KR20140090326A - PPS resin composition and method for preparing PPS fibers - Google Patents

Abstract

The present description may provide a polyphenylene sulfide resin composition including a polyphenylene sulfide resin and carbon nanotube and a method for preparing a polyphenylene sulfide fiber, wherein the carbon nanotube is dispersed in the polyphenylene sulfide resin and is mixed with the polyphenylene sulfide resin, thereby restraining the increase of a pack pressure during spinning fiber and improving fiber strength.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition,

The present invention relates to a polyphenylene sulfide resin composition and a method for producing polyphenylene sulfide fibers, and more specifically, polyphenylene sulfide resin; And a carbon nanotube dispersed in the polyphenylene sulfide resin. The polyphenylene sulfide resin composition and the polyphenylene sulfide resin composition, which have an increased fiber strength while suppressing an increase in pack pressure during fiber spinning, And a method for producing the fiber.

Polyphenylene sulfide resin (hereinafter referred to as "PPS resin") is a semicrystalline thermoplastic resin which is a resin belonging to the super engineering plastic group having high heat resistance, chemical resistance, self flame retardancy, and insulation, and its chemical structure is a para- Is a rigid polymer with a sulfur atom attached to it.

The characteristics of PPS resin are that the heat distortion temperature is over 260 ° C and the long-term usable temperature of UL standard is 240 ° C, which is the highest level of heat resistance. Another characteristic of PPS resins is that they have excellent chemical resistance. No organic solvents have been found to dissolve PPS resins at temperatures below 200 ° C, and they have chemical resistance next to fluororesin (PTFE).

Currently, PPS resin is used mainly in electrical and electronic parts and automobile parts by compounding more than 85% of the total market with other fillers, and the fiber and related products are estimated to be less than 15%.

PPS resin has been known as the most suitable resin for harsh environmental conditions (high temperature, acid, alkali, etc.) due to its high heat resistance, self-flame resistance and excellent chemical resistance. However, Only a wide range of PPS resins were produced and were not suitable for use in textiles.

In fact, the PPS resin having a small molecular weight was intended to increase the molecular weight of the PPS resin to induce crosslinking reaction between the PPS resin through aging after polymerization and to increase the molecular weight to use the PPS resin for the fiber. However, the unevenness of the fiber property due to the unevenness of the crosslinking reaction, In addition, since the PPS branching chain is weakened and cut off due to excessive oxidation, and a large amount of gel is generated, it causes production problems such as frequent cutting of fiber yarn during fiber spinning.

It is an object of the present invention to provide a polyphenylene sulfide resin composition and a method for producing polyphenylene sulfide fiber having an improved fiber strength while suppressing an increase in pack pressure during fiber spinning .

The above object of the present invention can be achieved by the present invention described below.

According to the present invention, polyphenylene sulfide resin; And a carbon nanotube, wherein the carbon nanotube is dispersed and mixed in the polyphenylene sulfide resin to provide a polyphenylene sulfide resin composition.

Further, according to the present invention, there is provided a process for producing polyphenylene sulfide fibers obtained by kneading the polyphenylene sulfide resin composition, followed by melt spinning, winding and stretching.

The present invention will be described in more detail as follows.

The present invention provides a polyphenylene sulfide resin composition having improved fiber strength while suppressing an increase in pack pressure during fiber spinning, and has technical features for producing polyphenylene sulfide fibers from the polyphenylene sulfide resin composition.

Specifically, the present disclosure includes polyphenylene sulfide resins; And carbon nanotubes, wherein the carbon nanotubes are dispersed and mixed in the polyphenylene sulfide resin.

Particularly, in the present invention, by including carbon nanotubes as a reinforcing material which does not interfere with the stretching of the polymer chains through the spinning and drawing processes and does not act as a defect, The polyphenylene sulfide resin composition having improved fiber strength can be provided.

The carbon nanotubes used in the present invention include, but are not limited to, carbon nanotubes having diameters in the range of 10 to 400 nm, 50 to 300 nm, or 80 to 150 nm, and G band and D band in the Raman spectrum It is preferable that the ratio of the intensities (I _D / I _G ) of the reinforcing fibers has a value of 1 to 15, 2 to 10, or 4 to 8 in view of the reinforcing material for improving the fiber strength.

The content of the carbon nanotubes is preferably in the range of 0.01 to 0.1% by weight, 0.03 to 0.08% by weight, or 0.04 to 0.06% by weight based on the total weight of the polyphenylene sulfide resin composition, The advantage can be effectively achieved.

In addition, by including nano-clay, it is possible to enhance the fiber strength by forming an effective reinforcing material with carbon nanotubes.

