JP5004853B2 - Silver mirror layer forming method and carbon fiber composite material having silver mirror layer - Google Patents

Description

  The present invention relates to a silver mirror layer forming method and a carbon fiber composite material having a silver mirror layer, and in particular, has a decorative property on a shaft or the like of a golf club formed of a carbon fiber composite material using a silver mirror reaction. The present invention relates to a silver mirror layer forming method capable of performing silver plating, and a carbon fiber composite material having a silver mirror layer.

  Conventionally, a carbon fiber (carbon fiber) having excellent mechanical properties such as high strength and high elasticity is known. This carbon fiber and an epoxy resin, a polyamide resin, a phenol resin, an unsaturated polyester resin, or the like are so-called. A carbon fiber composite material (carbon composite) that is used as a matrix (matrix) and has excellent lightness has been manufactured. Such carbon fiber composite materials are used in many industrial fields, for example, taking advantage of high strength and light weight, and a part of main components (main wings) of aircraft fuselage in the aerospace industry or for launching It is used for nozzles of propulsion rockets. On the other hand, in the automobile industry, it is used as a part of a body frame or a part of an exterior part.

  With such use, members that have been constructed using metal materials such as iron and stainless steel can be replaced with carbon fiber composites, which can contribute to improved fuel consumption and improved performance through weight reduction. become.

  On the other hand, in addition to the basic industrial fields such as the aerospace industry and the automobile industry described above, development and manufacture of products utilizing the excellent mechanical properties of carbon fiber composite materials have been made. For example, it is applied to various sports and leisure goods such as a shaft of a golf club, a fishing rod, or a tennis racket. Here, golf clubs, tennis rackets, and the like need to be operated by a user (player) holding them for a long time and swinging them strongly during a swing or stroke. Therefore, it is required to be lightweight so that it does not feel fatigue even after long-term use, and it has high elasticity and high repulsive force so that it can extend the flight distance when hitting the ball or perform a sharp return ball. It was sought after. Therefore, the carbon fiber composite material is one of particularly suitable materials when used for the above-mentioned leisure goods.

  However, carbon fiber composite materials often have a black color derived from carbon fiber as a whole, and when used in leisure goods such as those described above that have a strong taste and taste, the design and decoration of the product surface In many cases, certain restrictions were imposed on. Further, in the case of a golf club or the like, it is necessary to pay attention to the weight balance when used, and the preparation of the weight balance in the case of excessive decoration may be complicated. Therefore, when decorating a carbon fiber composite material, a material that hardly affects the weight balance has been desired.

  Therefore, for example, a synthetic resin coating layer made of synthetic resin is provided on the surface of the composite material of the carbon fiber composite material, and further, a decoration layer obtained by physical vapor deposition of metal is formed, and a transparent or translucent resin protective layer is formed thereon. An article for leisure such as a golf club provided with a golf ball has been researched and developed (see Patent Document 1). Thus, the film is thinned by a well-known plating technique or vapor deposition technique such as vacuum vapor deposition, sputtering, or ion plating included in physical vapor deposition (PVD), and a metal film (aluminum or Titanium etc.) can be formed as a plating film. Thereby, compared with the conventionally well-known plating method such as chrome plating, the adhesion of the carbon fiber composite material to the composite material surface becomes stronger. In particular, golf clubs, tennis rackets, and the like are subjected to a strong impact at the moment of impact when the ball is hit, and the shaft or the like may be bent in an arc shape due to elastic deformation. When such bending is repeated, there is a high possibility that the plating layer (decoration layer) is peeled off from the surface of the elastically deformed portion or a defect such as a crack is generated. Therefore, as described above, by providing a synthetic resin coating layer and further providing a decoration made of metal thereon, adhesion between the decoration layer and the synthetic resin coating layer is improved, and defects such as peeling occur. Less. Furthermore, by covering with a protective layer, even when the carbon fiber composite material is subjected to some force (impact) from the outside, it is possible to prevent scratches and the like.

JP 7-79669 A

  However, the above-described method for plating a metal thin film sometimes has the following problems. That is, when a metal decoration layer (thin film layer) is to be formed using a physical vapor deposition (PVD) method, a target article (such as a shaft) is accommodated in a predetermined vapor deposition section of a vapor deposition apparatus, and is subjected to a vacuum. Alternatively, it is necessary to ionize the metal under reduced pressure and deposit it on the surface of the article, and a large cost is required to introduce such equipment. Therefore, the manufacturing cost of articles such as golf clubs itself increases, and the unit price of the product may increase. Further, when vapor deposition such as ion plating is performed, a long vapor deposition time (thin film formation time) may be required for each article. For this reason, the vapor deposition time per article becomes long, which is not suitable for large-scale production.

  Therefore, the initial capital investment does not require a great cost, the processing time for forming the plating layer is relatively short, and the adhesion that enables a large number of plating processes in a predetermined time is excellent. A method for forming a plating layer (metal layer) and production of a carbon fiber composite having these on the surface have been expected.

