KR20030018975A - Fiber surface modificating apparatus and thereof method by using plasma in low temperature and pressure - Google Patents

Abstract

PURPOSE: An apparatus and method for modifying the surface of a fiber by introducing gas on the fiber surface to be treated or coating a polymerizable monomer in vapor phase is provided. Therefore, the apparatus is simple in structure and easy to install, the method reduces the cost of production by use of microwave and pulse power. CONSTITUTION: The fiber surface modifying apparatus comprises: a vacuum chamber(1) connected to a connection path(1a); a constant speed motor(7) and clutch brake(21) each installed on an axis of a roller with a sample(6) to cause the sample to be wound or unwound on the roller; a magnetron(2) disposed in the longitudinal direction thereof on the periphery of the connection path; a quartz(17) and waveguide path(16) for uniformly guiding oscillated electromagnetic waves into the interior of the connection path; a power supply(3) for applying high voltage; a vacuum pump(5) installed on one side of the vacuum chamber; and a gas supply tank(8) and monomer storage tank(9) for pouring plasma atmospheric gas and a polymerizable monomer into the interior of the connection path.

Description

FIBER SURFACE MODIFICATING APPARATUS AND THEREOF METHOD BY USING PLASMA IN LOW TEMPERATURE AND PRESSURE}

In the present invention, the fiber fabric is automatically controlled in a vacuum state to enable large area and large capacity treatment, and at the same time, gas is applied to the surface of the fiber to be treated, or a polymerization monomer is applied in a gaseous phase (gas state) to produce hydrophilic, The present invention relates to a fiber surface modification apparatus and method using low temperature and low pressure plasma to physically modify the surface of the fiber in accordance with hydrophobicity, static electricity, charging, dyeing, moisture resistance, waterproofness, and the like to impart functionality to the textile product.

Recent improvements in living standards and technological developments have further diversified consumer needs for textile products.

For example, water-repellent textile products, water-resistant textile products that do not stick to dust, water-absorbed textile products that absorb water well, fragrance-oriented textile products, sweat passing through and rainwater And the like, which are made of moisture-permeable waterproof textile products which do not enter.

In order to produce these characteristics, a large amount of chemicals and water are usually used, thereby causing a large amount of wastewater and harmful gases, which may cause fatal damage to the human body, and also increase an environmental burden for treating them.

Therefore, various environmentally friendly fiber surface modification methods have been required without generating waste water or harmful gases, and for example, methods using RF plasma (Domestic Patent Application Nos. 1986-699, 1991-11576, and Ilbo Publication No. 59). -223363); Graft copolymerization of monomers by plasma treatment (Domestic Patent Application No. 1986-8905); Chemical treatment method; The plasma ion implantation method (Domestic Patent Application No. 1996-10740), the atmospheric pressure corona discharge treatment method, etc. are disclosed.

The method using RF plasma is a method of modifying the fiber surface by inserting fibers between the discharge electrodes (-) and the counter electrodes (+) at regular intervals inside the vacuum chamber and generating gas by injecting gas. Generally, high frequency output 100 ~ 300W, frequency 13.56MHz, pressure 1 ~ 3 Torr, processing time 3 ~ 7 minutes are required.

Monomer graft copolymerization method is a technique that can form a relatively excellent thin film on the surface of the workpiece by applying acrylic acid, methacrylic acid, arylamine, aryl alcohol, 2-vinylpyridine, 4-vinylpyridine, acrylonitrile, Chemical treatment has the advantage of predicting the functional groups formed on the fiber surface by chemical reaction.

Plasma ion implantation is a method that can reform the sub-surface deep layer. The RF power for plasma generation is 200W, and when the pulse-off voltage 0V ~ 1Kv and pulse frequency 10Hz ~ 500KHz are applied, It is a method using a strong electric field formed.

Atmospheric pressure corona discharge treatment method is to rotate or move the fiber to be surface treated in a roll or conveyor method and input the set treatment conditions (temperature, moving speed, discharge power, gas mixture ratio) and all processes are automatically executed by the operating program. It is a method to achieve a homogeneous fiber surface modification effect even in the case of mass processing.

