JP6316001B2 - Surface decoration structure for fishing gear parts or bicycle parts - Google Patents

Description

  The present invention relates to a surface decoration structure for a fishing tackle component or a bicycle component that coats the surface of a fiber reinforced resin fishing tackle component or bicycle component.

Examples of the decorative structure for fishing gear parts or bicycle parts include the following.
(1) Metallic painting technology to fix by baking or brushing urethane or epoxy resin paint,
(2) Some decorative materials use advanced coating techniques such as vacuum deposition, CVD, PVD, and sputtering.
However, in (1), there are aspects in which the color sensation such as vividness and gloss on the painted surface is not sufficient. On the other hand, in (2), rainbow color development using refraction of light is possible, and although there are sufficient aspects in color sense, the device is large and requires advanced manufacturing technology. There are aspects that are difficult to adopt.
Therefore, it is also considered to form a decorative structure using a silver mirror reaction that exhibits a sufficient performance even with a relatively simple device and decorative properties (Patent Document 1).

JP 2009-84596 A (paragraph numbers [0032] to [0035])

However, in the production method using the silver mirror reaction, sufficient corrosion resistance and toughness cannot be obtained, and the mechanical strength is inferior.
Moreover, as shown in FIG. 13 (b), the process in silver mirror coating requires a water washing process almost every time the process is completed, which makes the manufacturing process complicated, and there is room for improvement in terms of the manufacturing process. is there. Furthermore, a special spraying means called a two-head painting gun is required, which is a heavy burden in terms of equipment.

  The object of the present invention is to provide a fishing tackle component that is excellent in decorativeness while maintaining the effect that a vivid surface decoration structure can be achieved without using a large-scale device with sufficient corrosion resistance and toughness. It is in providing a decorative structure for bicycle parts.

〔Constitution〕
The characteristic configuration of the invention according to claim 1 is that the surface of the component body made of fiber reinforced resin has an inner coating layer, a silver thin film coating layer on the inner coating layer, and an outer coating on the silver thin film coating layer. Laminate paint layers,
The grain thin coating layer is made of an ink coating containing silver metal complex amine as a ligand, so that others spiral or straight, are forms form on the surface of the inner coating layer with a gap The operational effects are as follows.

[Action]
As will be described later, the silver metal complex having an amine as a ligand exhibits sufficient fluidity only by diluting with an alcohol, so that the painting process can be achieved with a simple work form such as spraying or brushing. That is, as shown in FIG. 13 (a), the coating process may be an inner coating process for forming an inner coating layer, a silver surface thin film coating process, a drying process, and an outer coating process for forming an outer coating layer. Therefore, the painting process can be shortened and simplified. The spraying means does not require a special gun like the conventional silver mirror coating, and the equipment is less burdensome.

In addition, the silver surface has a high surface density and is closely connected by melting and joining the precipitated silver particles when heated, so that the surface decoration properties such as brightness, density and smoothness compared to metallic coating It presents a high surface.
On the other hand, when a silver metal complex having amine as a ligand is applied on the inner coating layer, the amine of the silver metal complex reacts with an unreacted resin (isocyanate or silicon compound having an epoxy group) in the inner coating layer. Then, when a coating for the outer coating layer is applied on the silver thin film coating layer formed by applying the silver metal complex, the amine remaining in the silver thin film coating layer forms a resin that forms the outer coating layer. react.
This increases the bonding force between the silver thin film coating layer and the inner and outer coating layers.

〔effect〕
Therefore, it does not require a large-scale device and is a simple work form, but avoids delamination and erosion at the interface between the silver thin film coating layer and the inner and outer coating layers, and has high corrosion resistance and sufficient It was possible to form a silver thin film coating layer exhibiting excellent decorativeness.

  However, in the above description, after forming the inner coating layer on the surface of the component main body, the silver surface thin film coating layer is formed on the surface of the inner coating layer, but only by applying the silver surface in a certain smooth state, The silver surface thin film coating layer has a poor surface.

Therefore, the following improvements were made. That is, when the ink paint described above is applied to the surface of the inner coating layer, a decorative portion region such as a figure or a pattern can be formed. As a result, the surface can be made more attractive as compared with the case where there is no decorative portion region.
In addition, the formation of the decorative portion region can suppress the conspicuous surface of the inner coating layer, and can make the presence of the silver surface thin film coating layer stand out.

〔Constitution〕
The characteristic configuration of the invention according to claim 3 or 4 is as follows:
Laminate an inner coating layer on the surface of the component body made of fiber reinforced resin, a thin silver coating layer on the inner coating layer, and an outer coating layer on the silver coating layer.
The silver thin film coating layer is made of an ink paint containing a silver metal complex having an amine as a ligand, and is formed on the surface of the inner coating layer by arranging triangular, quadrangular, round, or star-shaped figures. The operational effects are as follows.

[Function and effect]
When the ink paint described above is applied to the surface of the inner coating layer, a decorative region such as a figure / pattern can also be formed. As a result, the surface can be made more attractive as compared to the case where there is no decorative portion.
Moreover, the formation of the decorative portion region makes it possible to make the defects formed on the surface of the inner coating layer inconspicuous, and to make the presence of the silver surface thin film coating layer stand out.

