JP2010031318A - Plated article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plated article manufactured by an electroless plating method, wherein a metal plating film shows excellent adhesion to a substrate and is uniform without any exposed portions (unevenness). <P>SOLUTION: The plated article is manufactured by forming a primer layer 2 on the substrate, subsequently applying either an undercoat containing reducing polymer particulates and a binder on the primer layer 2 to form a coating film layer 3 or an undercoat containing conductive polymer pariculates and a binder on the primer layer 2 and carrying out an undoping treatment of the conductive polymer pariculates to form a coating film layer, and forming a metal film on the coating film layer by chemical plating using an electroless plating solution. In the above case, at least 60% of the reducing polymer particulates 5 is present within an upper half of the coating film layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a plated product produced by an electroless plating method, which has a metal plating film excellent in adhesion to a substrate, and is uniform without an exposed portion (unevenness) on the surface of the film. .

  There has been proposed an electroless plating method in which an electric circuit is produced by forming a conductive polymer layer on a substrate and plating the conductive polymer layer.

In Patent Document 1, a catalyst layer containing an oxidizing agent having a property that the oxidative polymerization property of a monomer disappears or decreases by light irradiation is formed on a substrate film, and after polymerizing a conductive polymer on the catalyst layer, A method of chemically plating a metal film from an electroless plating solution on a conductive polymer is disclosed.
Japanese Patent No. 3069942

  However, in the method disclosed in Patent Document 1, since the oxidizing agent used for polymerizing the conductive polymer cannot be removed, the conductive polymer is subjected to oxidative polymerization and further subjected to electroless plating. This oxidizing agent remains under the conductive polymer layer. The remaining oxidizing agent oxidizes the metal plating film (copper, nickel, etc.) formed by the electroless plating method. As a result, the metal plating film corrodes violently. The adhesion between the film and the substrate film was very weak, and it was difficult to withstand medium to long-term practical use.

  The metal plating film obtained by the method described in Patent Document 1 is very weak in adhesion to the base film, which is one of important evaluation items of the metal plating film. As described above, the main cause of the decrease in adhesion is considered to be that the metal plating film was corroded by the oxidizing agent, but in addition, the base film-oxidant layer-conductive polymer layer-metal plating. Since a multilayer structure such as a film is formed, it is considered that peeling between the layers is likely to occur.

  The present invention has no problem that the adhesion of the metal plating film in the electroless plating method is reduced, that is, the adhesion between the metal plating film and the substrate is excellent, and in addition, on the surface of the metal plating film. An object of the present invention is to provide a plated product manufactured by an electroless plating method that is uniform without an exposed portion (unevenness) and a manufacturing method thereof.

  As a result of intensive studies to solve the above problems, the present inventors have found that metal plating formed by electroless plating can be achieved by using reducing polymer fine particles and a binder in a coating layer for forming a metal plating film. When the adhesion of the film can be increased and a primer layer is provided between the coating layer and the substrate, the adhesion between the coating layer and the substrate can be increased, and the coating layer is formed. In this case, if more than 60% of the reducing polymer fine particles are present in the upper half of the coating layer, the adhesion of the metal plating film can be further increased, and in addition, the coating surface The amount of catalyst metal adsorbed on the surface is increased, thereby finding that the metal plating film formed on the coating film can be a uniform film surface with no exposed portion (unevenness) even in a thin coating layer, The present invention has been completed.

That is, the present invention
1. A primer layer is formed on a substrate, and a coating layer is formed thereon by applying a base coating containing reducing polymer fine particles and a binder, or conductive polymer fine particles and a binder on the primer layer. The coating is produced by applying a base coating material containing, forming a coating layer by dedoping the conductive polymer fine particles, and chemically plating a metal film on the coating layer from an electroless plating solution A plated article in which 60% or more of the reducing polymer fine particles are present in the upper half of the coating layer,
2. When the shape of the substrate is a film, the binder is present in an amount of 0.1 to 10 parts by mass with respect to 1 part by mass of the reducing polymer fine particles, and the thickness of the coating layer is 20 nm to 500 nm. , Plated products.
3. When the shape of the base material is a molded product, the binder is present in an amount of 0.1 to 10 parts by weight with respect to 1 part by weight of the reducing polymer fine particles, and the thickness of the coating layer is 100 nm to 50 μm. It is related to the plated product.

