Water-repellent treatment for through-hole fishing rods

Abstract

To provide a water-repellent agent for through-hole fishing rods with improved water-repellent performance. [Solution] The water-repellent agent of the present invention is used in a through-hole fishing rod having a rod tube with a continuous convex portion formed along the axial direction on its inner surface, and comprises a first powder having large-diameter particles, a second powder having small-diameter particles, a binder that holds the first powder and the second powder, and an organic solvent, characterized in that the content of the second powder is greater than that of the first powder.

Description

Technical Field

[0001] The present invention relates to a water-repellent treatment agent for a through-type fishing rod, which is used for a through-type fishing rod and is used to improve the water repellency of a fishing line insertion part.

Background Art

[0002] Conventionally, an outer guide fishing rod that guides a fishing line from a reel through an outer guide and a through-type fishing rod that guides a fishing line from a reel through the inside of the fishing rod are known. Since the through-type fishing rod inserts the fishing line inside the rod tube, it is liable to receive sliding resistance from the inner surface of the rod tube. For this reason, for example, as disclosed in Patent Document 1, a spiral protrusion is formed along the axial direction on the inner surface of the rod.

[0003] Further, Patent Document 1 described above discloses forming a water-repellent layer on the inner surface of the rod tube and forming such a water-repellent layer by a spraying instrument such as a spray. The material (water-repellent agent) for forming the water-repellent layer is formed by mixing fluororesin particles, a binder member that holds the fluororesin particles, and an organic solvent.

[0004] Among the water-repellent agents, as the binder member, a fluororesin that is not in particle form, a silicone resin, an acrylic resin, an epoxy resin, a urethane resin, etc. are used. Further, as the organic solvent, toluene, n-heptane, hexane, methyl ethyl ketone, a fluorine-based solvent AK225 (trade name of Asahi Glass), etc. are used.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The known water-repellent agents described above have room for improvement in terms of leveling properties when applied by spray. Specifically, because spiral-shaped protrusions are formed on the inner surface of the rod tube of a through-hole fishing rod, the water-repellent agent may not be uniformly distributed at the boundary between the base of the protrusions and the inner surface of the rod tube, which may result in insufficient water-repellent performance.

[0007] The present invention aims to provide a water-repellent agent for through-hole fishing rods that is used on the inner surface of a rod tube having a continuous spiral protrusion and has improved water-repellent performance, and a spray for applying such a water-repellent agent for through-hole fishing rods. [Means for solving the problem]

[0008] The water-repellent agent for through-hole fishing rods according to the present invention is used in through-hole fishing rods having a rod tube with a continuous convex portion formed on its inner surface along the axial direction, and comprises a first powder having large-diameter particles, a second powder having small-diameter particles, a binder that holds the first powder and the second powder, and an organic solvent, characterized in that the content of the second powder is greater than that of the first powder.

[0009] When a water-repellent agent for through-hole fishing rods containing the above-mentioned constituent materials is applied to the inner surface of a through-hole fishing rod, small-diameter particles fill the gaps between the large-diameter particles. In this case, since the powder content of the small-diameter particles is greater than that of the large-diameter particles, the small-diameter particles uniformly fill the boundary between the protrusions formed on the inner surface of the rod tube and the inner surface of the rod tube, resulting in even application and improved water-repellent performance.

[0010] Furthermore, the aforementioned water-repellent agent for through-hole fishing rods can be filled into a spray bottle and applied to the inner surface of the rod tube by the user. [Effects of the Invention]

[0011] According to the present invention, a water-repellent agent for through-hole fishing rods with improved water-repellent performance, and a spray for applying such a water-repellent agent for through-hole fishing rods can be obtained. [Brief explanation of the drawing]

