TWI438301B - Metal plated article of molded form and method for producing it - Google Patents

Description

Plating of molded article and method of producing the same

The present invention relates to a plated product of a molded article produced by an electroless plating method and a method for producing the same, and more particularly to a metal plating film which is excellent in productivity and excellent in adhesion to a substrate. The surface of the film has no exposed portion (unevenness) and is a uniform plated product of a molded article produced by electroless plating and a method for producing the same.

In particular, it is suitable for plating for decoration such as electromagnetic wave shielding applied to a casing, and decorative parts such as automobile parts.

In JP-A-2007-100174 (Patent Document 1), it is disclosed that a resin molded body (made of a polystyrene resin or a polystyrene-based resin) is formed by electroless plating treatment. An excellent adhesion method for plating a film.

However, in this method, it is necessary to perform a number of steps before forming a plating film on the above-mentioned resin molded body by electroless plating.

In other words, as a pretreatment method, it is necessary to obtain (1) a swelling step for improving the hydrophilicity (a good adhesion and appearance of the plating film) in order to obtain an appropriate roughening during the etching treatment. (2) a first etching treatment which is treated with an aqueous solution containing permanganate, and (3) containing a material selected from the group consisting of inorganic acid and perchloric acid, to achieve moderate coarsening and hydrophilicity of the surface of the resin molded body A second etching treatment in which an aqueous solution of at least one of the groups consisting of an acid and a peroxyacid is treated.

Further, in Patent Document 1, it is described that in the case where the surface of the resin molded body is seriously contaminated, the degreasing treatment is performed before the swelling step, and the permanganate remaining after the second etching step is removed. The treatment with an aqueous solution containing a reducing agent is carried out as necessary.

Further, in the examples of Patent Document 1, it is apparent that a plating film having excellent adhesion is not formed without performing the above-described complicated etching treatment or the like.

Patent Document 1: JP-A-2007-100174

An object of the present invention is to provide a metal plating film which is excellent in productivity and which does not require the complicated etching treatment described in Patent Document 1, and which has excellent adhesion to a substrate, and has no exposed portion on the surface of the film ( A plating material of a molded article produced by electroless plating and a method for producing the same, which is uniform.

The present inventors have found that a coating film containing a reducing polymer fine particle is applied onto a resin film such as a 2-axis stretched PET film or a PI film to form a coating layer or a conductive coating before the electroless plating treatment. After the coating layer is formed by the coating of the polymer microparticles, the polymer microparticles in the coating layer are reduced by dedoping by alkali treatment or the like, and the etching treatment is not performed, and the etching treatment is not performed. A metal plating film having excellent adhesion to the substrate can be obtained, and the surface of the film has no exposed portion (unevenness) and is a uniform plating material.

However, as a result of performing plating by a molded article having a shape having irregularities, for example, it is found that the formation of the coating layer is performed by spraying or dipping due to the shape of the unevenness, and thus, the resin film is formed. In the case where the coating layer is formed on the upper side, it is difficult to form the coating layer uniformly even if the film thickness is not increased. Therefore, the coating layer (for example, 0.5 μm or more) having a certain thickness is formed to perform electroless plating. In this case, the metal plating film having excellent adhesion to the substrate has no exposed portion (unevenness) on the surface of the film, and it is difficult to obtain a uniform plating material.

Therefore, the inventors of the present invention have obtained a metal plating film having excellent adhesion to a substrate even when a molded article having a coating layer having a certain thickness is formed, and there is no exposed portion on the surface of the film ( As a result of careful review of the method of uniform plating, it has been found that as long as the mass ratio of the polymer fine particles and the binder constituting the coating layer is set to a certain range, the electroless plating is applied to the coating film. The size of the catalytic metal block on the layer is set to be less than or equal to a certain extent, and the amount per unit area of the catalytic metal adsorbed on the surface of the coating layer is set to a specific range, even if it is formed to a certain extent In the molded article of the coating layer (0.5 to 100 μm), a metal plating film having excellent adhesion to the substrate can be obtained, and the surface of the film has no exposed portion (unevenness) and is a uniform plating material. The present invention has been completed.

That is, the present invention relates to

(1) A plating material which forms a coating layer containing conductive polymer microparticles and a binder on a surface of a molded article, and is formed by adsorption of a catalytic metal by electroless plating on the coating layer. Metal plating film plating, and

The binder is present in an amount of 0.1 to 10 parts by mass based on 1 part by mass of the conductive polymer fine particles, and the thickness of the coating layer is 0.5 to 100 μm, and the size of the catalytic metal block adsorbed on the coating layer is is 150nm or less, and the amount adsorbed per unit area of the metal from the catalyst layer of the coating film was 0.1μg / cm ² to 3.0μg / cm ^{2, (2)} the above (1) according to the plating, wherein 60% or more of the conductive polymer fine particles are present in the upper half of the coating layer, and the conductive polymer fine particles have an average particle diameter of 10 to 100 nm. (3) A method of producing a plating material The electroless plating of the metal film is carried out by electroless plating, and A) the reductive polymer microparticles and the binder of 0.1 to 10 parts by mass based on 1 part by mass of the reducing polymer microparticles are applied to the molded article. a step of forming a coating layer having a thickness of 0.5 to 100 μm, B) a step of forming a metal plating film by electroless plating on the coating layer by adsorption of a catalytic metal, and adsorbing a catalyst metal block on the above coating layer Small as 150nm or less, and the adsorbed amount per unit area of the metal from the catalyst layer of the coating film formed as the method of 0.1μg / cm ² to 3.0μg / cm ² of step, (4) In the method according to the above (3), the reducing polymer microparticles are subjected to dedoping treatment to obtain reductive fine particles.

Here, the term "the size of the catalytic metal block" used herein means a block in which the catalyst metal deposited on the surface of the coating layer is agglomerated, and a scanning micrograph of the surface of the coating layer is in the range of 20 μm × 20 μm. The catalyst metal blocks appearing are selected from the larger ones, and the average size of the blocks is measured.

In addition, the size of the block means the value obtained by actually measuring the length of the longest side of each block and the length of the shortest side.