  In the plated product of the present invention, a primer layer is formed on the surface of a substrate, a coating layer containing reducing fine polymer particles and a binder is formed on the surface of the primer layer, and metal plating is formed on the coating layer. Although the film is formed by an electroless plating method, since the coating layer uses fine particles that have already been polymerized, an oxidizing agent that is a polymerization catalyst is not used. There is no problem.

  Moreover, the adhesiveness of a metal plating film and a base material can be improved by using a binder.

  The coating layer in the plated product according to the present invention is such that 60% or more of the reducing polymer fine particles are present in the upper half of the coating layer. Since the abundance ratio is increased and the adhesion between the primer layer and the coating film layer is improved, as a result, the adhesion between the metal plating film and the substrate is improved.

  In addition, since the abundance ratio of the reducing polymer fine particles is high near the surface of the coating layer, the amount of the catalytic metal adsorbed on the surface increases. As a result, the metal plating film to be formed is thin. Even in the coating layer, it can be made uniform with no exposed portion (unevenness).

The plated product of the present invention can be produced in the same manner by using not only reducing polymer fine particles but also conductive polymer fine particles. In this case, before conducting electroless plating, it is necessary to dedoped conductive polymer fine particles to make it reducible. However, in the plated product of the present invention, a thin layer (conductive high Excellent adhesion and uniformity can be maintained even in the molecular fine particle layer).
In addition, the plated product of the present invention, for example, reduces and adsorbs a catalytic metal such as palladium on a coating layer containing reducible polymer fine particles formed on a substrate, and adsorbs the catalytic metal such as palladium. In this case, the reduction of the catalytic metal such as palladium and the adsorption to the fine polymer particles are shown in the figure below in the case of polypyrrole, for example. It is considered to be in a state.
That is, the reducing polymer fine particles (polypyrrole) reduce palladium ions to adsorb palladium (metal) on the polymer fine particles, whereby the polymer fine particles (polypyrrole) are ionized. And doped with palladium, and as a result, develops conductivity.

  The present invention will be described in more detail.

The plated product of the present invention is
A) forming a primer layer on the substrate,
B) A coating film in which a coating containing reducing polymer fine particles and a binder is applied on the primer layer, and 60% or more of the reducing polymer fine particles are present in the upper half of the coating film layer. Forming a layer,
C) Manufactured by chemically plating a metal film on the coating layer from an electroless plating solution.

  The substrate of the present invention is not particularly limited. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polylactic acid, acrylic resins such as polymethyl methacrylate, polypropylene resins, polycarbonate resins, polystyrene resins and polyvinyl chloride resins. , Polyamide resin, polyimide resin, polyetherimide resin, polyacetal resin, polyether ether ketone resin, cyclic polyolefin resin, polyethylene resin, polyphenylene sulfide resin, liquid crystal polymer, modified polyphenyl ether resin, polysulfone resin, PC / ABS (polycarbonate ABC) resin, ASA / PC (acrylonitrile styrene acrylate / polycarbonate) resin, ABS (acrylonitrile butadiene styrene) resin, phenol Resin, glass, alumina and the like. Especially, it is difficult to carry out chemical electroless plating, such as polyether ether ketone resin and liquid crystal polymer, etc. Engineered plastics, glass, and a substrate with excellent adhesion without etching. be able to.

  Examples of the base material include self-adhesive soft synthetic resins such as polyolefin elastomers, polyethylene elastomers, polyurethane elastomers, silicon resins, butyl rubber, soft polyvinyl chloride, and fluorine resins.

  The shape of the substrate is not particularly limited, and examples thereof include a plate shape (including a sheet shape) and a film shape. In addition, examples of the base material include a molded product obtained by molding a resin by injection molding or the like. And by providing the plated product of the present invention on this molded product, for example, a decorative plated product for automobiles can be created, or on a film made of a polyimide resin, a polyether ether ketone resin, a liquid crystal polymer, or the like. For example, an electric circuit product can be produced by providing the plated product of the present invention as a whole or in a pattern.