  On the other hand, as one method of electroless plating, a so-called “silver mirror reaction” in which silver is precipitated on a glass surface or the like using a reduction reaction from an alkaline silver compound solution (for example, a silver nitrate solution) has been known. A technique for forming a silver mirror layer using this reaction has also been developed. This silver mirror reaction can be performed with a simple configuration that does not require special equipment as compared with the PVD method described above, and can be performed in the atmosphere (normal pressure).

  Therefore, in view of the above circumstances, the present invention can form a silver mirror layer using a silver mirror reaction on the composite material surface of the carbon fiber composite material with a relatively simple configuration, and has excellent adhesion to the composite material surface. An object of the present invention is to provide a silver mirror layer forming method applicable to leisure goods and a carbon fiber composite material having a silver mirror layer.

  In order to solve the above-mentioned problems, the silver mirror layer forming method of the present invention is described as follows: “An undercoat layer having surface smoothness by spraying and curing a resin undercoat component on the surface of a composite material of a carbon fiber composite material An undercoat layer constructing step for constructing and spraying a stannous chloride solution on the surface of the constructed undercoat layer, and performing an activation treatment for activating the silver mirror reaction on the coat layer surface A stannous chloride solution spraying step, a stannous chloride solution removing step in which pure water is sprayed onto the surface of the coat layer, and the stannous chloride solution on the surface of the coat layer is washed away and removed; and the stannous chloride solution A silver nitrate solution spraying step of spraying a silver nitrate solution prepared to a predetermined concentration on the surface of the coat layer washed away with a solution, and a silver compound and an alcohol on the surface of the coat layer sprayed with the silver nitrate solution. A silver / ammonia mixed solution formed by mixing a monia component and a nitrogen-containing solution containing a nitrogen-containing compound are sprayed independently and mixed in the vicinity of the surface of the coat layer, whereby the surface of the coat layer is subjected to the silver mirror reaction. A silver mirror layer forming step of forming a thin film silver mirror layer, and an unreacted solution removing step of spraying pure water onto the surface of the silver mirror layer of the formed silver mirror layer to wash away and remove the unreacted solution on the surface of the silver mirror layer; The silver mirror layer surface is sprayed with a rinsing liquid containing an inorganic sodium compound, the silver mirror reaction suppression step for suppressing the progress of the silver mirror reaction on the coat layer surface, and pure water is sprayed on the silver mirror layer surface, Rinse solution removing step of washing and removing the rinse solution on the surface of the silver mirror layer, and sending air to the surface of the silver mirror layer from which the rinse solution has been washed away so that water droplets and / or on the surface of the silver mirror layer are removed. Is an air blowing step for scattering impurities by wind pressure, a drying step for drying the silver mirror layer after the air blowing step at a predetermined temperature, and a resin top coat component is sprayed on the surface of the silver mirror layer and cured. And a topcoat layer construction step of constructing a topcoat layer for protecting the silver mirror layer ”.

  Here, the undercoat layer refers to, for example, a carbon fiber using a resinous undercoat component mainly composed of a one-component curable resin or a two-component curable acrylic resin, an epoxy resin, and a urethane resin. The composite material is sprayed on the surface of the composite material in a liquid state using a spraying means such as a spray. And the undercoat layer which has surface smoothness is formed by performing a hardening process at predetermined temperature. Note that this is a well-known technique that is processed in advance when electroless plating is performed on a non-conductive material such as a plastic resin, and an existing technique can be applied. Therefore, detailed description is omitted here.

  Here, it is generally known that the carbon fiber composite material is a non-conductive material composed of carbon fibers and a matrix, and the surface of the composite material has relatively large unevenness. Therefore, even if the silver mirror layer is formed in such a state, the silver mirror layer is applied according to the unevenness, and it is difficult to construct a clean silver mirror layer. Therefore, an undercoat layer is constructed so as to fill the unevenness, and the surface smoothness with the reduced unevenness is ensured. In order to construct the undercoat layer, a normal spray gun is used to spray the composite material surface at a high pressure.

  On the other hand, a stannous chloride solution is an aqueous solution in which stannous chloride is added to pure water, and such stannous chloride is a well-known material that has been conventionally used to increase its reducibility in a silver mirror reaction. It is. As a result, the stannous chloride solution adheres to the surface of the coat layer of the undercoat layer constructed with surface smoothness, and a chemical erosion effect is exhibited in part. Such a stannous chloride solution is necessary in a small amount to activate the silver mirror reaction. After spraying, the stannous chloride solution is quickly washed away with pure water, and only a very small amount of stannous chloride solution remains on the surface of the coating layer. Will be.