The nano-clay used in the present invention includes, but is not limited to, montmorillonite, bentonite, kaolinite, mica, hectorite, hectorite, fluorite, saponite, bederite, nontronite, stevensite, vermiculite , Salicide, volcon scoite, suconite, magadoite, and kenyaite.

The content of the nano-clay is preferably in the range of 0.01 to 0.05% by weight, 0.03 to 0.05% by weight, or 0.01 to 0.03% by weight based on the total weight of the polyphenylene sulfide resin composition, Can be effectively achieved.

Further, as the coupling agent, at least one selected from an amine-based coupling agent, a silane-based coupling agent, and a transition metal-based coupling agent may be included. The transition metal-based coupling agent may be, for example, a titanium-based coupling agent, a zirconium coupling agent, or the like.

The content of the coupling agent may be effectively crosslinked in the range of 0.01 to 0.1% by weight, 0.03 to 0.08% by weight, or 0.04 to 0.06% by weight based on the total weight of the polyphenylene sulfide resin composition.

Further, although the polyphenylene sulfide resin in the present invention is not limited thereto, the polyphenylene sulfide resin is obtained by melt polymerization and has a weight average molecular weight (Mw) of 30,000 to 50,000, or 35,000 to 45,000 as measured by GPC (gel permeation chromatography) And a melt index (melt index at 315 캜 under a load of 5 kg, hereinafter referred to as MI) of 200 to 500 g / 10 min, or 300 to 450 g / 10 min, or 350 to 400 g / It is preferable in view of the aspect.

The content of the polyphenylene sulfide resin may be limited only by the content of the carbon nanotubes or, if necessary, the amount of the nanoclay, the content of the coupling agent, or the content of the conventional additives such as the lubricant and the antioxidant. May be 99.5 to 99.97% by weight, or 99.5 to 99.7% by weight, based on the total weight of the polyphenylene sulfide resin composition.

The polyphenylene sulfide resin used in the present invention may be a homopolymer of polyphenylene sulfide or a copolymer of polyphenylene sulfide and another comonomer. In this case, there is no particular limitation as long as it is a comonomer copolymerizable with the polyphenylene sulfide monomer.

The polyphenylene sulfide resin composition according to the present invention may contain a lubricant, an antioxidant, a light stabilizer, a reaction catalyst, a releasing agent, a pigment, a dye, an antistatic agent, a conductivity imparting agent, an electromagnetic shielding agent, , A processing aid, a metal deactivator, a suppressing agent, a fluorine-based antistatic agent, an inorganic filler, an organic fiber, and an anti-friction wear-resisting agent.

Further, the present invention can provide a polyphenylene sulfide resin comprising a polyphenylene sulfide resin composition which is constituted as described above, which improves the fiber strength during fiber spinning and suppresses an increase in packing pressure.

Specifically, gel content is a factor for confirming inhibition of the pack pressure rise. The gel content was measured with a capillary rheometer at a measurement temperature of 310 DEG C and a shear rate of 4000 sec < -1 > at a melt viscosity of 300 to 600 poise and a temperature of 260 DEG C or higher, , The carbon nanotubes and nano-clay are dispersed in the resin and act as an effective reinforcing material mixture. Therefore, the gel content is relatively lowered and the packing pressure is increased during the fiber spinning .

In addition, it can be confirmed that the value measured by a tensile measuring instrument (INSTRON) was improved to 3.0 g / denier or more, or 3 to 5 g / denier or more, as also described in the following examples. It is believed that the carbon nanotubes and nano-clay are dispersed in the resin and act as an effective reinforcing material mixture, thereby improving the fiber strength.

In the present invention, the operation conditions of the extruder to be used for smoothly performing the melting and kneading of the composition can be set normally, and can be appropriately selected depending on the kind of the base material and the type of additive and the like. For example, the temperature of the twin-screw extruder is 280 to 320 ° C and the speed is 200 to 250 rpm.

Further, in the present invention, the operating conditions for smoothly spinning the fiber of the composition can be set normally, and can be appropriately selected depending on the kind of the base material, the kind of the additive, and the like. For example, the fiber spinning can be melt-spun at a spinning temperature of 270 to 340 ° C., 300 to 340 ° C., or 320 to 340 ° C., a discharge rate of 20 g / min or less, or 20 to 10 g / min.

Further, after the above-described fiber spinning, winding and drawing are performed to obtain a polyphenylene sulfide fiber in which the fiber strength is improved and the pack-up rise is suppressed.

The winding and stretching conditions to be applied can be set normally, and can be appropriately selected depending on the kind of the base material and the type and condition of the additive. For example, the winding can be performed at a spinning speed of 600 to 10,000 mm / min or 800 to 10,000 mm / min. Specifically, the stretching can be carried out at a stretching temperature of 90 to 150 ° C or 130 to 150 ° C, Fold, or 3.5 to 3.7 times.