However, these published methods have the following problem.

In the case of RF plasma treatment method for modifying and strengthening the fiber surface, it is difficult to arrange the electrode structure of anode and cathode at regular intervals in a closed space in a vacuum state. Impedance matching box is required to reduce the reflection of the input stage. Plasma does not occur stably if the impedance change is severe due to the change of vacuum degree, resistance, surface area, and grounding method of the vacuum chamber. There is a problem.

In addition, in the graft copolymerization method, AC 60Hz and RF 13.56MHz should be used, so as described above, the arrangement of the electrode structure is complicated, and a matching box is required due to the reflection of the input and output terminals. In the case of a chemical treatment method, the treatment process is cumbersome and causes a problem of treating a waste liquid which is a contaminant.

In addition, in the case of the surface modification method of the polymer material by plasma ion implantation, there is a problem that a matching box is required by simultaneously combining the RF plasma and the pulse voltage, and the pulse power source must be designed separately.

In addition, the method of corona discharge treatment at atmospheric pressure has a problem that the modified layer is very thin and easily deteriorates with time after treatment, and it is difficult to optimize processing process variables such as humidity in the atmosphere.

The present invention has been made in view of the above-mentioned problems of the prior art, and has been devised to solve this problem. A large area and large capacity continuous processing are possible by continuously moving the treated fiber through a means having an automatic speed control function using a roller. Inert gas suitable for water repellency and hydrophilicity, waterproof, charging, electrostatic, dyeing, etc. on the fiber surface at low temperature and low pressure by using low temperature and low pressure plasma that can achieve simple and uniform discharge effect, such as helium, neon, argon, or nitrogen The surface is modified using the physical effect of forming fine unevenness on the surface of the fiber by the plasma etching effect and the functional group formed on the surface of the fiber to be treated by selecting oxygen, CF ₄ gas, etc. and introducing the monomer for polymerization into the gas phase. Disclosed is an apparatus and method for fiber surface modification using a low temperature and low pressure plasma capable of polymerization. There is a purpose in the title.

1 is a schematic block diagram showing one possible embodiment according to the present invention;

FIG. 2 is an enlarged view illustrating main parts of a tension roller constituting the apparatus of FIG. 1; FIG.

3 is an enlarged view illustrating main parts showing means for controlling a driving speed of a tension roller constituting the apparatus of FIG. 1;

4 is a schematic block diagram showing another possible embodiment according to the present invention;

5 and 6 are enlarged views of main parts of FIG. 4.

Explanation of symbols on the main parts of the drawings

1,1 ': vacuum chamber 1a: connecting passage

2: magnetron 3: power supply

4: waveguide 5,5 ': vacuum pump

6,6 ': Sample 7,26: constant speed motor

21,28: clutch brake 32: guide roll

42: electrode 43: cooling pipe

The above object of the present invention and the dumbbell-shaped vacuum chamber connected by the connecting passage and the inside hollow; A constant speed motor and a clutch brake each provided on an axis of the roll on which the sample is wound so that the sample provided in a roll shape inside the vacuum chamber is wound / recommended while moving from one side to the other side through a connecting passage; A magnetron arranged in the longitudinal direction on the outer circumferential surface of the connection passage; Qualts and waveguides for uniformly guiding the electromagnetic wave oscillated in connection with the magnetron into the connection passage; A power supply connected to the magnetron and applying a high voltage; A vacuum pump installed at one side of the vacuum chamber; Fiber surface using a low-temperature low-pressure plasma, characterized in that it comprises a gas supply tank and a monomer storage tank connected to the connecting passage and installed in the adjacent side so as to inject the plasma atmosphere gas and the polymerization monomer into the connecting passage. By providing a reforming device.

