KR20120078428A - Manufacturing apparatus of precursor for carbon fiber and carbon fiber - Google Patents

Abstract

PURPOSE: An apparatus for fabricating precursor fibers for carbon fibers is provided to prevent fiber-fiber fusion and to enhance product quality. CONSTITUTION: An apparatus for fabricating precursor fibers comprises a comb guide(9) at the front end of an emulsion bath(3) and a hot air dryer(4) at the back end of the emulsion bath. The comb guide has a support mounted vertical from a spinning fiber processing direction; and a rotation bar which is separately rotational in constant interval. The temperature of the air supplied from the hot air dryer is 130-170 Deg.C.

Description

Precursor fiber manufacturing apparatus for carbon fiber and carbon fiber manufactured using the same

The present invention relates to a precursor fiber manufacturing apparatus for carbon fibers, and more particularly, to prepare a carbon fiber having excellent quality and quality by installing a simple device before and after applying the emulsion to prevent the close-up or deadlock of the precursor fiber and the flame-resistant flame retardant yarn. It relates to a precursor fiber manufacturing apparatus for carbon fibers and a carbon fiber produced using the same.

Carbon fiber wet-spins, dry-spins, or dry-spins a spinning solution which consists of a PAN polymer used as a precursor, and manufactures a carbon fiber precursor fiber. It is common to heat this fiber in the oxidizing atmosphere of 200-400 degreeC temperature, and to convert it into a flame resistant fiber, and to heat and carbonize in inert atmosphere at least 300-2000 degreeC temperature.

In order to obtain a high-performance carbon fiber, in each of the above-described manufacturing processes, wet and dry spinning is performed, since internal wrinkles and damage can be reduced by creating a wrinkle-free and smooth fiber surface as compared to wet spinning. In order to prevent affixing and fusion of fibers of such precursor fibers, generally, an amino-modified silicone-based emulsion capable of increasing heat resistance by a silicone-based emulsion, in particular a crosslinking reaction, has been widely used industrially.

However, when the emulsion is applied to the wet and dry spun fiber, it is difficult to make the emulsion uniform and encapsulate due to the smooth surface properties. When the oil agent is excessively attached, the oil agent that is excessively attached to the fiber surface generates adhesion between the fibers and the fibers, and thus the bonded fiber has a problem in that it is difficult to inject oxygen during the flameproofing process so that the density of the flame resistant yarn and the structure are not uniform. . These fibers remain affixed to the carbonization process, causing a decrease in carbon fiber strength and quality.

Then, the oil gum (Gum) dropped from the fiber becomes an adhesive, which is deposited on a drying roller or a guide in the precursor manufacturing process, which causes the fiber to be wound up or the thread to be degraded in operability. Productivity is also lowered because it is easy to deposit in the furnace and damage subsequent fiber bundles.

On the other hand, when the oil agent adheres less than an appropriate level, the fusion preventive property between the fibers and the fibers becomes insufficient, resulting in macro or fusion yarns, which causes a decrease in the strength of the carbon fibers.

The present invention has been invented to solve problems such as affixing precursor fibers caused by inadequate application of the emulsion, or fusion between fiber-fibers of the emulsion added to the excess, and the present invention is a simple apparatus before and after applying the emulsion. The purpose of the present invention is to provide a precursor fiber manufacturing apparatus for carbon fiber and a carbon fiber manufactured using the same, which can produce high-quality, high-quality carbon fiber by preventing the affix or emulsion from being attached to the fiber excessively. .

The apparatus for producing carbon fiber precursor fibers according to the present invention includes a comb guide installed at the front end of the emulsion bath and a hot air dryer installed at the rear end of the emulsion bath, wherein the comb guide comprises: a support installed perpendicular to the direction in which the spinning fibers are run; And at least three or more rotary bars rotatably installed at regular intervals perpendicular to the support, wherein the hot air dryer is a device capable of supplying high-temperature air vertically in the advancing direction of the spinning fiber. do.

According to another preferred feature of the invention, the distance between the rotating bar is 165 ~ 230mm.

According to another preferred feature of the invention, the temperature of the air supplied from the hot air dryer is 130 ~ 170 ℃.

Carbon fiber produced using the above-described manufacturing apparatus according to the present invention is characterized in that the tensile strength is 4.9GPa or more.

In preparing the precursor fiber for carbon fiber according to the present invention, it prevents fusion between the affix and the fiber and the fiber, and prevents the gum from causing the roll dryer surface. The precursor fiber thus prepared is able to prevent close-up and uniform flame resistance to produce a carbon fiber having high quality properties, quality.

1 is a schematic view of the manufacturing process of the carbon fiber precursor fiber according to the present invention,
2 is a schematic diagram of a comb guide according to the present invention;
3 is a schematic view of a hot air dryer according to the present invention.

The manufacturing apparatus of the precursor fiber for carbon fiber according to the present invention includes a comb guide installed at the front end of the emulsion bath and a hot air dryer installed at the rear end of the emulsion bath. To be possible.

