JP2011074407A - Method for manufacturing plated object having three-dimensional shape - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plated object of a three-dimensional shape having excellent adhesiveness wherein the plating is deposited without separating a coating layer even when forming a base material in a complicated three-dimensional shape. <P>SOLUTION: A method for manufacturing a plated object of a three-dimensional shape includes (1) a step of providing a coating film layer consisting of reducing polymer particles and binder, on a base material, (2) a step of executing the three-dimensional forming on the base material having the coating film layer thereon, and (3) a step of providing a plating film by an electroless plating method on the coating film layer. The amount of the reducing polymer in the coating film layer after the three-dimensional forming is 80-500 pieces/μm<SP>2</SP>. The reducing polymer particles are obtained by executing the de-dope processing of conductive polymer particles. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a three-dimensional plated product.

  Conventionally, the method described in Patent Document 1 has been proposed as a method of providing a plating film on a three-dimensional shaped substrate. Specifically, a resin mixture is prepared by uniformly dispersing fine metal particles or an organometallic compound having an average particle diameter of 1 to 200 nm in a curable binder resin composition, and the resin mixture is applied to the surface of a non-conductive substrate. Applying to form a coating layer, irradiating the surface of the resin mixture coating layer with energy rays, performing a three-dimensional molding operation on a non-conductive substrate having the resin mixture coating layer formed on the surface, the three-dimensional Proposed to selectively form a plating film by electroless plating only on the surface irradiated with energy by applying a plating film by electroless plating on the surface of a non-conductive substrate that has been subjected to molding operation Has been.

JP 2006-135176 A

  However, when the substrate is molded into a complicated three-dimensional shape, the uniaxial stretching ratio may exceed 600% with respect to the original size, or the biaxial stretching ratio may exceed 200% with respect to the original size. There was a problem that the coating layer was divided and horizontal conduction was not obtained.

  Therefore, the present invention provides a plated article having a three-dimensional shape with excellent adhesion, in which the coating is deposited without breaking the coating layer even when the substrate is molded into a complicated three-dimensional shape. The purpose is to do.

  The method for producing a three-dimensional plated product according to claim 1 of the present invention includes: 1) a step of providing a coating layer composed of reducing polymer fine particles and a binder on a substrate; and 2) the coating layer is And 3) a step of applying a three-dimensional molding to the provided base material, and 3) a step of providing a plating film by an electroless plating method on the coating layer. Moreover, the abundance of the reducing polymer in the coating layer after three-dimensional molding is 80 to 500 / μm 2. Further, as the reducing polymer fine particles, conductive polymer fine particles are dedoped to form reducing polymer fine particles.

  Even when the substrate was molded into a complicated three-dimensional shape, the coating layer was deposited without breaking the coating layer, and a plated product with excellent adhesion could be obtained.

  The present invention includes: 1) a step of providing a coating layer composed of reducing fine polymer particles and a binder on a substrate; 2) a step of performing three-dimensional molding on the substrate provided with the coating layer; And a step of providing a plating film by an electroless plating method on the coating layer.

  First, 1) A process of providing a coating film layer such as reducing fine polymer particles and a binder on a substrate will be described.

  In the step 1) of the present invention, a coating layer is provided by applying a base coating containing reducing polymer fine particles and a binder to the entire surface of the substrate or in a pattern. The thickness of the coating layer is preferably in the range of 0.1 to 100 μm.

  The reducing polymer fine particle used in the present invention is not particularly limited as long as it is a polymer having a π-conjugated double bond having a conductivity of less than 0.01 S / cm. For example, polyacetylene, polyacene, polypara Examples include phenylene, polyparaphenylene vinylene, polypyrrole, polyaniline, polythiophene, and various derivatives thereof, and preferably polypyrrole. Further, as the reducing polymer fine particles, conductive polymer fine particles may be dedoped to obtain reducing polymer fine particles.

