JP5946119B2 - Plasma processing method, plasma processing apparatus, and manufacturing method of long object - Google Patents

Description

The present invention relates to a plasma processing method, a plasma processing apparatus, and a method for manufacturing a long object that perform plasma processing by bringing plasma into contact with a long object .

  In recent years, many fishing lines that have been colorfully painted have come to be seen, and suppression of peeling of the paint has become an issue.

  As shown in FIG. 12, the production process of the painted fishing line is first washed with an aqueous solution containing a surfactant to remove dirt and oil adhering to the surface of the undyed line in step (a). Followed by drying to remove moisture adhering to the yarn in step (b). Next, in step (c), the dyed solution is applied to the washed yarn or dyed by immersing the yarn in the dyed solution. The dyed yarn is heated in step (d) to fix the dye, and a painted fishing line is obtained.

  In this manufacturing process, the wettability of the dyeing liquid onto the yarn surface is improved by washing with water in step (a) and drying in step (b) before dyeing the yarn.

  It is common to perform a modification treatment on the surface of a substrate in this way in the painting process, not limited to fishing lines, and various methods have been reported. Patent Document 1 describes that surface treatment is performed on synthetic fibers and chemical fibers, cloths, woven fabrics, and nonwoven fabrics made of these using atmospheric pressure glow discharge plasma. According to an embodiment described in Patent Document 1, it is described that a surface of a polyester cloth is hydrophilized by performing an atmospheric pressure glow discharge plasma treatment, thereby flexographic printing with water-based ink on the surface. The effect of making it easy is described.

  Furthermore, it is possible to sterilize or clean the surface of the substrate by bringing the substrate into contact with plasma, and various applications are conceivable.

  In Patent Document 2, a plurality of electrodes are provided on the outer peripheral surface of a cylindrical tube, and a glow discharge plasma is generated in the tube under atmospheric pressure by applying a voltage to the electrodes so as to have a potential difference in the length direction. The device to be made is described.

JP-A-6-182195 JP-A-4-334543

  However, although plasma treatment is very excellent in surface modification, there is variation in the plasma density distribution in the treatment chamber, and the surface of a cylindrical long object such as a fiber is treated uniformly. It is necessary to provide a certain amount of processing time.

  In addition, when the present inventors conducted an experiment in which plasma treatment was performed on an electrically conductive yarn using the apparatus described in Patent Document 2, abnormal discharge was generated between the electrode and the electrically conductive yarn. Was generated, and plasma was generated so as to cling to the electrically conductive yarn, making it difficult to generate plasma normally. From this experiment, it became clear that it was difficult to perform plasma treatment on the electrically conductive yarn using the apparatus described in Patent Document 2.

  In addition, there is a great demand to perform a modification treatment on the surface of not only fishing lines but also long objects such as fibers and tubes and fabrics made of long objects.

  In order to solve these problems, in the present invention, a plasma having a high density is selectively passed through a plasma having a varied density distribution, so that the plasma can be rapidly applied to a long object. A plasma processing method and a plasma processing apparatus excellent in operability using the plasma processing method and the plasma processing method capable of performing uniform and uniform surface treatment on the surface of a long workpiece while performing the treatment The purpose is to provide a scale.

In order to achieve the above-described object, the plasma processing method of the present invention is a plasma processing method for performing plasma processing by bringing a plasma into contact with a long object, and the plasma has a density distribution. Plasma treatment is performed on the long object to be processed while the long object to be processed is selectively spiraled and passed through a region having a high plasma density. And

  According to the plasma processing method of the present invention as described above, the plasma processing is performed on the long workpiece while selectively passing through the region where the plasma density is high, so that the plasma processing can be performed efficiently. Further, it is possible to perform uniform plasma processing while suppressing generation of processing variations due to plasma density differences.

In order to achieve the above-described object, the first plasma processing apparatus of the present invention includes at least a first cylindrical portion in which plasma is generated and a longitudinal direction of an outer peripheral surface of the first cylindrical portion. Two or more ring-shaped electrodes, a plasma generation gas introduction portion for introducing a plasma generation gas into the first cylindrical portion, and an elongated shape provided inside the first cylindrical portion A guide portion that guides the object to be processed so as to travel in the region where the plasma density is high, and the guide portion is composed of a plurality of guide members arranged in the longitudinal direction of the first cylindrical portion, The plurality of guide members are formed in a shape that guides the elongate object to be processed so as to spirally advance the region of the first cylindrical portion where the plasma density is high. To do.