In addition, the above object of the present invention comprises the steps of mounting a sample in the form of a roll inside the vacuum chamber; When the sample is mounted, vacuuming the vacuum chamber to a predetermined vacuum through a vacuum pump, and then filling the vacuum chamber with monomer and atmosphere gas or atmosphere gas alone and re-vacuuming the vacuum chamber before charging again; Driving a constant speed motor to transfer a sample when the vacuum is completed; Modifying the surface of the sample being transferred by generating a low temperature and low pressure plasma through microwave or pulse power through a voltage application means at the same time as the sample transfer; It is achieved by providing a fiber surface modification method using a low temperature low pressure plasma, characterized in that it comprises the step of winding the surface-modified sample to desorb from the vacuum chamber.

The present invention makes the enclosed space in a vacuum state, using a high-density 300MHz ~ 30GHz microwave, pulse voltage 1kv ~ 20kv, pulse frequency 10Hz ~ 600KHz, pulse width 1sec ~ 60sec variable pulse power, respectively, large capacity, large It was used as a principle to modify the surface of the fiber by the plasma effect of the high molecular radical, electron plasma effect and polymerization of monomer during the transfer of the fiber by the roller which can handle the area.

Nearly the same plasma state (Ne = 10 ⁸ ~ 10 ¹² cm ^-3 ) is obtained by DC plasma and RF plasma, but much higher electron density (Ne = 10 ¹¹ cm ^-3 ) is achieved by plasma using microwave. Obtained.

Here, plasma is an ionized state by applying heat or electrical energy to an electrically neutral gas from the outside, which is electrons, photons, ionized atoms or molecules, free-active groups, and neutral atoms or molecules. It is composed of a totally electrically neutral state. When a thermal energy is applied to a gas, each atom or molecule is a fourth material state, not a solid, liquid, or gas, which is dissociated into electrons and cations.

Plasma is classified as a high temperature or low temperature plasma for convenience. A representative example of high temperature plasma is the sun. At this time, molecules or atoms have high energy and are applied to arc welding or ceramic coating.

On the other hand, when electricity is discharged to a gas, energy is transmitted only to electrons with light mass, but energy is not transferred to heavy ions or molecules, and plasma is generated even when the thermal energy of gases except electrons is low, which is called low temperature plasma. .

When the high-density plasma energy is irradiated to the gas, free electrons in the atoms absorb the plasma energy and are separated into ions and electrons of high energy level, and ions and electrons maintain a high density at about the same density, and coexist plasma.

Since the gas containing these ions is in a chemically active state, hydrophobic fibers are hydrophilically modified depending on the mixed gas and monomers used to generate physical and chemical reactions on the surface of the polymer, which is a polymer compound, by high density plasma energy. Rather, it increases dyeability by acid dyes during dyeing (deep color effect), and in the case of wool fabrics, results in suppressing washing shrinkage.

For example, hydrophilic groups or radical reactions, such as -OH and -COOH groups, modify the fiber surface to increase water absorption, and form water and hydrophobicity on the fiber surface through fluorination.

This state varies greatly depending on the pressure of the gas, the strength of the electric field, the discharge current, the frequency, and the like, as well as the type of device, the gas used, and the type of monomer.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

1 is a schematic block diagram showing one possible embodiment according to the present invention.

According to FIG. 1, a dumbbell-shaped vacuum chamber 1 is provided which is hollow inside and closely connected by a connecting passage 1a.

A vacuum pump 5 is installed below the vacuum chamber 1, and a vacuum valve 11 and a vacuum sensor 13 are installed on a pipe connecting the vacuum pump 5 and the vacuum chamber 1. On both sides of the vacuum valve 11, exhaust valves 12 are bypassed.

In the vacuum chamber 1, a sample 6, which is an object to be processed, such as a fiber, is wound in a roll shape, and one end of the sample 6 is installed in the vacuum chamber on the other side via the connecting passage 1a. It is disposed so as to be wound by the motor 7.

The constant speed motor (7) is preferably a low-speed synchronous motor (EMPS MOTOR) that has no gear head, is operated at a high torque, and has the characteristics of constituting a control system by a controller.

This is because, in the case of the low speed synchronous motor, there is no voltage change according to the RPM, and constant speed operation is possible without slip phenomenon even when the load is added or decreased, and there is no phenomenon that torque is not reduced even during the shift operation.