The binder used in the present invention is not particularly limited. For example, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), carbonized Examples thereof include hydrogen resins, ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resins, urethane resins, melamine resins, acrylic resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicon resins.
The amount of binder used is in the range of 0.1 to 60 parts by mass with respect to 1 part by mass of reducing or conductive polymer fine particles. If the binder exceeds 60 parts by mass, it may be difficult to deposit a plating film by an electroless plating method, and if the binder is less than 0.1 parts by mass, peeling between the substrate and the coating film layer easily occurs. It may be difficult to obtain good adhesion.

  Further, an inorganic filler may be contained in the base coating material containing the reducing polymer fine particles and the binder. The inorganic filler is not particularly limited, and examples thereof include carbon black, titanium oxide, and silica particles. The amount of the inorganic filler used is not particularly limited, but is preferably in the range of 0.05 to 1.5 parts by mass with respect to 1 part by mass of the binder. When the amount of the inorganic filler used exceeds 1.5 parts by mass with respect to 1 part by mass of the binder, peeling between the base material and the coating layer is likely to occur, and it may be difficult to obtain good adhesion. Moreover, when it becomes less than 0.05 mass part, the plating film by an electroless plating method may become difficult to precipitate.

  The base coating material of the present invention may contain a solvent in addition to the above components. The solvent is not particularly limited, and specifically, aliphatic esters such as butyl acetate, aromatic solvents such as toluene and xylene, ketones such as methyl ethyl ketone, cyclohexanone and isophorone, and cyclic such as cyclohexane Saturated hydrocarbons, chain saturated hydrocarbons such as n-octane, chain saturated alcohols such as methanol, ethanol and n-octanol, aromatic esters such as methyl benzoate, and aliphatic ethers such as diethyl ether And mixtures thereof. Moreover, the solvent classified into terpenes, such as polyhydric alcohol derivative solvents, such as methyl cellosolve, hydrocarbon solvents, such as a mineral spirit, dihydroterpineol, and D-limonene, can also be used.

  Furthermore, the coating material can be added with a resin such as a dispersion stabilizer, a thickener, and an ink binder, depending on the application and the application target. Since the base coating material of the present invention can adjust the viscosity of the solution by including the above-mentioned components, it can be easily applied to the entire surface of the base material, and when a coating layer is provided in a pattern, screen printing is possible. Further, a fine line pattern having a line width of 1.0 mm or less can be printed with high accuracy by gravure printing, flexographic printing, offset printing, dry offset printing, pad printing, or the like.

  The base material that can be used in the present invention is not particularly limited as long as it is a material that can be plastically deformed in order to perform three-dimensional molding. For example, a polyester resin such as polyethylene terephthalate, polymethyl methacrylate, etc. Acrylic resin such as polypropylene resin, polycarbonate resin, polystyrene resin, polyvinyl chloride resin, polyamide resin, polyimide resin, polyamide / imide resin, polyacetal resin, polyphenylene ether resin, fluorine resin, polyarylate resin, polysulfone resin, polyphenylene sulfide Examples thereof include resins and polyether ether ketone resins. Moreover, the shape of the substrate is not particularly limited, but for example, a plate-like shape is used, and a thickness of 0.01 to 10 mm is preferably used.

  Then, 2) The process of giving a three-dimensional shaping | molding to the base material with which the said coating-film layer was provided is demonstrated.

  The three-dimensional molding of the present invention is to three-dimensionalize (three-dimensionalize) a substrate by performing vacuum molding, press molding, compressed air molding, or the like. The three-dimensional molding is preferably performed such that the biaxial stretching ratio is 800% or less with respect to the original size. If the biaxial stretching ratio exceeds 800%, the coating layer after the three-dimensional molding is Even if the amount of the reducing fine particles is 80 to 500 / μm 2, the plating film formed by the electroless plating method is difficult to be a continuous film, and horizontal conduction may not be obtained. For example, a three-dimensional conductive circuit It becomes difficult to use as an application.

