JP4512333B2 - Punch - Google Patents

Description

  The present invention relates to a fishing rod, and more particularly, to a type of fishing rod called a through rod in which a fishing line passage for inserting a fishing line is formed inside the rod body.

  In the fishing rod used for fishing, a fishing line is inserted into the rod body to insert the fishing line. The fishing line from the reel is inserted into the rod body, and is led out from the tip end of the rod. There is a type of “through hole”. Such a threading rod is less likely to get entangled or dandruff in the fishing line guide, compared to an “outer threading rod” in which a fishing line guide is arranged on the peripheral surface of the rod body to guide the fishing line. Has the merit of being less susceptible to wind. For this reason, recently, threading hooks have been widely used.

  However, in the case of a through rod, when the fishing line thrown into the water is wound up on the reel, the water attached to the fishing line along with the fishing line also passes through the fishing line passage inside the housing, so that the water adheres and accumulates in the fishing line passage. There is a risk that. In particular, in recent threading rods, many fishing line support protrusions are spirally formed in order to reduce the contact area between the fishing line and the inner circumferential surface of the fishing line passage. Such a fishing line support protrusion prevents the water accumulated in the fishing line passage from being drained. When water accumulates in the fishing line passage, the fishing line cannot be smoothly led out due to the resistance of the accumulated water, and the weight of the entire fishing rod is increased.

  Therefore, in order to solve such a problem, a method is disclosed in which a water-repellent coating film made of a fluorine-based material or the like is formed on the inner peripheral surface of a fishing line passage to suppress adhesion of water droplets (for example, Patent Documents). 1, see Patent Document 2). By forming the water-repellent coating film on the inner peripheral surface of the fishing line passage, water that tends to accumulate in the fishing line passage is smoothly drained.

However, the conventional punch with a water-repellent coating film has not been able to ensure sufficient durability of the water-repellent coating film. That is, the inner peripheral surface of the fishing line passage through which the fishing line is inserted is a harsh environment in which contact with the fishing line is repeated. The water-repellent coating film is required to have a characteristic that the water-repellent coating film does not easily peel off from the inner peripheral surface of the housing even if the contact with the fishing line is repeated. Conventional water-repellent coating films do not sufficiently meet such requirements, and further improvements are required.
Japanese Patent Laid-Open No. 10-42750 JP-A-11-299397

  The present invention provides a penetrating rod excellent in the water repellency of the fishing line passage and the maintenance of the water repellency.

  The through rod of the present invention includes a rod body having a fishing line passage for inserting a fishing line therein, and a water repellent coating film formed on the inner peripheral surface of the fishing line passage. This water-repellent coating film is obtained by a water-repellent coating composition containing a silicone acrylic block polymer, an α, β-unsaturated carbonyl group-containing material, silicone oil and hydrophobic silica. Is obtained by polymerizing a monomer mixture having an active methylene group value of 30 to 150 and a hydroxyl value or tetrahydrofurfuryl group value of 1 to 10 in the presence of an azo group-containing silicone macroinitiator. It is.

  The solid content mass ratio of the silicone acrylic block polymer and the α, β-unsaturated carbonyl group-containing material in the water-repellent coating composition is preferably 95/5 to 70/30.

  Hydrophobic silica is an aggregate of primary particles having an average particle size of several tens of nm, and may have an average particle size of 1 to 10 μm.

  Furthermore, the water repellent coating composition may further contain polytetrafluoroethylene particles having an average particle diameter of 0.2 to 5 μm.

  The through rod of the present invention is excellent in the water repellency of the fishing line passage and the maintenance of the water repellency. Therefore, even if it is used for a long time, the operability of the fishing rod is not impaired.

The present invention is described in detail below.
(Structure of the whole punch)
As shown in FIG. 1, a threading rod that employs one embodiment of the present invention is configured by connecting a plurality of tapered tubular bodies. For example, this penetrating hook is constructed by connecting a heel 1 and a heel 2, a middle heel 3, and a stylus 4 that are sequentially connected to the head side in a swing-out or side-by-side manner. However, the number of housings is not limited to this, and an arbitrary number is set as necessary.

  The main rod 1 is provided with a reel sheet 5 for detachably mounting the reel R on the peripheral surface thereof, and the fishing line L from the reel R is attached to the peripheral surface on the tip side of the reel sheet 5. A fishing line inlet 6 is formed for introduction into the inside. A fishing line introduction guide 7 for guiding the fishing line L to the fishing line introduction port 6 is further mounted on the circumferential surface of the main rod 1 near the fishing line introduction port 6.

  Moreover, the hollow inside each rod body of the former rod 2 to the tip rod 4 is a fishing line passage. A spiral fishing line support protrusion may be formed integrally with the tubular body portion on the inner peripheral surface of each of these rods. A water-repellent coating film 10 is formed on the inner peripheral surfaces of these fishing line passages as will be described in detail later. Further, a top guide 8 is attached to the end of the tip end 4 of the tip end.

In such a through rod, the fishing line L from the reel R is inserted into the main rod 1 from the fishing line introduction port 6 through the fishing line introduction guide 7. The fishing line L is sequentially inserted through the fishing line passages in the respective bodies and led out from the top guide 8.
(About the structure of Motogami 2)
Next, taking the former rod 2 as an example, a rod body in which a fishing line passage is formed will be described.