That is, as shown in FIG. 16, after the inner coating layer AC is formed, the surface is not sufficiently wiped off with moisture or the like, and a slight amount of moisture remains or fine dust or dirt. When the ink coating is applied from above with the adhesive applied, the streaky defects 42 affected by the silver-coated thin film coating layer AD may occur after the application. There was a risk of nonconformity.
In addition, the silver surface thin film coating layer itself is also affected, and the color development becomes darker and tends to be yellowish or bluish.
In particular, the surface of the silver film coating layer is required to be mirror-finished, so if there is a slight defect that lacks smoothness on the surface of the inner coating layer, it will affect the surface of the silver film coating layer. It is difficult to notice, but causes a certain application failure. If it does so, in order to eliminate the malfunction, once applied, it peels off and it becomes a rework.

  However, if the decoration area is formed in advance on the silver thin film coating layer, even if a defect occurs on the surface of the inner coating layer, it can be covered with the decoration area and cannot be seen from the front side. It becomes difficult.

〔Constitution〕
The characteristic configuration of the invention according to claim 5 or 6 is that the surface of the component body made of fiber reinforced resin has an inner coating layer, a silver thin film coating layer on the inner coating layer, and an outer surface on the silver thin film coating layer. Laminate paint layers,
The inner coating layer,
(1) a two-component resin coating formed by a reaction between an isocyanate group and a hydroxyl group;
(2) a two-part resin coating formed by reacting a resin having an amino group with a silicon compound having an epoxy group;
(3) a two-component or three-component resin coating in which the reaction (1) and the reaction (2) occur simultaneously;
(4) epoxy resin paint,
Select one of them to form
The outer coating layer,
(1) a two-component resin coating formed by a reaction between an isocyanate group and a hydroxyl group;
(2) a two-part resin coating formed by reacting a resin having an amino group with a silicon compound having an epoxy group;
(3) a two-component or three-component resin coating in which the reaction (1) and the reaction (2) occur simultaneously;
The effect is as follows.

[Action]
On the other hand, when a silver metal complex having amine as a ligand is applied on the inner coating layer, the amine of the silver metal complex reacts with an unreacted resin (isocyanate or silicon compound having an epoxy group) in the inner coating layer. Then, when a coating for the outer coating layer is applied on the silver thin film coating layer formed by applying the silver metal complex, the amine remaining in the silver thin film coating layer forms a resin that forms the outer coating layer. react.
This increases the bonding force between the silver thin film coating layer and the inner and outer coating layers.

〔effect〕
Therefore, it is possible to avoid delamination and erosion at the interface between the silver thin film coating layer and the inner and outer coating layers, and to form a silver thin film coating layer that exhibits high corrosion resistance and sufficient decoration. I was able to.

〔Constitution〕
The characteristic configuration of the invention according to claim 7 or 8 is that the silver metal complex is deposited by heating the silver metal complex, and the silver nanoparticles are connected and fixed. The function and effect are as follows.

[Function and effect]
Since the silver deposited from the silver metal complex is a nanoparticle, as will be described later, the silver particles are rapidly connected and bonded by the melting point drop, thereby forming a tight silver surface thin film coating layer.
Moreover, since the silver nanoparticles are slightly melted and not completely connected and fixed, they enter the boundary area with the outer coating layer, and in the boundary area, the density of the silver particles mixed in the resin paint is the outer coating layer. Will gradually increase from 1 to the thin film coating layer. Then, in the boundary region, a mixed gradient layer of silver and the resin paint that increases in density as it goes to the silver surface thin film coating layer is formed. By this, the adhesiveness of a silver surface thin film coating layer and an outer coating layer improves, the above-mentioned delamination can be suppressed and corrosion resistance can be improved.

〔Constitution〕
The characteristic configuration of the invention according to claim 9 or 10 is that the thickness of the silver surface thin film coating layer is in the range of 0.02 microns to 0.4 microns, and the function and effect thereof are as follows. .

[Function and effect]
In the above-described prior art (Japanese Patent Application Laid-Open No. 2009-84596), a thickness in a wide range of 0.1 to 10 microns is recommended for the thickness of the silver mirror film. During the peel test, cohesive failure occurs in the silver film coating layer.
That is, the part located in the outer side coating layer side and the part located in the inner side coating layer side in the silver surface thin film coating layer are separated from each other, and are easily separated at the intermediate position in the thickness direction of the silver surface thin film coating layer.
Therefore, it is desirable to set the thickness in the range of 0.02 microns to 0.4 microns. More preferably, the thickness is in the range of 0.02 to 0.25 microns.

〔Constitution〕
The characteristic configuration of the invention according to claim 11 or 12 is that an inner mixed gradient layer in which silver is mixed in a resin paint between the silver surface thin film coating layer and the inner coating layer, the silver surface thin film coating layer, An outer mixed gradient layer in which silver is mixed in the resin coating is formed between the outer coating layer and the ratio of mixing into the silver resin coating in the inner mixed gradient layer and the outer mixed gradient layer. The higher the ratio is, the closer to the silver thin film coating layer, the effects are as follows.

[Function and effect]
Between the silver thin film coating layer and the inner and outer coating layers, there is no partition line that clearly distinguishes both areas, and an inner and outer mixed gradient layer in which silver particles are mixed in the resin paint is formed. Yes.
Therefore, even when the silver thin film coating layer and the inner and outer coating layers are deformed by the fishing rod receiving an external force, both are less likely to peel off.
Moreover, in the inner / outer mixed gradient layer, since the mixing ratio of the silver particles mixed in the resin paint is higher as the silver thin film coating layer side is changed, the silver surface thin film coating layer side is changed to the inner / outer coating layer side. The stress propagation is smooth, and the occurrence of stress cracking or the like can be suppressed at that portion.