As described above, the polyphenylene sulfide fibers formed by the present invention have a gel content of 10 wt% or less, 4 wt% or less, a fiber strength of 3.0 g / denier or more, or 3 to 5 g / denier or more have.

As described above, according to the present invention, a polyphenylene sulfide resin composition having improved fiber strength while suppressing an increase in pack pressure during fiber spinning is provided, and polyphenylene sulfide fibers can be produced therefrom.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. Changes and modifications may fall within the scope of the appended claims.

[ Example  1 to 7]

The compositions were mixed according to the ingredients and the contents shown in Table 1 as Examples 1 to 7, and extruded by a twin-screw extruder at 200 to 250 rpm in a temperature range of 280 to 320 ° C. After final pelletization, the product was dried at 120 ° C. for 3 to 4 hours, and then yarn was produced by spinning / stretching with MST equipment. The properties were measured by the following method, and the results are shown in Table 1.

For reference, the specific materials used in the experiments are as follows:

A. Polyphenylene sulfide: PPS, Deyang Product name Hbo (weight average molecular weight (Mw): 45,000 g / mol, melt index (315 ° C, load of 5 kg): 200 to 500 g / 10 min).

B-1. Carbon nanotubes: linear, Mitsui, product NCT (diameter: 40-100 nm, product of intensity ratio of G band and D band (I _D / I _G ) using Raman spectrum (6.6-9.5)).

B-2. Carbon nanotube: Bundle type, Hanwha, product CM-250 (diameter: 10 to 15 nm, product ratio of G band to D band intensity ratio (I _D / I _G ) using Raman spectrum: 0.9 to 1.0).

B-3. Carbon nanotubes: twisted type, product name: E-Nanotech (diameter: 3 to 10 nm, product ratio of G band to D band intensity ratio (I _D / I _G ) using Raman spectrum: 0.9 to 1.0).

C. Nanoclays: Southern Clay Products, product name Cloisite ^® 93A

D-1. Coupling agent: Titanium-based, Kenrich Petrochemicals, Ken-React CAPOW Lica 38H

D-2. Coupling agent: silane series, GE silicones, silquest A-1100

E. Lubricant: Wax series, product name PE-190

F: Antioxidant: Product name IR1010

≪ Evaluation of physical properties &

* Fiber strength and elongation : measured by KS K 0860 method.

* Fineness : Measured by KS K 0315 method.

- draw ratio: calculated as the speed ratio of the supply roller and the take-up roller for sending out a non-drawn shrine in the drawing process, a take-up roller speed / feed roller speed.

* Paekap increase: 100 × (maximum paekap initial paekap) / initial paekap

* Gel content : It was added to purified 1-chloronaphthalene in a concentration of 0.75wt%, and was shaken at 250 ° C for 5 minutes. Then, while maintaining the high temperature, a pressure cap having a PTFE membrane filter with a pore size of 1 μm The gel content was measured according to the following equation after filtering by injection, drying at 150 DEG C for 1 hour under vacuum.

[Formula 1]

Gel content = (filtered gel weight / PPS sample weight) x 100

* Appearance evaluation : Appearance was judged by the naked eye, and evaluated as? (Excellent appearance),? (Excellent appearance),? (Good appearance) and X (poor appearance).

division Example One 2 3 4 5 6 7 article

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(%) Polyphenylene sulfide A 99.7 99.7 99.7 99.65 99.6 99.5 99.5 Carbon nanotubes B-1 0.1 0.1 0.1 0.05 0.05 0.05 0.05 B-2 B-3 Nano clay C 0.05 0.05 0.05 Coupling agent D-1 0.1 D-2 0.1 Lubricant E 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Antioxidant F 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Processing
Condition Discharge amount (g / m) 20 20 20 20 20 20 20 Decoupling (m / m) 600 800 1000 800 800 800 800 Properties Unfinished Shrine (d) 315 238 190 210 230 234 220 Fiber strength of unstretched fiber (g / d) 0.83 0.89 1.01 0.80 0.82 0.77 0.70 Stretching ratio (times) 3.9 4 3 3.8 3.5 3.7 3.7 (D) 82 63 63 60 68 66 60 Fiber strength (g / d) 4.07 4.11 3.10 3.86 3.60 3.22 3.16 Surface appearance ◎ ◎ ◎ ◎ ○ △ △ Pack pressure increase (%) 4.0 4.3 4.7 4.7 6.0 6.3 6.7 Gel content (%) 4.6 4.5 4.8 4.4 5.7 6.0 5.7

As shown in Table 1, when the carbon nanotubes and the nano-clay are added singly or in combination according to Examples 1 to 7 of the present invention, they act as reinforcing materials at a content of 0.1% or less, And fabricated with improved fiber strength.