  As shown in FIG. 2, the upper rod 2 is applied to the tubular main body portion 11, the fishing line support protrusion 12 formed in a spiral shape on the inner peripheral surface of the main body portion 11, and the inner peripheral surface of the main body portion 11. The water-repellent coating film 10 is formed.

  The tubular main body 11 is a tubular body made of a prepreg material in which reinforcing fibers such as carbon fiber and glass fiber are arranged and impregnated with a synthetic resin such as an epoxy resin. The hollow inside the tubular main body 11 is a fishing line passage for the fishing line L. The fishing line support protrusion 12 formed on the inner peripheral surface is also formed of the above-described prepreg material. The fishing line support protrusion 12 and the main body 11 are integrated when firing a predetermined prepreg material.

  The fishing line support projection 12 and the main body portion 11 form irregularities in the axial direction on the inner peripheral surface of the fishing line passage of the former upper rod 2. It is preferable to form the water-repellent coating film 10 only on the portion (excluding the surface portion that protrudes in the most in the fishing line passage 12).

  The water repellent coating film 10 is formed of a super water repellent coating composition containing a silicone acrylic block polymer, an α, β-unsaturated carbonyl group-containing material, silicone oil and hydrophobic silica. The water repellent coating film 10 has a so-called “super water repellency” performance. In the present specification, super water repellency means a property showing a water contact angle of 150 ° or more.

The super water-repellent coating composition forming the water-repellent coating film 10 will be described in detail below.
(About super water-repellent coating composition)
The super-aqueous coating composition for forming the water-repellent coating 10 is, as described above, a super-water-repellent coating containing a silicone acrylic block polymer, an α, β-unsaturated carbonyl group-containing product, silicone oil and hydrophobic silica. It is formed by the composition.

  This silicone acrylic block polymer is a monomer mixture having an active methylene group value of 30 to 150 and a hydroxyl value or tetrahydrofurfuryl group value of 1 to 10 in the presence of an azo group-containing silicone macroinitiator. It is obtained by polymerization. The azo group-containing silicone macroinitiator is not particularly limited. For example, the following formula (1) described in JP-B-2-33053 and JP-A-7-18139:

（式中、Ｒ₁は、同一又は異なって、水素原子、炭素数１〜６のアルキル基又はニトリル基を表わす。Ｒ₂は、同一又は異なって、水素原子又は炭素数１〜６のアルキル基を表わす。Ｒ₃は、同一又は異なって、水素原子、ハロゲン原子、置換若しくは非置換のアルキル基又はフェニル基を表わす。ｐ及びｑは、同一又は異なって、０〜６の整数を表わす。ｍは、０〜２００の整数を表わす。）
で表わされる繰り返し単位からなるアゾ基含有ポリシロキサンアミド等を挙げることができる。

Wherein R ₁ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group. R ₂ is the same or different and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ₃ is the same or different and represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or a phenyl group, and p and q are the same or different and each represents an integer of 0 to 6. m Represents an integer of 0 to 200.)
An azo group-containing polysiloxane amide composed of repeating units represented by

  As such an azo group-containing silicone macroinitiator, those having a silicone chain portion number average molecular weight of 2000 to 30000 are preferred. The azo group-containing silicone macroinitiator can be synthesized, for example, by reacting a diamine having a polysiloxane segment with a dibasic acid dihalide containing an azo group. As the azo group-containing silicone macroinitiator, VPS series (made by Wako Pure Chemical Industries, Ltd.), which is a 4,4′-azobis (4-cyanovaleric acid) bonded to a polydimethylsiloxane chain through an amide bond, is used. It is also possible.

  The monomer mixture used to produce the silicone acrylic block polymer has an active methylene group value of 30 to 150, and a hydroxyl value or a tetrahydrofurfuryl group value of 1 to 10. If the active methylene group value is less than 30, the resulting water repellent coating film is not sufficiently hardened, and the water repellency of the resulting water repellent coating film may decrease over time. Further, even if the active methylene group value exceeds 150, an effect commensurate with it cannot be obtained. On the other hand, when the hydroxyl value or the tetrahydrofurfuryl group value is less than 1, the adhesion to the fishing rod body is insufficient, and when it exceeds 10, the water repellency of the water-repellent coating film may be lowered. In addition, when the said monomer mixture has both a hydroxyl value and a tetrahydrofurfuryl group value, the total value needs to be contained in the said range.

  Since it has the above-mentioned active methylene group value, the monomer mixture contains an active methylene group-containing acrylic monomer. The active methylene group-containing acrylic monomer is not particularly limited. For example, 2-acetoacetoxyethyl (meth) acrylate, 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl ester, N- (2 -Cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) acrylamide, N-4- (acetoacetoxymethyl) benzylacrylamide, N- (2-acetoacetamidoethyl) benzylacrylamide, N- (2-acetoacetamidoethyl) ) Methacrylamide etc. can be mentioned. These may be used alone or in combination of two or more.

  On the other hand, since it has the hydroxyl value or the tetrahydrofurfuryl group value, the monomer mixture contains a hydroxyl group-containing acrylic monomer or a tetrahydrofurfuryl group-containing acrylic monomer. The hydroxyl group-containing acrylic monomer is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Examples include acrylates, adducts of 2-hydroxyethyl (meth) acrylate and ε-caprolactone (Placcel FM series or Plaxel FA series). Moreover, it does not specifically limit as said tetrahydrofurfuryl group acrylic monomer, For example, a tetrafurfuryl methyl (meth) acrylate etc. can be mentioned.

