JP5048131B2 - Metal-plated fishing line and method for manufacturing the same - Google Patents

Description

  The present invention relates to a fishing line to which metal plating is applied. It also relates to a method for producing such a fishing line.

  High-strength, low-elongation ultra-high molecular weight polyethylene multifilament yarns are widely used as fishing lines because they can accurately capture fish faith. However, since the multifilament yarn of ultra high molecular weight polyethylene has a low specific gravity, it is difficult to sink below the surface of the water, and it is easily affected by tidal currents and winds.

  Several methods for increasing the specific gravity of a fishing line have been proposed so far. For example, Patent Document 1 describes a fishing line in which a metal wire is covered with a plurality of resin fibers to make a string. The example describes a fishing line made of ultrahigh molecular weight polyethylene multifilament thread around a lead wire. However, using a metal wire is difficult to manufacture, and the flexibility of the fishing line becomes insufficient.

  Patent Document 2 describes a fishing line including a monofilament made of a resin containing a metal, but the obtained fishing line becomes hard and flexibility is greatly reduced. Patent Document 3 describes a fishing line in which a core thread formed by stringing a plurality of monofilaments is covered with a resin containing a metal. However, the durability of the formed coating was insufficient.

  Patent Document 4 describes a fishing line in which a surface of a synthetic resin line is coated with a metal or metal oxide thin film. Examples of the method for forming a thin film include sputtering, ion plating, and vacuum deposition, and describes that a thin film having a thickness of 10 to 10,000 mm is formed. However, since the thin film formed by this method is thin, the effect of increasing the specific gravity of the entire fishing line is low. Further, since a thin film of metal or metal oxide is formed only on the surface of the fishing line, there is a problem that it is easily peeled off by friction.

  Patent Document 5 describes a fishing line in which at least a part of an aramid fiber is coated with a heavy metal having a specific gravity of 5.0 or more by plating. As the plating method at this time, a method of twisting and stringing after plating the raw yarn and a method of plating after twisting and stringing are described, but in either case The inside of the fishing line is uniformly plated. Aramid fibers are originally rigid and insufficient in flexibility, but on the other hand, since they are further plated with metal, the flexibility is further impaired. Therefore, the aramid fishing line plated as described above is greatly inferior in reel winding and operability as compared with the fishing line that is normally used.

JP 2002-335836 A JP 2002-191274 A JP 2002-262742 A JP 2000-217483 A JP 2002-335837 A

  The present invention has been made to solve the above-described problems, and has an object to provide a fishing line that is excellent in flexibility, excellent in sedimentation property in water, and in which sedimentation performance is not easily lowered by use. is there. Moreover, it aims at providing the suitable manufacturing method of such a fishing line.

  The above-described problem is a fishing line that is a twisted or made string made of multi-filament yarns of ultra-high molecular weight polyethylene, and the outer surface of the multi-filament yarn is subjected to metal plating, and the single yarns constituting the multi-filament yarn are In the gap portion, metal plating is applied, the depth of the plating area from the outer surface of the multifilament yarn is larger than the equivalent circle diameter of the single yarn, and the center portion of the multifilament yarn is not plated. It is solved by providing the characteristic fishing line.

  At this time, it is preferable that the depth of the plating region is not more than 0.3 times the equivalent circle diameter of the multifilament yarn. It is also preferable that the depth of the plating region is 0.05 times or more the equivalent circle diameter of the multifilament yarn. It is also preferable that the single yarn fineness is 0.5 to 10 dtex, and the fineness of the multifilament yarn is 80 to 6000 dtex. Moreover, it is preferable that the fishing line settles in water, and it is more preferable that the time required for the fishing line cut to a length of 2 cm to settle from the water surface to a depth of 30 cm is 100 seconds or less.

  Moreover, the said subject is also solved by providing the manufacturing method of the said fishing line which performs metal plating by electroless plating with respect to the twist thread | yarn which consists of multifilament thread | yarn of ultra high molecular weight polyethylene, or a string-made thread | yarn.

  The fishing line of the present invention is excellent in flexibility, excellent in sedimentation in water, and the sedimentation performance is not easily lowered by use. Therefore, it is possible to provide a fishing line with excellent operability while taking advantage of the fishing line made of the ultra-high molecular weight polyethylene multifilament thread.