  Furthermore, the silver nitrate solution is an aqueous solution in which silver nitrate is dissolved in water, and includes a main material for depositing silver by a silver mirror reaction to form a silver mirror layer. Then, by pre-spraying the silver nitrate solution on the surface of the coat layer, it becomes possible to quickly deposit silver by the silver mirror reaction. On the other hand, the silver / ammonia mixed solution is a mixture of an aqueous solution of a silver compound partially containing silver nitrate and an aqueous ammonia solution exhibiting alkalinity at a predetermined ratio. The silver / ammonia mixed solution may be prepared separately before the silver mirror layer forming operation, and may be put into the same tank and mixed immediately before spraying with a spray gun or the like. Thereby, it is possible to prevent the reducing property due to the alkaline state from appearing until just before the formation of the silver mirror layer. Here, it is preferable to use silver nitrate or other silver compounds in the silver nitrate solution and the silver / ammonia mixed solution whose contents are each adjusted to 1% or less. That is, when a large amount of silver nitrate or the like is mixed in the solution, the amount of silver particles precipitated by the silver mirror reaction becomes excessive, and the silver mirror layer is likely to be uneven. Therefore, by forming the silver mirror layer as thinly as possible on the surface of the coat layer, it becomes possible to form a silver mirror layer having a stable quality without unevenness and cloudiness.

  On the other hand, the nitrogen-containing compound can be, for example, a nitrogen-containing heterocyclic compound partially containing a nitrogen atom in the molecule, and more specifically, pyrrole, pyrroline, pyrrolidine, imidazole, imidazoline, imidazole Examples include lysine, pyrazole, pyrazolidine, pyrazolidine, thiazole, thiazoline, thiazolidine, oxazole, oxazoline, oxazolidine, triazole, thiadiazole, oxadiazole, tetrazole, piperidine, piperazine, pyridine, pyridazine, pyrimidine, pyrazine, triazine and the like. . The nitrogen-containing compound is merely an example, and other compounds may be used as long as they function to form the silver mirror layer of the present invention.

  Further, the rinsing liquid is an aqueous solution containing an inorganic sodium compound such as sodium hydrogen carbonate, and is for stopping the progress of the silver mirror reaction on the surface of the alkali-reducing coat layer.

  The first tin chloride solution removing step, the unreacted solution removing step, and the rinsing liquid removing step can use, for example, a water jet mechanism provided with innumerable holes such as a shower head. Thereby, the residue or impurities adhering to the coat layer surface or the silver mirror layer surface are washed away with water (pure water). Therefore, unlike the above-described undercoat component, stannous chloride solution, silver / ammonia mixed solution, nitrogen-containing solution, topcoat component (details will be described later), it is not necessary to spray in the form of a mist.

  On the other hand, the air blow process is a process in which a strong wind is sent to the surface of the silver mirror layer by a blower or the like, and water drops or impurities are blown off by the wind pressure, and a well-known technique can be used. Furthermore, the topcoat layer can utilize substantially the same components as those used in the above-mentioned undercoat layer, and in order to improve the visibility of the formed silver mirror layer, It is required to be presented. The top coat layer may be either colorless and transparent or colored and transparent depending on the decoration.

  Therefore, according to the silver mirror layer forming method of the present invention, a structure in which an undercoat layer, a silver mirror layer, and a topcoat layer are laminated on the composite material surface of the carbon fiber composite material is constructed by performing the above-described steps. In addition, a silver mirror layer can be formed by a silver mirror reaction below the top coat layer that functions as a protective layer. In particular, on the surface of the coating layer that has been activated with the stannous chloride solution, the silver nitrate solution is sprayed and adhered in advance, and the silver / ammonia solution and the nitrogen-containing solution are sprayed at the same time, so that three types of solutions are obtained. The silver mirror reaction can be rapidly advanced on the surface of the coat layer using As a result, the formation of the silver mirror layer can be completed in a relatively short time of several seconds to several tens of seconds.

  Furthermore, the silver mirror layer forming method of the present invention includes, in addition to the above configuration, “the silver mirror layer forming step includes a first spray part for spraying the silver / ammonia mixed solution, and a second spray for spraying the nitrogen-containing solution”. Using a double spray gun in which the parts are arranged side by side and can spray the silver / ammonia mixed solution and the nitrogen-containing solution at the same timing, and near the spray ports of the first spray part and the second spray part In the mixing region set to 2), the mist-like silver / ammonia mixed solution and the nitrogen-containing solution are mixed and sprayed onto the surface of the coating layer.

  Therefore, according to the silver mirror layer forming method of the present invention, the mist-like silver / ammonia mixed solution and the nitrogen-containing solution are mixed with each other in the mixing region immediately before spraying on the coating layer surface, and the coating layer surface to which the silver nitrate solution is adhered It becomes possible to spray on. Thereby, a silver mirror reaction does not advance inside each spray part, and there is no possibility that a silver compound precipitates. Therefore, problems such as clogging of the spray portion do not occur, and the silver mirror layer forming process can be continuously executed for a long time.

  Furthermore, the silver mirror layer forming method of the present invention includes, in addition to the above configuration, “the silver mirror layer formed by the silver mirror layer forming step is such that the silver particles constituting the silver mirror layer are uniformly aligned on the surface of the coat layer. The top coat layer is formed and has an inter-particle gap between the silver mirror layer surface and the coat layer surface between the silver particles, and is constructed by the top coat layer construction step. In addition, at least a part of the resin-made top coat component passes through the interparticle voids from the surface of the silver mirror layer, reaches the surface of the coat layer and cures, whereby the surface of the silver particles of the silver mirror layer is cured. It may be constructed by covering and sandwiching.