According to such a first plasma processing apparatus of the present invention, the plasma generating gas is introduced into the first cylindrical portion from the plasma generating gas introducing portion, and the potential difference in the longitudinal direction with respect to the ring-shaped electrode is achieved. In the first cylindrical portion, a region with high density is not formed near the inner wall of the first cylindrical portion, and the guide portion is long in such a high plasma density region. By bringing the plasma into contact with the elongated workpiece to be processed, the plasma treatment can be performed by easily bringing the high density plasma into contact with the elongated workpiece. Furthermore, since the long object to be processed is guided by the guide member so that the region where the plasma density is high is spiraled, the surface of the long object to be processed is uniformly exposed to the region where the plasma density is high. The surface of the long object can be uniformly and uniformly plasma-treated. Furthermore, since the region where the plasma density is high is spirally advanced, a higher surface treatment effect can be obtained even at a short distance than when the region is linearly advanced. Therefore, the apparatus itself can be reduced in size.

In the second plasma processing apparatus of the present invention, the first cylindrical portion is formed by connecting a plurality of unit cylinders in the longitudinal direction.

According to the second plasma processing apparatus of the present invention, when a long object to be processed is set in the apparatus, after passing the long object to be processed through each unit cylinder, the unit cylinder The plasma processing apparatus can be assembled so as to be connected to each other, and has excellent operability.

In the third plasma processing apparatus of the present invention, a thin cylindrical insulating tube is provided inside the first cylindrical portion, and the insulating tube is disposed so as to pass through a region where the plasma density is low. It is characterized by.

According to the third plasma processing apparatus of the present invention as described above, it is possible to prevent the plasma generating gas from flowing to the low plasma density region by passing the insulating tube through the low plasma density region. Therefore, it is possible to reduce the running cost by suppressing unnecessary consumption of the plasma generating gas.

The fourth plasma processing apparatus of the present invention is characterized in that a refrigerant is introduced into the insulating tube.

According to the fourth plasma processing apparatus of the present invention, the plasma generated in the first cylindrical portion can be cooled to prevent the plasma temperature from rising. Even in the case of using a heat-sensitive material as an object, plasma treatment can be performed.

The fifth plasma processing apparatus of the present invention includes a first cylindrical portion in which plasma is generated, a ring-shaped electrode formed over the entire outer peripheral surface of the first cylindrical portion, and the first A plasma generating gas introduction part for introducing a plasma generating gas into one cylindrical part, and a long object to be processed spirally in the region where the plasma density is high inside the first cylindrical part. A plurality of guide members provided in the longitudinal direction of the first cylindrical portion in a shape that guides so as to advance to the inside of the first cylindrical portion so as to pass through a region where the plasma density is low And a thin cylindrical insulating tube, and a conductive material is introduced into the insulating tube.

According to the fifth plasma processing apparatus of the present invention, since a plasma is generated by providing a potential difference between the ring-shaped electrode and the conductive material and generating a dielectric barrier discharge, the plasma has a higher density. This makes it possible to form a uniform region and to perform uniform plasma treatment at high speed uniformly on a long workpiece.

The sixth plasma processing apparatus of the present invention is characterized in that the conductive material introduced into the insulating tube is a conductive liquid.

According to the sixth plasma processing apparatus of the present invention, since the conductive material is a conductive liquid, high adhesion to the inner wall of the insulating tube can be obtained, so that the dielectric barrier discharge can be efficiently performed. Can be generated.

The seventh plasma processing apparatus of the present invention is characterized in that the conductive liquid is formed to always flow inside the insulating tube.

According to such a seventh plasma processing apparatus of the present invention, it is possible to prevent the heat generated when the plasma is generated from being accumulated and to cool the plasma while supplying power.

An eighth plasma processing apparatus of the present invention includes a tank for storing the conductive liquid, introduces the conductive liquid from the tank to the inside of the insulating pipe, and supplies the tank from the inside of the insulating pipe. The conductive liquid is led out to the inside of the tank and the insulating tube so that the conductive liquid circulates.

According to the eighth plasma processing apparatus of the present invention, it is possible to suppress an increase in plasma temperature by circulating the conductive liquid.

The tenth plasma processing apparatus of the present invention is characterized in that the plasma generating gas introducing portions are provided at both ends of the first cylindrical portion, respectively.

Method for producing a long object of the present invention, in the plasma there are variations in the density distribution, the advance of the elongated article Do that a synthetic polymer compound fibrous selectively helical regions high density of the plasma In addition, the long object is made of the fibrous synthetic polymer compound having a modified surface by subjecting the long object to plasma treatment while passing through.

According to such a method for producing a long object of the present invention, it is possible to provide a long object having a desired surface state and having high hydrophilicity, for example.