[0012] [Figure 1] A diagram showing one embodiment of a through-line fishing rod. [Figure 2] Figure 1 shows the internal structure of the rod tube of a through-hole fishing rod. [Figure 3] A schematic diagram showing a magnified view of the spiral projection formed on the inner surface of the pipe shaft. [Figure 4] A schematic diagram showing the state in which large-diameter and small-diameter particles are mixed when the water-repellent agent for through-hole fishing rods of this embodiment is applied. [Figure 5] A photograph showing the comparative results of water droplet adhesion in the examples. [Figure 6] A photograph showing the comparative results of water repellency in the examples. [Figure 7] Table and graph showing the results of the contact angle test in the example. [Figure 8] A photograph showing the comparative results of water droplet adhesion in the examples. [Figure 9] A photograph showing the comparative results of water repellency in the examples. [Figure 10] A photograph showing the results of electron microscope observation of the example. [Figure 11] A photograph showing the appearance of the coating film in the example. [Figure 12] A photograph showing the comparative results of water droplet adhesion in the examples. [Modes for carrying out the invention]

[0013] The following describes embodiments of the water-repellent agent for through-hole fishing rods according to the present invention (hereinafter referred to as the water-repellent agent). Figures 1 to 3 show examples of through-hole fishing rods in which a water-repellent agent is used. Figure 1 shows the overall structure of the through-hole fishing rod, Figure 2 shows the internal structure of the rod tube of the through-hole fishing rod shown in Figure 1, and Figure 3 shows a magnified view of the spiral protrusions formed on the inner surface of the rod tube.

[0014] The telescopic fishing rod 1 shown in the figure has an extending structure in which the original rod tube 3, the middle rod tube 4, and the tip rod tube 5 are sequentially joined in an extending manner. The original rod tube 3 is provided with a fishing line introduction portion 9 for introducing the fishing line S fed out from the reel 10 attached to the reel seat 7 into each rod tube. And a top guide 10 for导出 the fishing line is provided at the tip of the tip rod tube 5.

[0015] Each of the above-mentioned rod tubes is made of FRP formed by winding a prepreg sheet. As shown in FIG. 2, spiral convex portions 12 are continuously formed along the axial direction on the inner surface of each rod tube. The convex portion 12 is formed so as to project from the inner surface 15 of the rod tube toward the axis, and the tip (top) 12a of the convex portion 12 is formed with a curved surface so as to reduce contact with the fishing rod.

[0016] A water repellent containing the following constituent materials is applied to such an inner surface 15. This water repellent may be applied to the inner surface 15 in advance, or may be applied from the open end by spraying when the user performs maintenance.

[0017] Hereinafter, the composition of the water repellent will be described. The water repellent according to this embodiment contains a first powder having large-diameter particles, a second powder having small-diameter particles, a binder, and an organic solvent.

[0018] The first powder is not particularly limited as long as it is composed of particles that can adhere uniformly to the water-repellent treated surface and form a fine uneven structure on the surface. However, in terms of having high hydrophobicity, it is particularly preferable that the powder contains fluororesin particles. Examples of fluororesins include PTFE (polytetrafluoroethylene), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride), PCTFE (polychlorotrifluoroethylene), ECTFE (chlorotrifluoroethylene-ethylene copolymer), PVD (polyvinyl fluoride), and other resins obtained by polymerizing fluoroolefins or by copolymerizing fluoroolefins with hydrocarbon monomers. Fluororesin particles may be composed of a single fluororesin, multiple fluororesins, or a fluororesin and other resins, but it is particularly preferable that they contain PTFE powder.

[0019] The first powder preferably has an average particle size in the range of 1 to 30 μm, and more preferably 2 to 22 μm. If the primary particle size is less than 1 μm or greater than 30 μm, the water repellency may be insufficient. Here, the average particle size of the powder in this embodiment refers to the average value of the primary particle size measured from atomic force microscope images. When the average particle size is 1 to 30 μm, the smaller second powder particles fit appropriately into the uneven structure formed by the larger first powder particles on the treated surface, and an even finer uneven structure is formed, reducing the contact area of ​​water droplets and improving water repellency.