1 is a schematic diagram of a manufacturing process for producing a carbon fiber precursor fiber according to the present invention. As shown in Fig. 1, the manufacturing process of the carbon fiber precursor fiber according to the present invention is performed by stretching the coagulated sand obtained from the wet and dry spinning in the washing tank (1), by hydrothermal stretching in the hot water bath (2), and before applying the emulsion. After passing through the squeegee roll (8) at a Kg pressure to remove a certain amount of water, and then through the combined guide (9) further installed by the present invention to enter the emulsion bath (3) after increasing the width.

2 is a schematic view of a comb guide according to the present invention. As shown in FIG. 2, the comb guide according to the present invention includes a support 10 and a rotation bar 11.

The support 10 is installed perpendicular to the running direction of the spinning fiber, preferably is installed horizontally with the ground perpendicular to the running direction of the spinning fiber. Rotating bar 11 is installed vertically of the support. At least three rotation bars 11 are installed, and each rotation bar is rotatable individually, and the spinning fiber 12 passes through the rotation bars 11 perpendicularly between the rotation bars 11. The spinning fiber 12 has a wider width while passing through the rotary bar 11, and the wider spinning fiber 12 enters the emulsion bath 3 in such a state so that the oil agent is uniformly applied to the fiber surface. If the rotation bar is less than three, the effect of increasing the width cannot be expected.

The distance between the rotation bar is 165 ~ 230mm, less than 165mm there is a problem that there is no uniform imparting effect of the emulsion, if it exceeds 230mm there is a problem that the width is too wide to give the excess oil and the drying efficiency is lowered.

On the other hand, the fiber imparted with the emulsion in the emulsion bath 3 is generally brought into contact with a heated roller to be dried. In the present invention, before passing through the roll dryer (5) was equipped with a hot air dryer 9 for maintaining a temperature of 130 ~ 170 ℃. If the temperature is less than 130 ℃, it does not dry well to the fiber, the drying efficiency is low, there is a problem of lowering the productivity, if it exceeds 170 ℃ moisture is not uniformly dried, the fiber surface is rapidly dried, part of the emulsion component There is a problem of hardening and rather deterioration of encapsulation.

3 is a schematic view of a hot air dryer according to the present invention. The hot air dryer 9 is a device capable of supplying high-temperature air in the vertical direction of the spinning fiber, and stretches the narrow fiber narrowed at the exit of the emulsion bath 3 again to remove the excess oil adhered. It prevents adhesion between fibers, prevents excessive adhesion of oil from adhering between fibers and causing gum on the roll dryer surface. After drying, steam stretching (6) and heat setting (7) to produce a precursor fiber for carbon fibers.

 Precursor fiber thus prepared is able to prevent close-up, uniform flame resistance is possible to produce a carbon fiber having high quality properties, quality.

That is, the carbon fiber produced using the manufacturing apparatus according to the present invention has a tensile strength of 4.9 GPa, since the precursor fiber which prevents the affixation of the precursor fiber or the fiber-fiber fusion using the apparatus according to the present invention is used. to be.

In addition, the carbon fiber using the manufacturing apparatus according to the present invention shows one or more macroffixes in the precursor fiber, one or less macrophages in the carbon fiber as measured by the method described below.

The precursor fibers and carbon fibers thus prepared are analyzed and evaluated as follows.

[Width Measurement]

The width of the yarn after passing through the comb guide, before the emulsion bath, and the yarn before and after the passage of the hot air dryer are measured with a ruler. After passing through the guiding bath before entering the tanning bath, the yarn width is calculated from the sum of the yarn widths between the rotating and rotating bars to calculate the yarn width of the entire 12K fiber. The width of the yarn before and after passing through the hot air fan measures the width from the edge of the 12K fiber to the edge.

[Close-up evaluation]

12K fibers (12,000 single fibers) are cut to a length of 5 mm in order to evaluate the macroscopic number of precursor fibers, flame resistant fibers and carbon fibers for carbon fiber production. The cut fibers are placed in a square tray and the D.I. 100 ml of water and 0.1 wt.% Of cationic surfactant are added to water, ultrasonic dispersion is carried out for 90 seconds, the dispersion is placed on a filter paper, and suction filtration is performed. However, precursor fiber uses black fiber paper.

Count the number of fibers by observing the fibers dispersed in the filter paper as follows.

Separate.

   0 ~ 1: ◎ (very good)

   1 to 3: ○ (Excellent)

   3 ~ 10: △ (bad)

10+: x very bad

 [Measurement of specific gravity of flame resistant fiber]

The specific gravity of the flame resistant fiber is measured by the liquid substitution method according to the method of JIS R7601 (1986). The immersion liquid is used without purifying ethanol. 1.0-1.5 g of flame resistant fiber is taken out, and it is dried for 2 hours at the temperature of 120 degreeC in air using a hot air dryer. After measuring dry mass A (g), it is immersed in ethanol of specific gravity known (specific gravity p), the fiber mass B (g) in ethanol is measured, and the specific gravity of flame-resistant fiber is calculated | required by following Formula.

Flame Retardant Fiber Specific Gravity = (A × ρ) / (A-B)

For one fiber, the flameproof fiber specific gravity is measured for 5 and CV% is obtained. From this deviation, the degree of uniformity of flame resistance was evaluated.