  The primer layer of the present invention is not particularly limited. For example, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin. Phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicon resin, and the like.

  The method for applying the primer layer to the substrate is not particularly limited, and printing or coating can be performed using, for example, a gravure printing machine, an inkjet printing machine, dipping, spraying, a spin coater, a roll coater, a screen printing machine or the like.

  The thickness of the primer layer is preferably in the range of 0.1 to 50 μm. When the thickness of the primer layer exceeds 50 μm, sufficient drying may not be achieved, and viscosity may remain, and adhesion to the substrate and the coating layer may be inferior. Conversely, if it is less than 0.1, high adhesion to the coating layer may not be maintained.

  The primer layer coating used in the present invention contains an organic solvent. The organic solvent to be used is not particularly limited as long as it does not damage the fine particles and can disperse the fine particles. Preferred examples include aromatic hydrocarbons such as benzene, toluene and xylene.

  The reducing polymer fine particle used in the present invention is a π-conjugated double in an O / W type emulsion obtained by mixing and stirring an organic solvent, water, an anionic surfactant and a nonionic surfactant. It is produced by adding a monomer having a bond and subjecting the monomer to 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 conductive 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, and the reducing polymer fine particles in the organic solvent phase are present. 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 collect 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 reductive polymer fine particles dispersed in the organic solvent thus obtained can be used as the reductive polymer fine particle component of the coating as it is, after being concentrated or dried.

  Further, for example, commercially available reducing polymer fine particles may be used as a component of the coating material, instead of the reducing polymer fine particles produced as described above.

  The coating material used in the present invention is a coating material containing reducing fine polymer particles and a binder.

  Examples of the binder include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, acetic acid. Examples thereof include vinyl, ABS resin, polyurethane resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and silicon resin.

  The amount of the binder used is 0.1 to 10 parts by mass with respect to 1 part by mass of the reducing polymer fine particles. When the binder exceeds 10 parts by mass, metal plating does not precipitate, and when the binder is less than 0.1 parts by mass, the adhesion to the substrate is weakened.

  The paint used in the present invention contains an organic solvent. The organic solvent to be used is not particularly limited as long as it does not damage the fine particles and can disperse the fine particles. Preferred examples include aromatic hydrocarbons such as benzene, toluene and xylene.

  Furthermore, the coating material used in the present invention can be added with a resin such as a dispersion stabilizer, a thickening agent, and an ink binder, depending on the application, application object, and the like.

  The coating material prepared above is applied onto the primer layer, and a coating layer in which 60% or more of the reducing polymer fine particles are present in the upper half of the layer is formed.

  The coating method of the base coating material containing the reducing polymer fine particles and the binder on the primer layer is not particularly limited. For example, using a gravure printing machine, an ink jet printing machine, dipping, spraying, a spin coater, a roll coater, a screen printing machine, etc. Can be printed or coated.

  The constitution in which 60% or more of the reducing polymer fine particles are present in the upper half of the coating layer is achieved by drying over time under mild conditions after the coating is applied.

  Specific methods include, for example, drying at a low temperature of 30 to 60 ° C. for a long time, drying by gradually increasing the temperature from a low temperature of 30 to 60 ° C., or a low temperature of 30 to 60 ° C. And higher temperatures (for example, 100 to 130 ° C.) or two or more different temperatures (for example, 30 to 60 ° C. → 65 to 90 ° C. → 100 to 130 ° C.). Can do.

  When drying at two or more different temperatures, for example, when toluene is used as the organic solvent, it is dried at 40 ° C. for 10 minutes, then dried at 80 ° C. for 10 minutes, and then dried at 120 ° C. for 10 minutes. A configuration in which 60% or more of the fine particles are present in the upper half of the coating layer can be employed.