[0020] The second powder is not particularly limited as long as it is a hydrophobic powder having a smaller particle size than the first powder, but it is especially preferable that it is a powder containing hydrophobic silica in order to improve the durability of the water-repellent effect. Examples of hydrophobic silica include silica particles obtained using known wet methods (such as the sol-gel method) or dry methods (such as the gas phase method), which are then treated with a hydrophobic treatment agent to introduce hydrophobic groups onto the particle surface, or silica particles treated with silicone oil.

[0021] Examples of hydrophobic treatment agents include organosilicon compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, hexamethyldisilazane, and tetramethyldisilazane. Examples of silicone oils include straight silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, as well as known modified silicone oils into which polyethers, epoxy, amines, carboxyl groups, aralkyl groups, fluoroalkyl groups, etc., have been introduced. In the present invention, hydrophobic silica treated with a hydrophobic treatment agent, particularly "Silohobic 100" manufactured by Fuji Silicia Chemical Co., Ltd., can be suitably used.

[0022] The second powder preferably has an average particle size in the range of 0.001 to 0.1 μm, and more preferably 0.001 to 0.01 μm. If the average particle diameter is 0.1 μm or less, the smaller diameter second powder particles can adequately penetrate the uneven structure formed by the larger diameter first powder particles on the treated surface, making it possible to obtain high water repellency.

[0023] In particular, the particle size ratio of the first powder (large-diameter particles) to the second powder (small-diameter particles) in this embodiment is 10:1 to 30000:1. By setting the particle size ratio within this range, as shown in Figure 4, a structure is formed on the water-repellent treated surface in which the gaps between the large-diameter particles of the first powder are filled with the small-diameter particles of the second powder, thereby improving water repellency. Furthermore, in water-repellent agents, the water repellency is improved by having the first powder and the second powder in a mass ratio of 1:1 to 1:4 (first powder:second powder). In particular, by including more of the second powder than the first powder, the high water-repellent effect can be sustained for a longer period of time.

[0024] The water-repellent agent according to this embodiment contains a silicone resin as a binder that holds the particles of the first and second powders and forms a film that adheres the powders to the water-repellent surface. Any of methyl silicones, phenyl silicones, or methylphenyl silicones can be used as the silicone resin, but it is particularly preferable to use a methyl silicone (such as dimethyl silicone) in which all organic substituents are methyl groups, and more preferably a methyl silicone oligomer. The silicone oligomer is a low molecular weight silicone resin having a three-dimensional network structure, and as a methyl silicone oligomer, for example, "KR-251" and "KR-242A" manufactured by Shin-Etsu Chemical Co., Ltd. can be suitably used.

[0025] In the water repellent of this embodiment, the content of silicone resin in relation to the total amount of the first powder and the second powder (powder:silicone resin) is preferably 50:50 to 70:30 by mass ratio, and the content in the water repellent is preferably 0.9 to 5.7% by mass. By using this ratio, the powder particles are more likely to float on the surface of the water-repellent treated surface, and the degree of adhesion to the treated surface is improved.

[0026] The organic solvent used in the water-repellent agent of this embodiment is not particularly limited as long as it is a hydrophobic organic solvent that can mix and disperse the above components, but it is especially preferable that it contains a fluorine-based solvent and n-heptane from the viewpoint of drying properties when applied to the inner surface of a rod. Examples of fluorine-based solvents include perfluorocarbon (PFC), hydrochlorofluorocarbon (HCFC), hydrofluorocarbon (HFC), hydrofluoroether (HFE), perfluoroether, hydrofluoroester, hydrofluoroolefin, and hydrochlorofluoroolefin (HCFO), and the use of hydrochlorofluoroolefin (for example, "AMOLEA AS-300" manufactured by AGC Inc.) is preferred in terms of compatibility with the powder and binder resin.