FIG. 1 is a side view showing a fishing rod. FIG. 2 is a side view of a bag material in which a spiral region is formed, showing a state where a decorative portion region is formed. FIG. 3 shows a state in which a decoration part region is formed, (a) is a simple circle formed in the direction of the axis X at a constant interval to form a decoration part region, (b) (C) is a pattern in which straight lines are arranged in a grid pattern, in which square areas are alternately painted to form a flag-shaped pattern. FIG. FIG. 4 shows a state in which a decoration part region is formed, (a) a simple circle arranged, (b) a simple triangle arranged, (c) a simple square arranged, (d) a simple star. It is a side view of the cocoon material which arranged the form. FIG. 5 is a side view of a bag material in which a decorative part region is formed and a blurred pattern or the like is formed. FIG. 6 is a perspective view showing an ink jet type coating apparatus and showing a state in which a decorative portion region is formed on the bag material. FIG. 7A is a longitudinal side view showing a coating structure having no clear layer or the like on the outer side of the outer coating layer, and FIG. 7B has two clear layers on the outer side of the outer coating layer. It is a vertical side view showing a coating structure, (c) a vertical side view showing a two-layer coating laminated structure of an outer coating layer of a first outer coating layer and a second outer coating layer. FIG. 8 is an explanatory diagram showing a state in which (a) a silver amine complex is applied on the inner coating layer, and (b) a state in which the amine is separated from the silver amine complex by heating and silver nanoparticles are deposited. It is explanatory drawing, (c) It is explanatory drawing which shows the state which the silver nanoparticle which precipitated was melt-coupled and the silver surface film was made. FIG. 9 is an explanatory diagram showing the degree of silver mixing in the inner mixed gradient layer between the inner coating layer and the silver thin film coating layer, and in the outer mixed gradient layer between the outer coating layer and the silver thin film coating layer. It is. FIG. 10 is a measurement graph showing the mixing ratio of silver and resin in the inner and outer mixed gradient layers. FIG. 11 is a photomicrograph of precipitated silver nanoparticles corresponding to FIG. FIG. 12A is a left side view showing a state in which a glass plate coated with a predetermined silver surface thin film coating layer is attached to the housing, and FIG. 12C is a film coated with a predetermined silver surface thin film coating layer and the like. It is a right view which shows the state which attached to the housing, (b) is a front view corresponding to above-described (a) and (c). FIG. 13A is a process diagram showing a silver surface thin film coating process of the present invention, and FIG. 13B is a process chart showing a silver mirror coating process. FIG. 14 is a side view showing the spinning reel. FIG. 15 is a side view showing a bicycle. FIG. 16 is a side view of a bag material showing a conventional defect.

[First Embodiment]
A fishing rod A used for fishing yamame trout and rock fish will be described. As shown in FIG. 1, the fishing rod A has a top guide 2 attached to the tip of the tip rod 1 and a fishing line guide 3 attached and fixed at an intermediate position of the tip rod 1 and is connected to the rod side in a side-by-side manner. The base 5 is arranged, and the reel seat 6 for mounting the spinning reel is attached to the base 5.

  Note that the tip rod 1 and the rod 5 constituting the fishing rod A are manufactured as follows. That is, reinforcing fibers such as carbon fibers are aligned in one direction, and the aligned reinforcing fibers are impregnated with a thermosetting resin (or thermoplastic resin) such as an epoxy resin to form a prepreg sheet. A plurality of prepreg sheets cut into a substantially trapezoidal shape are wound around a mandrel, and a firewood material formed by winding a plurality of prepreg sheets is placed in a furnace in a state of being wound around a mandrel and fired. Decentering, taking out the cylindrical cocoon material, cutting the cocoon material into a predetermined length, and finishing it to make a casing.

  As the reinforcing fiber constituting the prepreg, specifically, glass fiber, aramid fiber, alumina fiber, etc. can be used in addition to carbon fiber, and as the resin, in addition to epoxy resin, thermosetting such as phenol resin, polyester resin, etc. A thermoplastic resin such as a conductive resin or PV (E) can be used. Further, the prepreg may be configured by impregnating a woven fabric woven with reinforcing fibers with a resin.

  The coating applied to the outer peripheral surfaces of the intermediate rod 4 and the main rod 5 as components constituting the fishing rod A will be described. As shown in FIG. 7 (a), the coating composition is such that a transparent clear layer AG described later is not provided outside the outer coating layer AE, or a clear paint is used for the outer coating layer AE. As shown in FIG. 2B, two types of the color clear layer AF and the transparent clear layer AG provided on the outer coating layer AE will be described. For example, what is shown in FIGS. 7 (a) and 7 (b) is used for the intermediate basket 4 and the like, and what is shown in FIG. Note that this use is not fixed and can be freely selected.

As shown in FIG. 7 (a), the innermost coating layer AB is provided on the surface of the outer peripheral surface 4A such as the intermediate collar 4, and the inner coating layer AC is provided from above the innermost coating layer AB. A silver surface thin film coating layer AD is provided thereon, and an outer coating layer AE is provided on the silver surface thin film coating layer AD.
Similarly, as shown in FIG. 7B, it is possible to select whether the innermost coating layer AB is provided or not provided on the outer peripheral surface 4A such as the intermediate ridge 4, but the innermost coating is not provided. When the layer AB is provided, the inner coating layer AC is provided over the innermost coating layer AB, the silver surface thin film coating layer AD is provided over the inner coating layer AC, and the outer coating is applied over the silver surface thin film coating layer AD. A layer AE is provided, and further, a color clear layer AF and a transparent clear layer AG are formed on the outer coating layer AE.