  Moreover, it is preferable that the abundance of the reducing polymer on the surface of the coating layer after the three-dimensional molding is 80 to 500 / μm 2, and if it is less than 80 / μm 2, the plating film is formed by an electroless plating method. When provided, an undeposited portion of the plating film may be seen, and if it exceeds 500 / μm 2, a part of the plating film may be peeled off in the tape peeling test.

  Alternatively, the base material after three-dimensional molding may be set in an injection mold, and insert molding may be performed in which resin is filled on the side of the base material where the coating layer is not provided. At the same time, a molded product, a film, or the like may be laminated on the side of the substrate on which the coating layer is not provided. In addition, it is possible to perform insert molding filled with resin on the side where the coating layer of the substrate is provided, and then peel off only the substrate, that is, transfer the coating layer to the surface of the insert-molded resin layer, In this case, the insert-molded resin layer becomes the base material.

  Subsequently, 3) a step of providing a plating film by an electroless plating method on the coating film layer will be described.

  As described above, a plating film is provided on the coating layer after the steps 1) and 2) by an electroless plating method to obtain a plated product. The electroless plating method should be performed according to a generally known method. Can do. That is, after the substrate is immersed in a catalyst solution for attaching a catalytic metal such as palladium chloride, the substrate is washed with water and immersed in an electroless plating bath to obtain a plated product.

  The catalyst solution is a solution containing a noble metal (catalyst metal) having catalytic activity for electroless plating. Examples of the catalyst metal include palladium, gold, platinum, rhodium, etc. These metals may be simple substances or compounds. A palladium compound is preferable from the viewpoint of stability including a metal, and palladium chloride is particularly preferable among them. A preferred specific catalyst solution includes 0.05% palladium chloride-0.005% hydrochloric acid aqueous solution (pH 3). The treatment temperature is 20 to 50 ° C., preferably 30 to 40 ° C., and the treatment time is 0.1 to 20 minutes, preferably 1 to 10 minutes. By the above operation, the reducing polymer fine particles in the coating film become conductive polymer fine particles as a result.

  The base material treated as described above is immersed in a plating solution for depositing metal, thereby forming an electroless plating film. The plating solution is not particularly limited as long as it is a plating solution usually used for electroless plating. That is, metal, copper, gold, silver, nickel, etc. that can be used for electroless plating can all be applied, but copper is preferred. Specific examples of the electroless copper plating bath include, for example, an ATS add copper IW bath (Okuno Pharmaceutical Co., Ltd.). The treatment temperature is 20 to 50 ° C., preferably 30 to 40 ° C., and the treatment time is 1 to 30 minutes, preferably 5 to 15 minutes. The obtained plated product is preferably cured for several hours or more, for example, 2 hours or more in a temperature range lower than the Tg of the used substrate.

  In the present invention, a base coating using conductive polymer fine particles is applied to the entire surface or a pattern on the substrate, and the conductive polymer fine particles in the coating layer formed thereby are dedoped. It is related also to the manufacturing method of the plated object which has the whole surface or a pattern-like plating film by carrying out the chemical plating of the metal film from an electroless-plating liquid on this coating film layer after making it reducible. The timing of the dedoping treatment may be before three-dimensional shaping or after three-dimensional shaping.

  As the dedoping treatment in the above production method, reducing agents, for example, borohydride compounds such as sodium borohydride and potassium borohydride, alkylamine boranes such as dimethylamine borane, diethylamine borane, trimethylamine borane, and triethylamine borane, and And a method of reducing by treatment with a solution containing hydrazine or the like, or a method of treating with an alkaline solution.

  It is preferable to treat with an alkaline solution from the viewpoint of operability and economy. In particular, since the coating layer containing the conductive polymer fine particles can be thinned, it is possible to achieve dedoping by mild alkali treatment under mild conditions. For example, it is treated in a 1M aqueous sodium hydroxide solution at a temperature of 20 to 50 ° C., preferably 30 to 40 ° C., for 1 to 30 minutes, preferably 3 to 10 minutes.

  In addition, the plated product may be further plated with the same or different metal on the formed electroless plating film by electrolytic plating.