[0027] The content of organic solvents in a water-repellent agent is not particularly limited, but when a fluorine-based solvent and n-heptane are blended as organic solvents, including a higher amount of the fluorine-based solvent, which has high powder retention properties, than n-heptane increases the dispersion of the second powder and makes the coating film more uniform. The content (fluorine-based solvent:n-heptane) is preferably in the range of 1:1 to 2:1 by mass ratio.

[0028] In addition to the above components, the water-repellent agent of this embodiment may contain additives such as dispersants, leveling agents, antifungal agents, and catalysts as appropriate. The water-repellent agent of this embodiment can be produced by mixing the above components using a known method. In particular, it can be obtained by adding the first powder and the second powder to an organic solvent, dispersing the powder using ultrasound, a bead mill, a homogenizer, etc., and then adding and mixing other components such as silicone resin.

[0029] The manufactured water-repellent agent can be used, for example, by filling a spray container with the water-repellent agent together with a propellant and spraying it onto the inner surface of a through-hole fishing rod, which serves as the base material, and then drying the coating. In addition to spraying, it is also possible to form a water-repellent coating on the inner surface of the fishing rod by immersing or impregnating it with the water-repellent agent during the manufacturing process of the through-hole fishing rod, or by directly applying the water-repellent agent with an applicator, etc. However, application by spraying is preferred because it allows for repeated application of the water-repellent agent to the inner surface of the fishing rod. The thickness of the water-repellent coating formed on the inner surface of a through-hole fishing rod is not particularly limited, but a thickness of about 10 to 30 μm will provide a high water-repellent effect.

[0030] Figure 3 is a schematic diagram showing an enlarged view of one of the spiral protrusions of a through-hole fishing rod to which the water-repellent agent of this embodiment has been applied, filled in a spray container. With conventional water-repellent agents, the curvature between the protrusion and the inner surface of the rod tube is affected. While it is difficult to apply the water repellent uniformly to point areas, the water repellent of this embodiment allows small-diameter particles to penetrate between large-diameter particles even at such inflection points. In this case, since the resin powder content of the small-diameter particles is greater than that of the large-diameter particles, the powder of the small-diameter particles penetrates uniformly and evenly at the boundary between the protrusions formed on the inner surface of the rod and the inner surface of the rod, thereby improving water repellency.

[0031] Figure 4 is a schematic diagram showing the state of each component in the coating film of the water-repellent agent of this embodiment. After the coating 22 is applied to the water-repellent treated surface 21 and the volatile components have evaporated, the coating film 22 contains large-diameter particles 23, which are the first powder, and small-diameter particles 24, which are the second powder, dispersed and fixed in the hardened binder 25. As shown in Figure 4, the large-diameter particles 23 are dispersed almost uniformly in the coating film, and the small-diameter particles 24 are further interposed between the large-diameter particles 23, forming a fine uneven structure throughout the entire coating film. This uneven structure on the surface of the coating film prevents water droplets from adhering, resulting in extremely high water repellency. [Examples]

[0032] (Powder blending ratio) The water-repellent agents described in Examples 1 to 4 below were prepared and applied to a substrate (metal plate) and dried. Various tests were performed on the coating films of each example formed on the substrate. <Example 1> A water-repellent agent was obtained by adding PTFE powder with an average particle size of 2-4 μm (Fluo 300SM, manufactured by Micro Powders, Inc.) and hydrophobic silica with an average particle size of 0.01-0.05 μm (Silophobic 100, manufactured by Fuji Silicia Chemical Co., Ltd.) in a mass ratio of 1:2 to a mixture of hydrochlorofluoroolefin (AMOLEA AS-300, manufactured by AGC Inc.) and n-heptane, along with a methyl-based silicone oligomer (KR-251, manufactured by Shin-Etsu Chemical Co., Ltd.). The mixture was then dispersed and stirred using a bead mill. The ratio of powder to silicone oligomer content in the water-repellent agent was 50:50. <Example 2> A water repellent was prepared in the same manner as in Example 1, except that the content of PTFE powder and hydrophobic silica was set to 1:1. <Example 3> A water repellent was prepared in the same manner as in Example 1, except that the content of PTFE powder and hydrophobic silica was set to 2:1. <Example 4> A water repellent was prepared in the same manner as in Example 1, except that the content ratio of PTFE powder to hydrophobic silica was 5:1.