In addition, the term "thickness of the coating layer" as used above means that the thickest point and the thinnest point of the coating layer on the molded article are selected, and the thickness is measured by a micrometer. The average value.

According to the present invention, even in the case of having a concavo-convex shape, it is possible to form a coating layer having a certain thickness to a certain extent, and it is excellent in productivity, that is, it does not require complicated etching treatment, etc., by electroless plating. A metal plating film having excellent adhesion to a substrate is produced by a method, and a uniform plating material is formed on the surface of the film without an exposed portion (unevenness).

The above-described effects of the plating material of the present invention are obtained by adsorbing the catalyst on the coating layer by setting the mass ratio of the polymer fine particles constituting the coating layer to the binder to a certain range and performing electroless plating. The size of the metal block is set to be less than or equal to a certain value, and the amount per unit area of the catalyst metal adsorbed on the surface of the coating layer is set to a specific range. For this reason, it can be considered as follows.

In the plating method described in Document 1, for example, after the etching treatment, the surface of the substrate is treated with stannous chloride, and the palladium of the catalytic metal is adsorbed by the adsorption of the tin on the surface.

At this time, since the adsorbed palladium does not have a chemical action on the substrate, the adhesion between the substrate and the palladium is low, and thus the formed plating film tends to be poor in adhesion, however, because the substrate Since the adhesion to palladium is low, palladium tends to be uniformly adsorbed on the entire substrate, and therefore the size of palladium is rarely 10 nm or more.

On the other hand, in the present invention, the palladium is chemically bonded to the polymer fine particles by the reductive property of the polymer fine particles present on the surface of the coating layer, and the palladium is chemically bonded to the polymer fine particles (in combination, Since the polymer fine particles become electrically conductive and the adhesion between the substrate and palladium is high, it is easy to form a plating film having excellent adhesion. However, since the palladium is only collected on the surface of the coating layer. Since the polymer microparticles are adsorbed with high density, the proportion of the reducing polymer microparticles present on the surface is small, and the catalyst metal, for example, palladium or the like, aggregates and becomes large, and the scanning microscope of FIG. As shown in the photograph, the agglomeration of the palladium becomes large, and if it exceeds 150 nm, the palladium becomes easily peeled off from the surface of the substrate, and the aggregation is likely to cause aggregation failure. As a result, the plating film is densely formed. Reduced sexuality.

Therefore, it is considered that by setting the mass ratio of the polymer fine particles constituting the coating layer to the binder to a certain range, the ratio of the reducing polymer fine particles existing on the surface of the coating layer is maintained within a certain range, and adsorption is performed. The size of the catalytic metal block on the coating layer is controlled to a specific size or less (150 nm or less: for example, the scanning micrograph of Fig. 2), and the adhesion caused by the above is avoided, and the excellent adhesion is effective. By.

In addition to the above, although the size of the catalytic metal adsorbed on the coating layer is controlled to a specific range, if the amount per unit area of the catalytic metal adsorbed on the coating layer becomes excessive, it is considered that the contribution is subsidized. The adhesion between the adhesive of the adhesiveness and the metal plating film is reduced, whereby the adhesion between the coating layer and the metal plating film is lowered.

Therefore, by setting the amount per unit area of the catalyst metal adsorbed on the surface of the coating layer to a specific range, it is considered that the above-mentioned decrease in adhesion is avoided, and it contributes to exhibiting excellent adhesion.

In addition, the size of the catalytic metal block adsorbed on the coating layer is set to a specific range, and the amount per unit area of the catalytic metal adsorbed on the surface of the coating layer is set to a specific range. It is easily controlled by adjusting the concentration of the catalyst metal of the catalyst liquid used for the treatment, the processing temperature, and the processing time.

The coating layer in the plating material of the present invention is such that the ratio of the presence of the reducing polymer fine particles in the upper half is higher, for example, in which 60% or more of the particles in the fine particles are present in the upper half. The formation is preferred, whereby the presence ratio of the organic polymer (adhesive) on the lower side of the coating layer is increased, and the adhesion between the substrate and the coating layer is improved, so that the result is metal plating. The adhesion between the film and the substrate is improved.

Further, the presence ratio of the reducing polymer fine particles in the vicinity of the surface of the coating layer becomes high, so that the amount of adsorption of the catalytic metal on the surface becomes increased, and the metal plating film formed thereby is coated even in a relatively thin manner. The film layer is also not exposed (uneven) and can be made uniform.

In the plating material of the present invention, not only the reducing polymer fine particles but also the conductive polymer fine particles can be produced in the same manner. In this case, it is necessary to dedoping the conductive polymer fine particles to be reducible before electroless plating, and in the plating material of the present invention, even a film thickness of 0.5 to 100 μm is required. The coating layer also maintains excellent adhesion and uniformity.

In addition, the ratio of the presence of the polymer fine particles in the upper half of the coating layer is high, for example, 60% or more of the particles are present in the upper half, and only the reducing polymer particles or the conductive polymer particles are organically The design of the drying temperature and time after coating the substrate on the polymer (adhesive) can be easily achieved.

Further, the plating material of the present invention is reduced by a catalytic metal such as palladium by, for example, coating a layer containing a reducing polymer fine particle formed on a substrate. Adsorption is performed by forming a metal plating film on a coating layer on which a catalytic metal such as palladium is adsorbed. In this case, reduction of a catalytic metal such as palladium and adsorption to a polymer fine particle, such as polypyrrole, are considered to be In the state shown in the figure below.

That is, the palladium ions are reduced by the reducing polymer microparticles (polypyrrole), and the palladium (metal) is adsorbed on the polymer microparticles, whereby the polymer microparticles (polypyrrole) are ionized, that is, It is in a state of being doped with palladium, and as a result, it exhibits conductivity.

The invention will be described in further detail.

The plating method of the present invention can be produced by a method of chemically plating a metal film by an electroless plating solution, and is

A) a step of applying a coating layer containing a reducing polymer fine particle and a binder of 0.1 to 10 parts by mass based on 1 part by mass of the reducing polymer fine particle on a molded article to form a coating layer having a thickness of 0.5 to 100 μm And B) forming a metal plating film by electroless plating on the coating layer by adsorption of a catalytic metal, and setting the size of the catalytic metal block adsorbed on the coating layer to 150 nm. hereinafter, the manufacturing and the adsorbed amount per unit area of the metal from the catalyst layer of the coating film formed as the method of 0.1μg / cm ² to 3.0μg / cm ² of the step.