[Carbon Fiber Strength Measurement]

It measured according to the epoxy resin impregnation strand method prescribed | regulated to JIS-R-7601, and made the average value of the measurement frequency ten times into the strength of carbon fiber.

Example 1-3 and Comparative Example 1-3 which are described below show the conditions in each Example shown in Table 1 and Table 2, and each comparative example in the implementation method as described in the following comprehensive example.

It was done by using.

  Comprehensive Example

 : 99 wt.% Of acrylonitrile and 1.0 wt.% Of co-polymerizing monomer Itaconic acid was prepared by 20 wt.% Dimethyl sulfoxide solution polymerization of an acrylic copolymer. After polymerization, the spinning stock solution obtained by neutralizing the itaconic acid until the dope became pH 8.0-8.5 was prepared using 10 nozzles with 6,000 holes and a hole diameter of 0.12 mm, 10 ° C and 32.5wt% dimethyl sulfoxide (Dimethylsulfoxide, DMSO) Wet-dry spinning in a coagulation bath made of an aqueous solution, washed with coagulated sand, stretched 4 times in 65 ℃ hot water, passed through a 1.3Kg squeegee roll, and widened the width by adjusting the guide pin of the comb guide. In the emulsion bath. After imparting a silicone-based emulsion, the mixture is passed through a hot air dryer at 130 ° C., dried through a roll dryer heated at 150 ° C., and steam drawn to have a steam stretching ratio of 6 times. Through this process, a precursor fiber having 1.0 denier was produced.

The precursor fiber was flameproofed while extending | stretching with the draw ratio 1.0 in air of the temperature of 225-260 degreeC, and obtained the flameproof fiber of specific gravity 1.350. The obtained flame-resistant fiber performed the preliminary carbonization process, extending | stretching with a draw ratio 1.15 in nitrogen atmosphere of 300-700 degreeC temperature, and produced 800 tex carbon fiber in the nitrogen atmosphere of the maximum temperature of 1,500 degreeC.

In the above comprehensive example, the conditions described in Example 1 of Table 1 were adopted to prepare precursor fibers, flame resistant fibers, and carbon fibers. Analysis and evaluation of these fibers showed the results as shown in Tables 2 and 3.

  In the above comprehensive example, the conditions described in Example 2 of Table 1 were adopted to produce carbon fibers.

In the above comprehensive example, the conditions described in Example 3 of Table 1 were adopted to produce carbon fibers.

 Comparative Example 1)

 In the above comprehensive example, the conditions described in Comparative Example 1 of Table 1 were adopted to prepare carbon fibers.

  Comparative Example 2)

In the above comprehensive example, the conditions described in Comparative Example 2 of Table 1 were adopted to prepare carbon fibers.

Example and Comparative Example Setpoints  Kinds Emulsion bath
Before inflow
Number of rotating bars Rotation bar setting width before emulsion bath
(mm) Hot Air Dryer
Temperature (℃)  Example 1 4 600 130  Example 2 4 660 130  Example 3 4 720 120  Comparative Example 1 2 600 not used  Comparative Example 2 2 600 130

 Measure  Kinds Emulsion bath inflow
Real actual width (mm) Hot Air Dryer
Actual before inflow
Dead width (mm) Hot Air Dryer
Actual after inflow
Dead width (mm)  Example 1 540 490 515  Example 2 595 555 575  Example 3 630 580 600  Comparative Example 1 490 410 450  Comparative Example 2 490 410 450

 Analysis  Kinds Precursor
Fiber affix Flameproofing
Fiber affix Carbon fiber
affix Flameproof Specific Gravity
CV% Carbon fiber tensile strength
(GPa)  Example 1  ◎ △ △  20.8 4.90  Example 2  ◎ ○ ○ 14.5 5.05  Example 3  ◎ ○ ○ 10.6 5.23  Comparative Example 1  △ x x 31.8 4.38  Comparative Example 2  △ △ x 27.5 4.52

1: washing bath
2: hot water bath
3: emulsion bath
4: hot air dryer
5: dryer
6: steam drawing machine
7: open / close
8: squeegee roll
9: Combination guide
10: support
11: rotating bar
12: spinning fiber

Claims (4)

An apparatus for producing carbon fiber precursor fibers comprising a comb guide provided at the front end of an emulsion bath and a hot air dryer installed at the rear end of the emulsion bath,
The comb guide is a support installed perpendicular to the running direction of the spinning fiber; And
Includes at least three or more rotary bars rotatably installed at regular intervals perpendicular to the support;
The hot air dryer is a device for producing carbon fiber precursor fibers, characterized in that the device capable of supplying high-temperature air in the vertical direction of the spinning fiber. According to claim 1, wherein the distance between the rotation bar is a carbon fiber precursor fiber manufacturing apparatus, characterized in that 165 ~ 230mm. According to claim 1, wherein the temperature of the air supplied from the hot air dryer is the apparatus for producing carbon fiber precursor fiber, characterized in that 130 ~ 170 ℃. Carbon fiber precursor fiber produced using the manufacturing apparatus according to any one of claims 1 to 3, characterized in that the tensile strength is 4.9 GPa or more.

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