  The above-mentioned monomer mixture usually contains a monomer having no reactive functional group in addition to the above monomer. Such a monomer is not particularly limited, and examples thereof include other monomers such as aromatic monomers, alkyl (meth) acrylates, fluoroalkyl (meth) acrylates, (meth) acrylonitrile, and vinyl acetate. Can be mentioned.

  Furthermore, the monomer mixture can contain a monomer having a reactive group such as an epoxy group-containing monomer, a carboxyl group-containing monomer, or an amide group-containing monomer, if necessary. These monomers are preferably used in a range that does not affect various performances of stability in the water-repellent coating composition used in the present invention.

  The above-mentioned silicone acrylic block polymer can be obtained by polymerizing the monomer mixture by conventional bulk polymerization or solution polymerization in the presence of the azo group-containing silicone macroinitiator. The blending ratio of the monomer mixture and the silicone macroinitiator is within a range of 95/5 to 50/50 (monomer mixture / silicone macroinitiator) in terms of mass ratio when the total of both is 100 parts by mass. It is preferable. If it is outside the above range, the silicone acrylic block polymer may not have a good water repellency function and may have poor compatibility with other components. The blending ratio is more preferably 90/10 to 65/35.

The polymerization of the monomer mixture is initiated by the decomposition of the azo group-containing silicone macroinitiator while generating nitrogen (N ₂ ) by heating or light irradiation to produce radical species, and at the same time, the azo group-containing silicone macroinitiator. A radical segment having a polysiloxane segment generated from an initiator is introduced into an acrylic polymer, and the [(A1) (A2)] type or [( A1) (A2) (A1)] type silicone acrylic block polymer can be produced. The silicone acrylic block polymer contains 1 to 2 acrylic polymer blocks in the chain, and its number average molecular weight is usually on the order of tens of thousands.

  The α, β-unsaturated carbonyl group-containing product contained in the water-repellent coating composition undergoes Michael addition reaction with the active methylene group of the silicone acrylic block polymer, whereby the curing proceeds. The α, β-unsaturated carbonyl group is a functional group having a double bond between the α carbon and the β carbon with respect to the carbonyl group, and examples thereof include a methacrylate group, an acrylate group, a maleate group, and a fumarate group. Can do.

  The α, β-unsaturated carbonyl group-containing product preferably has two or more α, β-unsaturated carbonyl groups in one molecule from the viewpoint of curability. More preferably, it has 3 to 6 α, β-unsaturated carbonyl groups in one molecule.

  The α, β-unsaturated carbonyl group-containing product is not particularly limited, and includes, for example, (meth) acrylic acid ester of polyol, α, β-unsaturated dicarboxylic acid such as fumaric acid and maleic acid as an acid component. Unsaturated polyester polymer, epoxy polymer (meth) acrylic acid ester, (meth) acryloyl group-containing urethane compound, α, β-unsaturated carbonyl group-containing acrylic polymer, (meth) acryloyl group-containing polyether polymer and ( Examples thereof include a (meth) acryloyl group-containing silicone oligomer.

  In particular, as an α, β-unsaturated carbonyl group-containing product, a (meth) acrylic acid ester of a polyol is preferable because it is easily available industrially. The (meth) acrylic acid ester of polyol is an ester of polyol and (meth) acrylic acid, which is a compound having two or more hydroxyl groups. Here, the polyol may be a low molecular weight polymer or a polymer.

When the polyol has a low molecular weight, examples of the α, β-unsaturated carbonyl group-containing compound include ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-cyclohexyldimethanol di (meth) acrylate, 4,4′-isopropylidenedicyclohexanol di (meth) acrylate, bis ( Hydroxymethyl) tricyclo [5,2,1,0] decanedi (meth) acrylate, 1,3,5-tris (2-hydroxyethyl) cyanuric acid tri (meth) acrylate and the like. When combined The alpha, The β- unsaturated carbonyl group-containing material, for example, acrylic polyols, polyester polyols, polyether polyols, epoxy polyols, and polyurethane polyols and silicone polyols (meth) acrylic acid ester.

  The number average molecular weight of the α, β-unsaturated carbonyl group-containing product is preferably in the range of a lower limit of 200 and an upper limit of 5000. When the number average molecular weight is less than 200, the curability of the water-repellent coating film is lowered, which may affect film properties. On the other hand, when the number average molecular weight exceeds 5000, the reaction may not proceed sufficiently. The lower limit is more preferably 300, and the upper limit is more preferably 3000.

  The double bond equivalent of the α, β-unsaturated carbonyl group-containing product is preferably in the range of a lower limit of 100 and an upper limit of 1500. When the double bond equivalent is less than 100, an unreacted (meth) acrylate group remains in the resulting water-repellent coating film, and the weather resistance may be lowered, or it may be hard and brittle. Moreover, when the said double bond equivalent exceeds 1500, the crosslinking density of the coating film obtained will become small and a coating-film physical property and performance may fall. In addition, the double bond equivalent in this specification means the molecular weight per double bond. The upper limit is more preferably 1000.

  In the water-repellent coating composition, the solid content mass ratio of the silicone acrylic block polymer / the α, β-unsaturated carbonyl group-containing material is preferably in the range of 95/5 to 70/30. If it exceeds 95/5, the coating film adhesion may be insufficient, and if it is less than 50/50, the water repellency may decrease. From the viewpoint of curability, the functional group ratio of the active methylene group / α, β-unsaturated carbonyl group-containing body contained in the silicone acrylic block polymer is 1.0 / 2.0 to 1.0 / 0. It is preferable to set it within the range of .8.