  As another method, after a primer is applied on the substrate, a coating composed of a reducing polymer and a binder is applied at a timing when the primer is cured by 50 to 90%, and dried to form a coating layer. A configuration in which 60% or more of the fine particles are present in the upper half can be employed. When this method is employed, an uncured primer, a reducing polymer, and a paint composed of a binder are mixed, so that there is an intermediate layer in which the primer and the paint are mixed during curing. Then, this intermediate layer is defined as a coating layer composed of a reducing polymer and a binder, and the primer layer is defined as a layer composed of 100% binder.

  The thickness of the coating layer is preferably 20 to 500 nm when the shape of the substrate is a film. If the thickness is less than 20 nm, the metal may not precipitate and a plating film may not be formed. If the thickness exceeds 500 nm, the coating strength may decrease.

  The thickness of the coating layer is preferably 100 nm to 50 μm when the shape of the substrate is a molded product. If the thickness is less than 100 nm, the metal may not precipitate and a plating film may not be formed. If the thickness exceeds 50 μm, the coating strength may decrease.

The amount of catalytic metal that can be adsorbed on the surface of the coating layer is preferably 0.1 μg / cm ² or more.

If the adsorption amount is less than 0.1 μg / cm ² , a uniform metal plating film may not be obtained, or metal may not precipitate and a plating film may not be formed.

  The plated product of the present invention can also be produced in the same manner by using fine particles that have been reduced by conducting conductive polymer fine particles as the reducing polymer fine particles.

  For example, the conductive polymer fine particles used are prepared by adding a monomer having a π-conjugated double bond to an O / W type emulsion obtained by mixing and stirring an organic solvent, water, and an anionic surfactant. The monomer can be produced by 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 conductive polymer fine particles obtained may have a conductivity humidity dependency.

  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 the conductive polymer fine particle component of the coating as it is, after being concentrated or dried.

  Further, for example, commercially available conductive polymer fine particles can be used as a component of the paint, instead of the conductive polymer fine particles produced as described above.

  After coating the above-mentioned coating material containing conductive polymer fine particles and a binder on a substrate and forming a layer in which 60% or more of the conductive polymer fine particles are present in the upper half of the layer, the fine particles are By performing a de-doping treatment for reducing, a coating layer in which 60% or more of the reducing polymer fine particles are present in the upper half of the layer is formed.

  Examples of the binder include the same ones as exemplified above, and the amount used is 0.1 to 10 parts by mass with respect to 1 part by mass of the conductive polymer fine particles. When the binder exceeds 10 parts by mass, metal plating does not precipitate, and when the binder is less than 0.1 parts by mass, the adhesion to the substrate is weakened.

  Moreover, the said coating material contains an organic solvent. The organic solvent to be used is not particularly limited as long as it does not damage the fine particles and can disperse the fine particles. Preferred examples include aromatic hydrocarbons such as benzene, toluene and xylene.

  Further, the coating material can be added with a resin such as a dispersion stabilizer, a thickening agent, an ink binder, or the like according to the application, application object, or the like.

  The coating material prepared as described above is applied onto the base material to form a layer in which 60% or more of the conductive polymer fine particles are present in the upper half of the layer.

  Examples of the substrate include those similar to those exemplified above.

  Examples of the application method to the substrate include the same ones as exemplified above. .

  The constitution in which 60% or more of the reducing polymer fine particles are present in the upper half of the coating layer is achieved by drying over time under mild conditions after the coating is applied.

  Specific methods include, for example, drying at a low temperature of 30 to 60 ° C. for a long time, drying by gradually increasing the temperature from a low temperature of 30 to 60 ° C., or a low temperature of 30 to 60 ° C. And higher temperatures (for example, 100 to 130 ° C.) or two or more different temperatures (for example, 30 to 60 ° C. → 65 to 90 ° C. → 100 to 130 ° C.). Can do.

  When drying at two or more different temperatures, for example, when toluene is used as the organic solvent, it is dried at 40 ° C. for 10 minutes, then dried at 80 ° C. for 10 minutes, and then dried at 120 ° C. for 10 minutes. A configuration in which 60% or more of the fine particles are present in the upper half of the coating layer can be employed.