  Below, the specific method for manufacturing the reducing or electroconductive polymer fine particle which can be used in order to form a coating film layer is described.

(1) Production Method of Reducing Polymer Fine Particles Reducing polymer fine particles are contained in an O / W type emulsion obtained by mixing and stirring an organic solvent, water, an anionic surfactant and a nonionic surfactant. , A monomer having a π-conjugated double bond is added, and the monomer can be produced by oxidative polymerization.

  The monomer having a π-conjugated double bond is not particularly limited as long as it is a monomer used for producing a reducing polymer, and examples thereof include pyrrole, N-methylpyrrole, N-ethylpyrrole, and N-phenyl. Pyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N-methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3- Ethyl pyrrole, 3-n-butyl pyrrole, 3-methoxy pyrrole, 3-ethoxy pyrrole, 3-n-propoxy pyrrole, 3-n-butoxy pyrrole, 3-phenyl pyrrole, 3-toluyl pyrrole, 3-naphthyl pyrrole, 3 -Phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3-dimethyla Pyrrole derivatives such as nopyrrole, 3-diethylaminopyrrole, 3-diphenylaminopyrrole, 3-methylphenylaminopyrrole and 3-phenylnaphthylaminopyrrole, aniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, o- Aniline derivatives such as methoxyaniline, m-methoxyaniline, p-methoxyaniline, o-ethoxyaniline, m-ethoxyaniline, p-ethoxyaniline, o-methylaniline, m-methylaniline and p-methylaniline, thiophene, 3 -Methylthiophene, 3-n-butylthiophene, 3-n-pentylthiophene, 3-n-hexylthiophene, 3-n-heptylthiophene, 3-n-octylthiophene, 3-n-nonylthiophene, 3-n- Decylthiophene, Examples include thiophene derivatives such as 3-n-undecylthiophene, 3-n-dodecylthiophene, 3-methoxythiophene, 3-naphthoxythiophene and 3,4-ethylenedioxythiophene, preferably pyrrole, aniline, thiophene And 3,4-ethylenedioxythiophene and the like, more preferably pyrrole.

  Various anionic surfactants used in the production can be used, but those having a plurality of hydrophobic ends (for example, those having a branched structure in a hydrophobic group or those having a plurality of hydrophobic groups) are preferred. . By using such an anionic surfactant having a plurality of hydrophobic ends, stable micelles can be formed, and separation between the aqueous phase and the organic solvent phase is smooth after the polymerization. Reducible polymer fine particles dispersed in are easily available. Among anionic surfactants having multiple hydrophobic ends, di-2-ethylhexyl sodium sulfosuccinate (4 hydrophobic ends), di-2-ethyloctyl sodium sulfosuccinate (4 hydrophobic ends) and branched type Alkyl benzene sulfonate (two hydrophobic ends) can be preferably used.

  The amount of the anionic surfactant in the reaction system is preferably less than 0.05 mol, more preferably 0.005 mol to 0.03 mol, with respect to 1 mol of the monomer having a π-conjugated double bond. When the amount is 0.05 mol or more, the added anionic surfactant acts as a dopant, and the resulting fine particles exhibit conductivity. Therefore, in order to perform electroless plating using this, a dedoping step is required.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, alkyl glucosides, glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbidic fatty acid esters, polyoxyethylene fatty acid esters, fatty acid alkanolamides, poly Examples include oxyethylene alkylphenyl ethers. These may be used alone or in combination. In particular, those that stably form an O / W emulsion are preferred.

  The amount of the nonionic surfactant in the reaction system is preferably 0.2 mol or less, more preferably 0.2 mol or less with respect to 1 mol of the monomer having a π-conjugated double bond, in addition to the anionic surfactant. It is 05-0.15 mol. If the amount is less than 0.05 mol, the yield and dispersion stability are reduced. On the other hand, if the amount is 0.2 mol or more, it is difficult to separate the aqueous phase from the organic solvent phase after polymerization. It is not preferable because it becomes impossible to obtain.