  The water-repellent coating composition used in the present invention contains silicone oil. By including the silicone oil, the resulting coating film can be provided with water repellency over a long period of time.

  The silicone oil is not particularly limited, and examples thereof include conventionally known liquid polydimethylsiloxane. Moreover, about the reactive silicone which has reactive functional groups, such as a hydroxyl group, an amino group, and an epoxy group, as long as these reactive groups do not have a bad influence on a coating-film physical property, it can be used.

  The number average molecular weight of the silicone oil is preferably smaller than the silicone chain portion of the silicone acrylic polymer. Further, the lower limit of the number average molecular weight of the silicone oil is preferably about 1500. If the number average molecular weight is less than 1500, bleeding may occur.

  The silicone oil content in the water-repellent coating composition is preferably in the range of a lower limit of 1 part by mass and an upper limit of 50 parts by mass with respect to 100 parts by mass of the silicone acrylic block polymer solid content. If the content is less than 1 part by mass, the effect of maintaining the water repellency of the coating film cannot be obtained.

  In addition, the water-repellent coating composition used in the present invention further contains hydrophobic silica. The hydrophobic silica is present as a granular material in the coating film, thereby imparting fine irregularities to the coating film surface. As a result, the apparent contact angle of the coating film with respect to water is increased, and higher water repellency can be obtained.

  This hydrophobic silica is an aggregate of primary particles having an average particle diameter of several tens of nm, and preferably has an average particle diameter of 1 to 10 μm. A more preferable average particle diameter of the hydrophobic silica is 1 to 5 μm. If the thickness is less than 1 μm, sufficient water repellency cannot be obtained, and if it exceeds 10 μm, the surface roughness of the resulting coating film becomes too large and the water repellency may decrease. The average particle diameter can be determined by a well-known method such as a Coulter counter. The particle diameter of the primary particles is several tens of nanometers. In this specification, several tens of nanometers means a range of 10 nm or more and less than 100 nm.

  This hydrophobic silica is obtained by subjecting silica having an average particle size of several μm to silica of several tens of nanometers under basic conditions, and then subjecting it to secondary aggregation under acidic conditions to give a hydrophobic treatment. It is. As the hydrophobization treatment, a method of performing treatment so that the inorganic oxide powder surface has a hydrophobic group such as a lower alkyl group such as a methyl group or an ethyl group, or a fluorinated alkyl group, or a silicone oil is used. A surface treatment method by vapor phase adsorption can be mentioned.

  The hydrophobic silica is preferably silica that has been treated by adsorbing silicone oil in a gas phase, and commercially available products may include Nippon Sil SS series manufactured by Nippon Silica Kogyo. Moreover, it is preferable that content of hydrophobic silica exists in the range of the minimum of 10 mass% and the upper limit of 60 mass% with respect to solid content total mass of the said water-repellent coating composition. If the content is less than 10% by mass, the apparent water contact angle of the resulting water-repellent coating film does not increase, and super-water-repellency may not be obtained. Even if the content exceeds 60% by mass, not only the water repellency of the resulting coating film is not changed, but also the adhesion may be lowered. The lower limit is more preferably 20% by mass, and the upper limit is more preferably 55% by mass.

  In addition, as a water-repellent coating composition used here, it is preferable that the polytetrafluoroethylene particle | grains which have an average particle diameter of 0.2-5 micrometers are further included. By including the polytetrafluoroethylene particles, super water repellency can be maintained over a long period of time. The polytetrafluoroethylene particles are not particularly limited, and examples thereof include Lubron series manufactured by Daikin Industries, Ltd.

  The content of the polytetrafluoroethylene particles is preferably within a range of a lower limit of 10% by mass and an upper limit of 60% by mass with respect to the total solid content of the water-repellent coating composition. When the content is less than 10% by mass, the effect of imparting water repellency cannot be expected. When the content exceeds 60% by mass, the coating film adhesion may be lowered. The lower limit is more preferably 20% by mass, and the upper limit is more preferably 40% by mass.

In addition to the above components, the water-repellent coating composition may contain commonly used coating additives such as a sagging inhibitor, a leveling agent, an ultraviolet absorber, and an antioxidant. Moreover, it is also possible to contain various pigments as a coloring component as needed.
(Manufacturing method of Motogami 2)
Next, an outline of a method for manufacturing such a former bowl 2 will be described.

  First, a release material or the like is applied to the outer peripheral surface of a mandrel (core material) 100 having a predetermined taper as necessary. As shown in FIG. 3A, the release tape A is wound around the peripheral surface of the mandrel 100 while being spirally spaced apart.

  Subsequently, the first prepreg tape P1 is wound around the release tape A so as to fill the gap. The first prepreg tape is obtained by processing a predetermined prepreg material into a tape shape, and reinforcing fibers are aligned and oriented in the longitudinal direction of the tape. The first prepreg tape P1 finally constitutes the fishing line support protrusion 12.

  As shown in FIG. 3B, the prepreg sheet P2 is wound around the peripheral surfaces of the first prepreg tape P1 and the release tape A while further applying pressure. The prepreg sheet P2 is obtained by processing a predetermined prepreg material into a sheet shape. The reinforcing fibers are oriented so as to be approximately parallel to the axial direction of the mandrel 100. Such a prepreg sheet P2 is wound by several plies. However, a plurality of different prepreg sheets P2 may be wound instead of winding one prepreg sheet P2 by several plies. The prepreg sheet P2 finally constitutes the main body portion 11.

