphenylene sulfide composite multifilament manufacturing method comprising a second winding step of winding the contracted composite multifilament. The method of claim 4,
Polyphenylene sulfide composite multifilament manufacturing method, characterized in that the temperature of the first stretching roller in the stretching step is 70 ~ 90 ℃ and the temperature of the last stretching roller is 180 ~ 250 ℃. The method of claim 4,
Polyphenylene sulfide composite multifilament manufacturing method, characterized in that stretching at a draw ratio of 2.0 to 2.5 times in the stretching step. The method of claim 4,
The shrinking step is a polyphenylene sulfide composite multifilament manufacturing method, characterized in that it is carried out between the last stretching roller of the stretching step and the next roller.

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