  Therefore, according to the method for forming a silver mirror layer of the present invention, the liquid top coat component before curing passes through the interparticle voids and reaches the surface of the coat layer, thereby sandwiching the silver particles constituting the silver mirror layer from the surroundings. It becomes possible to be in a state. As a result, the silver mirror layer on the surface of the coat layer can be firmly adhered to the undercoat layer by the top coat layer, and the possibility of problems such as peeling is reduced.

  On the other hand, the carbon fiber composite material having a silver mirror layer of the present invention is a carbon fiber composite material having a silver mirror layer formed using the silver mirror layer forming method according to any one of the above, An undercoat layer constructed on the composite material surface of the composite material, wherein the coat layer surface is activated by a stannous chloride solution, and the coat layer using a silver nitrate solution, a silver / ammonia mixed solution, and a nitrogen-containing solution. A silver mirror layer formed by a silver mirror reaction on the surface and a top coat layer that is constructed on the surface of the silver mirror layer of the silver mirror layer and protects the silver mirror layer ”are mainly configured.

  Therefore, according to the carbon fiber composite material having a silver mirror layer of the present invention, the three types of solutions of the silver nitrate solution, the silver / ammonia mixed solution, and the nitrogen-containing solution are reacted on the surface of the activated undercoat layer. And a silver mirror layer formed. As a result, a silver mirror layer having a uniform thickness can be formed from silver particles regularly arranged on the surface of the coat layer, and a silver mirror layer free from cloudiness and unevenness can be constructed.

  Further, the carbon fiber composite material having a silver mirror layer according to the present invention may be added to the above-described configuration. “The silver mirror layer has silver particles constituting the silver mirror layer arranged uniformly on the surface of the coat layer, The silver particles further comprise interparticle voids communicating between the silver mirror layer surface and the coat layer surface, and the topcoat layer has at least part of a resinous topcoat component from the surface of the silver mirror layer. The interparticle void filling portion that passes through the interparticle voids, reaches the surface of the coat layer and cures, thereby covering the particle surfaces of the silver particles of the silver mirror layer and supporting the silver particles in a sandwiched state. May be included.

  Therefore, according to the carbon fiber composite material having a silver mirror layer of the present invention, the silver mirror layer is easily peeled off from the surface of the coat layer of the undercoat layer by filling the interparticle voids between the silver particles with the top coat layer. Can be prevented. As a result, it is possible to eliminate problems such as peeling of the silver mirror layer and scratches even when it is used in applications where elastic deformation and impact are repeatedly applied (for example, golf clubs).

  Furthermore, the carbon fiber composite material having the silver mirror layer of the present invention may be “used for at least one leisure article of a golf club, a fishing rod, and a tennis racket” in addition to the above-described configuration.

  Therefore, according to the carbon fiber composite material having the silver mirror layer of the present invention, it is possible to manufacture a golf club or the like in which the composite material surface is decorated with the silver mirror layer. Thereby, leisure goods with strong hobbies and tastes can be made into a wide range of colors and designs that the user prefers, and the monotonous color due to the conventional black color can be eliminated. Therefore, the user's willingness to purchase can be promoted.

  As an effect of the present invention, a carbon mirror composite material having a silver mirror layer having a simple finish and a beautiful finished surface (silver mirror layer surface) in a short time without using a relatively large-scale vapor deposition apparatus such as the PVD method can be obtained. Can be formed on top. Furthermore, since the adhesiveness with the carbon fiber composite material is excellent, the possibility that the silver mirror layer is peeled off or scratched is reduced even in a severe use environment where a strong impact such as a golf club is applied. Therefore, a silver mirror layer having excellent durability can be formed. As a result, certain restrictions are not imposed on the design and decorativeness, and it can be used as a material for leisure goods with strong hobbies and tastes.

  Hereinafter, a silver mirror layer forming method 1 according to an embodiment of the present invention, and a carbon fiber composite material having a silver mirror layer using the silver mirror layer forming method (hereinafter simply referred to as “composite material 2”) are shown in FIGS. 5 will be described. Here, FIG. 1 is a cross-sectional view showing a schematic configuration of a composite material 2 having a silver mirror layer 3 using the silver mirror layer forming method of the present embodiment, and FIGS. FIG. 4 is a flowchart schematically showing the flow of each step of the silver mirror layer forming method 1, and FIG. 5 is an enlarged view of the main part showing the vicinity of the silver mirror layer 3 of the composite material 2 in an enlarged manner. It is sectional drawing. Here, in the present embodiment, a golf club shaft is assumed as the carbon fiber composite material, and the silver mirror layer 3 is formed on the surface of the shaft to enhance the decorativeness.