  In this way, after winding the prepreg sheet P2 for an arbitrary ply, as shown in FIG. 3C, the second prepreg tape P3 is further wound around the outer periphery of the prepreg sheet P2 while applying pressure without any gaps in a spiral manner. The second prepreg tape P3 is also obtained by processing a predetermined prepreg material into a tape shape, and reinforcing fibers are aligned and oriented in the longitudinal direction of the tape. The second prepreg tape P3 also constitutes the main body 11 together with the prepreg sheet P2. The state of each prepreg laminated in this way is schematically shown in FIG.

  Thereafter, if necessary, a molding tape made of polyester, polypropylene, or the like is further wound around the outer peripheral surface of these prepregs to mold the bag material. The obtained raw material is fired in a furnace, the mandrel 100 is extracted, and the molding tape is peeled off from the outer peripheral surface. Further, the release tape A is peeled from the inner peripheral surface of the bag material from which the mandrel 100 is pulled out. By peeling off the release tape A, only the portion of the first prepreg tape P1 remains on the inner peripheral surface of the bag material.

  Then, necessary surface treatment is performed on the outer peripheral surface of the bag material, and the axial length is adjusted. And the above-mentioned water-repellent coating composition is apply | coated to the internal peripheral surface of this cocoon material. Examples of the method for applying the water-repellent coating composition include flow coating, spray coating, and brush coating. The selection is arbitrary.

  Here, a method of feeding the water-repellent coating composition into the bag material with a pressure device will be described. This method can be performed using an apparatus as shown in FIG. This device is composed of a pressure vessel 20, a composition storage vessel 21 disposed in the pressure vessel 20, and a pressurizing device 22 that pressurizes the inside of the pressure vessel 20. A pipe 23 is inserted into the pressurized container 20 from the upper surface thereof, and a liquid level detection sensor 24 is disposed above the pressurized container 20. In the composition storage container 21, a water-repellent coating liquid obtained by diluting the water-repellent coating composition with a solvent is stored. The lower end portion of the pipe 23 is inserted into the water-repellent coating liquid in the composition collection container 21, and the upper end portion is a connecting portion for connecting the straw material. One end of the heel material is connected to the connecting portion, and a silicone transparent cap 25 is fitted to the other end of the heel material. The liquid level detection sensor 24 detects the liquid level with the connecting portion and the cap 25.

  When the inside of the pressure container 20 is pressurized by the pressurizing device 22, the water-repellent coating liquid in the composition storage container 21 blows up from the pipe into the bag material. When the water-repellent coating liquid blows up to the transparent cap 25, the liquid level detection sensor 24 detects this, releases the pressurization of the pressurizing device 22, lowers the pressure in the pressure vessel 20, and again the water-repellent coating liquid. The liquid level returns to the connecting part. In this manner, the water repellent coating liquid can be passed through the bag material by this apparatus.

  After passing the water-repellent coating liquid through the bag material, the bag material is placed horizontally. First, as a first step, air is blown to volatilize the solvent of the water-repellent coating liquid. That is, while rotating the saddle material in the circumferential direction, the inside of the saddle material is blown from one side to the other. The preferable air blowing conditions are 1 to 3 kPa, 15 to 40 ° C., about 30 to 90 minutes, the rotational speed of the straw material is about 10 rpm, and the direction of rotation is reversed every 30 seconds. By blowing air while rotating the rod material under such conditions, the water-repellent coating liquid on the peripheral surface of the portion corresponding to the fishing line support protrusion 12 flows down to the other portion and the solvent of the water-repellent coating solution volatilizes. . In addition, when using a hydraulic blower, it is necessary to attach a filter to the blower so that the oil does not affect the water-repellent coating composition. Next, as a second step, heating is performed to cure the water repellent coating composition to form a water repellent coating film. It is preferable to heat the water repellent coating film at 60 to 120 ° C. for about 60 to 120 minutes. Also in this case, the bag material is rotated according to the first step.

  Thus, it is preferable that the film thickness of the water-repellent coating film applied to the inner peripheral surface of the bag material is in the range of a lower limit of 5 μm and an upper limit of 150 μm. When the film thickness is out of the above range, the water repellency persistence is not preferable. The lower limit is more preferably 15 μm, and the upper limit is more preferably 50 μm. Thereafter, necessary parts such as a fishing line guide are attached to the rod material to obtain the original rod 2.

  Here, the former bowl 2 is described as an example, but the other middle bowl 3 and the tip bowl 4 can be manufactured by the same manufacturing method.

  In addition, here, the case where the fishing line support protrusion is formed on the inner peripheral surface has been described, but it is naturally possible to apply the present invention to a through rod having a hook body that is not provided with the fishing line support protrusion. is there. Furthermore, although the water repellent coating film is not formed on the fishing line support protrusions here, the water repellent coating film may be formed on the entire peripheral surface of the housing including the fishing line support protrusions.

  Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” means “% by mass” unless otherwise specified.