2 is an optical micrograph of a cross section of a fishing line of Example 1. FIG. It is the figure which showed the several point which measured content of nickel. It is a graph of the result of having measured nickel content. It is a graph of the result of having measured nickel content. 2 is an electron micrograph before a wear test of a fishing line of Example 1. FIG. 2 is an electron micrograph after a wear test of a fishing line of Example 1. FIG. 3 is an optical micrograph of a cross section of a fishing line of Example 2. FIG. 4 is an optical micrograph of a cross section of a fishing line of Example 3. FIG. 4 is an optical micrograph of a cross section of a fishing line of Example 4. FIG. 4 is an optical micrograph of a cross section of a fishing line of Comparative Example 2.

  The fishing line of the present invention is made of ultra high molecular weight polyethylene multifilament yarn. The weight average molecular weight of the ultrahigh molecular weight polyethylene used here is 1 million or more, and preferably 2 million or more. At this time, it is preferable that the single yarn fineness is 0.5 to 10 dtex, and the fineness of the multifilament yarn is 80 to 6000 dtex. By using a fishing line containing a large number of thin single yarns, metal plating can be applied in the gaps between the single yarns of single fibers while maintaining flexibility. The single yarn fineness is more preferably 5 dtex or less, and even more preferably 3 dtex or less.

  The form of the multifilament yarn constituting the fishing line of the present invention is a twisted yarn or a stringed yarn. By using the twisted yarn or the string yarn, the single yarns are brought into contact with each other at high density, and the fishing line can be handled with good handling properties. Among them, the string yarn is more preferable because it is difficult for twisting to occur. In this case, a string is made using a plurality of multifilament yarns. In these cases, the fineness of the multifilament yarn that constitutes the fishing line refers to the fineness of the entire twisted yarn or stringed yarn.

  The fishing line of the present invention is manufactured by applying metal plating to an ultrahigh molecular weight polyethylene multifilament thread. The plating method is not particularly limited, but it is preferable to apply metal plating to the twisted yarn or the string yarn made of multifilament yarn of ultra high molecular weight polyethylene by electroless plating. When metal plating is applied uniformly to the center of the multifilament yarn, the flexibility inherent to the ultrahigh molecular weight polyethylene multifilament yarn is lost, and the flexibility required for fishing lines cannot be satisfied. . For this reason, it is preferable to apply metal plating by electroless plating after making it difficult for the plating solution to penetrate to the center of the multifilament yarn, using twisted yarn or string yarn made of multifilament yarn of ultra high molecular weight polyethylene. Thereby, a gradient distribution of the plating metal concentration is formed from the outer surface of the multifilament yarn to the inside.

  When performing metal plating, it is preferable to first clean and degrease the surface of a twisted yarn or a stringed yarn made of multifilament yarn. In such a degreasing process, it is preferable to wash with an alkaline cleaning liquid containing a surfactant and an alkali compound. Since polyethylene is a hydrophobic resin, it is preferable to sufficiently remove contamination due to hydrophobic components adhering to its surface. Further, in order to improve the adsorptivity and wettability of the catalyst, it is also preferable to perform a surface conditioning treatment by immersing in a surface conditioning solution composed of an aqueous solution containing a surfactant and no alkali compound. Polyethylene so that the catalyst solution and plating solution can pass smoothly through a slight gap between single yarns of ultra-high molecular weight polyethylene fiber that has become twisted or stringed yarn, and the plating region is formed to an appropriate depth with good reproducibility. It is important to adjust the surface state of the fiber with a surfactant. Although only one of these degreasing treatments and surface conditioning treatments can be adopted, it is preferable to perform both the degreasing treatments and the surface conditioning treatments in this order. Each of these treatments may be performed a plurality of times by appropriately changing the chemicals. Moreover, it is preferable to perform water washing and dehydration operation after each process.

  Subsequently, the multifilament yarn is catalyzed. The catalytic treatment is carried out by reducing the metal salt and attaching the metal to the surface of the multifilament yarn. As the metal salt, a palladium salt is preferably used, and it is preferable to attach metal palladium fine particles to the surface of the multifilament yarn. At this time, it is preferable to use a palladium salt and a stannous salt in combination. Thereafter, it is activated by treatment with an acid, if necessary, and then immersed in a plating solution containing a metal salt and a reducing agent to perform metal plating. The type of metal to be plated is not particularly limited, but nickel, copper, tin, gold, and the like can be employed, and nickel is particularly preferable. It is also preferable to apply a surface treatment agent after metal plating in order to improve hydrophilicity, smoothness or flexibility. Further, after the metal plating, the whole or a part of the fishing line may be colored. The above plating process may be performed by a batch process or a continuous process.