  As shown in FIGS. 1 to 5, the silver mirror layer forming method 1 of the present embodiment includes an undercoat layer construction step S1, a first tin chloride solution spraying step S2, a first tin chloride solution removing step S3, and a silver nitrate solution spraying step. S4, silver mirror layer formation step S5, unreacted solution removal step S6, silver mirror reaction suppression step S7, rinse liquid removal step S8, air blow step S9, drying step S10, and topcoat layer construction step S11. .

  And the composite material 2 which has the silver mirror layer 3 formed by the said silver mirror layer formation method 1 has as the cross-sectional structure the carbon fiber composite material 4 (henceforth "the pre-processing composite material 4" composite material surface 4a of the process target). On the surface, a resin undercoat layer 5 is formed. On the coat layer surface 5a, there is a silver mirror layer 3 in which silver particles AG are deposited in a film shape (layer shape) by a silver mirror reaction, and the silver mirror layer surface 3a. The multi-layer structure in which a resin-made top coat layer 7 for protecting the silver mirror layer 3 is laminated is formed (see FIG. 1).

  Here, each process of the silver mirror layer formation method 1 of this embodiment is further explained in full detail based on FIG. 2 thru | or FIG. First, the undercoat component 8 mainly composed of an acrylic resin is sprayed on the composite material surface 4a of the pre-treatment composite material 4 by a spray gun G1, and the composite material surface 4a is covered with the undercoat component 8 ( Undercoat layer construction step S1: See FIG. 2 (a)). Here, the undercoat component 8 is a liquid that is dissolved in an organic solvent, and can be made into a mist by the spray gun described above. Then, the pre-treatment composite material 4 sprayed with the undercoat component 8 is introduced into and held in a constant temperature bath maintained at a predetermined temperature (for example, around 60 ° C.) to evaporate the organic solvent contained therein, and further The coating component 8 can be cured. At this time, by using a two-component curable type or one-component curable acrylic resin as the undercoat component 8, the hard undercoat layer 5 is constructed on the composite material surface 4a by the above-described curing treatment.

  Here, the undercoat layer 5 to be constructed has a smooth surface due to the curing treatment from the liquid undercoat component 8, and the surface of the coat layer surface 5a of the undercoat layer 5 gradually becomes smooth. be able to. That is, the undercoat component 8 on the coat layer surface 5a immediately after being sprayed in the form of a mist is gradually leveled on the coat layer surface 5a in the curing process, and is finally smooth when the curing is completed. The undercoat layer 5 having a surface with a predetermined thickness is formed. As a result, the composite material surface 4a of the pre-process composite material 4 having relatively large unevenness is smoothed and covered. By smoothing the undercoat layer 5, the finished state of the silver mirror layer 3 and the composite material 2 that are finally formed can be made satisfactory, and further, the coat layer surface 5a of the silver mirror layer 3 by the silver mirror reaction. Adhesiveness to can also be good. In addition, the spray gun G1 used for spraying can utilize the well-known thing sprayed using a high pressure, and it is the same also below. At this time, it is necessary to prepare spray guns G2, G3, G4, etc. separately for each solution.

  Thereafter, a stannous chloride solution 10 in which stannous chloride is dissolved in water is sprayed onto the coat layer surface 5a of the constructed undercoat layer 5 at a high pressure using the spray gun G2. (First tin chloride solution spraying step S2: see FIG. 2B)). Here, the stannous chloride solution 10 is a well-known agent conventionally used for the purpose of activating the silver mirror reaction when the silver mirror reaction is performed, and the coating layer is formed by spraying the stannous chloride solution 10. The surface 5a can be activated. The first tin chloride solution 10 is for activating the silver mirror reaction, and the first tin chloride itself contained in the first tin chloride solution 10 is not contained in the silver mirror layer 3 and deposited. Therefore, it is not necessary that the excessive amount of the stannous chloride solution 10 is attached to the coat layer surface 5a. Therefore, pure water 11 is sprayed onto the coat layer surface 5a to wash away the adhering first tin chloride solution 10 (first tin chloride solution removing step S3: see FIG. 2B). Here, it is possible to spray the pure water 11 using the shower head SW. Thereby, the first tin chloride solution 10 is washed away from the coat layer surface 5a. In addition, it may be about several tens of seconds from performing the first tin chloride solution spraying step S2 to performing the first tin chloride solution removing step S3 in which the first tin chloride solution 10 is washed away.

  Then, the silver nitrate solution 12 is sprayed on the activated coating layer surface 5a by using a spray gun (silver nitrate solution spraying step S4: see FIG. 2C). Here, the silver nitrate solution 12 is prepared so that the silver nitrate content is 1% or less of the whole. That is, silver nitrate is attached to the coat layer surface 5a sprayed with the silver nitrate solution 12, and the silver nitrate is deposited on the coat layer surface 5a by a silver mirror reaction described later. That is, silver nitrate as a raw material for precipitating silver particles is applied in advance. At this time, the silver nitrate solution 12 is liquid (in the form of an aqueous solution), and is merely present on the coat layer surface 5a, and no fixing treatment or the like is performed.