The clutch brake 21 is installed on the axis of the support roll of the sample 6 in the vacuum chamber 1 which fixes the sample 6 to be released, and the tension sensor 22 is disposed at an adjacent position where the sample 6 is released. The tension of the sample 6, which is added and recommended, can be checked in real time.

The fiber, which is the sample 6, includes polyethylene, polypropylene, polyester, nylon, polystyrene, polyamide, PET, silk, wool, cotton and their fabrics.

The clutch brake 21 is electrically connected to the controller 20, the controller 20 is connected to the PLC inverter 15, and the PLC inverter 15 is connected to the constant speed motor 7.

A plurality of tension rollers 18 are installed at the inner center of the connection passage 1a along the longitudinal direction thereof, and a plurality of magnetrons 2 are fixed to both sides of the outer circumferential surface thereof, and the electromagnetic waves are refracted by the magnetron 2. A plurality of quality 17 and the waveguide 16 for connecting to the connection passage (1a) without passing through is installed.

These magnetrons 2, waveguides 16 and quartz 17 are coupled to the waveguide 4.

In particular, a reflection shade 23 is installed at the portion where the vacuum chamber 1 and the connection passage 1a are connected to prevent the discharge generated during the fiber surface modification from leaking toward the sample 6, thereby achieving a uniform treatment effect. desirable.

Each of the magnetrons 2 is connected to a power supply 3.

The power supply 3 is preferably a high density microwave having a wavelength of 1cm ~ 1m and a frequency of 300MHz ~ 30GHz band, which is for large capacity, large area processing.

Meanwhile, a monomer storage tank 9 and a gas supply tank 8 are installed at one outer side of the vacuum chamber 1.

The monomer storage tank (9) is any one selected from among the monomers acrylic acid, methacrylic acid, acrylamine, acrylonitrile, hexafluoropropene is stored, the gas supply tank (8) is hydrophobic, hydrophilic, waterproof on the fiber surface Inert gas suitable for charging, electrostatic, dyeing, etc., that is, helium, neon, argon or an atmosphere gas such as nitrogen, oxygen, CF ₄ , NH ₃ , SF ₆ is preferably used.

These monomer storage tank (9) and the gas supply tank (8) is connected to the inlet (19) by a connecting pipe 24, the inlet (19) is disposed in the longitudinal center portion of the connecting passage (1a).

The flow meter 14 is installed on the connection pipe 24, and each tank 8, 9 is provided with an injection valve 10.

In addition, the connection pipe 24 has a main connection relationship with the gas supply tank 8 and a secondary connection relationship with the monomer storage tank 9, and the type thereof is supplied using Bernoulli theorem, such as a Venturi tube. It is preferable to install such that the monomer is sucked and supplied by the pressure difference of the gas.

The flow meter 14 is provided to be installed so that a constant amount is continuously supplied without excessive gas and monomer supply. The flow meter 14 is a flow meter in which the height of the ball is quantitatively displayed by the action of a ball loaded in accordance with the specific gravity of the liquid and the gas inside the needle valve and the glass tube. This is a very useful flow control mechanism.

Fig. 2 is an enlarged view of a main part of the apparatus of the present invention, which shows a plurality of guide means installed inside the connecting passage 1a when the sample 6 to be processed is wound up by the constant speed motor 7. .

As shown, a plurality of tension rollers 18 for transporting the sample 6 while maintaining it at a constant tension are installed as described above, and the tension of the sample 6 transported along the tension roller 18 is increased. A tension sensor 22 is provided to measure and correct in real time, and a plurality of waveguides 16 guide the oscillated high frequency to the surface of the sample 6 on the adjacent upper side where the sample 6 is transported. Excreted

3 shows means for controlling the driving speed of the tension roller 18, which is one of the apparatuses of the present invention, and the driving of the constant speed motor 7 is based on the detection signal sent from the tension sensor 22. Direct control, the operation of the clutch brake 21 is a schematic of the installation and control process of the PLC inverter (15) having an electric signal system to control through the control converter (20).

The present invention made up of such a configuration has the following operational relationship.