  The fishing line of the present invention is not only metal-plated on the outer surface of the multifilament thread, but also metal-plated in the gap between the single yarns constituting the multifilament thread, and the center part of the multifilament thread Has a major feature in that it is not plated. It is surprising that metal plating is applied to the inside of the fishing line by the plating solution that has passed through the narrow gap between the single yarns of hydrophobic fibers such as polyethylene. Thereby, even if the surface of the fishing line is worn, the metal plating portion remains inside, so that the decrease in specific gravity can be suppressed and the sedimentation performance can be maintained. In addition, since a thin metal plating layer is formed on the surface of each single yarn, flexibility as a fishing line is not impaired. In addition, by applying plating treatment to ultrahigh molecular weight polyethylene fibers that are in close contact with each other as twisted yarn or stringed yarn, a gradient distribution of the plating metal concentration is formed from the outer surface to the inside of the multifilament yarn. Since the central part is not plated, the appropriate flexibility as a fishing line is not impaired. If the thick metal plating film is formed only on the outer surface of the fishing line, the metal plating film is easily peeled off due to wear, and if the entire fishing line is uniformly metal-plated, the flexibility of the fishing line is impaired.

  Specifically, it is important that the depth of the plating region from the outer surface of the multifilament yarn is larger than the equivalent circle diameter of the single yarn. That is, it is preferable that the plating region penetrates to a portion corresponding to the back side of the single yarn. As a result, a decrease in specific gravity due to wear can be effectively suppressed. The depth of the plating region from the outer surface is more preferably twice or more the equivalent circle diameter of the single yarn, and even more preferably three times or more. Here, the depth of the plating region means the depth at which the metal content in the cross section of the fishing line is quantified in the diameter direction and the content becomes 1% by mass or less. Here, the metal content is indicated by the ratio of the mass of the plated metal element to the total mass of the carbon element, the oxygen element, the silicon element, and the plated metal element. Although the quantification method is not particularly limited, it can be measured using a method capable of quantifying the amount of elements in a minute region, such as an electron beam microanalyzer. The measurement area at this time is preferably an area larger than the cross-sectional area of the single yarn.

  Moreover, it is also preferable that the depth of the plating region is 0.05 times or more the equivalent circle diameter of the multifilament yarn. As a result, the specific gravity of the entire fishing line can be increased, and a fishing line having excellent sedimentation properties with respect to water can be obtained. The depth of the plating region is more preferably 0.08 times or more the circle equivalent diameter of the multifilament yarn, more preferably 0.1 times or more, and particularly preferably 0.12 times or more. .

  On the other hand, for the flexibility and handling properties as a fishing line, the depth of the plating region is preferably 0.3 times or less the circle-equivalent diameter of the multifilament thread. When the depth of the plating region exceeds 0.3 times the equivalent circle diameter of the multifilament yarn, there is a risk that moderate flexibility as a fishing line is impaired. More preferably, the depth of the plating region is not more than 0.25 times the equivalent circle diameter of the multifilament yarn.

  The fishing line of the present invention preferably settles in water. The specific gravity of a fishing line made of multifilament yarn of ultra high molecular weight polyethylene is about 0.97, and usually floats in water. Furthermore, in actual fishing, it is inevitable that air is included in the gaps between the single yarns, so that even when a weight is used, the settling speed is slow. On the other hand, since the specific gravity of the fishing line of the present invention is increased by applying metal plating, even the fishing line alone can settle in water.

  When the fishing line of the present invention settles in water, the faster the sedimentation rate, the better. Specifically, the time required for the fishing line cut to a length of 2 cm to settle from the water surface to a depth of 30 cm is preferably 100 seconds or less, and more preferably 70 seconds or less.

  The fishing line of the present invention can increase the specific gravity while maintaining the high strength, low elongation and flexibility of the ultra-high molecular weight polyethylene multifilament thread, and its performance is less degraded against wear. It can be suitably used as a road line or Harris in various fishing such as throwing fishing, carp fishing, and fly fishing. The appearance also has a high-class feeling with metallic luster.