  Thereafter, a silver / ammonia mixed solution 13 obtained by mixing a silver compound solution containing silver nitrate containing silver nitrate containing 1% or less in advance and an ammonia solution in which ammonia is dissolved in water at a predetermined ratio. Then, the nitrogen-containing solution 14 is sprayed on the coat layer surface 5a sprayed with the silver nitrate solution 12 using a double spray gun DG (see silver mirror layer forming step S5: FIG. 3A). At this time, the silver / ammonia mixed solution 13 and the nitrogen-containing solution 14 are sprayed from the nozzle ports (spray ports) of the independent first spray portion and second spray portion, as shown in FIG. Both are mixed in the in-air mixing region M which is ejected and installed in the vicinity of each nozzle opening, and then sprayed onto the coat layer surface 5a to which the silver nitrate solution 12 is applied. Thereby, the mixed solution mixed in the mixing region M comes into contact with the coat layer surface 5a. As a result, the silver-containing mixed solution prepared alkaline with ammonia water is sprayed onto the sprayed coating layer surface 5a of the silver nitrate solution 12, whereby the silver component contained in the silver nitrate solution 12 and the silver compound solution undergoes a silver mirror reaction. To form a silver mirror layer 3. Here, the nitrogen-containing solution 14 functions as a reducing agent in the silver mirror reaction. The silver mirror layer 3 is formed on the coat layer surface 5a at the same time as the mixed spray of the silver / ammonia mixed solution 13 and the nitrogen-containing solution 14 is performed.

  Here, the double spray gun DG is capable of independently jetting the two solutions 13 and 14 from the nozzle ports and mixing them in the vicinity of the nozzle ports. Therefore, the silver / ammonia mixed solution 13 and the nitrogen-containing solution 14 do not mix until immediately before the silver mirror reaction, and react with each other on the solution supply path of the double spray gun DG, for example, no silver is deposited. Thereby, clogging in the solution supply path of the double spray gun DG can be prevented.

  Thereafter, similarly to the above-described first tin chloride solution removal step S3, pure water 11 is shower-injected onto the silver mirror layer surface 3a of the silver mirror layer 3 using the shower head SW (unreacted solution removal step S6: FIG. 3 (a)). Thereby, unreacted substances of the silver nitrate solution 12, the silver / ammonia mixed solution 13, and the nitrogen-containing solution 14 present on the coat layer surface 5 a are washed away by the pure water 11. As a result, only the silver mirror layer 3 remains on the coat layer surface 5a.

  Further, a rinsing liquid 15 made of a sodium hydrogen carbonate solution, which is an inorganic sodium compound prepared by adding sodium hydrogen carbonate at a predetermined concentration, is sprayed onto the silver mirror layer surface 3a using the spray gun G3 (silver mirror reaction suppression step S7: FIG. 3 (b)). Here, by spraying the rinse liquid 15, it is possible to suppress further progress of the silver mirror reaction in the formed silver mirror layer 3. That is, when the silver mirror reaction proceeds for a long time in the silver mirror layer 3, the silver mirror reaction proceeds excessively in a part of the formed layered silver mirror layer 3, resulting in defects such as unevenness and cloudiness. It may affect the finish. For this reason, the progress of the silver mirror reaction is stopped (suppressed) promptly so that the finish maintains a good state.

  Thereafter, similarly to the first tin chloride solution removal step S3 and the unreacted solution removal step S6, pure water 11 is shower-injected onto the silver mirror layer surface 3a using a shower head (rinse solution removal step S8: FIG. 3). (See (b)). As a result, the rinse solution 15 made of an inorganic sodium compound remaining on the silver mirror layer surface 3a is washed away. Thereafter, wind is applied to the silver mirror layer surface 3a using a blower, and mainly water droplets (including impurities) adhering to the silver mirror layer surface 3a are scattered by the wind pressure by the wind pressure (air blowing step S9: not shown), a predetermined temperature Introduced into a constant temperature bath (for example, around 60 ° C.) held in (drying step S10: not shown). Thereby, the water component remaining on the composite material surface 4a, the coat layer surface 5a, and the silver mirror layer surface 3a treated with a large amount of aqueous solution in each step can be evaporated and dried.

  And after fully drying, it takes out from a thermostat, and sprays the resin-made topcoat component 16 on the silver mirror layer surface 3a using the spray gun G4 (topcoat layer construction process S11: refer FIG.3 (c)). . Here, the silver mirror layer 3a formed on the coat layer surface 5a is not firmly in close contact with the coat layer surface 5a, but is almost on the surface. Therefore, the silver mirror layer 3 can be protected by spraying the resin top coat component 16 from above and curing it. As a result, even when a strong impact is applied to the composite material 2 of the present embodiment, there is no problem that the silver mirror layer 3 peels off. The top coat component 16 may be the same as the undercoat component 8 described above, or other epoxy resin or polyurethane resin may be used. Furthermore, although the topcoat component 16 is generally colorless and transparent, a desired colorant may be added to the topcoat component 16 to make it colored and transparent. Thereby, the decorativeness of the composite material 2 to be formed can be further enhanced, and design can be added to a particularly highly-preferred product such as a golf club shaft. As with the undercoat layer construction step S1, after the topcoat component 16 is sprayed, it is introduced into a constant temperature bath maintained at a predetermined temperature in order to cure the topcoat component 16, and a strong topcoat layer 7 is constructed. Processing is performed.