Performance evaluation of water-repellent coating [Synthesis Example 1]
Production of Silicone Acrylic Block Polymer Having Active Methylene Group and Hydroxyl Group 180.8 g of butyl acetate was added to a 500 mL glass container equipped with a stirring blade, a nitrogen introduction tube, a cooling condenser and a dropping funnel, and heated to 120 ° C. under a nitrogen atmosphere. Warm up. In that container, 30 g of VPS-1001 (azo group-containing silicone amide; manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 90 g of butyl acetate, 43.0 g of 2-acetoacetoxyethyl methacrylate, 2.8 g of HEMA, 57.5 g of cyclohexyl methacrylate, 16.8 g of 2-ethylhexyl methacrylate was added dropwise at a constant rate over 3 hours. Thereafter, the mixture was kept at 120 ° C. for 0.5 hour, and 0.3 g of tert-butyl peroxy 2-ethylhexanoate dissolved in 7.5 g of butyl acetate was added dropwise at a constant rate in 30 minutes. Furthermore, the objective block copolymer was obtained by continuing a heating at 110 degreeC for 1.5 hours. VPS-1001 has the following structure.

このようにして合成したブロック共重合体について、ＧＰＣを用いて得られた標準ポリスチレン換算の分子量の値は、Ｍｎ＝３４０００、Ｍｗ＝１１８４００、Ｍｗ／Ｍｎ＝３．４８であった。また、樹脂固形分は３２．１％であった。

With respect to the block copolymer synthesized in this manner, the molecular weight values in terms of standard polystyrene obtained using GPC were Mn = 34000, Mw = 118400, and Mw / Mn = 3.48. The resin solid content was 32.1%.

[Synthesis Example 2]
Production of Silicone Acrylic Block Polymer Having Active Methylene Group and No Hydroxyl Group Similar to Synthesis Example 1 except that HEMA was not used and cyclohexyl methacrylate was increased from 57.5 g to 60.2 g. A block copolymer was obtained.

  About this block copolymer, the value of the molecular weight of standard polystyrene conversion obtained using GPC was Mn = 32100, Mw = 116800, Mw / Mn = 3.64. The resin solid content was 31.6%.

[Synthesis Example 3]
Production of a hydroxyl group-containing silicone acrylic block polymer having a hydroxyl group and no active methylene group In a 500 mL glass container equipped with a stirring blade, a nitrogen introduction tube, a cooling condenser and a dropping funnel, 51.5 g of butyl acetate, methoxypropyl Acetate 116.5g was added and it heated at 120 degreeC by nitrogen atmosphere. In the container, 20 g of VPS-1001 dissolved in 60 g of butyl acetate, 47.9 g of cyclohexyl methacrylate, Plaxel FM-2D (manufactured by Daicel Industries, Ltd., 1: 2 adduct of 2-hydroxyethyl methacrylate and ε-caprolactone) 23 0.0 g and 2-hydroxyethyl methacrylate 9.0 g were added dropwise at a constant rate over 3 hours. Then, it hold | maintained at 120 degreeC for 0.5 hour, 0.2 g of azobisisobutyronitrile melt | dissolved in 5 g of butyl acetate was dripped at constant velocity in 30 minutes. Furthermore, the objective block copolymer was obtained by continuing a heating at 120 degreeC for 1.5 hours.

  Regarding the synthesized block copolymer, the molecular weight values in terms of standard polystyrene obtained using GPC were Mn = 9300, Mw = 96700, and Mw / Mn = 10.44. The hydroxyl value was 75.0 mgKOH / g, and the resin solid content was 27%.

[Example 1]
31.15 g of a silicone acrylic block polymer having an active methylene group and a hydroxyl group produced in Synthesis Example 1, 1.65 g of trimethylolpropane triacrylate as an α, β-unsaturated carbonyl group-containing substance, and KF-96 (Shin-Etsu as a silicone oil) Chemicals, viscosity 100 cs) 1.14 g, 7.178 g of SS178B (manufactured by Nippon Silica) as hydrophobic silica having an average particle diameter of 3 μm, and Lubron L-2 as polytetrafluoroethylene particles having an average particle diameter of 0.3 μm. 52 g, 0.03 g of tetrabutylammonium fluoride and 57.0 g of ethyl acetate as a catalyst were mixed to obtain a water-repellent coating composition.

  The water-repellent coating composition is applied to the inner peripheral surface of the cocoon material produced by the above-described manufacturing method by using a syringe, and air is blown into the cocoon material for 30 minutes by an air compressor. -Heated for about 60 minutes to cure the water-repellent coating composition to form a water-repellent coating film. In this way, a housing having a water repellent coating film formed on the inner peripheral surface of the fishing line passage was obtained. The film thickness of this water repellent coating film was 30 μm.

[Comparative Example 1]
In Example 1, instead of the silicone acrylic block polymer having an active methylene group and a hydroxyl group, 31.65 g of the silicone acrylic block polymer having an active methylene group produced in Synthesis Example 2 and having no hydroxyl group was used. A water-repellent coating composition was prepared in the same manner except that the amounts of tetrabutylammonium fluoride and ethyl acetate were changed to 0.02 g and 5.0 g, respectively, and a water-repellent coating film was formed on the inner peripheral surface of the fishing line passage I got a box.

[Comparative Example 2]
Instead of the silicone acrylic block copolymer having an active methylene group and a hydroxyl group, 33.11 g of the silicone acrylic block polymer having a hydroxyl group and having no active methylene group produced in Synthesis Example 3 was used, and tetrabutylammonium fluoride was used. A water-repellent coating composition was prepared in the same manner as in Example 1 except that 0.03 g and 45.0 g of ethyl acetate were used. And the housing which formed the water-repellent coating film in the inner peripheral surface of the fishing line channel | path was obtained.