  According to the plasma processing method of the present invention, in a plasma with a variation in density distribution, a plasma processing is performed at high speed on a long workpiece by selectively passing a region having a high plasma density, Uniform surface treatment can be performed evenly on the surface of a long workpiece.

  Moreover, according to the plasma processing apparatus of this invention, the plasma processing apparatus excellent in operativity can be provided.

  Furthermore, according to the plasma processing apparatus of the present invention, it is possible to perform effective plasma processing even on a long object to be processed made of a conductive material.

  Furthermore, by using the plasma processing method and the plasma processing apparatus of the present invention, it is possible to obtain a long product having a desired surface modification.

The schematic perspective view which shows the plasma processing apparatus of 1st Embodiment of this invention. FIG. 1 is an enlarged perspective view of a part of the plasma processing apparatus of the present invention shown in FIG. Sectional drawing of the principal part of the plasma processing apparatus of this invention shown in FIG. Schematic cross-sectional view showing the state of a guide section that guides a long object to be processed linearly Schematic cross-sectional view showing a state of guiding a long object to be processed spirally The perspective view which shows the plasma processing apparatus of this invention at the time of connecting a unit cylinder and forming a 1st cylindrical part. The expanded perspective view which cut | disconnected some plasma processing apparatuses of this invention at the time of arrange | positioning an insulating tube The expanded perspective view which cut | disconnected a part of plasma processing apparatus of 2nd Embodiment of this invention. Side view showing a plasma processing apparatus according to a third embodiment of the present invention. The side view which shows the plasma processing apparatus at the time of arrange | positioning two or more 2nd cylindrical parts in 3rd Embodiment of this invention. The side view which shows the plasma processing apparatus of this invention at the time of connecting a unit cylinder and a connection member and forming a 1st cylindrical part and a 2nd cylindrical part. Flow chart showing fishing line manufacturing process

  Hereinafter, specific embodiments of the plasma processing method and the plasma processing apparatus of the present invention will be described with reference to FIGS.

  The plasma processing method of the present invention is a method of performing plasma processing by bringing a plasma into contact with a long object to be processed, and there is a variation in the density distribution of the plasma. Plasma treatment is performed on a long workpiece while selectively passing through a region having a high plasma density.

  The long object to be processed includes fibers, twisted yarns, braided yarns, pipes, nanotubes, and combinations thereof, and may be made of any material such as inorganic materials and organic materials. In particular, the inorganic substance is stainless steel, tungsten, steel, and the like, and the organic substance is a polyamide resin, a fluorine resin, a polyester resin, a yarn formed from a polyolefin resin, and a composite yarn thereof.

  Specifically, nylon 6, nylon 66, nylon 12, etc. and polyamide polymers made of copolymers thereof, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene succinate, etc., and polyesters made of these copolymers Polymers, polyolefin polymers such as polyethylene and polypropylene, fluorine polymers such as polyvinylidene fluoride and polytetrafluoroethylene, acrylic polymers having acrylonitrile as the main chain, polyurethane polymers, and polymers having fiber-forming properties such as polylactic acid A spun yarn composed of monofilament, multifilament and cut fibers thereof, or a composite yarn such as a blended yarn or a blended yarn is used. The diameters of these fibers may be any diameter as long as they do not cause problems such as yarn breakage in the apparatus.

  A first embodiment of the plasma processing apparatus of the present invention using the plasma processing method of the present invention will be described.

  As shown in FIG. 1, the plasma processing apparatus 1 according to the first embodiment of the present invention is provided with a first cylindrical portion 2 formed of a cylindrical tube and an outer peripheral surface of the first cylindrical portion 2 to which power is applied from a power source P. At least two or more ring-shaped electrodes 3 arranged in the longitudinal direction so as to be in close contact with each other, and a plasma generating gas introducing portion 4 for introducing a plasma generating gas into the first cylindrical portion 2 And are provided. When the first cylindrical portion 2 is a cylindrical tube as in the present embodiment, the charges of the ring electrode 3 adjacent to the ring electrodes 3 arranged at least two or more are positive and negative charges. When a voltage is applied with a potential difference in the longitudinal direction so that the alternating currents are alternately arranged, the plasma density distribution varies within the first cylindrical portion 2, and the plasma density near the inner wall where the current density is high The density is the highest and the density of the plasma decreases as it approaches the central portion in the radial direction, and a uniform density distribution appears in the longitudinal direction of the first cylindrical portion 2.

  As shown in FIG. 2, a guide portion 5 including a plurality of disk-shaped guide members 5 a disposed in the longitudinal direction of the first tubular portion 2 is provided inside the first tubular portion 2. Yes. As shown in FIG. 3, the guide member 5 a has a smaller diameter than the guide member 5 a in the region where the plasma density appears inside the first cylindrical portion 2, that is, in the vicinity of the inner wall of the first cylindrical portion 2. At least one support hole 5c having a center on the concentric circle 5b and penetrating in the thickness direction of the guide member 5a is formed. A through hole 5d is formed at the center of the guide member 5a.