  As another method, after a primer is applied on the substrate, a coating composed of a reducing polymer and a binder is applied at a timing when the primer is cured by 50 to 90%, and dried to form a coating layer. A configuration in which 60% or more of the fine particles are present in the upper half can be employed. When this method is employed, an uncured primer, a reducing polymer, and a paint composed of a binder are mixed, so that there is an intermediate layer in which the primer and the paint are mixed during curing. Then, this intermediate layer is defined as a coating layer composed of a reducing polymer and a binder, and the primer layer is defined as a layer composed of 100% binder.

  The thickness of the coating layer is preferably 20 to 500 nm when the shape of the substrate is a film. If the thickness is less than 20 nm, the metal may not precipitate and a plating film may not be formed. If the thickness exceeds 500 nm, the coating strength may decrease.

  The thickness of the coating layer is preferably 100 nm to 50 μm when the shape of the substrate is a resin molded product. If the thickness is less than 100 nm, the metal may not precipitate and a plating film may not be formed. If the thickness exceeds 50 μm, the coating strength may decrease.

  The layer formed using the conductive polymer fine particles is subjected to dedoping treatment in order to make the fine particles reducible.

  As the dedoping treatment, a reducing agent, for example, a borohydride compound such as sodium borohydride or potassium borohydride, an alkylamine borane such as dimethylamine borane, diethylamine borane, trimethylamine borane, triethylamine borane, hydrazine, etc. The method of processing and reducing with the solution to contain, or the method of processing with an alkaline solution is mentioned.

  It is preferable to treat with an alkaline solution from the viewpoint of operability and economy.

  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.

The amount of the catalytic metal that can be adsorbed on the surface of the coating layer in which the fine particles are made reducible by the dedoping treatment is set to 0.1 μg / cm ² or more.

If the adsorption amount is less than 0.1 μg / cm ² , a uniform metal plating film cannot be obtained, or no metal is deposited and a plating film is not formed.

  Although the base material with the coating film layer formed as described above is made into a plated product by an electroless plating method, the electroless plating method can be performed according to a generally known method.

  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 0.02% palladium chloride-0.01% 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.

  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, chromium, 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.

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

Production Example 1: Preparation of Paint (Paints 1-7) Containing Reducing Polypyrrole Fine Particles 0.42 mmol Anionic Surfactant Perex OT-P (Kao Corporation), Polyoxyethylene Alkyl Ether Nonionic Surfactant Emulgen 409P (Kao Co., Ltd.) 2.1mmol, toluene 50mL, and ion-exchange water 100mL were added, and it stirred until it emulsified, hold | maintaining at 20 degreeC. 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.

  The solid content of the reducing polypyrrole fine particles in the toluene dispersion obtained above was about 1.3%, but the reducing properties shown in Table 1 were obtained by adding binders A and B in various parts by mass. A paint containing polypyrrole fine particles was prepared.

Here, the binders A and B in Table 1 mean the following, and the amount of the binder used indicates the number of parts of the binder used with respect to 1 part by mass of the reducing polypyrrole fine particles.
A: Super Becamine J-820: Melamine resin (manufactured by Dainippon Ink & Chemicals, Inc.)
B: Byron 240: Polyester resin (manufactured by Toyobo Co., Ltd.)
C: Technodyne AH7052: Epoxy resin (manufactured by Taoka Chemical Co., Ltd.)

Production Example 2: Preparation of paint containing conductive polypyrrole fine particles (paint 8) 1.5 mmol of anionic surfactant Perex OT-P (manufactured by Kao Corporation), 50 mL of toluene, and 100 mL of ion-exchanged water are added and kept at 20 ° C. And stirred until emulsified. 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 polymer fine particles having a reducing performance dispersed in toluene. The solid content of the conductive polypyrrole fine particles in the toluene dispersion obtained here was about 1.2%. Superbeccamin J-820 (Dainippon Ink Chemical Co., Ltd.) was used as a binder here. 1 part by mass with respect to 1 part by mass of the conductive polypyrrole fine particles to obtain paint 8.