In the present invention, a molded article is used as a substrate, and specific examples thereof include a PET resin, an LCP resin, a PPS resin, a PI resin, a PEI resin, a PEEK resin, and an olefin resin (for example, a PP resin, a COC resin, and a COP resin). Etc.), PC resin, ABS resin, ABS/PC resin, AS resin, HIPS resin, PS resin, MS resin, PA resin, PC/ASA resin, PPA resin, ceramics such as glass or alumina, metals such as magnesium alloy, and the like.

For the plating of the molded article, for example, plating for electromagnetic wave shielding applied to the casing, plating for decoration such as automobile parts, and plating for interior decoration, etc., may be mentioned.

The reducing polymer fine particles used in the present invention are not particularly limited as long as they have a π-conjugated double bond having a conductivity of less than 0.01 S/cm, and examples thereof include polyacetylene and poly Anthracene, polyparaphenylene, polyparaphenylenevinylene, polypyrrole, polyaniline, polythiophene, and various derivatives thereof may, for example, be polypyrrole.

Further, the reducing polymer fine particles are preferably polymer fine particles having a conductivity of 0.005 S/cm or less.

The reducing polymer fine particles can be used by synthesizing a monomer having a π-conjugated double bond, and can also be used as a commercially available reducing polymer fine particle.

The average particle diameter of the reducing polymer microparticles is preferably from 10 to 100 nm.

The binder used in the present invention may, for example, be polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polyester, polyfluorene, polyphenylene ether, polybutadiene, poly( N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamine, ethyl cellulose, vinyl acetate, ABS resin, polyurethane resin, melamine resin, unsaturated polyester Resin, alkyd resin, epoxy resin, enamel resin, and the like.

As the binder used in the present invention, an organic polymer having a carboxyl group can be used, and in particular, a styrene resin is used as a substrate, and in this case, as long as it is a compound having a carboxyl group in a molecule, It is not particularly limited, and examples thereof include an acrylic resin having a carboxyl group in a molecule, a vinyl chloride resin, an urethane resin, a styrene resin, and the like.

The Tg of the above resin is usually 60 ° C or higher, preferably 70 ° C or higher.

Further, in the case of using a mixture of resins, the organic polymer having a carboxyl group is not particularly limited as long as at least one of the above resins has a carboxyl group, and all of the resins do not have a carboxyl group.

Further, the amount of the carboxyl group in the case where the above-mentioned organic polymer having a carboxyl group is used is preferably such that the amount of the carboxyl group in the solid component in the coating material for forming the coating layer is in the range of 0.01 to 4.0 mmol/g. .

The above amount is preferably in the range of from 0.1 to 2.4 mmol/g.

The amount of the binder to be used is 0.1 parts by mass to 10 parts by mass based on 1 part by mass of the reducing polymer fine particles. When the amount of the binder exceeds 10 parts by mass, metal plating does not precipitate, and if the binder is less than 0.1 part by mass, the adhesion to the substrate is weak.

The coating material for forming a coating layer may contain a solvent in addition to the reducing polymer fine particles and the binder.

In the solvent, the reducing polymer fine particles are not damaged, and the reducing polymer fine particles are dispersed, and the binder is not particularly limited, and the molded article is a substrate. Largely dissolved people are not good. However, even a solvent which largely dissolves a molded article can be used by mixing with another solvent having low solubility to lower the solubility.

The organic solvent to be used may, for example, be an aliphatic ester such as butyl acetate, an aromatic solvent such as toluene or a ketone such as methyl ethyl ketone, a cyclic saturated hydrocarbon such as cyclohexane or a chain such as n-octane. Saturated hydrocarbons, chain saturated alcohols such as methanol, ethanol, and n-octanol, aromatic esters such as methyl benzoate, aliphatic ethers such as diethyl ether, and the like.

In addition, when a dispersion liquid previously dispersed in an organic solvent is used as the reducing polymer fine particles, the organic solvent used in the dispersion liquid may be used as a part or all of a solvent of the coating material.

In addition, the above-mentioned coating material may be added with a resin or a pigment such as a dispersion stabilizer, a tackifier, or an ink binder, depending on the application or the object to be coated.

The coating material prepared as described above is applied onto a molded article of a substrate, and if necessary, it is dried by heating or the like to form a coating layer.

The coating method of the above coating material is not particularly limited as long as it can uniformly form a coating layer, and for example, a spray coating, a screen printing machine, a gravure printing machine, an elastic printing machine, an ink jet printer, or an offset printing plate can be used. Printing or coating by a printing machine, a dipping, a spin coater, a roll coater, or the like is preferably applied to a molded article having irregularities, and is preferably sprayed or immersed.

The drying conditions are also not particularly limited and can be carried out at room temperature or under heating.

The drying temperature in the case of using a resin substrate having a low Tg as the substrate is preferably carried out at a temperature lower by 5 to 15 ° C than the Tg of the resin substrate to be used.

In the upper half of the coating layer, the ratio of the presence of the reducing polymer fine particles is increased, for example, 60% or more of the particles in the fine particles are formed in the upper half, and such a configuration is preferable. It is achieved by coating the coating material and drying it under mild conditions over time.

For the specific method, it can be achieved, for example, by raising the temperature at a low temperature of 30 to 60 ° C and drying for a long time, and slowly raising the temperature from a low temperature of 30 to 60 ° C and drying.

In the case where the temperature is different at two or more stages, for example, when toluene is used as the organic solvent, it is dried at 60 ° C for 10 minutes, dried at 60 ° C for 10 minutes, and then dried at 80 ° C for 10 minutes to become fine particles. More than 60% of the particles are present in the upper half of the coating layer.

The thickness of the formed coating layer is in the range of 0.5 μm to 100 μm.