  When performing the plasma treatment on the long workpiece W, as shown in FIG. 4, it is supported through the long workpiece W in the support hole 5c and has a high plasma density. The first cylindrical portion 2 is guided to the vicinity of the inner wall.

  By using the plasma processing apparatus 1 according to the first embodiment of the present invention as described above, even when plasma processing is performed using plasma with variations in plasma density, the surface of the long workpiece W is applied to the surface. On the other hand, since plasma processing can be performed by contacting high-density plasma, high-speed plasma processing is possible.

  Further, as shown in FIG. 5, the guide member 5a is provided so that the support holes 5c between the guide members 5a form a predetermined angle with respect to the longitudinal central axis of the first cylindrical portion 2, and each support is provided. When the long workpiece W is supported with respect to the hole 5c, the elongated workpiece W is spirally formed in a region where the plasma density of the first cylindrical portion 2 is high, that is, in the vicinity of the inner wall. Each guide member 5a may be formed in a shape that guides it so as to advance to the right.

  By adopting such a guide member 5a, for example, the second guide member 5a (2) is moved around the longitudinal central axis of the first tubular portion 2 with respect to the first guide member 5a (1). When formed with an inclination of 45 °, the long workpiece W moves from the guide member 5a (1) to the guide member 5a (2), so that high density plasma is generated in the guide member 5a (1). High-density plasma comes into contact with the portion of the outer peripheral surface that is shifted by 45 ° around the central axis from the position of the outer peripheral surface of the long workpiece W that has been in contact. Accordingly, the workpiece W is spirally advanced and passed by the eight guide members 5a disposed in the longitudinal direction of the first tubular portion 2 with an inclination of 45 ° in accordance with (1) to (8). As a result, high-density plasma can be brought into contact with the entire outer peripheral surface of the long workpiece W, so that the surface of the long workpiece can be uniformly and uniformly treated. And

  Furthermore, when the distance between each guide member 5a is the same, it is necessary for the workpiece W to make one round of the inner peripheral surface of the first cylindrical portion 2 by increasing the inclination provided in the guide member 5a. Since the distance to the longitudinal direction of the 1st cylindrical part 2 can be shortened, the plasma processing apparatus 1 can be reduced in size. Specifically, when the inclination is provided at 45 °, eight guide members 5a are required to make one round of the inner peripheral surface of the first tubular portion 2, whereas the inclination is provided at 90 °. The number of guide members 5a may be four to make one round of the inner peripheral surface of the first tubular portion 2, and the length of the first tubular portion 2 in the longitudinal direction can be ½ or less. .

  In the state where the long workpiece W is supported in the support hole 5c of the guide member 5a as shown in FIG. 4, each guide member 5a is rotated by a predetermined angle to obtain a long shape as shown in FIG. The workpiece W may be spirally advanced with respect to the longitudinal direction of the first cylindrical portion 2.

  Moreover, as shown in FIG. 6, it can be set as the 1st cylindrical part 2 by connecting the some unit cylinder 2a. By setting it as the 1st cylindrical part 2 like this, after passing the elongate to-be-processed object W with respect to the support part 5c of the guide member 5a, the unit cylinder 2a is connected, and the 1st cylindrical part 2 is connected. Therefore, even when a material having poor shape stability is processed as the long workpiece W, it can be easily set and the operability of the plasma processing apparatus 1 can be improved. Furthermore, when the guide member 5a is rotated so that the long workpiece W is advanced in a spiral shape, it is easily connected to the unit tube 2a while providing an angle. The object W can be made to advance spirally.

  Further, as shown in FIG. 7, a thin cylindrical insulating tube 6 is inserted into a space formed by the through hole 5d of the guide member 5a inside the first cylindrical portion 2. The plasma generation gas is introduced only into the space formed by the outer peripheral surface of the insulating tube 6 and the inner wall of the first cylindrical portion 2 to generate plasma, thereby reducing the amount of plasma generation gas used. The running cost can be reduced by suppressing the running cost.

  Moreover, since the temperature of the plasma can be prevented by introducing a coolant such as cooling water into the insulating tube 6, the plasma treatment is also performed on the long workpiece W that is weak against heat. Can do.