  For the innermost coating layer AB, an epoxy resin coating is selected. This innermost coating layer AB covers the reinforcing fibers that may be exposed on the surface of the rivet 5 or the like, and ensures the adhesion of the inner coating layer AC. Moreover, as shown in FIG.7 (c), on the surface of a cage | basket, in the state which dared to leave the molding tape trace 5a which spirally winds the outer peripheral surface of a cage | basket material, when a cage | casing body is baked, Etc. may be formed. The innermost coating layer AB is formed to level the molded tape mark 5a.

Next, the inner coating layer AC will be described. Four types of resin paints are selected for use in the paint layer.
(1) As a 1st resin coating material, the two-component acrylic urethane resin coating material formed by urethane reaction of an isocyanate group and a hydroxyl group is mentioned.
(2) Examples of the second resin paint include a two-component acrylic silicon resin paint formed by dehydration and dealcoholization condensation reaction of an acrylic resin having an amino group and a silicon compound having an epoxy group.
(3) Examples of the third resin paint include a two-component or three-component urethane-modified acrylic silicone resin paint in which urethane reaction and dehydration and dealcohol condensation reaction occur simultaneously.
(4) The fourth resin paint is an epoxy resin paint having an epoxy group.

Any one of such acrylic urethane resin paints, acrylic silicon resin paints, or both acrylic urethane resin paints and acrylic silicon resin paints, and epoxy resin paints can be used as the inner coating layer AC described above. .
For the application of these paints on the surface of the ridge, it is better to fix them by performing baking, brushing or spraying and then baking in a baking furnace.
Instead of acrylic urethane resin paint, polyester urethane resin paint or polycarbonate urethane resin paint can be used. Further, a urethane-modified acrylic silicone resin paint can be used instead of the acrylic silicone resin paint.

Next, the outer coating layer AE will be described. Three types of resin paints are selected for use in the paint layer.
(1) As a 1st resin coating material, the two-component acrylic urethane resin coating material formed by urethane reaction of an isocyanate group and a hydroxyl group is mentioned.
(2) Examples of the second resin paint include a two-component acrylic silicon resin paint formed by dehydration and dealcoholization condensation reaction of an acrylic resin having an amino group and a silicon compound having an epoxy group.
(3) Examples of the third resin paint include a two-component or three-component urethane-modified acrylic silicone resin paint in which urethane reaction and dehydration and dealcohol condensation reaction occur simultaneously.

Either one of the acrylic urethane resin paint, the acrylic silicon resin paint, or both of the acrylic urethane resin paint and the acrylic silicon resin paint may be used as the paint for the inner coating layer AC and the outer coating layer AE. it can.
For the application of these paints on the surface of the ridge, it is better to fix them by performing baking, brushing or spraying and then baking in a baking furnace.
Instead of acrylic urethane resin paint, polyester urethane resin paint or polycarbonate urethane resin paint can be used. Further, a urethane-modified acrylic silicone resin paint can be used instead of the acrylic silicone resin paint.
In addition, as the outer coating layer AE employed for the intermediate collar 4 or the like, a color clear paint may be used as described above instead of the acrylic urethane resin paint or the like.

The silver surface thin film coating layer AD will be described. Here, the silver surface thin film coating layer AD is formed by applying a silver complex with an amine. The silver complex with amine specifically refers to a complex with 2-ethylhexylamine combined with silver as a ligand.
However, as the amine, those having a simple structure such as methylamine, dimethylamine, and trimethylamine, and those having a complicated structure such as N, N-diisopropylethylamine are also employed.
The silver surface thin film coating layer AD is formed by the following process.
(1) Add a solvent such as isopropyl alcohol to the silver complex with amine to enhance fluidization.
(2) The fluidized silver complex is applied on the inner coating layer AC. As a method of application, a commonly used application method such as brushing or spraying is sufficient, but here, application is performed using an inkjet apparatus.

  An ink jet apparatus will be described. As shown in FIG. 6, the ink jet decoration device F includes an ink tank 31 that stores ink paint, and an ink jet head 32 that applies the ink paint supplied from the ink tank 31 to an object. It is. However, in the present invention, since the ink itself is of a single color containing a silver metal complex, the ink jet head 32 is processed into a single jet outlet.

  The inkjet head 32 is provided with a plurality of nozzles for supplying ink paint as droplets, receives operation information from a control means (not shown), rapidly heats the ink paint to promote droplet formation, and generates air bubbles. It is equipped with a heating medium to be ejected. This method is called a thermal jet method, but a piezo method may be adopted.

  A specific configuration for decorating the bag material coated with the inner coating layer AC will be described. As shown in FIG. 6, the bag material is attached to the mandrel 33, and the mandrel 33 and the bag material are configured to be rotatable around the axis of the mandrel 33. A decoration device F including an ink tank 31 and an inkjet head 32 is configured to be movable along the axis of a mandrel 33.