  As described above, according to the silver mirror layer forming method 1 of the present embodiment and the composite material 2 having the silver mirror layer 3 using the silver mirror layer forming method 1, the silver nitrate solution 12 is applied to the coat layer surface 5a in advance, and the silver solution / ammonia is further applied. By spraying a solution / nitrogen-containing solution using a double spray gun, a total of four types of solutions are mixed to form a silver mirror reaction, thereby forming the silver mirror layer 3. That is, the treatment and control of the reaction can be performed relatively easily as compared with the conventional method in which the product surface is so-called “silver plating” by a silver mirror reaction. Furthermore, since silver particles more than the required amount are not deposited by spray coating, it is possible to form a silver mirror layer 3 having a good finished state free from unevenness and cloudiness.

  Furthermore, the composite material 2 of the present embodiment formed by the above method has the following excellent effects. That is, as described above, the four types of solutions are used, and the silver mirror layer 3 formed by depositing a very small amount of silver particles AG on the coat layer surface 5a is constructed. Therefore, the silver particles AG on the coat layer surface 5a are It is expected that only a few layers are stacked. Therefore, when the topcoat component 16 is sprayed from above the silver mirror layer 3, the resinous liquid topcoat component 16 passes through the interparticle voids between the silver particles AG before the curing treatment, and the silver mirror layer The surface 3a may reach the coat layer surface 5a. As a result, the interparticle voids are filled with the top coat component 16. As a result, when the curing process proceeds in a state filled with the top coat component 16, the top coat layer 7 is sandwiched between the silver particle AG of the silver mirror layer 3 from both the coat layer surface 5a and the silver mirror layer surface 3a side. As a result, the adhesion degree of the silver mirror layer 3 is further improved (see FIG. 5). As a result, the silver mirror layer 3 protected by the top coat layer 7 may cause problems such as peeling from the coat layer surface 5a or cracking even when a strong impact such as a golf swing is applied. Lower.

  The present invention has been described with reference to examples of preferred embodiments. However, the present invention is not limited to these embodiments, and various modifications can be made without departing from the spirit of the invention as described below. Improvements and design changes are possible. That is, in the present embodiment, the type and concentration of the compound contained in the solution to be sprayed in each step, the blending ratio, and the like can be changed as appropriate, and the optimum one in the formation conditions can be selected.

  Furthermore, in this embodiment, although the temperature (air temperature) at the time of performing the process for forming the silver mirror layer 3 is not particularly mentioned, the temperature at which the process is performed may be adjusted to a constant temperature. Absent. That is, the progress of the silver mirror reaction may greatly depend on the temperature during the reaction. Therefore, in general, the reaction may be carried out at about room temperature (about 25 ° C.). For example, on a day with a high temperature of 30 ° C. or higher, or a day with a low temperature of 10 ° C. or lower, etc. The temperature may be adjusted. Here, if the room temperature is high, the progress of the silver mirror reaction is not promoted, and there is a possibility that unevenness and cloudiness may occur on the finished surface. On the other hand, if the room temperature is low, the silver mirror reaction does not proceed sufficiently and the silver mirror layer 3 is formed. It is assumed that there will be troubles. Therefore, it is necessary to adjust the temperature to be optimal for the silver mirror reaction.

  In addition, in the present embodiment, the composite material 2 in which the silver mirror layer 3 is formed is assumed to be a golf club shaft. However, the present invention is not limited to this, for example, a fishing rod, a tennis racket, etc. It may be used to enhance the decorativeness and design of other leisure goods. Furthermore, since the silver mirror layer 3 is formed, a highly light-reflective material can be constructed, so that it can be used as an alternative to conventional mirrors using glass or the like. In particular, since it is lighter than glass and there is no fear of breakage during handling, such a use seems to be a field that is particularly expected to be used.

It is sectional drawing which shows schematic structure of the composite material which has a silver mirror layer using the silver mirror layer formation method of this embodiment. It is explanatory drawing which shows typically the flow of each process of a silver mirror layer formation method. It is explanatory drawing which shows typically the flow of each process of a silver mirror layer formation method. It is a flowchart which shows the flow of each process of a silver mirror layer formation method. It is a principal part expanded sectional view which expands and shows the vicinity of the silver mirror layer of a composite material.