  Next, a second embodiment of the plasma processing apparatus 1 of the present invention will be described. In the second embodiment of the present invention, as shown in FIG. 8, the ring-shaped electrode 3 is formed so as to extend over the entire length of the outer peripheral surface of the first cylindrical portion 2, and the inside of the insulating tube 6 is made of copper. A conductive material 7 made of a cylindrical rod is inserted in close contact with the inner wall of the insulating tube 6. At this time, a plasma generating gas is introduced into a space formed by the inner wall of the first tubular portion 2 and the outer peripheral surface of the insulating tube 6, and power is supplied to the ring-shaped electrode 3 and the conductive material 7 using the power source P. And generating a dielectric barrier discharge by applying a voltage so as to provide a potential difference in the radial direction of the first cylindrical portion, thereby generating plasma.

  In a space formed by the inner wall of the first tubular portion 2 and the outer peripheral surface of the insulating tube 6, a plurality of guide members 5a are arranged in the longitudinal direction, and the long workpiece W is placed in the space. It is designed to support and guide.

  In the second embodiment, the conductive material 7 has been described as a copper cylindrical rod. However, in order to efficiently generate a discharge, the adhesion between the inner wall of the insulating tube 6 and the outer peripheral surface of the conductive material 7 is improved. The height is important, and it is more preferable to use, for example, an aqueous electrolyte solution such as a sodium chloride aqueous solution or seawater or a conductive liquid such as mercury as the conductive material 7, and the adhesion to the inner wall of the insulating tube 6 is extremely high. Thus, dielectric barrier discharge can be generated efficiently.

  In addition, the conductive liquid is formed to always flow inside the insulating tube 6. For example, a tank for storing a conductive liquid is provided, the conductive liquid is introduced from the tank into the insulating tube 6, and the conductive liquid is led from the inside of the insulating tube 6 to the tank. It is preferable to circulate the conductive liquid inside the insulating tube 6. By always flowing a conductive liquid, it can be cooled while supplying power, and an effect as a refrigerant can also be expected. In addition, the effect as a refrigerant | coolant can further be improved by cooling a conductive liquid in a tank or a flow path.

  By using the plasma processing apparatus 1 of the second embodiment as described above, it is possible to form a region where the plasma is denser, and to uniformly treat the long workpiece W at high speed uniformly. Can be applied.

  Examples using the plasma processing method of the present invention will be described below.

<Example>
Using the plasma processing apparatus 1 of the present invention, plasma processing was performed on the long workpiece W, and the processing effect was examined.

  In this example, as a long workpiece W, a polyamide monofilament having a diameter of 0.243 mm (a nylon / Nylon 66 85/15 copolymer) and a diameter of 0.268 mm were used. Samples were prepared using 400 denier / 384 filament ultrahigh molecular weight polyethylene fibers formed by combining four polyvinylidene fluoride monofilaments and four 100 denier / 96 filament ultrahigh molecular weight polyethylene fibers.

  The following describes how to create a detailed sample.

<How to create a sample>
The long workpiece W is provided by two yarn feed rolls with a nip roller provided with a predetermined plasma processing apparatus installation range (in this embodiment, an installation range of about 1 m is provided). The unprocessed long workpiece W is set so as to be conveyed from the raw yarn bobbin wound with the winding bobbin.

  In order to clarify the processing effect of the plasma processing apparatus 1 of the present invention, in addition to the plasma processing apparatus 1 of the present invention, a multi-gas plasma jet processing apparatus (multi-gas plasma manufactured by Plasma Concept Tokyo Co., Ltd.) is used for comparison. These were disposed in the plasma processing apparatus installation range, and the plasma treatment was performed on the long workpiece W.

  The aspect of each plasma processing apparatus will be described.

  In the plasma processing apparatus 1 of the present invention, a plasma irradiation range of about 18 cm was formed by arranging a plurality of copper electrodes on a glass tube having a diameter of 3 mm and a length of 1 m as shown in FIG. In the side wall on one end side of the glass tube, a plasma generating gas inlet for introducing the plasma generating gas is formed, and in order to suppress the discharge of the plasma generating gas at one end of the glass tube, The opening is narrowed with an adhesive film. Electric power is applied to each of the plurality of copper electrodes from a power supply device, and a voltage is applied so that a potential difference is provided in the longitudinal direction of the glass tube.

  In the multi-gas plasma jet processing apparatus, a plasma inlet is provided at a substantially central portion in the longitudinal direction of a plastic tube having a diameter of 8 mm and a length of 1 m, and an injection port of the multi-gas plasma jet generator is connected to the plasma inlet. The plasma is introduced into the tube so that the plasma flows in the opposite direction from the plasma inlet to both ends of the plastic tube. In the plasma processing on the workpiece, a long workpiece W is introduced from one end portion of the plastic tube and is led out from the other end portion. Plasma is brought into contact with the surface of W.