[0033] (Water droplet adhesion) Water was sprayed onto the water-repellent coating of each example using a spray bottle, and the amount of water droplets adhering to the coating was checked. The results of water droplet adhesion to the coating of each example are shown in Figure 5. (water sliding) The substrates coated with the water-repellent agent of each example were tilted at a 5° angle, and 10 μL of water was dropped onto the coating. The results of the water-repellent properties of the coatings of each example are shown in Figure 6. (Contact angle test) Substrates coated with the water-repellent agent of each example were immersed in water, and the contact angle (°) of water with respect to the water-repellent coating was measured using a contact angle meter for the substrates after 0, 2, 4, and 8 days of immersion. The table and graph showing the contact angle measurement results are shown in Figure 7.

[0034] As shown in Figures 5-7, a water-repellent effect was observed in all examples. However, the higher the ratio of hydrophobic silica to PTFE powder, the less water droplets adhered to the coating (Figure 5), the better the water sliding properties (Figure 6), and the higher the contact angle (Figure 7). In particular, when the PTFE powder:hydrophobic silica ratio was in the range of 1:1 to 1:2, the higher the ratio of hydrophobic silica, the better the water-repellent effect. It was found that the water repellency improved. Further testing confirmed that even when the hydrophobic silica blending ratio was increased to 1:4 for PTFE powder to hydrophobic silica, the material still exhibited satisfactory water repellency.

[0035] (Binder comparison) The water-repellent agents described in Examples 5 to 7 below were prepared and applied to a substrate (CFRP [Carbon Fiber Reinforced Plastics] board) and dried. Various tests were performed on the coating films of each example formed on the substrate. <Example 5> PTFE powder with an average particle size of 2-4 μm (Fluo 300SM, manufactured by Micro Powders, Inc.) and hydrophobic silica with an average particle size of 0.01-0.05 μm (Silophobic 100, manufactured by Fuji Silicia Chemical Co., Ltd.) were added to a mixture of hydrochlorofluoroolefin (AMOLEA AS-300, manufactured by AGC Inc.) and n-heptane, along with a methyl-based silicone oligomer (KR-251, manufactured by Shin-Etsu Chemical Co., Ltd.), in a mass ratio of 1:2. The mixture was then dispersed and stirred using a bead mill to obtain a water-repellent agent. <Example 6> A water repellent was prepared in the same manner as in Example 5, except that a methylphenyl-based silicone oligomer (KR112, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of a methyl-based silicone oligomer. <Example 7> A water repellent was prepared in the same manner as in Example 5, except that a methylphenyl-based silicone oligomer (KR112, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of a methyl-based silicone oligomer.

[0036] (Water droplet adhesion) Water was sprayed onto the water-repellent coating of each example using a spray bottle, and the amount of water droplets adhering to the coating was checked. The results of water droplet adhesion to the coating of each example are shown in Figure 8. (water sliding) The substrates coated with the water-repellent agents of each example were tilted at a 10° angle, and 10 μL of water was dropped onto the coating. Figure 9 shows the results of the water-repellency of the coatings of each example and comparative example. (Observation by electron microscope) The water-repellent coating films of each example were observed under a scanning electron microscope (SEM) at 2000x magnification. Microscopic images of the coatings of each example and comparative example are shown in Figure 10.

[0037] As shown in Figures 8 and 9, all examples exhibited water repellency, but Example 5, which contained a methyl-based silicone oligomer, showed particularly good water-repellent properties (Figure 8) and low water adhesion (Figure 9). Furthermore, as shown in Figure 10, the coating film of Example 5 had an exposed surface with uneven structures formed by powder particles, while Examples 6 and 7, which contained a methylphenyl-based silicone oligomer as a binder, showed a tendency for the powder particles to sink into the binder and be covered by the binder.