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

(1) Depth of plating area The fishing line of the sample is embedded with resin (paraffin or the like), and the content of the plated metal element is measured from the fiber surface to the inside. The field emission scanning electron microscope “JSM-7000F” manufactured by JEOL Ltd. ”Was quantitatively analyzed by the ZAF method with an electron beam microanalyzer attached to the above. In the measurement, the content of carbon element, oxygen element, silicon element and plated metal element (here nickel element) is measured continuously from the fiber surface to the inside, and carbon element, oxygen element, silicon element and plating are measured. The distance to the location where the ratio of the mass of the plated metal element to the total mass of the plated metal elements was 1% by mass (approximately the detection limit) or less was defined as the depth of the plating region. The measurement was performed in a rectangular area of 10 μm in the diameter direction of the fishing line and 40 μm in the vertical direction for each measurement point. Measurement was performed in two directions intersecting at right angles in the cross section of the fishing line, and the average value of four points was obtained. The measurement conditions are as follows.
・ Acceleration voltage: 15.0kV
・ Irradiation current: 2.066 nA
・ Valid time: 60.00 seconds

(2) Put the pure water 1000 cm ³ graduated cylinder sedimentation time 1000 cm ^3, yarn 2cm lengths were charged, it was measured sedimentation time of up to a position below the water surface 30 cm. Five points were measured per sample, and the average value was taken as the sedimentation time.

(3) Abrasion test One end of a thread having a test length of 110 cm is fixed to a thread fixing jig, a load of 150 g is applied to the other end, and the thread fixing jig is moved to move the thread fixing jig to a room temperature water having a diameter of 20 mm. The yarn was reciprocated five times on the friction body of the coarse grindstone (WA abrasive grain # 60). The reciprocating conditions were such that the contact angle with the friction body was 90 °, the reciprocating speed of the yarn was 90 times / minute, and the reciprocating distance was 17 cm (based on Japanese Patent Laid-Open No. 2001-208663).

Example 1
Four pieces of 165 dtex / 140f of ultra high molecular weight polyethylene fiber “Dyneema” manufactured by Toyobo Co., Ltd. were used to obtain a multifilament yarn of 660 dtex / 560f (No. 3). This ultra high molecular weight polyethylene fiber is made of polyethylene having a weight average molecular weight of about 4 million. The circle equivalent diameter of the multifilament yarn is about 350 μm, and the circle equivalent diameter of the single yarn is about 12 μm.

[Degreasing process]
The multifilament yarn is formed into a skein shape with a circumference of 70 cm and a weight of about 100 g, and an alkaline cleaning solution containing sodium borate 20 g / liter, sodium phosphate 20 g / liter, and a nonionic surfactant 10 g / liter is used. The bath was immersed in a cleaning solution at a bath ratio of 1:50 and a temperature of 90 ° C. and treated for 20 minutes with stirring. Thereafter, washing with water and dehydration were performed.

[Surface adjustment process]
Next, in order to improve the adsorptivity and wettability of the catalyst, it was immersed for 5 minutes under the conditions of a bath ratio of 1:50 and a temperature of 40 ° C. using a surface conditioning solution containing 5 g / liter of a nonionic surfactant. Thereafter, washing with water and dehydration were performed.

[Catalysis process]
Next, a commercially available stannous chloride / palladium chloride colloidal solution of 50 g / liter and 35% by weight hydrochloric acid is immersed in a mixture of 150 g / liter at a bath ratio of 1:50 at room temperature for 5 minutes to adhere the catalyst. It was. Thereafter, washing with water and dehydration were performed.

[Activation process]
Subsequently, the catalyst was activated by immersing in an aqueous solution diluted with 75% dilute sulfuric acid to 150 g / liter for 5 minutes at a bath ratio of 1:50 at room temperature. Thereafter, it was washed with water and dehydrated.

[Plating process]
Then, using a commercially available electroless nickel plating solution (containing nickel salt, complexing agent, hypophosphorous acid, ammonia water, etc.), bathing ratio is 1:50, pH 9.5, and soaking and stirring at room temperature for 15 minutes. The electroless plating process was performed. Thereafter, it was washed with water, dehydrated and dried to obtain a metal-plated yarn.

[Oiling process]
Next, in order to improve flexibility, smoothness, and hydrophilicity, a commercially available oiling agent (adjusted with silicone oil, wax, surfactant, etc.) was adjusted to 10 g / liter, a bath ratio of 1:50, and a temperature of 50 ° C. The oiling was performed by dipping and stirring for 20 minutes. Then, it dehydrated and dried to obtain a metal-plated fishing line.