  A single gas or mixed gas of argon gas, helium gas, oxygen gas and carbon dioxide gas was used as the plasma generating gas.

  A sample conveys a long workpiece W from a raw yarn bobbin to a take-up bobbin at a predetermined conveyance speed, and plasma irradiation is performed by each plasma processing apparatus provided in a plasma processing apparatus installation range provided therebetween. Processing is performed, and the processed long workpiece W is aligned on the winding bobbin so that there is no space between the yarns and wound around a single layer. In this example, a bobbin having a diameter of 50 mm and a winding width of 65 mm was used as the winding bobbin.

  A method for measuring the contact angle of the sample will be described.

<Measurement method of contact angle>
A portable contact angle meter PG-X manufactured by FIBROsystemAB (Sweden) was used as the measurement apparatus. In the measurement, a measuring device was set on the yarn that was aligned and wound around the sample, and pure water was dropped on the yarn to detect the contact angle between the aligned yarn row and pure water. In addition, a contact angle shows that it is a hydrophilic surface, so that a value is small, and it shows that it is a water-repellent surface, so that a value is large.

  First, using a multi-gas plasma jet processing apparatus, the difference in the processing effect depending on the gas type on each object to be processed was examined. Table 1 shows the results of the gas type, gas flow rate, sample transport speed, and contact angle before / after treatment used for plasma treatment of each sample. In the table, F1 represents a polyamide monofilament, F2 represents a polyvinylidene fluoride monofilament, and F3 represents an ultrahigh molecular weight polyethylene fiber.

  When the material is polyamide monofilament as F1, No. in Table 1 As shown in FIG. 1, a high hydrophilization effect was obtained by performing plasma treatment using a plasma generation gas in which 1% by volume of oxygen gas was added to 100% by volume of argon gas. In addition, no. 2 and no. As shown in FIG. 3, when the plasma treatment was performed using a plasma generation gas in which 1% by volume of carbon dioxide gas was added to 100% by volume of helium gas, No. 3 with a gas flow rate of 5 L / min. In No. 2, a slightly hydrophilizing effect was observed, and the gas flow rate was 10 L / min. In No. 3, a high hydrophilization effect was observed. No. 4 and no. As shown in FIG. 5, when the plasma treatment was performed using a plasma generating gas in which 1 volume% of oxygen gas was added to 100 volume% of the herim gas, No. 5 having a gas flow rate of 5 L / min. In No. 4, although a slightly hydrophilizing effect was observed, No. 4 with a gas flow rate of 10 L / min. On the other hand, the result of 5 showed a water repellency effect.

  When the material is polyvinylidene fluoride monofilament as F2, No. As shown in FIG. 6, the plasma treatment is performed using a plasma generating gas in which 1% by volume of oxygen gas is added to 100% by volume of argon gas. It was. No. As shown in FIG. 7, a slight hydrophilization effect was observed when plasma treatment was performed using a plasma generation gas in which 1 volume% of carbon dioxide gas was added to 100 volume% of helium gas. Conversely, no. As shown in FIG. 8, when plasma treatment is performed using a plasma generating gas in which 1% by volume of oxygen gas is added to 100% by volume of helium gas, the contact angle is increased and a water repellent effect is recognized. As a result.

  Similarly, when the raw material was ultra-high molecular weight polyethylene fiber as F3, it showed hydrophilicity before the treatment, and it penetrated in about 1 second 30 when pure water was dropped. No. 9 and no. As shown in FIG. 10, by performing plasma treatment using a plasma generation gas of carbon dioxide gas 100 volume% and argon gas 100 volume%, the result shows that the dripped pure water is so hydrophilic that it permeates in an instant. became.

  Next, using the plasma processing apparatus of the present invention or the comparative multi-gas plasma jet processing apparatus, the contact angle is measured when the polyamide monofilament (F1) and the polyvinylidene fluoride monofilament (F2) are subjected to plasma processing. The processing effect of the plasma processing apparatus of the present invention was examined. Table 2 shows the results of measurement of the processing apparatus, gas type, gas flow rate, sample transport speed, and contact angle before / after processing used for processing each sample.

  When the material is polyamide monofilament as F1, No. in Table 2 Ny1 and No. As shown in Ny2, the hydrophilization effect was observed in the samples subjected to the plasma treatment using either the plasma treatment apparatus of the present invention or the comparative multi-gas plasma jet treatment apparatus. However, in the sample processed using the comparative multi-gas plasma jet processing apparatus, since the contact angle is uneven, it is considered that the object to be processed is not uniformly processed. On the other hand, in the sample using the plasma processing apparatus of the present invention, such contact angle unevenness was not recognized, and the surface of the object to be processed could be uniformly treated.