  In the production, the organic solvent forming the organic phase of the emulsion is preferably hydrophobic. Among these, toluene and xylene, which are aromatic organic solvents, are preferable from the viewpoint of the stability of the O / W emulsion and the affinity with the monomer having a π-conjugated double bond. Although the amphoteric solvent can polymerize a monomer having a π-conjugated double bond, it is difficult to separate the organic phase and the aqueous phase when the produced reducing polymer fine particles are recovered.

  The ratio of the organic phase to the aqueous phase in the emulsion is preferably 75% by volume or more in the aqueous phase. When the water phase is 20% by volume or less, the amount of the monomer having a π-conjugated double bond is reduced, and the production efficiency is deteriorated.

  Examples of the oxidizing agent used in the production include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, potassium persulfate, ammonium persulfate and peroxidation. Peroxides such as hydrogen can be used. These may be used alone or in combination of two or more. Even a Lewis acid such as ferric chloride can polymerize a monomer having a π-conjugated double bond, but the produced particles may aggregate and be unable to be finely dispersed. Particularly preferred oxidizing agents are persulfates such as ammonium persulfate.

  The amount of the oxidizing agent in the reaction system is preferably 0.1 mol or more and 0.8 mol or less, more preferably 0.2 to 0.6 mol with respect to 1 mol of the monomer having a π-conjugated double bond. is there. If the amount is less than 0.1 mol, the degree of polymerization of the monomer decreases, making it difficult to separate and recover the polymer fine particles. On the other hand, if the amount is 0.8 mol or more, the particles are aggregated to increase the particle size of the polymer fine particles, resulting in poor dispersion stability. To do.

The polymer fine particle production method is performed, for example, in the following steps:
(A) a step of preparing an emulsion by mixing and stirring an anionic surfactant, a nonionic surfactant, an organic solvent and water;
(B) a step of dispersing a monomer having a π-conjugated double bond in an emulsion,
(C) oxidative polymerization of the monomer,
(D) A step of separating the organic phase and collecting the polymer fine particles.

  Each of the above steps can be performed using means known to those skilled in the art. For example, the mixing and stirring performed at the time of preparing the emulsion is not particularly limited. For example, a magnetic stirrer, a stirrer, a homogenizer, or the like can be selected as appropriate. The polymerization temperature is 0 to 25 ° C, preferably 20 ° C or less. If the polymerization temperature exceeds 25 ° C., side reactions occur, which is not preferable.

  When the oxidative polymerization reaction is stopped, the reaction system is divided into an organic phase and an aqueous phase. At this time, unreacted monomers, oxidizing agents and salts remain dissolved in the aqueous phase. When the organic phase is separated and recovered and washed several times with ion-exchanged water, reducing polymer fine particles dispersed in an organic solvent can be obtained.

  The polymer fine particles obtained by the above production method are fine particles mainly composed of a polymer of a monomer derivative having a π-conjugated double bond and containing an anionic surfactant and a nonionic surfactant. And the characteristic is that it has a fine particle size and is dispersible in an organic solvent. The polymer fine particles are spherical fine particles, and the average particle size is preferably 10 to 100 nm. By making fine particles with a small average particle diameter as described above, the surface area of the fine particles becomes extremely large, and even with fine particles of the same mass, more catalytic metals can be adsorbed, thereby reducing the thickness of the coating layer. It becomes possible. The conductivity of the obtained polymer fine particles is less than 0.01 S / cm, and preferably 0.005 S / cm or less.

  The reducing polymer fine particles dispersed in the organic solvent thus obtained can be used as they are as the reducing polymer fine particle component of the base coating.

(2) Method for Producing Conductive Polymer Fine Particles The conductive polymer fine particles used are, for example, π in an O / W type emulsion obtained by mixing and stirring an organic solvent, water and an anionic surfactant. -It can be produced by adding a monomer having a conjugated double bond and subjecting the monomer to oxidative polymerization.