When the thickness of the coating layer is too small, it may be difficult to form the coating layer uniformly. Therefore, the thickness of the coating layer is preferably 0.5 μm or more. In addition, even if the film thickness of the coating layer is increased, for example, the coating film strength can be maintained even if it exceeds 100 μm. However, if the coating layer is too thick, the coating film strength is lowered depending on the type of the binder, the blending ratio, and the like. In other words, the thickness of the coating layer is preferably set to 100 μm or less.

The substrate on which the coating layer containing the reducing polymer fine particles produced as described above is formed into a plating material by electroless plating, and the electroless plating method can be carried out according to a generally known method.

In other words, the substrate is immersed in a catalyst liquid for adhering a catalytic metal such as palladium chloride, and then washed with water or the like, and immersed in an electroless plating bath to obtain a plating material.

The catalyst liquid contains a solution of a noble metal (catalyst metal) having catalytic activity for electroless plating, and examples of the catalyst metal include palladium, gold, platinum, rhodium, etc., and the metals are monomers or The compounds are all acceptable, and the viewpoint of the stability of the catalytic metal is preferably a palladium compound, particularly preferably palladium chloride.

A specific 0.05% palladium chloride-0.005% aqueous hydrochloric acid solution (pH 3) can be mentioned as a suitable specific catalyst liquid.

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 are, as a result, conductive polymer microparticles.

Further, in the step of adsorbing the above-mentioned catalytic metal such as palladium chloride on the coating layer, the size of the adsorbed catalytic metal block is controlled to be 150 nm or less, and each unit of the above-mentioned catalytic metal adsorbed is adsorbed. The amount of the area is controlled to be from 0.1 μg/cm ² to 3.0 μg/cm ² .

When the size of the adsorbed catalytic metal block exceeds 150 nm, the catalytic metal is liable to be peeled off from the surface of the substrate, and aggregation failure is likely to occur, and as a result, the adhesion of the plating film is lowered.

Further, the amount adsorbed per unit area of the catalytic metal of less than 0.1μg / ² cm & lt when, unevenness does not uniformly form the metal plating film, in the case where more than 3.0μg / cm ^2, the can This causes a decrease in the adhesion between the metal plating film and the coating layer.

In addition, the size of the adsorbed catalytic metal block is set to be 150 nm or less, and the amount per unit area of the adsorbed catalytic metal is set to be 0.1 μg/cm ² to 3.0 μg/cm ² , which can be adjusted by The concentration of the catalyst liquid, the processing temperature, and the processing time are easily controlled.

That is, the size of the adsorbed catalyst metal can be mainly controlled by the concentration of the catalytic metal in the above-mentioned catalyst liquid. If the concentration is lowered, the catalytic metal becomes small, and if the concentration is increased, the catalyst is increased. Metals tend to become larger.

The amount of the adsorbed catalyst metal can be mainly controlled by the treatment time of the solution. If the treatment time is shortened, the amount of the adsorbed catalyst metal is reduced. If the treatment time is prolonged, the adsorbed catalyst is adsorbed. The amount of metal tends to increase.

Further, the treatment temperature mainly controls the speed of the adsorption, and if the treatment temperature is lowered, the adsorption rate of the catalytic metal is lowered, and if the treatment temperature is increased, the adsorption speed tends to increase, so that the treatment temperature rises. The tendency to increase the amount of adsorbed catalyst metal is greater than the increase in the adsorbed catalyst metal.

By the above treatment, the substrate on which the catalyst metal is adsorbed on the coating layer is immersed in the plating solution for depositing the metal, thereby forming an electroless plating film.

The plating solution is not particularly limited as long as it is a plating solution which is usually used for electroless plating.

That is, metals, copper, gold, silver, nickel, and the like which can be used for electroless plating are all applicable, and copper is preferred.

Specific examples of the electroless copper plating bath include, for example, ATS ADDCOPPER IW bath (manufactured by 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 plating material is preferably aged at room temperature or under heating for several hours or more, for example, two hours or more, and the substrate to be used has a low Tg such as a styrene resin substrate. It is preferred to be aged at a temperature range of 5 to 15 ° C lower than the Tg.

According to the above-described method, it is excellent in productivity, that is, a plating product of a molded article produced by electroless plating, which is not required to be subjected to complicated etching treatment, and has a metal plating excellent in adhesion to a substrate. The film was uniform in the absence of an exposed portion (unevenness) on the surface of the film.

Further, the present invention relates to a method for producing a reducing polymer fine particle by dedoping a conductive polymer fine particle.

In the production method, the conductive polymer fine particles contained in the coating layer are dedoped to form reducing polymer fine particles by forming the coating layer by using the conductive polymer fine particles instead of the reducing polymer fine particles. Thereafter, the adsorption of the catalyst metal is achieved by forming a metal plating film by electroless plating.

Specifically, it consists of the following steps C) to E).

C) a step of applying a coating containing a conductive polymer fine particle and a binder of 0.1 to 10 parts by mass based on 1 part by mass of the conductive polymer fine particle on a molded article to form a coating layer having a thickness of 0.5 to 100 μm And D) a step of dedoping the conductive polymer microparticles contained in the coating layer to form a reducing polymer microparticle, and E) adsorbing the catalytic metal on the coating layer by electroless plating. a step of forming a metal plating film, and setting a size of the catalyst metal block adsorbed on the coating film layer to 150 nm or less, and an amount per unit area of the catalytic metal adsorbed on the coating film layer as 0.1μg / cm ² to 3.0μg / cm ² of step

The above step C) can be carried out under the same conditions as the above-mentioned step A) except that the reducing polymer fine particles are replaced by the conductive polymer fine particles.

The conductive polymer fine particles used in the above-mentioned production method are not particularly limited as long as they are conductive polymers having a π-conjugated double bond, and examples thereof include polyacetylene and polyacene. Polyparaphenyl, polystyrene, polypyrrole, polyaniline, polythiophene, and various derivatives thereof may, for example, be polypyrrole.

The conductive polymer fine particles can be used by synthesizing a monomer having a π-conjugated double bond, and can also be used in commercially available conductive polymer fine particles.

The average particle diameter of the above-mentioned reducing polymer fine particles is preferably from 10 to 100 nm.