The configuration described above, while rotating the rod material, by moving the decoration device F, based on the operation information from the control means, the surface of the rod material A in dot form as droplets by adjusting the ink coating To apply. As shown in FIG. 2, the decoration part area | region which consists of the spiral 34 with a predetermined length is produced. Although the adjacent spiral 34 may have a width l (diameter of droplets applied in the form of dots) separated as shown in the drawing, the adjacent spiral 34 may be completely hidden so that the inner coating layer AC is completely hidden. The pitch t may be drawn in a state where they are in contact with each other such that the pitch t is the same as the width l of the spiral 34.
Thereby, the decoration part region can be formed in one stroke of the decoration device F.

Although the decoration part area | region was formed by forming the spiral 34 above, the following figures etc. may be sufficient.
(1) As shown in FIG. 3A, the decoration portion region may be formed by forming a plurality of simple circles 35 in the direction of the axis X at regular intervals instead of the spiral 34.
(2) As shown in FIG. 3B, the decorative portion region may be formed by arranging straight lines 36 in a lattice pattern.
(3) As shown in FIG. 3 (c), in the case where the straight lines 36 are arranged in a lattice pattern, the square regions may be alternately filled to form a flag-like pattern to form the decorative portion region.
(4) As shown in FIG. 4, (a) a simple circle 37 arranged, (b) a simple triangle 38 arranged, (c) a simple square 39 arranged (some of which are filled in the square) (D) A simple star shape 40 may be arranged.

Next, a combination of the following figures and patterns may be applied by changing the density at which the dot droplets are applied.
That is, as shown in FIG. 5, the blur pattern portion 41B in which the dot density gradually changes, the dark color portion 41C having the maximum dot density outside the blur pattern portion 41B, and the blur pattern portion outside the dark color portion 41C. 41B, a connecting portion 41D in which the dot-like droplets are slightly large and coarse in density is arranged.
The decorative portion region is formed by repeatedly spreading the blur pattern portion 41B and the dark color portion 41C over the entire candy material.

(3) Next, the applied intermediate iron 4 and the like are baked in a baking furnace at a temperature of 100 ° C. to 170 ° C. for 10 minutes to 60 minutes. Then, at the same time as the alcohol component evaporates, the binding force between 2-ethylhexylamine as a ligand and silver decreases, and the 2-ethylhexylamine leaves the silver particles and is reduced by the reducing action of the amine, Silver nanoparticles fold out. This state is the state shown in FIG.
As shown in the micrograph in FIG. 11, the size of the nanoparticles is about 15-20 nano.
(4) As described above, the silver nanoparticles group deposited on the inner coating layer AC are partially melt-bonded as shown in FIG. Form.

In general, the melting temperature of the silver bulk is around 962 ° C., but in this case, since the silver particles have a nano-unit particle size, a melting point drop occurs, and a relatively gentle sintering heat of 100 ° C. Even in the added state, melting is promoted, and the precipitated silver particles are melt-bonded to form a silver surface thin film. Such a decrease in melting point eliminates damage to the dough body.
Thus, the film thickness of the formed silver surface thin film coating layer AD is measured.

The film thickness is measured by the following method.
The measuring device uses ESCA (Investigative X-ray photoelectron spectroscopic analyzer). That is, sputtering is performed by irradiating + argon particles emitted from an electron gun, and the element is identified by performing spectrum analysis of the popping element, and the film thickness is measured from the irradiation depth.

Samples to be measured are as follows. A film corresponding to the silver thin film coating layer AD is applied to the surface of the glass plate 8A by a spraying method to produce two samples (glass plate 1 and glass plate 2). As shown in FIGS. 12A and 12B, the single sample is attached to the outer peripheral surface of the casing 7 in a posture along the tangential direction.
The other sample is a sample (film) in which three layers of an inner coating layer AC, a silver surface thin film coating layer AD, and an outer coating layer AE are formed on the film 8B. As shown in FIGS. 12 (c) and 12 (b), it is attached to the outer peripheral surface of the housing 7 in a posture along the circumferential direction instead of a posture along the tangential direction in this case.
When measuring, the measurement is performed by reciprocating the housing 7 around the axis X and reciprocating in the direction of the axis X.

  The measurement results are described as follows. The unit for displaying the film thickness is nanometer (nm).

The reason why a sample with a film such as a glass plate or a film is used is that it can be measured in an ESCA apparatus.

Next, the innermost coating layer AB, the inner coating layer AC, the silver surface thin film coating layer AD, and the outer coating layer AE are formed through the following manufacturing process.
That is, as shown in FIG. 13 (a), after the innermost coating layer AB, the inner coating layer AC, and the silver surface thin film coating layer AD are formed, a drying step is provided. The coating layer AE and the clear layer are formed, and there is no washing process used in the case of a silver mirror reaction surface in the production process.

Next, as shown in FIG. 9, reaction in the inner mixed gradient layer ACD of the inner coating layer AC and the silver surface thin film coating layer AD, and in the outer mixed gradient layer ADE of the silver surface thin film coating layer AD and the outer coating layer AE. A form is demonstrated.
In the inner mixed gradient layer ACD and the outer mixed gradient layer ADE, a mixed gradient layer is formed in which the silver particles forming the silver thin film coating layer AD are mixed with the resin of the inner coating layer AC and the outer coating layer AE. The mixed state in the mixed gradient layer indicates a gradient state in which the proportion of silver particles increases toward the side of the silver surface thin film coating layer AD. As described above, it is considered that not only physically the silver particles and the resin are mixed, but also the mixed gradient layer has a chemically bonded state as described below.