  Examples of the monomer having an π-conjugated double bond and the anionic surfactant are the same as those exemplified in the production of the reducing fine particles, and preferably pyrrole, aniline, thiophene and 3,4- Ethylenedioxythiophene etc. are mentioned, More preferably, pyrrole is mentioned.

  The amount of the anionic surfactant in the reaction system is preferably less than 0.2 mol, more preferably 0.05 mol to 0.15 mol, with respect to 1 mol of the monomer having a π-conjugated double bond. If the amount is less than 0.05 mol, the yield and dispersion stability decrease, while if the amount is 0.2 mol or more, the resulting conductive polymer fine particles may have a humidity dependency on the conductivity.

  In the production, the organic solvent forming the organic phase of the emulsion is preferably hydrophobic. Among these, toluene and xylene, which are aromatic organic solvents, are preferable from the viewpoint of the stability of the O / W emulsion and the affinity with the monomer. Although the amphoteric solvent can polymerize a monomer having a π-conjugated double bond, it becomes difficult to separate the organic phase and the aqueous phase when the produced conductive polymer fine particles are recovered.

  The ratio of the organic phase to the aqueous phase in the emulsion is preferably 75% by volume or more in the aqueous phase. When the water phase is 20% by volume or less, the amount of the monomer having a π-conjugated double bond is reduced, and the production efficiency is deteriorated.

  Examples of the oxidizing agent used in the production include the same as those exemplified in the production of the reducing fine particles, but a particularly preferred oxidizing agent is a persulfate such as ammonium persulfate. The amount of the oxidizing agent in the reaction system is preferably 0.1 mol or more and 0.8 mol or less, more preferably 0.2 to 0.6 mol with respect to 1 mol of the monomer having a π-conjugated double bond. is there. If the amount is less than 0.1 mol, the degree of polymerization of the monomer decreases, making it difficult to separate and collect the conductive polymer fine particles. On the other hand, if the amount is 0.8 mol or more, the particles are aggregated to increase the particle size of the conductive polymer fine particles. , Dispersion stability deteriorates.

The method for producing the conductive polymer fine particles is performed, for example, in the following steps:
(A) a step of preparing an emulsion by mixing and stirring an anionic surfactant, an organic solvent and water;
(B) a step of dispersing a monomer having a π-conjugated double bond in an emulsion,
(C) a step of oxidatively polymerizing the monomer and causing the anionic surfactant to contact and adsorb the polymer fine particles;
(D) A step of separating the organic phase and collecting the conductive polymer fine particles.

  Each of the above steps can be performed using means known to those skilled in the art. For example, the mixing and stirring performed at the time of preparing the emulsion is not particularly limited. For example, a magnetic stirrer, a stirrer, a homogenizer, or the like can be selected as appropriate. The polymerization temperature is 0 to 25 ° C, preferably 20 ° C or less. If the polymerization temperature exceeds 25 ° C., side reactions occur, which is not preferable.

  When the oxidative polymerization reaction is stopped, the reaction system is divided into an organic phase and an aqueous phase. At this time, unreacted monomers, oxidizing agents and salts remain dissolved in the aqueous phase. When the organic phase is separated and recovered and washed several times with ion-exchanged water, conductive polymer fine particles dispersed in an organic solvent can be obtained.

  The conductive polymer fine particles obtained by the above production method are fine particles mainly composed of a monomer derivative having a π-conjugated double bond and containing an anionic surfactant. And the characteristic is that it can disperse | distribute in a fine particle size and an organic solvent. The polymer fine particles are spherical fine particles, and the average particle size is preferably 10 to 100 nm. By using fine particles with a small average particle size as described above, the surface area of the fine particles becomes extremely large, and even with fine particles of the same mass, more catalyst metal can be adsorbed when dedoped and reduced. Thus, the coating layer can be made thin.

  The conductive polymer fine particles dispersed in the organic solvent thus obtained can be used as they are as the conductive polymer fine particle component of the base coating.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example.