[0038] (Organic solvent blend ratio) The water-repellent agents described in Examples 8 to 11 below were prepared and applied to a substrate (the spiral structure on the inner surface of a through-hole fishing rod) and dried. The appearance of the coating film formed on the substrate according to each example was observed and the water droplet adhesion properties were checked. <Example 8> PTFE powder with an average particle size of 2-4 μm (Fluo 300SM from Micro Powders, Inc.) and hydrophobic silica with an average particle size of 0.01-0.05 μm (Silophobic 100 from Fuji Silicia Chemical Co., Ltd.) are mixed in a mass ratio of 1:2 with a methyl-based silicone oligomer (KR-251 from Shin-Etsu Chemical Co., Ltd.) Both were added to a 2:1 mixture of hydrochlorofluoroolefin (AMOLEA AS-300, manufactured by AGC Inc.) and n-heptane, dispersed in a bead mill, and stirred to obtain a water-repellent agent. The ratio of powder to silicone oligomer content in the water-repellent agent was 50:50. <Example 9> A water repellent was prepared in the same manner as in Example 6, except that the content of hydrochlorofluoroolefin (AMOLEA AS-300, manufactured by AGC Inc.) and n-heptane was set to 1:1. <Example 10> A water repellent was prepared in the same manner as in Example 6, except that the content of hydrochlorofluoroolefin (AMOLEA AS-300, manufactured by AGC Inc.) and n-heptane was set to 1:2. <Example 11> A water repellent was prepared in the same manner as in Example 6, except that the content of hydrochlorofluoroolefin (AMOLEA AS-300, manufactured by AGC Inc.) and n-heptane was set to 1:4.

[0039] Figure 11 shows the appearance of the water-repellent coatings in Examples 8-11. The higher the ratio of hydrochlorofluoroolefin, the higher the uniformity of the coating (Examples 8, 9), while the lower the ratio, the more the water-repellent agent adhered to the helical structure (Examples 10, 11). Figure 12 shows the results of water droplet adhesion, indicating that the higher the ratio of perfluorocarbon, the less fine water droplets adhered (Examples 8, 9). [Explanation of Symbols]

[0040] 1 fishing rod 3. Main shaft 4 Middle rod tube 5. Tip section of the rod 7 Reel Seat 9. Fishing line entry point 10 Top Guides 50 reels S fishing line 12 Convex part 12a Tip (Top) 15. Inner self 21 Water-repellent treated surface 22 Coating film 23. First powder (large diameter particles) 24. Second powder (small diameter particles) 25 Binders

Claims

1. Used in a through-hole fishing rod having a rod tube with a continuous convex portion formed along the axial direction on its inner surface, A first powder having large-diameter particles, A second powder comprising small-diameter particles, A binder that holds the first powder and the second powder, It contains organic solvents, A water-repellent agent for through-hole fishing rods, characterized in that the content of the second powder is greater than that of the first powder.

2. The water-repellent agent for through-hole fishing rods according to claim 1, wherein the first powder is PTFE powder having an average particle size of 1 to 30 μm, and the second powder is hydrophobic silica having an average particle size of 0.001 to 0.1 μm.

3. The water-repellent agent for through-hole fishing rods according to claim 1, wherein the binder contains a methyl-based silicone resin.

4. The water-repellent agent for through-hole fishing rods according to claim 1, wherein the organic solvent contains a fluorine-based solvent.

5. The water-repellent agent for through-hole fishing rods according to claim 4, wherein the organic solvent further contains n-heptane, and the content of the fluorine-based solvent is equal to or greater than the content of the n-heptane.

6. A spray containing the water-repellent agent for through-hole fishing rods described in any one of claims 1 to 5.

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