[Comparative Example 3]
34.03 g of a silicone acrylic block polymer having an active methylene group and no hydroxyl group produced in Synthesis Example 2, 2.64 g of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd .: HM01 straight type) as an isocyanate curing agent, as a curing catalyst 0.005 g of dibutyltin laurate and 20.0 g of ethyl acetate were mixed to obtain a water-repellent coating composition. Using the obtained water-repellent coating composition, a casing having a water-repellent coating film formed on the inner peripheral surface of the fishing line passage was obtained.

[test]
The following evaluation tests were performed on the water-repellent coating film of each casing obtained as described above.

<Water repellency>
The water repellency was evaluated by measuring the water contact angle and the water falling angle.

  For these measurements, a contact angle meter (Kyowa Interface Chemical Co., Ltd., CA-C) was used. The water drop angle is determined as the inclination angle of the test plate when a predetermined amount of water droplets start to slide, and even if the water contact angle shows a predetermined value, the water drop angle is accepted. If it is not within the range, the super water repellency required in the present invention cannot be obtained.

  When the water contact angle is 150 ° or more, it is judged to have super water repellency. On the other hand, if the water falling angle is 15 ° or less in super water repellency, it is considered acceptable. The amount of water droplet used at the time of measuring the water falling angle was 10 μl.

<Adhesion>
The coating film was scratched with a nail to evaluate adhesion. A film that is not peeled off at all or is only a part even if it is peeled off is considered acceptable.

<Maintenance of coating film performance>
Moreover, whether the performance of the coating film was maintained over a long period of time was evaluated by measuring the water contact angle and the water falling angle after the coating film was immersed in warm water. Specifically, after the coating film is immersed in warm water of 40 ° C., the air layer formed on the coating film surface is forcibly removed by water pressure so that the warm water comes into contact with the washing surface, and then 1 hour later. The coating film was taken out and air-dried for 30 minutes, and the water contact angle and water falling angle were measured.

[result]
The results of the above evaluation are shown in Table 1.

表１より明らかなように、実施例１の竿体はその内部の釣糸通路内において優れた撥水特性を示している。

As is clear from Table 1, the rod body of Example 1 exhibits excellent water repellency in the fishing line passage inside.

Durability evaluation of water repellent coating [Example 2]
A casing formed by applying the water-repellent coating composition according to Example 1 to the inner peripheral surface of the cocoon material obtained by the above-described manufacturing method was produced. Here, the application method of the water-repellent coating composition on the cocoon material is obtained by diluting the water-repellent coating composition according to Example 1 with a 35% diluent and applying the water-repellent coating composition into the cocoon material by a pressure device. I used the method of sending in. The rods manufactured in this way are the tip rod (# 1), the middle rod (# 2), and the former bowl (# 3). These rods were connected to the tip side of the marshmallow to obtain a four-joint through rod.

[Comparative Example 4]
A fluorine-based water-repellent coating composition was used as the water-repellent coating composition, and others were obtained in the same manner as in Example 2 to obtain a four-piece continuous thread.

[test]
The following evaluation tests were conducted on the two through-holes obtained as described above.

<Real investment test>
A reel was attached to each through rod of each of Example 2 and Comparative Example 4 obtained, and the fishing line was inserted into the fishing line passage, and a weight was attached to the tip of the fishing line. He actually cast weights into the sea. The actual throwing distance in each actual throwing was set to 20 m or more, and the fishing line led out from the penetrating rod was once immersed in seawater and then wound on a reel.

  After 100 actual throws, it was disassembled into each of the cocoon basket (# 1), the middle cocoon (# 2), and the former cocoon (# 3), and air was blown into each skeleton for 10 seconds. The water inside the body was drained once. In this state, the weight of each housing was measured. Thereafter, each chassis was submerged in the water tank, and after lifting from the water tank, the weight of each chassis was measured. And the difference of the weight of each housing before submerged in the water tank and each housing after submerging in the water tank was measured. This difference in weight is considered to be the weight of water that has entered and remained in each enclosure when submerged in the aquarium. Further, the same measurement was performed before the actual throwing test (initial stage), after the actual throwing number of 200 times, after 350 times, and after 500 times.

  Furthermore, after blowing air for 10 seconds inside each of the body of the heads (# 1) to Motogami (# 3) and draining the water inside the bodies once, the bodies are connected to each other. It was a through hole, and its tip side was tilted and fixed at an angle of 10 degrees from the horizontal. After that, about 10 cc of water is injected from the top guide into the fishing line passage, and the water is distributed inside each frame. Then, the fishing line is inserted into the fishing line passage of each frame and led out from the top guide. And the magnitude of force required to start the fishing line moving was measured. This measurement was repeated several times, and the maximum value was taken as the measured value. This difference in the magnitude of the force is considered to reflect the resistance of the fishing line to be led out by the water remaining in the fishing line passage (internal resistance of the fishing rod).

  The results are shown in Table 2.

表２から明らかなように、実施例２は、比較例４に比較して５００投近くまで残存水量が小さく抑えられている。長期に渡って各竿体内の撥水塗膜がその撥水性を維持していることが理解できる。また、内部抵抗も比較例４に比較して抑えられている。

As is clear from Table 2, the amount of residual water in Example 2 is reduced to nearly 500 throws compared to Comparative Example 4. It can be understood that the water-repellent coating film in each casing maintains its water repellency for a long time. Also, the internal resistance is suppressed as compared with Comparative Example 4.