The thickness of the formed coating layer is in the range of 0.5 μm to 100 μm.

When the thickness of the coating layer is too small, it may be difficult to form the coating layer uniformly. Therefore, the thickness of the coating layer is preferably 0.5 μm or more. In addition, even if the film thickness of the coating layer is increased, for example, the coating film strength can be maintained even if it exceeds 100 μm. However, if the coating film layer is too thick, the coating film strength may be lowered depending on the type or blending ratio of the binder. Therefore, the thickness of the coating layer is preferably set to be 100 μm or less.

The dedoping treatment in the step D) may, for example, be a boron hydride compound containing a reducing agent such as sodium borohydride or potassium borohydride, dimethylamine borane, diethylamine borane or trimethylamine borane. A method of reducing a solution of an alkylamine borane such as triethylamine borane or a hydrazine or the like, or a method of treating with an alkaline solution.

From the standpoint of operability and economy, it is preferred to treat it with an alkaline solution.

In particular, a layer formed by using conductive polymer microparticles can be dedoped by a short-time alkali treatment.

For example, it is treated in a 1 M 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 above step E) can be carried out under the same conditions as the above step B).

Further, the present invention relates to a plating material which can be produced by the above-described manufacturing method to form a coating layer containing conductive polymer microparticles and a binder on the surface of a molded article, and electroless plating on the coating layer. The coating forms a plating of a metal plating film by adsorption of a catalytic metal, and

The binder is present in an amount of 0.1 to 10 parts by mass based on 1 part by mass of the conductive polymer fine particles, and the thickness of the coating layer is 0.5 to 100 μm, and the size of the catalytic metal block adsorbed on the coating layer is The amount of the catalyst metal per unit area of 150 nm or less and adsorbed on the coating layer is from 0.1 μg/cm ² to 3.0 μg/cm ² .

In addition, it is preferable that 60% or more of the particles of the conductive polymer fine particles are present in the upper half of the coating film layer, and the conductive polymer fine particles have an average particle diameter of 10 to 100 nm.

The "size of the catalyst metal block" in the present invention means a block in which the catalyst metal is deposited on the surface of the coating layer, and the catalyst shown in the range of 20 μm × 20 μm on the surface of the coating layer. The metal block is selected from the larger 10, and the average size of the block is measured.

In addition, the size of the block means the value obtained by actually measuring the length of the longest side of each block and the length of the shortest side. Further, the "thickness of the coating layer" in the present invention means that the thickest point and the thinnest point of the coating layer on the molded article are selected, and the average value is measured by the micrometer. .

Further, in the plating material of the present invention, a primer layer may be provided on the surface of the molded article in order to improve the adhesion between the surface of the molded article and the coating layer.

The formation of the primer layer may be a method of applying a primer coating on the surface of a molded article, forming a smooth coating film, or laminating a resin film formed by a primer coating on the surface of the molded article. Method, etc.

The primer coating material is not particularly limited as long as it has good adhesion to the molded article and/or has good adhesion to the coating layer formed on the primer layer.

For the above primer coating, the same compound as that used for the formation of the coating layer can be used.

As described above, when the same compound as the binder used for the formation of the coating layer is used as the primer coating, the primer layer is integrated with the coating layer, and as a result, the high adhesion is effective. good.

Examples of the above compounds include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polyester, polyfluorene, polyphenylene ether, polybutadiene, and poly(N-vinyl). Carbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamine, ethyl cellulose, vinyl acetate, ABS resin, polyurethane resin, melamine resin, unsaturated polyester resin, alkyd Resin, epoxy resin, enamel resin, etc.

Hereinafter, a specific method for producing conductive or reducing polymer fine particles which can be used for producing the plating material of the present invention will be described.

(1) Method for producing reduced polymer microparticles

The reducing polymer fine particles may be added to the O/W type emulsion obtained by mixing an organic solvent and water with an anionic surfactant and a nonionic surfactant, and having a π-conjugated double bond. The monomer is produced by oxidative polymerization of the monomer.

The monomer having a π-conjugated double bond is not particularly limited as long as it is used for producing a reducing polymer, and examples thereof include pyrrole, N-methylpyrrole, and N- Ethylpyrrole, N-phenylpyrrole, N-naphthopyrrole, N-methyl-3-methylpyrrole, N-methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N- Phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-n-propoxypyrrole, 3-n-butoxypyrrole, 3-phenylpyrrole, 3-tolylpyridylpyrrole, 3-naphthylpyrrole, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3 Pyrrole derivatives such as dimethylaminopyrrole, 3-diethylaminopyrrole, 3-diphenylaminopyrrole, 3-methylphenylaminopyrrole and 3-phenylnaphthylaminopyrrole, aniline, O-chloroaniline, m-chloroaniline, p-chloroaniline, o-methoxyaniline, m-anisidine, p-methoxyaniline, o-ethoxyaniline, m-ethoxyaniline, p-ethoxyaniline, ortho Aniline derivatives such as aniline, 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-decylthiophene, 3-positive Thiophene derivatives such as mercaptothiophene, 3-n-undecylthiophene, 3-n-dodecylthiophene, 3-methoxythiophene, 3-naphthyloxythiophene and 3,4-ethylenedioxythiophene, suitable Examples thereof include pyrrole, aniline, thiophene, and 3,4-ethylenedioxythiophene. Preferred examples thereof include pyrrole.

Further, in the anionic surfactant used in the above production, various substances may be used, and those having a plurality of hydrophobic terminals (for example, those having a branched structure of a hydrophobic group or a complex hydrophobic group) are preferred. By using such an anionic surfactant having a plurality of hydrophobic terminals, a stable micelle can be formed, and the separation of the aqueous phase and the organic solvent phase after the polymerization is smooth, and the reduction in the organic solvent phase can be easily obtained. Polymer microparticles.

Even among the anionic surfactants having a plurality of hydrophobic terminals, sodium di-2-ethylhexyl sulfosuccinate (4 hydrophobic ends), di-2-ethyloctyl sulfosuccinate ( Four hydrophobic terminals and two branched chain alkylbenzene sulfonates (two hydrophobic ends) can be suitably used.