  When the material is polyvinylidene fluoride monofilament as F2, No. FC1 and No. As shown in FC2, in the sample subjected to the plasma treatment using the plasma treatment apparatus of the present invention, the contact angle of pure water was 0.0 °, and a high hydrophilization effect was observed, but for comparison, In the sample using the multi-gas plasma jet processing apparatus, the contact angle increased. From this, it was clarified that by using the plasma processing apparatus of the present invention, it is possible to perform uniform plasma processing evenly on the object to be processed, and a high surface modification effect can be obtained.

  Furthermore, in order to examine the processing effect in the plasma processing apparatus of the present invention using the polyvinylidene fluoride monofilament as the material F2, pure water for the sample when the processing speed of the workpiece is changed and the plasma processing is performed. The contact angle results of No. FC1, No. FC3 and No. This will be described using FC4.

  When the transfer speed is 5 m / min or 10 m / min, No. FC1 and No. As shown in FC3, pure water penetrated in an instant and the contact angle was 0.0 °, and a high hydrophilic effect was recognized. Furthermore, when the conveyance speed is increased to a conveyance speed of 20 m / min, no. As shown in FC4, although the contact angle of the pure water after the treatment decreased and a hydrophilizing effect was recognized, the surface modification until the pure water penetrated was not achieved. From this result, it can be seen that the longer the plasma irradiation time to the object to be processed, the higher the surface modification effect.

  Thus, by using the plasma processing apparatus of the present invention, it is possible to obtain a high surface modification effect on the long workpiece W. Furthermore, a uniform and uniform plasma treatment can be performed on the surface of the workpiece.

  In addition, a third embodiment of the plasma processing apparatus 1 of the present invention will be described.

  In the third embodiment of the present invention, as shown in FIG. 9, for example, plasma is stably generated even when a plasma treatment is performed on a long workpiece W having electrical conductivity such as tungsten or steel. In addition, the embodiment was invented to enable good plasma processing, and at least one second cylindrical portion integrally formed so as to penetrate perpendicularly to the first cylindrical portion 2. 8 is provided. Further, by introducing a plasma generating gas from the plasma generating gas introducing portion 4 into the first cylindrical portion 2 and applying a voltage so as to provide a potential difference in the longitudinal direction with respect to the ring-shaped electrode 3, Plasma generated inside the first cylindrical portion 2 is introduced into the second cylindrical portion 8.

  In addition, by providing a plug that can be freely opened and closed in the second cylindrical portion 8, it is possible to perform plasma processing on the long object to be processed in the first cylindrical portion 2.

  At this time, in the ring-shaped electrode 3, as shown in FIG. 9, the ring-shaped electrode 3 disposed at a position adjacent to the second cylindrical portion 8 is preferably grounded. Even when the elongated workpiece W having electrical conductivity passes through the portion where the first cylindrical portion 2 intersects, abnormal discharge occurs because the adjacent ring-shaped electrode 3 is in the grounded state. In this way, plasma can be stably generated and introduced into the second cylindrical portion 8.

  Further, it is preferable that the plasma generating gas introducing portions 4 are provided at both ends of the first cylindrical portion 2 respectively, and the second cylindrical portion 8 is made to flow by the flow of the plasma generating gas introduced from both sides. Since the plasma generated in this way can be easily introduced and a higher density plasma can be introduced into the second cylindrical portion 8, plasma processing can be performed on the long workpiece W at high speed. Can be applied.

  Further, when a plurality of second cylindrical portions 8 are provided for the first cylindrical portion 2, as shown in FIG. 10, between the second cylindrical portion 8 and the second cylindrical portion 8. Therefore, it is preferable to further provide a plasma generation gas introduction part 4 for introducing a plasma generation gas at the center so that the matching ring electrodes 3 are provided on both sides.

  In the case of adding a gas such as oxygen gas, carbon dioxide gas and hydrogen gas in order to improve the processing effect to the plasma generating gas, or when adding a deposit for the purpose of chemical vapor deposition, the second cylindrical shape is used. It is preferable to perform the plasma treatment so as to be directly introduced into the portion 8.

  Further, when the first cylindrical portion 2 is formed by connecting a plurality of unit cylinders 2a in the longitudinal direction, the first cylindrical portion 2 and the second cylindrical portion 8 intersect as shown in FIG. A cross-shaped connecting member 9 is provided in the portion to be connected, and the unit tube 2a is connected to a pair of openings 9a, 9c facing the connecting member 9 to form the first cylindrical portion 2, and the connecting member 9 is opposed to the unit tube 2a. The other pair of openings 9b, 9d is configured as the second cylindrical portion 8. In this way, by forming the plasma processing apparatus 1 by connecting the unit cylinder 2a and the connecting member 9, after passing the long workpiece W through the unit cylinder 2a and the connecting member 9, the unit cylinder 2a. Since the plasma processing can be performed by connecting the connecting member 9 and the connecting member 9 so that the plasma processing can be performed, the plasma processing apparatus having excellent operability can be obtained.