Example 1
[Production Example 1] Preparation of Reducing Polypyrrole Fine Particle Dispersion Anionic Surfactant Perex OT-P (Kao Corporation) 0.42 mmol, Polyoxyethylene Alkyl Ether Nonionic Surfactant Emulgen 409P (Kao Corporation) 2 .1 mmol, 10 mL of toluene and 100 mL of ion-exchanged water were added and stirred until emulsified while maintaining at 20 ° C. To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 1 hour, and then 6 mmol of ammonium persulfate was added to conduct a polymerization reaction for 2 hours. After completion of the reaction, the organic phase was recovered and washed several times with ion-exchanged water to obtain reducing polypyrrole fine particles having reducing performance dispersed in toluene.

[Production Example 2]: Preparation of base coating material Binder: Byron 23CS: Amorphous polyester resin (Toyobo Co., Ltd.) and inorganic filler: Aerosil 200: Powdered silica (Nihon Aerosil Co., Ltd.) in a solid content ratio : Inorganic filler = 4: 1.15 was mixed, and after pre-stirring, it was dispersed by a three-roll mill.
Next, the reducing polypyrrole fine particle dispersion liquid prepared in Production Example 1 (solid content: 5.0%) is mixed with the dispersion liquid containing the binder and the inorganic filler prepared as described above at a solid content ratio. It mix | blended so that it might become type | system | group filler = 1: 4: 1.15, and the ground coating material was obtained by performing stirring and defoaming.

[Step 1]: Printing on base material As a base material, an amorphous polyethylene terephthalate sheet having a thickness of 650 μm: Nova Clear (manufactured by Mitsubishi Plastics Co., Ltd.) is used, and a base coating is formed on the base material so that the thickness is 4 μm. The pattern was printed with a printing machine.
In addition, it printed with the plate | board which forms the straight line of L / S = 1.0mm / 1.0mm, and heat-dried for 10 minutes in 70 degreeC hot-air oven.

[Step 2]: Molding Subsequently, a sheet on which a pattern was printed by a screen printer was vacuum formed using a mold having a stretching ratio of 400%.

[Step 3]: Electroless Plating The vacuum-formed sheet was immersed in a 0.05% palladium chloride-0.005% hydrochloric acid aqueous solution at 35 ° C. for 5 minutes and then washed with washing water. Next, the sheet is immersed in an electroless copper plating bath ATS add copper IW bath (Okuno Pharmaceutical Co., Ltd.) for 20 minutes at 35 ° C., so that copper plating is applied only to the portion where the printed film is formed. A sheet was obtained.

(Example 2)
[Step 2]: A sheet in which copper plating was applied only to the portion where the printed film was formed by the same method as in Example 1 was obtained except that the stretching ratio was 200% at the time of molding.

(Example 3)
[Step 2]: A sheet in which copper plating was applied only to the portion where the printed film was formed by the same method as in Example 1 was obtained except that the stretch ratio was 800% at the time of molding.

(Comparative Example 1)
[Production Example 2] of [Production Examples 1 and 2]: At the time of preparation of the base coating, blended so that the reducing fine particles: binder: inorganic filler = 12: 4: 1.15 in the solid content ratio, and stirred The base coating material was prepared in the same manner as in Example 1 except that the base coating material was obtained by defoaming.
[Step 2] of [Steps 1 to 3]: Copper plating is performed only on the portion where the printed film is formed by the same method as in Example 1 except that the stretch ratio is 100% during molding. Sheet was obtained.

(Comparative Example 2)
[Production Example 2] of [Production Examples 1 and 2]: At the time of preparation of the base coating, it is blended so that the reducing fine particles: binder: inorganic filler = 0.67: 4: 1.15 in the solid content ratio. The base coating material was prepared in the same manner as in Example 1 except that the base coating material was obtained by stirring and defoaming.
[Step 2] of [Steps 1 to 3]: Copper plating is performed only on the portion where the printed film is formed by the same method as in Example 1 except that the stretching ratio is 800% during molding. Sheet was obtained.