The amount of the anionic surfactant in the reaction system is preferably from less than 0.05 mol, more preferably from 0.005 mol to 0.03 mol, per 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 obtained fine particles exhibit conductivity. Therefore, in order to perform electroless plating using the above, a step of dedoping is necessary.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, alkyl glucosides, glycerin fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Polyoxyethylene fatty acid esters, fatty acid alkanolamines, polyoxyethylene alkylphenyl ethers. These may be used in combination of one or more of them. It is particularly preferable to form an O/W emulsion in a stable manner.

The amount of the nonionic surfactant in the reaction system is preferably 1 mol with respect to the monomer having a π-conjugated double bond, and 0.2 mol or less with the anionic surfactant, more preferably 0.05~. 0.15 mol. When the yield is less than 0.05 mol, the yield or dispersion stability is lowered. On the other hand, when it is 0.2 mol or more, separation of the aqueous phase and the organic solvent phase after polymerization becomes difficult, and a reducing polymer in the organic solvent phase cannot be obtained. Microparticles are therefore not good.

The organic solvent which forms the organic phase of the emulsion in the above production is preferably hydrophobic. Among them, in particular, an aromatic organic solvent, toluene or xylene, is preferred from the viewpoints of the stability of the O/W type latex and the affinity with a monomer having a π-conjugated double bond. Even if the amphoteric solvent can carry out polymerization of a monomer having a π-conjugated double bond, it is difficult to separate the organic phase from the aqueous phase when the produced reduced 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. When the aqueous 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.

As the oxidizing agent used in the above production, for example, an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid or chlorosulfonic acid, an organic acid such as an alkylbenzenesulfonic acid or an alkylnaphthalenesulfonic acid such as potassium persulfate can be used. , peroxides such as ammonium persulfate and hydrogen peroxide. These may be used alone or in combination of two or more. Even a Lewis acid such as ferrous chloride can polymerize a monomer having a π-conjugated double bond, and the formed particles aggregate and cannot be finely dispersed. A particularly suitable 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, per mol of the monomer having a π-conjugated double bond. When the degree of polymerization of the monomer is less than 0.1 mol, it is difficult to collect the polymer fine particles, and on the other hand, when it is 0.8 mol or more, the particle size of the polymer fine particles is increased, and the dispersion stability is deteriorated.

The method for producing the polymer microparticles is carried out, for example, in the following steps: (a) a step of mixing an anionic surfactant, a nonionic surfactant, an organic solvent, and water to prepare an emulsion, and (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 (d) a step of separating the organic phase to recover the polymer fine particles.

The foregoing steps can be carried out by methods known to those skilled in the art. For example, the mixing and stirring performed at the time of preparation of the emulsion is not particularly limited, and can be suitably selected, for example, by using a magnetic stirrer, a stirrer, a homogenizer or the like. Further, the polymerization temperature is 0 to 25 ° C, preferably 20 ° C or less. If the polymerization temperature exceeds 25 ° C, the occurrence of side reactions is therefore poor.

If the oxidative polymerization reaction is stopped, the reaction system is divided into two phases of an organic phase and an aqueous phase, and at this time, unreacted monomers, oxidizing agents and salts are dissolved in the aqueous phase and remain. Here, when the organic phase is separated and recovered by washing with ion-exchanged water several times, the reducing polymer fine particles dispersed in the organic solvent can be obtained.

The polymer microparticles obtained by the above-described production method are mainly composed of a polymer of a monomer derivative having a π-conjugated double bond, and are microparticles containing an anionic surfactant and a nonionic surfactant. . Further, it is characterized by having a fine particle diameter and being dispersible in an organic solvent.

The polymer microparticles are spherical microparticles, and the average particle diameter is preferably from 10 to 100 nm.

As described above, by forming the fine particles having a small average particle diameter, the surface area of the fine particles becomes extremely large, and even if the fine particles of the same mass are used, the catalyst metal having a large amount of adsorption can be used, whereby the thin film formation of the coating layer becomes possible.

The conductivity of the obtained polymer microparticles is less than 0.01 S/cm, preferably 0.005 S/cm or less.

The reducing polymer fine particles dispersed in the organic solvent thus obtained can be directly concentrated, concentrated, or dried to use a reducing polymer fine particle component as a coating material.

(2) Method for producing conductive polymer microparticles

The conductive polymer microparticles to be used may be a monomer having an π-conjugated double bond by, for example, an O/W type emulsion obtained by mixing an organic solvent with water and an anionic surfactant. The monomer is produced by oxidative polymerization.

The monomer and the anionic surfactant having a π-conjugated double bond may be the same as those exemplified in the production of the reducing fine particles, and examples thereof include pyrrole, aniline, thiophene and 3,4. - Ethylene dioxythiophene or the like, preferably pyrrole.

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, per mol of the monomer having a π-conjugated double bond. When the yield is less than 0.05 mol, the yield or dispersion stability is lowered. On the other hand, when it is 0.2 mol or more, the conductive polymer microparticles obtained may have a moisture dependency of conductivity.

The organic solvent which forms the organic phase of the emulsion in the above-mentioned production is preferably hydrophobic. Among them, in particular, an aromatic organic solvent, toluene or xylene, is preferred from the viewpoints of the stability of the O/W emulsion and the affinity with the monomer. Even if the amphoteric solvent can carry out polymerization of a monomer having a π-conjugated double bond, it is difficult to separate the organic phase from 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. When the aqueous 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.

The oxidizing agent used in the above-mentioned production may be the same as those exemplified in the production of the reducing fine particles, and a particularly suitable 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, per mol of the monomer having a π-conjugated double bond. When the amount of polymerization of the monomer is less than 0.1 mol, it is difficult to separate and collect the conductive polymer fine particles. On the other hand, when it is 0.8 mol or more, the particle size of the conductive polymer fine particles is increased, and the dispersion is stable. Sexual deterioration.