The chemical bonding state in the inner mixed gradient layer ACD will be described.
(1) When an acrylic urethane resin paint is used as the inner coating layer AC First, as shown by the following formula, a urethane reaction between an isocyanate group and a hydroxyl group occurs.

Next, the unreacted isocyanate in this has reacted with the amine in the silver surface thin film coating layer AD.

(2) When an acrylic silicone resin paint is used as the outer coating layer AE Here, a glycidylsilane curing agent is employed as the silicon compound.
In this reaction, it is considered that an amine in the silver surface thin film coating layer AD and an epoxy group in a silicon compound as a curing agent are reacted.

The primary amine and the like described above are generated and exist in the inner mixed gradient layer ACD.

The chemical bonding state in the outer mixed gradient layer ADE will be described.
(3) When an acrylic urethane resin paint is used as the outer coating layer AE, the isocyanate has reacted with the remaining amine in the silver surface thin film coating layer AD.

(4) When an acrylic silicon resin paint is used as the outer coating layer AE, a glycidylsilane curing agent is employed as the silicon compound.
The reaction here is considered that the residual amine in the silver surface thin film coating layer AD and the epoxy group in the silicon compound as a curing agent are reacted.

The primary amine described above is produced and is present in the outer mixed gradient layer ADE.

Further, other reactions in the inner mixed gradient layer ACD and the outer mixed gradient layer ADE will be described.
In the inner mixed gradient layer ACD of the silver surface thin film coating layer AD and the inner coating layer AC and the outer mixed gradient layer ADE of the silver surface thin film coating layer AD and the outer coating layer AE, in addition to the reaction described above, By such a reaction, the connection and fixing state of the silver surface thin film coating layer AD and the inner surface coating layer AC and the silver surface thin film coating layer AD and the outer surface coating layer AE are strong. That means

As shown in the above reaction formula, during the curing reaction between the metal film of the silver surface thin film coating layer AD and acrylic silicon, the above hydrolysis occurs, and the OH group separated at this time improves the adhesion with the metal. It is thought to work as a bond.

Further, in the inner mixed gradient layer ACD and the outer mixed gradient layer ADE, silver as a metal is mixed together with the resin paint, and this is the silver surface thin film coating layer AD, the inner coating layer AC, and the silver surface thin film coating layer. The connection and fixing state between the AD and the outer coating layer AE is made strong.
That is, in the silver surface thin film coating layer AD, the raw material silver is not all sintered to construct a silver surface structure. Some silver is mixed with the resin paint in the inner mixed gradient layer ACD and the outer mixed gradient layer ADE. As shown in FIG. 9, the proportion of silver mixed increases as the silver surface thin film coating layer AD is closer. That is, the proportion of silver mixed in the resin paint indicates an inclined state that increases as the distance from the silver surface thin film coating layer AD increases.

The inclination state can be calculated from the ratio of silver and resin paint protruding from the coating layer by using the above-mentioned ESCA for the coating layer of the three-layer film 8B prepared as a sample.
The data is shown in FIG.
According to this, it can be seen that when the vertical axis represents the elemental degree of integration (%) and the horizontal axis represents the sputter depth (nm), the proportion of silver increases as it approaches the silver surface thin film coating layer AD. That is, there is a portion corresponding to the outer coating layer AE up to a sputter depth of about 0 nm to 200 nm, and between the first point (a) where carbon (C) and silver (Ag) cross over 200 nm. Indicates that a portion corresponding to the outer mixed gradient layer ADE in which the content of carbon (C) decreases and the content of silver (Ag) increases is formed.

Next, a second point (b) where carbon (C) and silver (Ag) intersect again between the sputter depths of 400 nm and 600 nm appears, and the second point (b) and the first point (a) It can be seen that a portion corresponding to the silver-surface thin film coating layer AD is formed in between.
It can be seen that a portion corresponding to the inner mixed gradient layer ACD in which carbon (C) increases and silver (Ag) decreases is formed near the sputter depth of 600 nm.
It can be seen that there is a portion corresponding to the inner coating layer AC between a sputter depth of 700 nm and 1000 nm, and a portion exceeding 1000 nm is a portion corresponding to the film 8B as a sample piece.
As described above, the intermediate ridge 4 and the former ridge 5 were painted. Therefore, an adhesion evaluation test of these coatings was performed.

When the test piece has a single outer coating layer AE,
(B) Select epoxy resin paint for innermost coating layer AB,
(B) Select either acrylic urethane resin paint, acrylic silicone resin paint, epoxy resin paint, urethane modified acrylic silicone resin paint for inner coating layer AC,
(C) For the outer coating layer AE, select either acrylic urethane / acrylic silicone resin paint or urethane-modified acrylic silicone resin paint,
And tested.

As the test results, the best results were obtained by selecting and combining an epoxy resin paint for the innermost coating layer AB, a urethane-modified acrylic silicone resin paint for the inner coating layer AC, and a urethane-modified acrylic silicone resin paint for the outer coating layer AE. showed that.
Considering this test result, by selecting and combining the urethane-modified acrylic silicone resin paint on the outer coating layer AE, the adhesion with the silver metal containing an amino group containing an isocyanate group / epoxy group is improved, It is thought to have a positive effect on water resistance.

Also, the inner coating layer AC is made of a urethane-modified acrylic silicone resin paint, like the outer coating layer AE, so that the amine of the silver metal complex containing the amine used to form the silver surface thin film coating layer AD is It is considered that it remains and reacts with the isocyanate group and the epoxy group of the inner coating layer AC to exhibit good bonding strength.
Also, the test results are supported by the fact that a portion of the silver deposited in the boundary area between the outer coating layer AE and the silver surface thin film coating layer AD is mixed to form a mixed gradient layer of silver and resin paint. It is thought that.