First, the sample 6 is wound into the vacuum chamber 1 in the form of a roll, the vacuum pump 5 is operated, and the vacuum valve 11 is opened to operate the vacuum pump 5 until the vacuum degree reaches 100 mmTorr. .

When it is detected that the degree of vacuum in the vacuum chamber 1 has reached 100 mmTorr by the vacuum sensor 13, the injection valve 10 of the gas supply tank 8 is opened, and the stored atmospheric gas is charged into the vacuum chamber 1. Inject until the vacuum reaches 1 Torr.

At this time, the electromagnetic wave oscillated from the magnetron 2 is connected to the waveguide 16 and the quartz 17 for transmitting the inside of the vacuum chamber 1 without refracting, and the magnetron 2 attached to the waveguide 4 is 2000V or more. Microwaves in the 300MHz ~ 30GHz band is applied to the top and bottom of the vacuum chamber 1 through the power supply 3 for applying a high voltage.

At the same time, the constant speed motor 7 is driven by using the PLC inverter 15 to gradually wind the sample 6.

When the winding operation of the sample (6), which is a fiber, the appropriate tension is checked through the tension sensor (22) to control the entanglement and tension of the sample (6).

Meanwhile, in the monomer storage tank 9, the Bernoulli principle is applied to the surface of the fiber, which is the sample 6, while being supplied into the vacuum chamber 1 in a gaseous state when gas is injected.

At this time, the processing width of the fiber (sample 6) is 1000 ~ 2000mm, the modification speed of the fiber surface is 5 ~ 50 m / min, the area showing a uniform treatment effect in one place of the magnetron (2) is 40cm, which is processed at the time of winding The distance between the fiber and the magnetron (2) is preferably maintained at about 15 cm, and when the fiber length exposed to the plasma is 2 m, the exposure rate is 25 seconds when the modification speed is 5 m / min, and 3 seconds when the 50 m / min is 50 m / min. It is preferable to make it.

The plasma is a low temperature, low pressure plasma.

The reason why the plasma treatment time is different as described above is to obtain a stable and uniform fiber surface modification effect after plasma treatment. The type of fiber fabric used for surface modification is polyethylene, polypropylene, nylon, PET, silk, wool, cotton. This is because the surface energy values, which are the characteristics of each fiber surface, are different, so that different plasma treatment times are required to show hydrophilicity, hydrophobicity, water repellency, and electrostatic properties depending on the type of fiber fabric being modified. .

In particular, the processing speed (feeding) of the sample 6 is controlled by the constant speed motor 7 and the clutch brake 21 in the PLC inverter 15 which receives the detection signal from the tension sensor 22 maintaining the proper tension. The roller on which the sample 6 is mounted can be maintained at a constant speed, for example, 5 to 50 m / min processing speed.

The finished sample 6 is detached from the vacuum chamber 1 to finish the surface modification of the fiber.

Figure 4 is a schematic block diagram showing another possible embodiment according to the present invention, Figure 5 is an enlarged view of the main portion of Figure 4, Figure 6 is a schematic view showing an electrode structure according to another possible embodiment of the present invention It is a cross section.

According to FIGS. 4 to 6, a sealed substantially rectangular vacuum chamber 1 ′ is provided, and the vacuum chamber 1 ′ includes a vacuum pump 5 ′, a vacuum valve 11 ′, and an exhaust valve 12 ′. ) And the vacuum sensor 13 'are installed in the same structure as in the case of FIG.

In addition, the vacuum chamber 1 'is connected to the gas supply tank 8' by a connection pipe 24 ', and the flow meter 14' as described above is installed on the connection pipe 24 '. do.

The gas stored in the gas supply tank 8 'is preferably one selected from inert gases such as helium, neon, argon, and other gases such as nitrogen, oxygen, CF ₄ , and NH ₃ .

This is because the gas is suitable for hydrophobicity, hydrophilicity, waterproofing, charging, electrostatic, dyeing and the like on the surface of the fiber to be processed.

Inside the vacuum chamber 1 ', a sample 6' is provided in the form of a roll so as to be wound and wound.