The method for producing the conductive polymer microparticles is carried out, for example, by the following steps: (a) mixing an anionic surfactant, an organic solvent, and water to prepare an emulsion, and (b) having a π-conjugate a step of dispersing a monomer of a double bond in an emulsion, (c) oxidatively polymerizing a monomer, contacting a polymer microparticle with an anionic surfactant, and (d) separating the organic phase to recover a high conductivity The step of molecular microparticles.

The foregoing steps can be carried out by methods known to those skilled in the art. For example, the mixing and stirring performed at the time of preparation of the emulsion is not particularly limited, and can be suitably selected, for example, by using a magnetic stirrer, a stirrer, a homogenizer or the like. Further, the polymerization temperature is 0 to 25 ° C, preferably 20 ° C or less. If the polymerization temperature exceeds 25 ° C, the occurrence of side reactions is therefore poor.

If the oxidative polymerization reaction is stopped, the reaction system is divided into two phases of an organic phase and an aqueous phase, and at this time, unreacted monomers, oxidizing agents and salts are dissolved in the aqueous phase and remain. Here, when the organic phase liquid is recovered and washed several times with ion-exchanged water, the conductive polymer fine particles dispersed in the organic solvent can be obtained.

The conductive polymer fine particles obtained by the above-described production method are mainly composed of a monomer derivative having a π-conjugated double bond, and are fine particles containing an anionic surfactant. Further, it is characterized by a fine particle size and can be dispersed in an organic solvent.

The polymer microparticles are spherical microparticles, and the average particle diameter is preferably from 10 to 100 nm.

As described above, by forming the fine particles having a small average particle diameter, the surface area of the fine particles becomes extremely large, and even if the fine particles of the same mass are subjected to the de-doping treatment to be reductive, the catalyst metal can be adsorbed more. Thereby, thin film formation of the coating layer is possible.

The conductive polymer fine particles dispersed in the organic solvent thus obtained can be directly concentrated, concentrated, or dried to use a conductive polymer fine particle component as a coating material.

[Examples]

The invention is further illustrated in the following examples, but the invention is not limited by the examples.

Example 1: Manufacture of plating

1.5 mmol of an anionic surfactant PELEX OT-P (manufactured by Kao Co., Ltd.), 50 mL of toluene, and 100 mL of ion-exchanged water were added, and the mixture was stirred at 20 ° C until emulsification. To the obtained emulsion, 21.2 mmol of a pyrrole monomer was added, and the mixture was stirred for 1 hour, followed by the addition of 6 mmol of ammonium persulfate for 2 hours of polymerization. After the completion of the reaction, the organic phase was recovered and washed with ion-exchanged water several times to obtain conductive polymer fine particles having an average particle diameter of 50 nm dispersed in toluene. The solid content of the conductive polypyrrole fine particles in the toluene dispersion obtained here is about 1.2%, and here as the binder ARASTAR 700 (manufactured by Arakawa Chemical Industry Co., Ltd., styrene maleic acid) to be electrically conductive The conductive polypyrrole coating was obtained by adding 1 part by mass of the polypyrrole fine particles to a compounding ratio of 0.5 part by mass.

A small spray gun W-101-102P (manufactured by ANEST Iwata Co., Ltd., caliber: 1.0 mm) was used to obtain a polycarbonate resin (CALIBRE (registered trademark) 301 at a pressure of 0.3 MPa at 10 cm × 10 cm. -22m Sumitomo Dow Co., Ltd.) coated to a thickness of 5 μm.

The obtained film was dried at 40 ° C for 10 minutes, and then dried at 70 ° C for 30 minutes to obtain a polycarbonate resin having a coating film formed thereon.

The film thickness of the formed polypyrrole coating film was measured using an electronic micrometer-K402B (manufactured by ANRITSU Co., Ltd.).

The polycarbonate resin formed on the coating film produced above was surface-treated by immersing in a 1 M sodium hydroxide aqueous solution at 35 ° C for 5 minutes. Next, after immersing in 100 ppm of palladium chloride-0.01 M hydrochloric acid aqueous solution at 35 ° C for 5 minutes, it was washed with ion-exchange water. Next, the polycarbonate resin was immersed in an electroless plating bath ATS ADDCOPPER IW bath (manufactured by Okuno Pharmaceutical Co., Ltd.), and immersed at 35 ° C for 10 minutes to perform copper plating. Thereafter, it was thickened to a copper film thickness of 40 μm by copper sulfate plating.

Example 2

In addition to the catalyst treatment conditions, 200 ppm of palladium chloride-0.01 M hydrochloric acid aqueous solution was used, and the solution was immersed at 45 ° C for 5 minutes, and the size of the catalyst metal adsorbed on the coating layer was set to 150 nm, which was adsorbed to the coating. The same operation as in Example 1 was carried out except that the amount of the catalyst metal on the film layer was set to 3.0 μg/cm ² to obtain a plating material.

Example 3

In addition to the conductive polypyrrole coating, the ARSTAR 700 (manufactured by Arakawa Chemical Industries Co., Ltd., styrene maleic acid) is added in an amount of 0.1 part by mass based on 1 part by mass of the conductive polypyrrole. The same operation as in Example 1 was carried out to obtain a plating.

Example 4

In addition to the conductive polypyrrole coating, the ARSTAR 700 (manufactured by Arakawa Chemical Industries, Ltd., styrene maleic acid) is added in an amount of 10 parts by mass based on 1 part by mass of the conductive polypyrrole. The same operation as in Example 1 was carried out to obtain a plating.

Example 5

The same operation as in Example 1 was carried out except that the thickness of the coating layer was changed to 0.5 μm to obtain a plating material.

Example 6

The same operation as in Example 1 was carried out except that the thickness of the coating layer was changed to 100 μm to obtain a plating material.

Example 7

The same operation as in Example 1 was carried out except that the coating of the coating was changed from spray coating to dip coating to obtain a plating.

Example 8

A plating material was obtained in the same manner as in Example 1 except that the material of the substrate was designated as ABS, and PORIMENT (registered trademark) (manufactured by Nippon Shokubai Co., Ltd., acrylamide) was used as the binder.

Example 9

The same operation as in Example 1 was carried out except that the material of the substrate was set to PC/ABS, and the same operation as in Example 1 was carried out using SOLBINE MFK (manufactured by Nissin Chemical Industry Co., Ltd., vinyl chloride vinyl acetate) to obtain a plating material. .