(Comparative Example 3)
Adjustment of the coating material for plating bases containing Ag nanoparticles was performed as follows.
The binder resin solution was Epiklon HP (manufactured by DIC Corporation): 7 parts by mass, Epicoat 828EL (manufactured by Mitsubishi Chemical Corporation): 3 parts by mass, and YH-307 (manufactured by Japan Epoxy Resin Co., Ltd.): 13.8 as a curing agent. Mass part, Amicure-PN- (Ajinomoto Fine Techno Co., Ltd.): 0.3 part by mass as an amine-based curing catalyst, KBM403 (Shin-Etsu Chemical Co., Ltd.): 0.1 part by mass as a coupling agent, Stir and mix to adjust.
Next, Ag nanoparticle: Perfect Silver (manufactured by Vacuum Metallurgical Co., Ltd.) is blended in the binder resin solution so that the binder: Ag nanoparticle = 7: 3 in a solid content ratio, and uniformly dispersed with three rolls. I let you. Subsequently, the dispersed solution was dried under reduced pressure, and the organic solvent was removed to obtain an Ag nanoparticle paste.

Subsequently, an amorphous polyethylene terephthalate sheet having a thickness of 650 μm: Nova Clear (manufactured by Mitsubishi Plastics Co., Ltd.) is used as a base material, and a coating material for plating base containing Ag nanoparticles is formed on the base material so that the thickness becomes 20 μm. The pattern was printed on a screen printer. In addition, it printed with the plate | board which forms the straight line of L / S = 1.0mm / 1.0mm, and heat-dried for 10 minutes in 70 degreeC hot-air oven.
Thereafter, ultraviolet rays were irradiated using an ultraviolet exposure machine under the conditions of wavelength: 365 nm and energy density: 45 J / cm 2.

  Subsequently, vacuum forming was performed using a mold having a stretching ratio of 800%.

  Subsequently, the vacuum-formed sheet is immersed in an electroless copper plating bath: ATS Adcopper IW bath (Okuno Pharmaceutical Co., Ltd.) for 20 minutes at 35 ° C., so that only the portion where the printed film is formed is copper. A sheet with plating was obtained.

(Abundance of reducing fine particles after molding)
In the sheet | seat obtained in Examples 1-3 and Comparative Examples 1-3, the surface of the pattern printing base material in which electroless plating was given was image | photographed with the transmission electron microscope (The JEOL Co., Ltd. product: JEM-1200EXM). The number of reducing fine particles on the coating layer surface was counted from the image.

(Evaluation test)
About the sheet | seat obtained in Examples 1-3 and Comparative Examples 1-3, the metal-plating precipitation property by electroless plating, electroconductivity, and adhesiveness were evaluated, and it showed in Table 1.
The evaluation method is as shown below.

<Plating precipitation>
After the electroless plating treatment, the precipitation was visually evaluated.
Undeposited part is not seen: ○
Undeposited part was seen: ×

<Conductivity>
In the plating film provided on the stretched portion of the base sheet, conduction was confirmed using a tester.
Tester resistance is less than 1000Ω: ○
Tester resistance is 1000Ω or more: ×

<Adhesion>
Cellophane tape was affixed to and peeled from the pattern printing substrate on which electroless plating was applied, and the adhesion of the plating film was evaluated.
No peeling of plating film: ○
There is peeling of the plating film: ×

Claims (3)

1) A step of providing a coating layer composed of reducing polymer fine particles and a binder on a substrate,
2) A step of performing three-dimensional molding on the base material provided with the coating layer;
3) A method for producing a three-dimensional plated product comprising a step of providing a plating film by an electroless plating method on the coating layer. Method for producing abundance of the reducing polymer in the coating layer surface after three-dimensional molding, plating of three-dimensional shape according to claim 1, characterized in that the 80 to 500 pieces / [mu] m ^2.   The method for producing a three-dimensional plated product according to claim 1 or 2, wherein the reducing polymer fine particles are obtained by dedoping conductive polymer fine particles into reducing polymer fine particles.