[Second Embodiment]
In the said embodiment, applying to the fishing rod A was demonstrated. In the second embodiment, a point that can be applied to a reel, in particular, a spinning reel B will be described.
As shown in FIG. 14, the spinning reel B includes a reel body 12 having a handle 11, a thread winding spool 13 that is non-rotatable on the reel body 12, and a rotor 14 that rotates by winding fishing line around the spool spool 13. And is configured. Two bail support portions 15 are extended forward on the front end side of the rotor 14 with the center of rotation interposed between them, and one of the bail support portions 15 is supplied with fishing line wound from the tip side on a spool 13 A guide roller 16 is attached to guide the guide.

  In the configuration of the spinning reel B described above, it is effective to manufacture the reel body 12, the spool 13 for spooling, the rotor 14 and the like with fiber reinforced resin and apply the coating shown in the first embodiment. However, as shown in FIG. 7A, the innermost coating layer AB is provided, the inner coating layer AC is provided from the innermost coating layer AB, and the silver surface thin film coating layer AD is provided on the inner coating layer AC. The outer coating layer AE can be provided on the silver surface thin film coating layer AD. You may employ | adopt as the outer side coating layer AE what was created with the color clear coating material. Further, the resin paint to be selected is also arbitrary.

Alternatively, as shown in FIG. 7B, the innermost coating layer AB is provided, the inner coating layer AC is provided on the innermost coating layer AB, and the silver surface thin film coating layer AD is provided on the inner coating layer AC. An outer coating layer AE is provided on the silver thin film coating layer AD, a color clear layer AF is formed on the outer coating layer AE, and a transparent clear layer AG is formed on the color clear layer AF. can do.
However, in this case, the inner coating layer AC may be directly coated on the surface of the reel body 12 without providing the innermost coating layer AB.

[Third Embodiment]
Here, the form which applies the above-mentioned coating form to the bicycle C is demonstrated. As shown in FIG. 15, the bicycle C includes a suspension frame 23 supported by the front and rear wheels 26, a handle frame 24 attached to the upper portion of the suspension frame 23, and a body frame 22 including the suspension frame 23 and the like. It is configured. A front derailleur 21 for an exterior transmission is attached to the seat tube 22A in the middle of the body frame 22, and a rear derailleur 25 is attached to the rear end of the body frame 22.

It is effective to form the wheel portion of the front wheel 26 described above with fiber reinforced resin and apply the coating described in the first embodiment to the wheel portion. That is, as shown in FIGS. 7A and 7B, the innermost coating layer AB is provided, the inner coating layer AC is provided from above the innermost coating layer AB, and the silver surface thin film coating layer is provided on the inner coating layer AC. A configuration may be adopted in which an AD is provided and the outer coating layer AE is provided on the silver surface thin film coating layer AD.
Furthermore, the color clear layer AF and the transparent clear layer AG may be formed on the outer coating layer AE, but it is possible to arbitrarily select whether or not to form them. Further, the resin paint to be selected is also arbitrary.

As shown in FIG. 7C, the body frame 22 that bears a particularly large load employs a coating structure including a two-layer structure of a first outer coating layer AE1 and a second outer coating layer AE2, so that a relatively heavy load is applied. A paint structure including a single layer structure of the outer paint layer AE shown in FIG.
As described above, the weight of the bicycle is reduced by forming it on a fiber reinforced resin pipe such as the body frame 22, and a high-quality bicycle is provided by improving the decoration on the silver surface. it can.

[Fourth Embodiment]
For the purpose of reducing the weight of parts and improving the surface corrosion resistance, the silver surface thin film coating layer AD is applied directly to the surface of the component, and the outer surface coating layer AE and the transparent surface are transparent on the silver surface thin film coating layer AD. A configuration may be adopted in which only one clear layer AF or one outer coating layer AE is provided.

[Another embodiment]
(1) Symbols, special characters, and the like are included in addition to figures / patterns to form the decoration area. What is necessary is just to use many these and to exhibit the function like a pattern.
(2) The point of using the ink jet apparatus F to form the silver surface thin film coating layer AD has been described, but other methods such as a spray method and a brush coating method can be used.
(3) The object to be painted described in the first embodiment can be applied to a cooler box, a lure, a hook, a fishing line guide, or the like as a fishing tool.
(4) As the coating structure formed on the component surface, the innermost coating layer AB may not be provided, and the inner coating layer AC may be directly applied to the component surface. In particular, when the aim is to reduce the weight of the cocoon, such as with a tip, the inner coating layer AC may be applied directly to the surface of the component, and only one transparent clear layer as the outermost coating layer may be provided.
(5) The outer coating layer AE may be formed in two layers as shown in FIG. That is, the first outer coating layer AE1 can be formed on the silver surface thin film coating layer AD, and the second outer coating layer AE2 can be formed on the first outer coating layer AE1. As the resin paint adopted for the first outer paint layer AE1 and the second outer paint layer AE2, either the acrylic urethane resin paint or the acrylic silicon resin paint, or the acrylic urethane resin paint adopted as the outer paint layer AE. And acrylic silicone resin paint can be used.
Moreover, the first outer coating layer AE1 and the second outer coating layer AE2 do not need to use the same resin paint, and may be applied to different ones. This two-layer structure can be used as a marshal.