Comparative example 1

In addition to the catalyst treatment conditions, 20 ppm of palladium chloride-0.01 M hydrochloric acid aqueous solution was used, and the solution was immersed in the solution at 35 ° C for 5 minutes, and the size of the catalyst metal adsorbed on the coating layer was set to 20 nm, which was adsorbed to the coating. The same operation as in Example 1 was carried out except that the amount of the catalyst metal on the film layer was 0.05 μg/cm ² to obtain a plating material.

Comparative example 2

In addition to the catalyst treatment conditions, 500 ppm of palladium chloride-0.1 M hydrochloric acid aqueous solution was used, and the solution was immersed at 50 ° C for 5 minutes, and the size of the catalyst metal adsorbed on the coating layer was set to 200 nm. The same operation as in Example 1 was carried out to obtain a plating.

Comparative example 3

In addition to the catalyst treatment conditions, 50 ppm of palladium chloride-0.01 M hydrochloric acid aqueous solution was used, and the solution was immersed in the solution at 35 ° C for 20 minutes to set the amount of the catalyst metal adsorbed on the coating layer to 4 μg/cm ² . The same operation as in Example 1 was carried out to obtain a plating.

Comparative example 4

In addition to the conductive polypyrrole coating, the ARSTAR 700 (manufactured by Arakawa Chemical Industries Co., Ltd., styrene maleic acid) is added in an amount of 0.05 parts by mass based on 1 part by mass of the conductive polypyrrole. The same operation as in Example 1 was carried out to obtain a plating.

Comparative Example 5

In addition to the conductive polypyrrole coating, the ARSTAR 700 (manufactured by Arakawa Chemical Industries Co., Ltd., styrene maleic acid) is added in an amount of 15 parts by mass based on 1 part by mass of the conductive polypyrrole. The same operation as in Example 1 was carried out to obtain a plating.

Comparative Example 6

The same operation as in Example 1 was carried out except that the thickness of the coating layer was changed to 0.3 μm to obtain a plating material.

Comparative Example 7

The same operation as in Example 1 was carried out except that the thickness of the coating layer was changed to 110 μm to obtain a plating material.

Test example 1

Among the plating materials of Examples 1 to 9 and Comparative Examples 1 to 7 produced as described above, various evaluation tests were carried out, and the results were summarized in Table 1.

In addition, evaluate the test project and its evaluation method. The evaluation criteria are as follows.

. Pd (palladium) amount

The catalyst-treated sample was cut into about 3 cm × 4 cm, palladium was extracted with nitric acid (1 + 9), and then quantified by flame-free atomic absorption spectrophotometry.

. Pd (palladium) particle size

The material after the catalyst treatment was observed by a scanning microscope ISM-6700F (manufactured by JEOL Ltd.), and the average particle diameter of 10 pieces of the palladium block was determined to be a palladium particle size.

. Film uniformity

The coating layer after the coating was applied was visually evaluated. In addition, the evaluation criteria are as follows.

○: No unevenness was applied, and there was no exposed portion of the substrate.

×: There is an uncoated portion, and a part of the substrate is exposed.

. Plating appearance

The state of the plating film was visually observed, and the exposed area of the substrate was measured.

In addition, the evaluation criteria are as follows.

○: It was completely covered, and it was precipitated without unevenness.

△: It is completely covered, and some parts have plaques.

×: The exposed portion of the substrate was not completely covered.

. Tape test

Based on the JIS H8504 tape test method, 100 pieces of square streaks of 2 mm side length were cut with a cutter, and a tearing test by tape was performed.

In addition, the evaluation criteria are as follows.

○: no peeling

×: peeling off

. Peel strength

The measurement was carried out in accordance with JIS C6471.

. Peeling section

The peeled surface was visually observed to determine whether the peeling occurred between which layers.

A: substrate-coating layer

B: coating layer - copper plating film

C: Peeling occurred in the coating layer due to a decrease in the strength of the coating film.

Further, in Table 1, ABS means an acrylonitrile butadiene styrene copolymer, PC means a polycarbonate resin, and a polypyrrole 1 binder ratio means a mass ratio of a polypyrrole to a binder.

Fig. 1 is a scanning micrograph of the surface of a coating film in the case where the size of the catalytic metal exceeds 150 nm.

Fig. 2 is a scanning micrograph of the surface of the coating film in the case where the size of the catalyst metal is 150 nm or less.

Claims (4)

A plating material is formed on a surface of a molded article to form a coating layer containing conductive polymer microparticles and a binder, and metal plating is formed on the coating layer by adsorption of a catalytic metal by electroless plating. The film-forming material is characterized in that the binder is present in an amount of 0.1 to 10 parts by mass based on 1 part by mass of the conductive polymer fine particles, and the coating layer has a thickness of 0.5 to 100 μm and is adsorbed on the coating layer. The size of the catalytic metal block is 150 nm or less, and the amount per unit area of the catalytic metal adsorbed on the coating layer is from 0.1 μg/cm ² to 3.0 μg/cm ² . The plating material of the first aspect of the invention, wherein 60% or more of the conductive polymer fine particles are present in the upper half of the coating layer, and the average particle diameter of the conductive polymer particles is 10 To 100nm. A method for producing a plating material, which is a method for producing a plating material by electroless plating of a metal film, which is characterized by the following steps; A) coating a molded article to form a thickness a step of coating a coating layer of 0.5 to 100 μm, the coating comprising reducing polymer microparticles and 0.1 to 10 parts by mass of the binder with respect to 1 part by mass of the reducing polymer microparticles, and B) permeating the coating layer The step of forming a metal plating film by electroless plating by adsorbing the catalytic metal, and setting the size of the catalytic metal block adsorbed on the coating layer to 150 nm or less, and adsorbing to the coating layer amount per unit area of the catalyst metal on the above-described set of 0.1μg / cm ² to 3.0μg / step ² of cm. The method of claim 3, wherein the conductive polymer microparticles are subjected to dedoping treatment to obtain reducing microparticles as the reductive polymer microparticles.