[ Comparative Example  1 to 6]

The yarn was prepared in the same manner as in Example 1 except that the yarn was produced in accordance with the composition shown in Table 2, and the properties of the yarn were measured and shown in Table 2.

division Comparative example One 2 3 4 5 6 article

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(%) Polyphenylene sulfide A 99.8 99.7 99.7 99.5 99.65 99.45 Carbon nanotubes B-1 0.3 0.05 0.05 B-2 0.1 B-3 0.1 Nano clay C 0.1 0.3 Coupling agent D-1 D-2 Lubricant E 0.1 0.1 0.1 0.1 0.1 0.1 Antioxidant F 0.1 0.1 0.1 0.1 0.1 0.1 Processing
Condition Discharge amount (g / m) 20 20 20 20 20 20 Decoupling (m / m) 800 800 800 800 800 800 Properties Unfinished Shrine (d) 206 233 228 240 236 239 Fiber strength of unstretched fiber (g / d) 0.77 0.78 0.72 0.60 0.61 0.50 Stretching cost 3.4 3.2 3.2 3.0 2.8 2.8 (D) 67 73 70 81 84 86 Fiber strength (g / d) 2.51 1.18 1.05 1.66 1.12 1.20 Surface appearance △ △ △ X X X Pack pressure increase (%) 7.3 4.5 4.6 6.8 20.0 25.7 Gel content (%) 4.3 4.6 5.0 7.0 15.7 22.7

As shown in Table 2, in the case of Comparative Example 1 in which carbon nanotubes were not used or Comparative Examples 2 and 3 in which the carbon nanotubes were not in a linear form, .

In addition, in the case of the linear carbon nanotubes exhibiting the fiber strength effect and Comparative Examples 4 to 6 in which the nano clay content alone or the composite content was more than 0.1%, there were disadvantages such as a decrease in physical properties, an increase in packing pressure and an increase in gel content .

Claims (16)

Polyphenylene sulfide resin; And a carbon nanotube, wherein the carbon nanotube is dispersed and mixed in the polyphenylene sulfide resin.
The method according to claim 1,
Wherein the carbon nanotube has a diameter of 10 to 400 nm and a intensity ratio (I _D / I _G ) of a G band and a D band in a Raman spectrum is 1 to 15. The polyphenylene sulfide resin composition .
The method according to claim 1,
Wherein the content of the carbon nanotubes is in the range of 0.01 to 0.1% by weight based on the total weight of the composition.
The method according to claim 1,
Wherein the composition comprises a nano-clay; and the nano-clay is dispersed and mixed in the polyphenylene sulfide resin.

5. The method of claim 4,
The nano-clay may be selected from the group consisting of montmorillonite, bentonite, kaolinite, mica, hectorite, hectorite, fluorite, saponite, bederite, nontronite, stevensite, vermiculite, Wherein the polyphenylene sulfide resin composition is at least one selected from dibutyl phthalate, ditallow, and kenyanite.
5. The method of claim 4,
Wherein the content of the nano-clay is in the range of 0.01 to 0.05% by weight based on the total weight of the composition.
The method according to claim 1,
Wherein the composition comprises at least one coupling agent selected from an amine-based coupling agent, a silane-based coupling agent, and a transition metal-based coupling agent.
8. The method of claim 7,
Wherein the content of the coupling agent is in the range of 0.01 to 0.1% by weight based on the total weight of the composition.
The method according to claim 1,
Wherein the polyphenylene sulfide resin has a weight average molecular weight (Mw) of 30,000 to 50,000.
The method according to claim 1,
The polyphenylene sulfide resin had a melt index (MI, 315 캜, 5 kg load) 200 to 500 g / 10 min. ≪ / RTI >
The method according to claim 1,
Wherein the content of the polyphenylene sulfide resin is in the range of 99.5 to 99.97 wt% based on the total weight of the composition.
A process for producing a polyphenylene sulfide fiber characterized by kneading the polyphenylene sulfide resin composition of any one of claims 1 to 11, followed by melt spinning, winding and drawing.
13. The method of claim 12,
Wherein the kneading is performed by spinning and drawing the pellets extruded at 280 to 320 DEG C at 200 to 250 rpm in a twin-screw extruder.
13. The method of claim 12,
Wherein the melt spinning is melt-spun at a spinning temperature of 270 to 340 占 폚 and a discharge rate of 20 g / min or less.
13. The method of claim 12,
Wherein the winding is performed at a spinning speed of 600 to 10,000 mm / min.
13. The method of claim 12,
Wherein the stretching is performed at a stretching temperature of 90 to 150 DEG C at least two times the elongation of the polyphenylene sulfide fiber.