The clutch brake 28 is provided on the side where the sample 6 'is recommended, and the constant speed motor 26 is provided on the side to be wound.

The constant speed motor 26 and the clutch brake 28 are driven and controlled by the PLC inverter 29, in particular the clutch brake 28 is to be controlled by the PLC inverter 29 via the control converter 30 desirable.

In addition, it is preferable to control the driving of the constant speed motor 26 by continuously checking the tension of the sample 6 'to be wound by installing a tension sensor 25 on the outside of the constant speed motor 26. Do.

A tension roller 27 is installed on an adjacent side where the sample 6 'is wound, and a plurality of electrode rods 42 are installed at a distance from the constant speed motor 26 and the clutch brake 28, and the sample 6 A plurality of guide rolls 32 are installed on both sides and between the electrodes 42 to allow ') to travel between the electrodes 42.

Therefore, the specimen 6 'is tensioned through the tension roller 27 via the plurality of electrode rods 42 and the guide rolls 32 in the state of being initially wound on the roll on which the clutch brake 28 is installed. 26) is wound on the roll, the surface modification operation by the plasma treatment is performed in this transfer process.

In particular, the electrode 42 is preferably arranged to alternate the anode and the cathode, the cooling pipe 43 is placed into the electrode 42 to allow the coolant to flow to remove the temperature influence of the fiber sample itself.

As the means for applying a voltage to the electrode 42, it is preferable to use a pulsed power supply that varies in pulse voltage of 1kv to 20kv, pulse frequency of 10Hz to 600KHz, and pulse width of 1sec to 60sec.

The pulsed power supply is connected to the generator 3 'and then connected to each electrode 42.

Since the power supply does not use an RF plasma, a separate plasma can be obtained without the need for a separate impedance matching box. In particular, the pulse power has the advantage of controlling the direction of movement of ions, electrons, and radicals generated in the plasma. .

In addition, the gas rod 31 is disposed between the electrode rods 42 so as to smoothly induce plasma surface modification, and the gas supplied from the gas supply tank 8 'is guided to an adjacent position of the sample 6'. At the same time, it is preferable to guide the electrode 42 to the nearest state to maintain the plasma atmosphere inside the vacuum chamber 1 'in an optimal state.

The fiber surface modification apparatus according to another possible embodiment of the present invention having such a configuration is operated as follows.

The vacuum pump 5 'is operated in a state in which the fiber sample 6' to be processed is arranged as shown in the figure so as to be wound and recommended, so that the vacuum degree inside the vacuum chamber 1 'is maintained at 700 mmTorr.

In this state, gas such as helium, neon, argon or nitrogen, oxygen, CF ₄ , NH ₃ stored in the gas supply tank 8 'is charged into the vacuum chamber 1'.

Subsequently, the vacuum pump 5 'was again operated to maintain the vacuum degree inside the vacuum chamber 1' at 700 mmTorr, and the pulse voltage 1kv to 20kv, pulse frequency 10Hz to 600KHz, and pulse width 1sec ~ By applying a pulse power variable to 60sec to generate a low-temperature, low-pressure plasma and irradiating the generated plasma to the surface of the sample (6 ') moving at a constant speed to modify the fiber surface.

At this time, the distance between the electrodes is 15cm, the fiber length exposed to the plasma 8 ~ 10m, the plasma treatment time has a processing time of 100 seconds when the processing speed is 5m / min, and has a processing time of 10 seconds when the processing speed is 50m / min This is preferred.

The sample 6 'which has been processed is released from the vacuum chamber 1' with the pulse power off while the vacuum degree of the vacuum chamber 1 'is released.

Hereinafter, experimental examples using the apparatus and method of the present invention will be described.

Experimental Example 1

The 100% polyethylene sample was treated with oxygen and argon under low temperature and low pressure, and the pressure of the used gas was 400 mTorr, respectively, to generate 2.45 GHz of microwaves in the microwave of 1 to 10 GHz.