<Seawater pickling test>
In each of Example 2 and Comparative Example 4, the head spear (# 1), the middle spear (# 2), and the former spear (# 3) constituting the through-holes were completely immersed in artificial seawater. One day later, each chassis was pulled up from the artificial seawater, and air was blown into each chassis for 10 seconds to drain the water inside each chassis once. In this state, the weight of each housing was measured. Thereafter, each chassis was submerged in the water tank, and after lifting from the water tank, the weight of each chassis was measured. And the difference of the weight of each housing before submerged in the water tank and each housing after submerging in the water tank was measured. Moreover, the same measurement was performed before immersion in artificial seawater (initial stage), 3 days, 5 days, 10 days, and 14 days after immersion in artificial seawater.

  Furthermore, after blowing air for 10 seconds inside each of the body of the heads (# 1) to Motogami (# 3) and draining the water inside the bodies once, the bodies are connected to each other. It was a through hole, and its tip side was tilted and fixed at an angle of 10 degrees from the horizontal. After that, about 10 cc of water is injected from the top guide into the fishing line passage, and the water is distributed inside each frame. Then, the fishing line is inserted into the fishing line passage of each frame and led out from the top guide. And the magnitude of force required to start the fishing line moving was measured. This measurement was repeated several times, and the maximum value was taken as the measured value.

  The results are shown in Table 3.

表３から明らかなように、実施例２は、比較例４に比較して、釣糸通路内の撥水性を長期に渡って維持している。

As is apparent from Table 3, Example 2 maintains the water repellency in the fishing line passage for a long period of time as compared with Comparative Example 4.

<Running test>
Example 2 and Comparative Example 4 Corresponding to 250 km of fishing line with artificial seawater attached to the tip rod (# 1), middle rod (# 2), and former rod (# 3) constituting the through rod Then, the fishing line passage inside each housing was run. After traveling, the air was blown into each housing for 10 seconds, and the water inside each housing was drained once. In this state, the weight of each housing was measured. Thereafter, each chassis was submerged in the water tank, and after lifting from the water tank, the weight of each chassis was measured. And the difference of the weight of each housing before submerged in the water tank and each housing after submerging in the water tank was measured. This difference in weight is considered to be the weight of the water that has entered and remained in each enclosure when submerged in the aquarium. The same measurement is also performed before the fishing line travels (initial stage).

  Furthermore, after blowing air for 10 seconds inside each of the body of the heads (# 1) to Motogami (# 3) and draining the water inside the bodies once, the bodies are connected to each other. It was a through hole, and its tip side was tilted and fixed at an angle of 10 degrees from the horizontal. After that, about 10 cc of water is injected from the top guide into the fishing line passage, and the water is distributed inside each frame. Then, the fishing line is inserted into the fishing line passage of each frame and led out from the top guide. And the magnitude of force required to start the fishing line moving was measured. This measurement was repeated several times, and the maximum value was taken as the measured value.

  The results are shown in Table 4.

表４から明らかなように、実施例２は、比較例４に比較して、釣糸通路内の撥水性を長期に渡って維持している。

As apparent from Table 4, Example 2 maintains the water repellency in the fishing line passage for a long period of time as compared with Comparative Example 4.

1 is an overall view of a threading rod that employs one embodiment of the present invention. The expanded sectional view of the former upper collar 2 of the through-through collar of FIG. The figure which showed the manufacturing process of Motokami 2 The figure which showed the lamination | stacking state of the prepreg in the manufacturing process of the former upper 2. The figure which showed an example of the apparatus for apply | coating a water-repellent coating-film composition in the raw material.

Explanation of symbols

2 Original upper ridge 3 Middle ridge 4 Ear tip 10 Water repellent coating 11 Main body 12 Fishing line support protrusion

Claims (5)

Have a fishing line passage for a fishing line is inserted therein, said a rod body provided with a line-holding protrusions formed in a spiral shape on the inner peripheral surface of the fishing line passage, water-repellent formed in said inner peripheral surface of the fishing line passage With a coating,
The water repellent coating film is obtained by a water repellent coating composition containing a silicone acrylic block polymer, an α, β-unsaturated carbonyl group-containing material, silicone oil and hydrophobic silica,
The silicone-acrylic block polymer, a monomer mixture containing an acrylic monomer having an active methylene group-containing monomer and a hydroxyl group are those obtained by polymerizing in the presence of an azo group-containing silicone macroinitiator, the A medium-through bowl having an active methylene group value of 30 to 150 and a hydroxyl value of 1 to 10 in the monomer mixture .   The through hole of Claim 1 with which the said water-repellent coating film is apply | coated by the method of sending the said water-repellent coating composition with a pressurization apparatus. Wherein said silicone-acrylic block polymer of the water-repellent coating composition alpha, solid mass ratio of the content of the β- unsaturated carbonyl group-containing body is a 95 / 5-70 / 30, according to claim 1 or 2の 中 through description. The hydrophobic silica is a aggregate of primary particles having an average particle diameter of several 10 nm, have an average particle diameter of 1 to 10 [mu] m, rod through inside according to any one of claims 1 to 3 . The through hole in any one of Claims 1-4 in which the said water-repellent coating composition further contains the polytetrafluoroethylene particle | grains which have an average particle diameter of 0.2-5 micrometers.

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