  The optical microscope photograph of the cross section of the obtained fishing line is shown in FIG. The black part is the nickel-plated part. It can be seen that metal plating is applied not only on the outer surface of the multifilament yarn but also in the gap portion between the single yarns constituting the multifilament yarn. In accordance with the method described in “(1) Depth of plating region”, the nickel content is measured at a plurality of points in the horizontal and vertical directions using an electron beam microanalyzer mounted on a field emission scanning electron microscope. It was measured. FIG. 2 shows the measurement position on the optical micrograph. The resulting graphs are shown in FIGS. The depth of the plating area in the obtained fishing line was 52 μm.

  The obtained fishing line was subjected to an abrasion test according to the above method. A photograph of the fishing line before the wear test and an electron micrograph of the fishing line after the wear test are shown in FIGS. 5 and 6, respectively. The settling time before the wear test and the settling time after the wear test were 54 seconds and 74 seconds, respectively. As shown in FIG. 6, it can be seen that the sedimentation property is maintained even in the case of intense wear. These results are summarized in Table 1. Furthermore, when sea fishing was actually carried out, the fishing line was easy to sink in seawater, it was moderately flexible, and operability was good.

Examples 2-4
In Example 1, metal plating was performed in the same manner as in Example 1 except that the electroless plating treatment time was 30 minutes (Example 2), 10 minutes (Example 3), and 5 minutes (Example 4), respectively. Got the fishing line. Optical micrographs of the cross section of the obtained fishing line are shown in FIGS. 7, 8 and 9, respectively. The obtained fishing line was tested in the same manner as in Example 1. The results are summarized in Table 1. When actually fishing in the sea, the fishing line was easy to sink in seawater, it was moderately flexible, and the operability was good. However, with regard to Example 4, the operability decreased due to a decrease in sedimentation after repeated use several times.

Comparative Example 1
In Example 1, an electroless plating treatment was not performed, and the test was performed on the multifilament yarn obtained by stringing in the same manner as in Example 1. The results are summarized in Table 1. When actually fishing in the sea, the fishing line was difficult to sink in seawater, and the operability was poor.

Comparative Example 2
Four pieces of 55 dtex / 48f of ultra high molecular weight polyethylene fiber “Dyneema” manufactured by Toyobo Co., Ltd. were used to obtain a multifilament yarn of 220 dtex / 192f (No. 1). This ultra high molecular weight polyethylene fiber is made of polyethylene having a weight average molecular weight of about 4 million. The circle equivalent diameter of the single yarn of this multifilament yarn is about 12 μm. The multifilament yarn thus obtained was plated by the same operation as in Example 2 (electroless plating treatment time: 30 minutes) to obtain a metal-plated fishing line.

  Using the three metal-plated fishing lines obtained in this way, stringing was performed again to obtain a multifilament thread of 660 dtex / 576f (No. 3). An optical micrograph of the cross section of the obtained fishing line is shown in FIG. The obtained fishing line was tested in the same manner as in Example 1. The results are summarized in Table 1. When actually fishing in the sea, the fishing line was easy to sink in seawater, but lacked flexibility, and it was inferior in reelability and operability.

Claims (7)

  A fishing line which is a twisted or made string made of multifilament yarn of ultra high molecular weight polyethylene, and the outer surface of the multifilament yarn is subjected to metal plating, and in the gap portion between the single yarns constituting the multifilament yarn The fishing line is also characterized in that metal plating is applied, the depth of the plating area from the outer surface of the multifilament yarn is larger than the equivalent circle diameter of the single yarn, and the center portion of the multifilament yarn is not plated.   The fishing line according to claim 1, wherein the depth of the plating region is not more than 0.3 times the equivalent circle diameter of the multifilament thread.   The fishing line according to claim 1 or 2, wherein a depth of the plated region is 0.05 times or more a circle equivalent diameter of the multifilament thread.   The fishing line according to any one of claims 1 to 3, wherein the single yarn fineness is 0.5 to 10 dtex, and the fineness of the multifilament yarn is 80 to 6000 dtex.   The fishing line according to any one of claims 1 to 4, which settles in water.   6. The fishing line according to claim 5, wherein the time required for the fishing line cut to a length of 2 cm to settle from the water surface to a depth of 30 cm is 100 seconds or less.   The method for producing a fishing line according to any one of claims 1 to 6, wherein metal plating is performed by electroless plating on a twisted yarn or string-made yarn made of multifilament yarn of ultra high molecular weight polyethylene.

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