Table 1 below shows the contact angle measurement results according to the treatment speed. As the treatment speed is slower, the contact angle is lower, and the samples with the increased treatment speed also have improved hydrophilicity and absorption characteristics.

division Gas used Processing speed argon Oxygen Before treatment 80 80 5 m / min 16 8 25m / min 25 18 50 m / min 38 32

Experimental Example 2

Microwave low-temperature, low-pressure plasma at 1 GHz to 10 GHz using CF ₄ gas was performed on 100% polystyrene fibers. The pressure of the used gas was 400 mTorr and was generated by generating a microwave of 2.45 GHz.

Table 2 below shows the contact angle measurement results according to the treatment speed, and it was found that the contact angle was increased by forming a hydrophobic film on the surface of the sample fiber.

Therefore, it could be confirmed that hydrophilicity, hydrophobicity, waterproofness, moisture resistance, and dyeability can be imparted to the fiber surface modification reinforcement purpose.

Processing speed Gas Used (CF ₄ ) Before treatment 75 5 m / min 110 25m / min 103 50 m / min 95

Experimental Example 3

100% polyester fiber was polymerized with hexafluoropropene (HFP, CF ₃ -CF ₃ = CF ₂ ) as monomer at 5m / min and 25m / min at a frequency of 2.45 GHz and a pressure of 0.3 Torr in a vacuum chamber. The polyester fibers were unloaded in the vacuum chamber.

Subsequently, the treated fibers were tested in hydrothermal and water repellent water at 100 ° C. in boiling water, treated with a heater for 7 hours, dried at 120 ° C. for 30 minutes, and water was dropped onto the polyester fiber fabric.

As a result, it has hydrophobicity and water repellency effect and excellent durability at 5m / min and 25m / min treatment speed as shown in Table 3 below, which shows the water repellency and hydrophobic characteristics conditions after low temperature and low pressure plasma hexafluoropropene polymerization using microwave. can confirm.

division Hexafluoropropene (HFP, CF ₃ -CF ₃ = CF ₂ ) Hexafluoropropene (HFP, CF ₃ -CF ₃ = CF ₂ ) frequency 2.45 GHz 2.45 GHz pressure 0.3 0.3 Processing speed 5 m / min 25m / min Sample fiber polyester polyester Monomer injection vacuum One One

Experimental Example 4

100% of nylon 6 fibers were treated according to the conditions shown in Table 4, respectively, and then polymerized with acrylic acid.

100% nylon 6 fiber after the treatment was exposed to air, and its hydrophilicity and dyeing characteristics were examined. As a result, it showed a constant contact angle within 20 ° C even after 7 days. Its surface area was enhanced by conventional RF plasma, corona, and electron ion implantation methods. It has been shown that it shows excellent hydrophilicity, moist water, and dyeing characteristics in a large capacity.

division Acrylic acid Acrylic acid frequency 2.45 GHz 2.45 GHz pressure 0.4 Torr 0.4 Torr Processing speed 5 m / min 25 m / min Sample fiber Nylon 6 Nylon 6 Plasma Treatment Gas argon argon Monomer injection vacuum 10 Torr 10 Torr Monomer temperature 310 K 310 K

Experimental Example 5

Oxygen and argon gas were put into 100% polystyrene samples, respectively, and low-temperature and low-pressure plasma were performed. 500 [sccm] was used for each of the used gases, and the pulse width for generating plasma was 50 sec and the pulse frequency was 200 KHz.

Table 5 below confirmed the treatment speed and the hydrophilic characteristics of each gas by contact angle measurement.

Processing speed Before treatment 5 m / min 25m / min 50 m / min Oxygen 81 5 11 15 argon 81 9 16 23

As described in detail above, the present invention provides the following effects.

First, the structure is simple and easy to install because it does not need to install the matching box that is required and additionally the difficulty of the electrode arrangement of the existing RF plasma method.

Second, by using microwave and pulse power of the electrodeless discharge type, manufacturing cost can be lowered and uniform fiber surface modification effect can be obtained stably.

Third, since the fiber can be processed continuously and is suitable for large-capacity and large-area processing, it is easy to process high-performance fibers such as industrial filters, medical care, air, and the environment.