  The present invention can provide a product with good visibility by applying an ink paint mainly composed of a silver metal complex to not only fishing equipment but also bicycle parts having parts made of fiber reinforced resin.

4 Intermediate cage (component body)
5 Genroku (part body)
12 Reel body (component body)
14 Rotor (component body)
22 Body frame (component body)
24 Handle frame (component body)
34 Spiral (decoration area)
AB innermost coating layer AC inner coating layer AD silver thin film coating layer AE outer coating layer AE1 first outer coating layer AE2 second outer coating layer AF color clear layer AG transparent clear layer

Claims (12)

Laminate an inner coating layer on the surface of the component body made of fiber reinforced resin, a thin silver coating layer on the inner coating layer, and an outer coating layer on the silver coating layer.
The fishing tackle component, wherein the silver surface thin film coating layer is made of an ink paint containing a silver metal complex having an amine as a ligand, and a spiral or a straight line is formed on the surface of the inner coating layer at intervals. Decoration structure. Laminate an inner coating layer on the surface of the component body made of fiber reinforced resin, a thin silver coating layer on the inner coating layer, and an outer coating layer on the silver coating layer.
The silver thin film coating layer is made of an ink paint containing a silver metal complex having an amine as a ligand, and a spiral or straight line is formed on the surface of the inner coating layer with a space therebetween. Decorative structure. Laminate an inner coating layer on the surface of the component body made of fiber reinforced resin, a thin silver coating layer on the inner coating layer, and an outer coating layer on the silver coating layer.
The silver thin film coating layer is made of an ink paint containing a silver metal complex having an amine as a ligand, and is formed on the surface of the inner coating layer by arranging triangular, quadrangular, round, or star-shaped figures. Decorative structure for fishing gear parts. Laminate an inner coating layer on the surface of the component body made of fiber reinforced resin, a thin silver coating layer on the inner coating layer, and an outer coating layer on the silver coating layer.
The silver thin film coating layer is made of an ink paint containing a silver metal complex having an amine as a ligand, and is formed on the surface of the inner coating layer by arranging triangular, quadrangular, round, or star-shaped figures. A decorative structure for bicycle parts. The inner coating layer,
(1) a two-component resin coating formed by a reaction between an isocyanate group and a hydroxyl group;
(2) a two-part resin coating formed by reacting a resin having an amino group with a silicon compound having an epoxy group;
(3) a two-component or three-component resin coating in which the reaction (1) and the reaction (2) occur simultaneously;
(4) epoxy resin paint,
Select one of them to form
The outer coating layer,
(1) a two-component resin coating formed by a reaction between an isocyanate group and a hydroxyl group;
(2) a two-part resin coating formed by reacting a resin having an amino group with a silicon compound having an epoxy group;
(3) a two-component or three-component resin coating in which the reaction (1) and the reaction (2) occur simultaneously;
The decorative structure for a fishing gear part according to claim 1 or 3, wherein any one of the above is selected and formed. The inner coating layer,
(1) a two-component resin coating formed by a reaction between an isocyanate group and a hydroxyl group;
(2) a two-part resin coating formed by reacting a resin having an amino group with a silicon compound having an epoxy group;
(3) a two-component or three-component resin coating in which the reaction (1) and the reaction (2) occur simultaneously;
(4) epoxy resin paint,
Select one of them to form
The outer coating layer,
(1) a two-component resin coating formed by a reaction between an isocyanate group and a hydroxyl group;
(2) a two-part resin coating formed by reacting a resin having an amino group with a silicon compound having an epoxy group;
(3) The two- or three-component resin paint in which the reaction (1) and the reaction (2) occur simultaneously is selected and formed. Decorative structure for bicycle parts.   6. The silver surface thin film coating layer is formed by depositing silver nanoparticles by heating the silver metal complex and connecting and fixing the silver nanoparticles. Decoration structure for fishing gear parts described in 1.   7. The silver thin film coating layer is formed by depositing silver nanoparticles by heating the silver metal complex and connecting and fixing the silver nanoparticles. Decorative structure for bicycle parts as described in 1.   The decorative structure for a fishing tackle part according to any one of claims 1, 3, 5, and 7, wherein the thickness of the thin silver film coating layer is in the range of 0.02 to 0.4 microns.   The bicycle part decorative structure according to any one of claims 2, 4, 6, and 8, wherein the thickness of the silver-coated thin film coating layer is in the range of 0.02 microns to 0.4 microns.   An inner mixed gradient layer in which silver is mixed in the resin coating between the silver surface thin film coating layer and the inner coating layer, and silver in the resin coating between the silver surface thin film coating layer and the outer coating layer. In the inner mixed gradient layer and the outer mixed gradient layer, the ratio of mixing into the silver resin paint is higher as it is closer to the silver surface thin film coating layer. The decorative structure for a fishing gear part according to any one of claims 1 or 3, 5, 7, and 9.   An inner mixed gradient layer in which silver is mixed in the resin coating between the silver surface thin film coating layer and the inner coating layer, and silver in the resin coating between the silver surface thin film coating layer and the outer coating layer. In the inner mixed gradient layer and the outer mixed gradient layer, the ratio of mixing into the silver resin paint is higher as it is closer to the silver surface thin film coating layer. The decorative structure for a bicycle part according to any one of claims 2 and 4, 6, 8, and 10.