  By using the plasma processing apparatus 1 of the third embodiment of the present invention as described above, the first cylindrical portion 2 passes through the long cylindrical workpiece W having electrical conductivity through the second cylindrical portion 8. Since the generated plasma and the long workpiece W are brought into contact with each other inside the second cylindrical portion 8 and the long workpiece W is subjected to plasma treatment, the electrical conductivity is increased. It is possible to suppress abnormal discharge between the long object to be processed W and the ring-shaped electrode 3, generate plasma stably, and have a long object to be electrically conductive. Plasma processing to W can be easily performed.

  The plasma processing apparatus of the present invention is not limited to the first embodiment and the second embodiment, and various modifications can be made without departing from the features of the present invention. For example, the first embodiment In the second embodiment, the guide member 5a is described as a shape in which a plurality of support holes 5c are formed in a disk. However, a ceramic snare type is provided on the circumferential portion of the inner wall of the first cylindrical portion 2. You may form so that the elongate to-be-processed object W may be guided by installing the existing thread path guide of a dock tail type or a loop type.

DESCRIPTION OF SYMBOLS 1 Plasma processing apparatus 2 1st cylindrical part 2a Unit cylinder 3 Ring-shaped electrode 4 Gas generating part for plasma generation 5 Guide part 5a Guide member 5b Concentric circle 5c Support hole 5d Through-hole 6 Insulating tube 7 Conductive material 8 Second cylindrical part 9 Connecting members 9a, 9b, 9c, 9d Opening W Long object P Power supply

Claims (10)

In the plasma processing method of performing plasma processing by bringing plasma into contact with a long workpiece,
The plasma has a variation in density distribution,
The plasma processing is characterized in that the long processing object is subjected to plasma processing while selectively passing spirally through the region having a high plasma density and passing the long processing object. Method. A first tubular portion in which plasma is generated;
At least two ring-shaped electrodes provided in the longitudinal direction of the outer peripheral surface of the first cylindrical portion;
A plasma generating gas introducing portion for introducing a plasma generating gas into the first cylindrical portion;
A guide portion that is provided inside the first cylindrical portion and guides a long object to be processed so as to advance in a region where the plasma density is high,
The guide part is composed of a plurality of guide members arranged in the longitudinal direction of the first cylindrical part,
The plurality of guide members are formed in a shape that guides the elongate object to be processed so as to spirally advance the region of the first cylindrical portion where the plasma density is high. Plasma processing equipment.   The plasma processing apparatus according to claim 2, wherein the first cylindrical portion is formed by connecting a plurality of unit cylinders in the longitudinal direction. A thin cylindrical insulating tube is provided inside the first cylindrical portion,
The plasma processing apparatus according to claim 2, wherein the insulating tube is disposed so as to pass through a region where the plasma density is low.   The plasma processing apparatus according to claim 4, wherein a refrigerant is introduced into the insulating tube. A first tubular portion in which plasma is generated;
A ring-shaped electrode formed over the entire length of the outer peripheral surface of the first tubular portion ;
A plasma generating gas introducing portion for introducing a plasma generating gas into the first cylindrical portion;
A plurality of long objects to be processed are provided in the longitudinal direction of the first cylindrical portion inside the first cylindrical portion so as to guide the long processed object to advance in a spiral manner in the region where the plasma density is high. A guided member;
A thin tubular insulating tube disposed inside the first tubular portion so as to pass through a region where the plasma density is low;
The inside of the insulating tube, characterized and to pulp plasma processing apparatus that conductive material is introduced.   The plasma processing apparatus according to claim 6, wherein the conductive material introduced into the insulating tube is a conductive liquid.   8. The plasma processing apparatus according to claim 7, wherein the conductive liquid is formed so as to always flow inside the insulating tube. A tank for storing the conductive liquid;
The conductive liquid is introduced from the tank to the inside of the insulating tube, and the conductive liquid is led from the inside of the insulating tube to the tank. The plasma processing apparatus according to claim 7, wherein the liquid is circulated. In a plasma with uneven density distribution,
The Do that long object from synthetic polymer compound fibrous subjected to plasma treatment in the long product while passing by selectively proceed helically area high density of the plasma, the modified surface A method for producing a long product, comprising producing a long product comprising the above-mentioned fibrous synthetic polymer compound.

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