Claims (9)

A dumbbell-shaped vacuum chamber 1 connected by a connecting passage 1a and hollowed therein; Constant speed motors are respectively provided on the shaft of the roll provided with the sample 6 so that the sample 6 provided in a roll form inside the vacuum chamber 1 moves from one side to the other side through the connecting passage 1a and is wound / reeled. (7) and the clutch brake 21; Magnetrons 2 arranged in the longitudinal direction on the outer circumferential surface of the connection passage 1a; A quality (17) and a waveguide (16) connected to the magnetron (2) to uniformly guide the oscillated electromagnetic waves into the connection passage (1a); A power supply (3) connected to the magnetron (2) and applying a high voltage; A vacuum pump 5 installed at one side of the vacuum chamber 1; It comprises a gas supply tank (8) and a monomer storage tank (9) connected to the connecting passage (1a) and installed in the adjacent side so as to inject the plasma atmosphere gas and the polymerization monomer into the connecting passage (1a) Fiber surface modification apparatus using a low temperature low pressure plasma, characterized in that. The fiber surface modification apparatus according to claim 1, wherein a reflection shade 23 is installed at a portion where the connection passage 1a and the vacuum chamber 1 are connected to each other to prevent leakage of electromagnetic waves. The fiber using the low temperature low pressure plasma according to claim 1, wherein the power supply 3 is a high frequency my wave power supply for oscillating a high density microwave having a frequency range of 300 MHz to 30 GHz and a wavelength of 1 cm to 1 m. Surface modification device. The fiber using the low temperature low pressure plasma according to claim 1, wherein the monomer stored in the monomer storage tank 9 is any one selected from acrylic acid, methacrylic acid, acrylamine, hexafluoropropene, and acrylonitrile. Surface modification device. The method of claim 1, wherein the gas stored in the gas supply tank 8 is any one selected from helium, argon, nitrogen, neon, oxygen, CF ₄ , SF ₆ , NH ₃ . Fiber surface modification device. A rectangular vacuum chamber 1 'hollow inside; A constant speed motor 26 and a clutch brake 28 fixed on a roll shaft on which the sample 6 'is mounted to wind / reel the sample 6' provided in the vacuum chamber 1 '; A plurality of electrode rods 42 in which an anode and a cathode are alternately arranged so that the sample 6 'may be progressed in a zigzag form while being subjected to a predetermined tension; A plurality of guide rolls 32 fixed to each outside of the electrode rods 42; A vacuum pump 5 'connected to the vacuum chamber 1'; A gas supply tank 8 'installed at an adjacent position for supplying the sectional gas inside the vacuum chamber 1' and connected by a connection pipe 24 '; Fiber surface modification apparatus using a low-temperature low-pressure plasma, characterized in that it comprises a pulsed power supply connected to the electrode 42 to apply pulsed power. The fiber surface modification apparatus of claim 6, wherein the pulse applied through the pulse power supply is variable with a pulse voltage of 1kv to 20kv, a pulse frequency of 10Hz to 600KHz, and a pulse width of 1sec to 60sec. The fiber surface modification apparatus according to claim 6, wherein a plurality of cooling pipes (43) through which cooling water flows are inserted into the electrode (42). Mounting samples 6, 6 'in roll form inside the vacuum chamber 1, 1'; When the samples 6 and 6 'are mounted, the vacuum chambers 1 and 1' are vacuumed to a predetermined vacuum through the vacuum pumps 5 and 5 ', and then the monomers and the atmosphere gas or the atmosphere gas alone are used to vacuum the chambers 1 and 1'. ') And re-vacuum back to vacuum prior to charging; When the vacuum is completed, driving the constant speed motors 7 and 26 to transfer the samples 6 and 6 '; Modifying the surface of the sample (6,6 ') by transferring the sample (6,6') and generating a low-temperature, low-pressure plasma through microwave or pulse power through a voltage application means at the same time; A method of modifying a fiber surface using a low temperature low pressure plasma, comprising: winding a surface-treated sample (6, 6 ') and detaching it from a vacuum chamber (1,1').