Production Example 3: Preparation of Paint (Paint 9) Containing Reducing Polyaniline Fine Particles Anionic Surfactant Perex OT-P (manufactured by Kao Corporation) 0.42 mmol, Sorbitan Fatty Acid Ester Nonionic Surfactant Rheodor SP-O30V (Kao) 0.424mmol, polyoxyethylene sorbidan fatty acid ester 2.12mmol (manufactured by Kao Corporation), toluene 50mL, and ion-exchanged water 100mL were added and stirred until emulsified while maintaining at 20 ° C. To the obtained emulsion, 21.2 mmol of aniline monomer was added and stirred for 1 hour, and then 4 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 polyaniline fine particles having reducing performance dispersed in toluene. The solid content of the reducing polyaniline fine particles in the toluene dispersion obtained here was about 1.4%. Superbeccamin J-820 (Dainippon Ink Chemical Co., Ltd.) was used as a binder here. 1 part by mass with respect to 1 part by mass of the reducing polyaniline fine particles to obtain paint 9.

Production Example 4: Using a soft film C as a base material, a primer layer is formed on the base material. Super Becamine J-820 (manufactured by Dainippon Ink Chemical Co., Ltd.) is coated as a primer on the base material. The film was dried at 120 ° C. for 10 minutes to produce a flexible film having a 100 nm thick primer layer.

Production Example 5: Using soft film D as a base material and forming a primer layer on the base material Byron 240: Polyester resin (manufactured by Toyobo Co., Ltd.) as a primer is coated on the base material, and 120 ° C. Was dried for 10 minutes to produce a flexible film having a 100 nm thick primer layer.

Production Example 6: Using a flexible film E as a base material, forming a primer layer on the base material, coating an epoxy resin (Aronmite AS-60, manufactured by Toagosei Co., Ltd.) as a primer on the base material, A soft film in which a primer layer having a thickness of 100 nm was formed by drying at 120 ° C. for 10 minutes was produced.

Production Example 7: Using resin molded product F as a base material, forming a primer layer on the base material A liquid containing an epoxy resin (manufactured by Taoka Chemical Industries, Ltd., Technodyne AH7052) as a primer on the base material A resin molded article having a primer layer having a thickness of 5 μm was produced by dipping into a phase and drying at 150 ° C. for 30 minutes.

Production Example 8: Coating layer is formed on soft films C, D, E on which primer layer is formed. Coating material 1 to 9 prepared above is coated on the primer layer, and as shown in Table 2, various coating layers are formed. A soft film having a coating layer having a film thickness was produced.

Production Example 9: Coating layer is formed on resin molded product F on which a primer layer is formed. As shown in Table 2, the primer layer is dipped into a liquid phase containing the coating material 5 prepared as described above. A resin molded product having a 5 μm coating layer was produced.

  For coating films 1 to 7 and 10 to 14 in Table 2, after coating the paint, it was dried at 40 ° C. for 10 minutes, then dried at 80 ° C. for 10 minutes, and then dried at 120 ° C. for 10 minutes. The fine particles present in the upper half of the film layer were 60% or more, and the same operation was performed on the coating film 9 so that the fine particles present in the upper half of the conductive polymer fine particle layer were 60% or more. Further, in the coating film 8, after dipping, drying at 40 ° C. for 10 minutes, then drying at 80 ° C. for 10 minutes, and then drying at 120 ° C. for 10 minutes to remove fine particles present in the upper half of the coating film layer. 60% or more.

  Moreover, in the coating films 15 and 16 in Table 2, after coating with a paint, the coating film layer was dried at 120 ° C. for 5 minutes to form a coating film layer in which fine particles were uniformly dispersed.

The base materials C, D, and E in the table mean the following.
C: Soft film PET, trade name Cosmo Shine A4100, manufactured by Toyobo Co., Ltd. D: Soft film PP, trade name OP U-0, manufactured by Tosero Co., Ltd. E: Soft film LCP, trade name VecstarFA, Kuraray ( Co., Ltd. F: resin molded product PEEK, trade name VESTAKEEP4000CF30, EVONIK Co., Ltd.