Explanation of symbols

1 Silver mirror layer forming method 2 Composite material (carbon fiber composite material having a silver mirror layer)
3 silver mirror layer 3a silver mirror layer surface 5 undercoat layer 5a coat layer surface 7 topcoat layer 8 undercoat component 10 stannous chloride solution 11 pure water 12 silver nitrate solution 13 silver / ammonia mixed solution 14 nitrogen-containing solution 15 rinse solution 16 top Coating component AG Silver particles S1 Undercoat layer construction process S2 Tin chloride solution spraying process S3 Tin chloride solution removing process S4 Silver nitrate solution spraying process S5 Silver mirror layer forming process S6 Unreacted solution removing process S7 Silver mirror reaction suppressing process S8 Rinse Liquid removal process S9 Air blow process S10 Drying process S11 Topcoat layer construction process

Claims (6)

An undercoat layer construction step of constructing an undercoat layer having surface smoothness by spraying and curing a resin undercoat component on the composite surface of the carbon fiber composite material;
A stannous chloride solution spraying step of spraying a stannous chloride solution on the surface of the coat layer of the constructed undercoat layer and performing an activation treatment to activate the silver mirror reaction on the surface of the coat layer;
A first tin chloride solution removing step of spraying pure water on the surface of the coat layer and washing away the first tin chloride solution on the surface of the coat layer;
A silver nitrate solution spraying step of spraying a silver nitrate solution prepared at a predetermined concentration on the surface of the coat layer washed away with the first tin chloride solution;
A silver / ammonia mixed solution obtained by mixing a silver compound and an ammonia component on the surface of the coat layer sprayed with the silver nitrate solution, and a nitrogen-containing solution containing a nitrogen-containing compound are independently sprayed, and the vicinity of the coat layer surface. In the silver mirror layer forming step of forming a thin film silver mirror layer by the silver mirror reaction on the surface of the coat layer by mixing in
An unreacted solution removal step of spraying pure water onto the silver mirror layer surface of the formed silver mirror layer to wash away and remove the unreacted solution on the surface of the silver mirror layer;
A silver mirror reaction suppression step of spraying a rinse solution containing an inorganic sodium compound on the surface of the silver mirror layer and suppressing the progress of the silver mirror reaction on the surface of the coat layer;
Rinse solution removing step of spraying pure water onto the surface of the silver mirror layer and washing away the rinse solution on the surface of the silver mirror layer;
An air blowing step of sending air to the surface of the silver mirror layer where the rinse liquid has been washed away, and causing water droplets and / or impurities on the surface of the silver mirror layer to be scattered by wind pressure;
A drying step of drying the silver mirror layer after the air blowing step at a predetermined temperature;
A method for forming a silver mirror layer, comprising: a top coat layer construction step for constructing a top coat layer for protecting the silver mirror layer by spraying and curing a resin top coat component on the surface of the silver mirror layer . The silver mirror layer forming step
The first spray part for spraying the silver / ammonia mixed solution and the second spray part for spraying the nitrogen-containing solution are arranged in parallel to spray the silver / ammonia mixed solution and the nitrogen-containing solution at the same timing. Use possible double spray gun,
In the mixing region set in the vicinity of each spraying port of the first spray part and the second spray part, the mist-like silver / ammonia mixed solution and the nitrogen-containing solution are mixed and sprayed on the surface of the coating layer. The method for forming a silver mirror layer according to claim 1. The silver mirror layer formed by the silver mirror layer forming step is
The silver particles constituting the silver mirror layer are uniformly arranged on the surface of the coat layer, and there are interparticle voids communicating between the silver mirror layer surface and the coat layer surface between the silver particles. Formed,
The topcoat layer constructed by the topcoat layer construction step is
At least a part of the top coat component made of resin passes through the interparticle voids from the surface of the silver mirror layer, reaches the surface of the coat layer and hardens, thereby covering the particle surface of the silver particles of the silver mirror layer The silver mirror layer forming method according to claim 1, wherein the silver mirror layer is formed by being sandwiched. A carbon fiber composite material having a silver mirror layer formed using the silver mirror layer forming method according to any one of claims 1 to 3,
An undercoat layer constructed on the surface of the carbon fiber composite material and the surface of the coat layer being activated by a stannous chloride solution;
A silver mirror layer formed by a silver mirror reaction on the surface of the coat layer using a silver nitrate solution, a silver / ammonia mixed solution, and a nitrogen-containing solution;
A carbon fiber composite material having a silver mirror layer, comprising a top coat layer that is constructed on a surface of the silver mirror layer of the silver mirror layer and protects the silver mirror layer. The silver mirror layer is
The silver particles constituting the silver mirror layer are uniformly arranged on the surface of the coat layer, and further include interparticle voids communicating between the silver mirror layer surface and the coat layer surface between the silver particles. And
The topcoat layer is
At least a part of the resin-made top coat component passes through the interparticle voids from the surface of the silver mirror layer, reaches the surface of the coat layer and hardens, thereby covering the particle surface of the silver particles of the silver mirror layer. 5. The carbon fiber composite material having a silver mirror layer according to claim 4, further comprising an interparticle void filling portion that supports the silver particles in a sandwiched state.   6. The carbon fiber composite material having a silver mirror layer according to claim 4, wherein the carbon fiber composite material is used for a leisure article of at least one of a golf club, a fishing rod, and a tennis racket.

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