Production Example 9: Production of plated product by chemical electroless plating method A film (coating films 1 to 7 and 9 to 16) and a molded article (coating film 8) on which the coating layer produced above was formed were prepared in the following manner. After being immersed in a 02% palladium chloride-0.01% hydrochloric acid aqueous solution at 35 ° C. for 5 minutes, it was washed with tap water. Next, the film was dipped in an electroless copper plating bath ATS Adcopper IW bath (Okuno Pharmaceutical Co., Ltd.), and dipped at 35 ° C. for 10 minutes for copper plating. The coating film 9 was immersed in a 1M aqueous sodium hydroxide solution at 35 ° C. for 5 minutes, surface-treated to form a coating film layer, and then the same operation was performed. The plated products produced from the coating films 1 to 14 were designated as Examples 1 to 14, respectively, and the plated products produced from the coating films 15 to 16 were designated as Comparative Examples 1 and 2, respectively.

  A schematic photograph of a cross-sectional view of the plated products of Examples 1 to 14 taken with a transmission electron microscope (manufactured by JEOL Ltd .: JEM-1200 EXM) is shown in FIG. FIG. 2 shows a schematic photograph of a cross-sectional view of the plated product of No. 1 and 6 taken with a transmission electron microscope (manufactured by JEOL Ltd .: JEM-1200 EXM).

Test example 1
Various evaluation tests were performed on the plated products of Examples 1 to 14 and Comparative Examples 1 and 2 manufactured above, and the results are summarized in Table 3. The evaluation test items, evaluation methods and evaluation criteria are as follows.

-Plating appearance The state of the plating film was observed visually, and the substrate exposed area was measured. The evaluation criteria were as follows.
○: Completely coated, no substrate exposure Δ: About 50% substrate exposure ×: 100% substrate exposure

-Plating film thickness Three points on the plating surface were measured with an electrolytic film thickness meter CT-1 (manufactured by Denso Co., Ltd.), and the average value was defined as the film thickness.

-Tape test According to the JIS H8504 tape test method, 100 pieces of 2 mm square strips were made with a cutter, and then a peeling test with a tape was performed. The evaluation criteria were as follows.
○: No peeling Δ: About 50% peeling ×: 90% or more peeling

-Peel strength Measurement was performed according to JIS C6471.

-Reducing fine particle abundance ratio The coating film was cut into a width of 60 nm using an ultramicrotome (manufactured by Leica Co., Ltd .: Ultracut S), and a transmission electron microscope (manufactured by JEOL Ltd .: JEM-1200 EXM). ) From the area ratio of the particle part and the binder part. In addition, the value which calculated the average value after creating 10 samples and measuring it similarly was used.

It is the figure which modeled the transmission electron microscope photograph of sectional drawing of the plated object of Example 1 thru | or 14. It is the figure which modeled the transmission electron micrograph of sectional drawing of the plated object of the comparative examples 1 and 2. FIG.

Explanation of symbols

1: Base film 2: Primer layer 3: Coating layer 4: Metal plating film 5: Reducing polymeric fine particles

Claims (3)

  A primer layer is formed on a substrate, and a coating layer is formed thereon by applying a base coating containing reducing polymer fine particles and a binder, or conductive polymer fine particles and a binder on the primer layer. The coating is produced by applying a base coating material containing, forming a coating layer by dedoping the conductive polymer fine particles, and chemically plating a metal film on the coating layer from an electroless plating solution A plated article in which 60% or more of the reducing polymer fine particles are present in the upper half of the coating layer.   When the shape of the substrate is a film, the binder is present in an amount of 0.1 to 10 parts by mass with respect to 1 part by mass of the reducing polymer fine particles, and the thickness of the coating layer is 20 nm to 500 nm. The plated product according to claim 1, wherein:   When the shape of the base material is a molded product, the binder is present in an amount of 0.1 to 10 parts by weight with respect to 1 part by weight of the reducing polymer fine particles, and the thickness of the coating layer is 100 nm to 50 μm. The plated product according to claim 1, wherein: