JP5991597B2 - Plating product manufacturing method and plating product - Google Patents

Description

The present invention relates to a method for manufacturing a plated product and a plated product.

As a circuit component constituting an electronic component, a circuit component in which a circuit made of copper or the like is formed on the surface of a base material made of resin or ceramic is widely known. A circuit is formed using electrolytic plating.
On the other hand, demands for smaller circuit parts, higher density wiring, and higher design continue to increase, and multilayered 2-dimensional circuits such as printed wiring boards and finer wiring cannot meet these demands. ing.

Therefore, as one measure corresponding to these demands, a molded circuit device (MID: Molded Interconnect Device) in which a circuit or the like is formed on the surface of a three-dimensional structure such as an injection molded product has been proposed.
As a method of manufacturing the molded circuit component (MID), for example, a material (LSD material) in which a catalyst necessary for electroless plating has been kneaded in advance is molded by injection molding or the like, and then A method has been proposed in which only the portion of the obtained molded body where the circuit is formed is irradiated with laser light to increase the catalytic activity of the laser light irradiated portion, and then the circuit is formed on this portion by electroless plating. (For example, refer to Patent Documents 1 and 2).
However, this method has a problem that the selection range of the material resin is narrow and the LSD material itself is expensive.

As another method for forming a circuit using electroless plating on the surface of a resin material, for example, after forming a coating layer containing conductive polymer fine particles made of polypyrrole or polyaniline on the surface of the resin material A method has been proposed in which palladium, which is a catalytic metal, is attached to the coating layer, and then a metal layer is formed by electroless plating (see, for example, Patent Documents 3 and 4).

However, in the method using conductive polymer fine particles made of polypyrrole or polyaniline, an electroless plating film having a good appearance cannot be formed, and there is a region where the plating film has not yet been deposited. There was a problem that it was inferior in productivity because it was slow.

Special table 2004-510061 gazette Special table 2004-534408 gazette JP 2008-163371 A JP 2010-1511 A

An object of the present invention is to provide a method for producing a plated product, which can produce a plated product in which a metal layer having a good appearance is formed on the surface of a substrate with a small number of steps and in a short time. And

As a result of intensive studies to solve the above problems, the present inventors applied a composition containing a polythiophene-based conductive polymer to the surface of the substrate to form a conductive polymer layer, and then applied the conductive polymer layer to the conductive polymer layer. The inventors found that a metal layer having a good appearance can be produced in a short number of steps and in a short time by attaching a metal catalyst and performing electroless plating, and completed the method for producing a plated product of the present invention. .

That is, the manufacturing method of the plated product of the present invention is at least:
(1) A step of applying a composition containing a polythiophene-based conductive polymer to part or all of the surface of the substrate (A) to form a conductive polymer layer (B),
(2) A step of attaching a metal catalyst to the conductive polymer layer (B) to form a conductive polymer layer (C) containing the metal catalyst, and
(3) forming a metal layer (D) by electroless plating on the conductive polymer layer (C);
It is characterized by going through.

In the method for producing a plated product, the composition containing the polythiophene conductive polymer preferably further contains a leveling agent.
In the method for producing a plated product, the polythiophene conductive polymer is composed of poly (3,4-disubstituted thiophene) or a composite of poly (3,4-disubstituted thiophene) and polyanion. Is preferred.
Moreover, it is preferable that the composition containing the said polythiophene type conductive polymer contains the compound containing an acrylic group, the compound which has an epoxy group, polyester, a polyurethane, an acrylic resin, or an epoxy resin.

In the method for producing a plated product of the present invention, the substrate (A) is preferably a resin substrate.
The resin resin of the resin base is epoxy resin, polyacetal, polyamide, polyphthalamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, syndiotactic polystyrene, polyacrylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyether It is preferably at least one selected from the group consisting of ketone, polyimide, polyetherimide, fluororesin, liquid crystal polymer, polyethylene terephthalate, ABS resin and nylon.

The plated product of the present invention is manufactured using the method for manufacturing a plated product of the present invention.
The plated product is preferably a circuit component, an electromagnetic wave shielding member, or a decorative article.

Since the method for producing a plated product of the present invention undergoes at least the above-described steps, is it possible to produce a plated product in which a metal layer having a good appearance is formed on the surface of the substrate in a small number of steps and in a short time? it can.
Note that the reason why a metal layer having a good appearance can be formed in a short time is that a conductive polymer layer formed by applying a composition containing a polythiophene-based conductive polymer is a conductive high layer made of polypyrrole or polyaniline. Compared to a coating layer containing molecular fine particles, a metal catalyst such as palladium is more easily attached, and the metal catalyst is attached at a high density to a conductive polymer layer formed by applying a composition containing a polythiophene-based conductive polymer. I guess that is because it can.
Moreover, since the plated product of the present invention is manufactured using the method for manufacturing a plated product of the present invention, the plated product includes a metal layer having a very good appearance.

First, the method for manufacturing a plated product of the present invention will be described in the order of steps.
The method for producing a plated product of the present invention includes at least
(1) A step of applying a composition containing a polythiophene-based conductive polymer to part or all of the surface of the substrate (A) to form a conductive polymer layer (B),
(2) A step of attaching a metal catalyst to the conductive polymer layer (B) to form a conductive polymer layer (C) containing the metal catalyst, and
(3) forming a metal layer (D) by electroless plating on the conductive polymer layer (C);
It is characterized by going through.

In the method for producing a plated product, first, (1) a step of forming a conductive polymer layer (B) by applying a composition containing a polythiophene-based conductive polymer to part or all of the surface of the substrate (A). I do.
In this step, the conductive polymer layer (B) is formed on part or all of the surface of the substrate (A). Here, the position where the conductive polymer layer (B) is formed is electroless in the subsequent step. It corresponds to the position where the metal layer (D) is formed by plating.

The base (A) is not particularly limited as long as the metal layer is formed by electroless plating, and examples thereof include a resin base, a ceramic base, and a glass base. The production method of the present invention is advantageous in that the range of selection of the material of the substrate is wide.
Examples of the resin material for the resin base include epoxy resin, polyacetal, polyamide, polyphthalamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, syndiotactic polystyrene, polyacrylate, polysulfone, polyethersulfone, and polyphenylene sulfide. , Polyether ketone, polyimide, polyether imide, fluororesin, liquid crystal polymer, polyethylene terephthalate, ABS resin, nylon, and resin alloys containing two or more of these resins.
Among these, polyamide, polycarbonate, syndiotactic polystyrene, liquid crystal polymer, polyethylene terephthalate, ABS resin, nylon, and a resin alloy containing at least one selected from the group consisting of these resins are preferably used in the present invention. Is done.

The composition containing the polythiophene-based conductive polymer (hereinafter also referred to as a conductive composition in the present specification) is composed of a polythiophene-based conductive polymer and, if necessary, other components such as a leveling agent and a binder resin. Containing.
The polythiophene-based conductive polymer is polythiophene or a derivative thereof, or a composite of polythiophene or a derivative thereof and a dopant such as a polyanion.
As the polythiophene conductive polymer, poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and polyanion is preferable. This is because it is extremely excellent in conductivity and chemical stability. Furthermore, a conductive polymer layer is formed using a conductive polymer composition containing poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and a polyanion. In this case, since the thin film can be formed at a low temperature in a short time, the productivity is extremely excellent.

As the poly (3,4-disubstituted thiophene), poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) is particularly preferable.
As the poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene), the following formula (I):

A polythiophene in a cationic form consisting of repeating structural units represented by Here, R ¹ and R ² each independently represent a hydrogen atom or a C _1-4 alkyl group, or a C _1-4 alkylene group which may be substituted together.
Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
Examples of the optionally substituted C _1-4 alkylene group formed by combining R ¹ and R ² include a methylene group, a 1,2-ethylene group, and a 1,3-propylene group. 1,4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene Groups and the like. Preferred are a methylene group, 1,2-ethylene group, and 1,3-propylene group, and a 1,2-ethylene group is particularly preferred. As the polythiophene having an alkylene group, poly (3,4-ethylenedioxythiophene) is particularly preferable.

The poly anion forms a complex by forming an ion pair with the polythiophene (derivative), and the polythiophene (derivative) can be stably dispersed in water.
Examples of the poly anion include carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (for example, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyisoprene sulfonic acid, etc.), and the like. Can be mentioned. These carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as aromatic vinyl compounds such as acrylates, styrene, vinyl naphthalene, etc. It may be. Among these, polystyrene sulfonic acid is particularly preferable.

The polystyrene sulfonic acid preferably has a weight average molecular weight of more than 20000 and 500,000 or less. More preferably, it is 40000-200000. If polystyrene sulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene conductive polymer in water may be lowered. The weight average molecular weight of the polymer is a value measured by gel permeation chromatography (GPC). For the measurement, an ultrahydrogel 500 column manufactured by Waters was used.

The content of the polythiophene-based conductive polymer in the conductive composition is preferably 0.01~50.0mg / ^{m 2,} and more preferably 0.1 to 10.0 mg / ^{m 2.} If it is less than 0.01 mg / m ² , the proportion of the polythiophene-based conductive polymer in the conductive polymer layer decreases, and the metal deposition rate becomes slow, which may be disadvantageous in terms of process, while 50.0 mg This is because if it exceeds / m ² , the ratio of the polythiophene-based conductive polymer in the conductive polymer layer increases, the metal deposition rate becomes too fast, and it becomes difficult to control the thickness of the metal layer.

The conductive composition may contain other components in addition to the polythiophene-based conductive polymer. For example, a binder, a water-soluble antioxidant, a crosslinking agent, a surfactant, a leveling agent, a solvent, etc. You may contain.

(binder)
The binder is used for the purpose of improving the adhesion between the conductive composition and the substrate (A) and the strength of the conductive polymer layer (B) to be formed.
Examples of the binder include an acrylic group-containing compound, an epoxy group-containing compound, polyester, polyurethane, acrylic resin (polyacrylate, polymethacrylate), epoxy resin, polyvinyl acetate, polyvinylidene chloride, polyamide, polyimide, and the like. Homopolymer; copolymer obtained by copolymerizing monomers such as styrene, vinylidene chloride, vinyl chloride, alkyl acrylate, alkyl methacrylate; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- And alkoxysilane compounds such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These binders may be used independently and may use 2 or more types together.

In these, the compound containing an acrylic group, the compound which has an epoxy group, polyester, a polyurethane, an acrylic resin, or an epoxy resin is preferable, for example.
The reason is that the adhesion to the substrate is good, and it is possible to impart excellent strength to the conductive polymer layer relatively easily.

Examples of the compound containing an acrylic group include a compound having an acrylic group soluble in water and alcohol, for example, an acid group such as at least one acrylic group and a carboxyl group, an acid anhydride group, a sulfonic acid group, and a phosphoric acid group. And the like.
The compound having an epoxy group includes a compound having an epoxy group soluble in water and alcohol, for example, an acid group such as at least one epoxy group and a carboxyl group, an acid anhydride group, a sulfonic acid group, and a phosphoric acid group. And the like.

Examples of the acrylic resin include (meth) acrylic resins and vinyl ester resins. As these acrylic resins, for example, a polymer containing a polymerizable monomer having an acid group such as a carboxyl group, an acid anhydride group, a sulfonic acid group, or a phosphoric acid group as a constituent monomer may be used. Examples thereof include a single or copolymer of a polymerizable monomer having a group, a copolymer of a polymerizable monomer having a acid group and a copolymerizable monomer, and the like.
The (meth) acrylic resin may contain a (meth) acrylic monomer as a main constituent monomer (for example, 50 mol% or more). It is sufficient that at least one of the monomers has an acid group. As the (meth) acrylic resin, for example, a (meth) acrylic monomer having the above acid group [(meth) acrylic acid, sulfoalkyl (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, etc.) alone Or a copolymer, the (meth) acrylic monomer optionally having an acid group and another polymerizable monomer having an acid group [other polymerizable carboxylic acid, polymerizable polyvalent carboxylic acid or Anhydride, vinyl aromatic sulfonic acid, etc.] and / or the above copolymerizable monomers [e.g., (meth) acrylic acid alkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile, aromatic vinyl monomer, etc.] , Other polymer monomers having the above acid groups and (meth) acrylic copolymerizable monomers [for example, (meth) acrylic acid alkyl ester, hydroxyalkyl (meth) Acrylate, glycidyl (meth) acrylate, and copolymers of (meth) acrylonitrile, etc.].

Among these (meth) acrylic resins, polymers containing at least (meth) acrylic acid, for example, (meth) acrylic acid- (meth) acrylic acid ester polymers (acrylic acid-methyl methacrylate copolymer, etc.) , (Meth) acrylic acid- (meth) acrylic acid ester-styrene copolymers (acrylic acid-methyl methacrylate-styrene copolymers, etc.) are preferred.

Examples of the vinyl ester resin include a polymerizable monomer having an acid group (for example, (meth) acrylic acid, vinyl sulfonic acid, etc.), a vinyl ester monomer, and, if necessary, other copolymerizable monomers. And copolymers with monomers (α-olefins and the like).

Although content of a binder is not specifically limited, 0.1-17000 weight part is preferable with respect to 100 weight part of solid content of a polythiophene type conductive polymer in conversion of solid content, and 0.5-5000 weight part is more preferable. .
If the content is less than 0.1 parts by weight, the strength of the conductive polymer layer becomes weak and may cause the detachment of the conductive polymer when immersed in the plating solution. If it exceeds, the proportion of the polythiophene-based conductive polymer in the conductive polymer layer decreases, and the deposition rate of the metal by plating becomes slow, which may be disadvantageous in the process.

(Water-soluble antioxidant)
The water-soluble antioxidant is a compound for suppressing deterioration over time in the heat resistance, moist heat resistance test and the like of the conductive polymer layer (B) to be formed.
The water-soluble antioxidant is not particularly limited, and examples thereof include reducing or non-reducing water-soluble antioxidants. Examples of the water-soluble antioxidant having reducibility include L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, D (-)-isoascorbic acid (erythorbic acid), sodium erythorbate, erythorbic acid Compounds having a lactone ring substituted with two hydroxyl groups such as potassium; monosaccharides or disaccharides (excluding sucrose) such as maltose, lactose, cellobiose, xylose, arabinose, glucose, fructose, galactose, mannose; , Flavonoids such as rutin, myricetin, quercetin, kaempferol, sanmerin (registered trademark) Y-AF; two phenolic hydroxyl groups such as curcumin, rosmarinic acid, chlorogenic acid, hydroquinone, 3,4,5-trihydroxybenzoic acid that's all Compounds; cysteine, glutathione, a compound having a pentaerythritol tetrakis (3-mercapto butyrate) thiol groups, such as and the like. Non-reducing water-soluble antioxidants include, for example, oxidative degradation such as phenylimidazolesulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate. The compound which absorbs the ultraviolet-ray which causes this is mentioned. These may be used alone or in combination of two or more.

Among these, at least one compound selected from the group consisting of a compound having a lactone ring substituted with two hydroxyl groups and a compound having two or more phenolic hydroxyl groups is preferable. ) -Isoascorbic acid or Sanmerin Y-AF is more preferred.

The content of the water-soluble antioxidant is preferably 0.001 to 500 parts by weight, more preferably 0.05 to 250 parts by weight, with respect to 100 parts by weight of the solid content of the polythiophene conductive polymer. ˜100 parts by weight is particularly preferred.
When the content is less than 0.001 part by weight, the heat resistance and heat-and-moisture resistance of the conductive polymer layer may not be sufficiently improved. On the other hand, when the content exceeds 500 parts by weight, the polythiophene in the conductive polymer layer may be lost. In some cases, the proportion of the conductive polymer in the system is reduced, the deposition rate of the metal by plating is slow, and the strength of the conductive polymer layer is reduced.

(Crosslinking agent)
The crosslinking agent is used for the purpose of further improving the strength of the conductive polymer layer (B) to be formed.
The crosslinking agent may be used in combination with a binder for the purpose of crosslinking the binder, or a self-crosslinking film of the crosslinking agent may be formed without using the binder. As a catalyst for crosslinking, an acidic group of a dopant may be used, or an organic acid or an inorganic acid may be newly added. Moreover, you may add a heat sensitive acid generator, a radiation sensitive acid generator, an electromagnetic wave sensitive acid generator, etc.

Examples of the crosslinking agent include melamine-based, polycarbodiimide-based, polyoxazoline-based, polyepoxy-based, and polyisocyanate-based crosslinking agents. These crosslinking agents may be used independently and may use 2 or more types together.

Although content of the said crosslinking agent is not specifically limited, 0.1-17000 weight part is preferable with respect to 100 weight part of solid content of the said polythiophene type conductive polymer in conversion of solid content, and 1-1000 weight part is more. preferable.
When the content is less than 0.1 part by weight, the strength of the conductive polymer layer may be insufficient. On the other hand, when the content exceeds 17000 parts by weight, the polythiophene-based conductive polymer is present in the conductive polymer layer. May decrease, and the deposition rate of metal by plating may be slow, which may be disadvantageous in terms of process.

(Surfactant)
The surfactant is not particularly limited as long as it improves leveling properties and can form a uniform conductive polymer layer (B).
Examples of the surfactant include polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, Siloxane compounds such as perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-containing organic compounds such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol; polyoxyethylene Polyether compounds such as alkyl phenyl ethers, propylene oxide polymers, ethylene oxide polymers; coconut oil fatty acid polymers Carboxylic acids such as citrate salts and gum rosins; Castor oil sulfates, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, phosphate esters, succinate esters, and other ester compounds; alkyl aryl sulfonate amines Examples thereof include salts, sulfonate compounds such as dioctyl sodium sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; amide compounds such as coconut oil fatty acid ethanolamide; and acrylic copolymers. Among these, siloxane compounds and fluorine-containing compounds are preferable from the viewpoint of leveling properties, and polyether-modified polydimethylsiloxane is particularly preferable.

Although content of the said surfactant is not specifically limited, 0.001-2300 weight part is preferable with respect to 100 weight part of solid content of the said polythiophene type conductive polymer in conversion of solid content, 0.01-500 weight Part is more preferred.
When the content is less than 0.001 part by weight, it may be difficult to form a uniform film thickness of the conductive polymer layer. On the other hand, when the content exceeds 2300 parts by weight, the polythiophene-based conductive material in the conductive polymer layer may be difficult. The proportion of the conductive polymer is reduced, and the metal deposition rate by plating may be slow, or the strength of the conductive polymer layer may be reduced.

(Leveling agent)
Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, Siloxane compounds such as fluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-containing organic compounds such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol; polyoxyethylenealkyl Polyether compounds such as phenyl ether, propylene oxide polymer, ethylene oxide polymer; coconut oil fatty acid polymer Carboxylic acids such as salt and gum rosin; castor oil sulfates, phosphate esters, alkyl ether sulfates, ester compounds such as sorbitan fatty acid esters, sulfonate esters, succinate esters; alkylaryl sulfonate amine salts, sulfosuccinic acid Examples thereof include sulfonate compounds such as dioctyl sodium; phosphate compounds such as sodium lauryl phosphate; amide compounds such as coconut oil fatty acid ethanolamide; and acrylic copolymers. These leveling agents may be used independently and may use 2 or more types together.

Although content of the said leveling agent is not specifically limited, 0.001-2300 weight part is preferable with respect to 100 weight part of solid content of an electroconductive composition in conversion of solid content, and 0.01-500 weight part is more. preferable.
When the content is less than 0.001 part by weight, it may be difficult to form the conductive polymer layer uniformly. On the other hand, when the content exceeds 2300 parts by weight, the polythiophene-based conductivity in the conductive polymer layer may be difficult. There are cases where the polymer content decreases, the metal deposition rate by plating becomes slow, or the strength of the conductive polymer layer decreases.

In the conductive composition, the surfactant plays a role of facilitating formation of a conductive polymer layer free of repellency by reducing the surface tension of the conductive composition, thereby improving wettability to the substrate. Fulfill.
In addition, the leveling agent is uniformly oriented on the surface of the film after the conductive composition is applied to the substrate, and the evaporation of the solvent from the surface of the film of the conductive composition is made uniform during the drying process. In this case, the Benard Cell phenomenon can be prevented and the state in which the change in the surface tension during the drying process can be kept small, so that the orange peel, crater and floating mottle of the conductive polymer layer after drying can be suppressed.
That is, the surfactant has a function of improving the wettability to the substrate by lowering the surface tension of the conductive composition. On the other hand, the leveling agent has a function of suppressing the phenomenon that the conductive polymer layer formed during drying of the conductive composition becomes non-uniform.

Since the conductive composition is a composition in which the conductive polymer is uniformly dispersed, orange peel, craters, and floating mottle tend to be generated in the formed conductive polymer layer when a leveling agent is not blended. And when the said orange peel etc. arise in a conductive polymer layer, it becomes difficult to carry | support a catalyst of electroless plating uniformly in a surface, and an unevenness | corrugation tends to arise in the metal layer after electroless plating. . When such irregularities occur, the appearance is not a mirror surface.
On the other hand, when a leveling agent is added to the conductive composition, a uniform layer can be formed on the formed conductive polymer layer without producing orange peel, craters, and mottled spots. The plating catalyst is uniformly supported in the surface, the metal layer after electroless plating becomes uniform, and the appearance of the metal layer tends to be a mirror surface.

The conductive composition may contain a solvent. It is preferable that the solvent does not remain in the conductive polymer layer (B) to be formed.
In addition, although what dissolve | melts all the components of an electroconductive composition is called a "solvent" and what disperse | distributes an insoluble component is called a "dispersion medium", in this specification, all are ""Solvent".
(solvent)
Examples of the solvent include alcohols such as water, methanol, ethanol, 2-propanol, and 1-propanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monomethyl ether and diethylene glycol monomethyl. Glycol ethers such as ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; Glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; Propylene glycol, dipropylene glycol, tripropylene glycol, etc. Propylene rubber Coles: propylene glycol such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether Ethers: propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; tetrahydrofuran; acetone; acetonitrile and the like It is. These may be used alone or in combination of two or more.

Among these, water or a mixture of water and an organic solvent is preferable.
When water is used as the solvent, the water content is preferably 20 to 1000000 parts by weight, and more preferably 200 to 500000 parts by weight with respect to 100 parts by weight of the solid content of the polythiophene conductive polymer.
The reason is that if the amount is less than 20 parts by weight, the viscosity may be high and handling may be difficult. If the amount exceeds 1000000 parts by weight, the solution may become too dilute and it may be difficult to adjust the film thickness. It is.

Moreover, when using the mixture of water and an organic solvent, as an organic solvent, methanol, ethanol, or 2-propanol is preferable.
In this case, the content of the organic solvent is not particularly limited, and is preferably 20 to 700000 parts by weight and more preferably 200 to 350,000 parts by weight with respect to 100 parts by weight of the solid content of the conductive polymer. Moreover, when using water and an organic solvent together, the ratio of both (ratio of water and organic solvent) is preferably 100: 0 to 5:95, and more preferably 100: 0 to 30:70.

As a method for applying the conductive composition to part or all of the surface of the substrate (A), a known application method can be used. Examples of the application method include spin coating, gravure coating, bar coating, dip coating, curtain coating, die coating, and spray coating. Furthermore, printing methods such as screen printing, spray printing, ink jet printing, relief printing, intaglio printing, and lithographic printing can also be applied. What is necessary is just to select suitably from these methods according to the objective.

Moreover, after apply | coating the said electroconductive composition, you may perform a drying process and a heat processing as needed.
When the applied conductive composition is dried, the method is not particularly limited. For example, the conductive composition may be dried using a dryer such as an air dryer, a hot air dryer, or an infrared dryer. Further, when a dryer having a heating means (hot air dryer, infrared dryer, etc.) is used, drying and heating can be performed simultaneously. Further, in addition to these dryers, a heating / pressurizing roll having a heating / pressurizing function, a press machine, or the like may be used.
The drying conditions are not particularly limited, but conditions of 50 to 250 ° C. for about 10 seconds to 2 hours are preferable, and conditions of 70 to 2000 ° C. for about 30 seconds to 1 hour are more preferable.

Moreover, in this process, you may perform the dedope process with respect to the said polythiophene type conductive polymer before apply | coating the said conductive composition, or after apply | coating the said conductive composition.
Note that it is not necessary to perform a dedoping treatment on the polythiophene-based conductive polymer, and when the dedoping treatment is not performed, the number of steps of the production method of the present invention can be reduced, so that productivity can be improved. .
Moreover, depending on the case, when the dedoping treatment is not performed, the plating property is improved, that is, the time for starting the plating deposition or the time until the plating reaches a predetermined thickness may be shortened.

When performing the said dedope process before apply | coating the said electroconductive composition, what is necessary is just to perform by the following method, for example.
That is, for example, a basic compound that does not react with the polythiophene-based conductive polymer may be added to the polythiophene-based conductive polymer aqueous dispersion. In this case, the basic compound is not particularly limited, and examples thereof include inorganic basic compounds such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, organic analogs such as ammonia analogs, hydrazine, and alkylamines. A compound or the like can be used.
The pH of the aqueous solution after dedoping is preferably 9 or more.

Moreover, what is necessary is just to perform by the following methods, for example, when performing the said dedope process after apply | coating the said electroconductive composition.
That is, for example, an aqueous solution of a basic compound that does not react with a polythiophene-based conductive polymer may be added to a substrate coated with a polythiophene-based conductive polymer composition. In this case, the basic compound is not particularly limited. For example, an aqueous solution of an inorganic basic compound such as sodium hydroxide, potassium hydroxide, or lithium hydroxide, an organic analog such as ammonia analog, hydrazine, or alkylamine. An aqueous solution of a reactive compound can be used. The pH of the aqueous solution is preferably 9 or more.

In the method for producing a plated product of the present invention, next, (2) a step of forming a conductive polymer layer (C) containing a metal catalyst by attaching a metal catalyst to the conductive polymer layer (B) is performed. .
Here, for example, the substrate (A) on which the conductive polymer layer (B) is formed may be immersed in a catalyst bath containing a metal catalyst, and then washed with water and dried.
The metal catalyst is not particularly limited as long as it is a metal catalyst used for electroless plating, for example, a simple metal such as palladium, gold, platinum, rhodium, silver, iron, cobalt, nickel, zinc, or these The metal compound of these is mentioned.
Of these, palladium compounds are preferred, and palladium chloride is more preferred. This is because the stability of the catalyst bath is excellent.

The temperature of the catalyst bath is preferably 20 to 50 ° C. The reason is that it is the optimum temperature at which the metal can be deposited uniformly.
The immersion time in the catalyst bath is preferably 1 to 60 minutes. The reason is that if it is less than 1 minute, it becomes difficult to control the thickness of the metal layer, and if it exceeds 60 minutes, the productivity is remarkably lowered.

In the method for producing a plated product of the present invention, next, (3) a step of forming a metal layer (D) by electroless plating on the conductive polymer layer (C) is performed.
Here, the base (A) on which the conductive polymer layer (C) containing the metal catalyst is formed is immersed in an electroless plating bath to form the metal layer (D) on the conductive polymer layer (C).

The metal constituting the metal layer (D) is not particularly limited as long as it is a metal deposited by electroless plating. For example, copper, silver, gold, nickel, chromium, tin, zinc, palladium, rhodium, ruthenium, Examples include antimony, bismuth, germanium, cadmium, cobalt, indium, and alloys thereof.
Of these, copper is preferred. This is because the material is inexpensive and has high performance in circuit, wiring, and electromagnetic wave shielding applications.

The type of electroless plating bath and electroless plating conditions are not particularly limited, and conventionally known electroless plating baths and electroless plating conditions can be applied.
Specifically, for example, when the metal catalyst is palladium and ATS add-copper IW is used as an electroless copper plating bath, the electroless plating bath temperature is set to 10 to 50 ° C. and immersed for 1 to 120 minutes. Thus, an electroless copper plating film having a thickness of 0.1 to 20 μm can be formed. Further, when the substrate (A) on which the conductive polymer layer (C) containing the metal catalyst is formed is immersed in the electroless plating bath, the substrate (A) may be shaken.

Although the thickness of the said metal layer (D) is not specifically limited, 0.1-100 micrometers is preferable.
The reason is that the thickness of the metal layer is necessary for applications such as circuits, wiring, electromagnetic shielding, and decoration.
The thickness of the metal layer (D) can be adjusted, for example, by appropriately changing the immersion time in the electroless plating bath.

Through such steps (1) to (3), a plated product in which the metal layer (D) is formed on part or all of the surface of the substrate (A) can be produced.
In the method for producing a plated product according to the present invention, after the metal layer (D) is formed by electroless plating, electrolytic plating is performed by a conventionally known method to form an electrolytic plating layer on the metal layer (D). Also good.
Thereby, the thickness of the metal layer formed on the surface of the substrate (A) can be easily increased.

In the method for producing a plated product according to the present invention, the metal layer (D) is previously formed in a wider range than the desired range, and then the unnecessary portion of the metal layer (D) is removed by etching. Good.
Specifically, when a circuit component is manufactured as a plated product, for example, a metal layer (D) is formed by electroless plating over a range (for example, the entire surface) of the surface of the substrate (A) that is wider than a portion where a circuit is formed. ), An etching resist may be formed on a portion of the metal layer (D) to be a circuit, and then an etching process may be performed to form a circuit on the surface of the substrate (A) (full additive) Method), and after forming a metal layer (D) by electroless plating over a wider area (for example, the entire surface) of the surface of the substrate (A) than the portion where the circuit is formed, the circuit of the metal layer (D) A plating resist is formed on the part which does not become, and an electrolytic plating layer is formed on the metal layer (D) by further electrolytic plating. Thereafter, the plating resist is peeled off and the metal layer located under the plating resist ( D) A circuit may be formed on the surface of the base body (A) by performing the etching process (semi-additive method), and further, a wider area than the part of the surface of the base body (A) where the circuit is formed (for example, the entire surface) ) To form a metal layer (D) by electroless plating, and then form an electrolytic plating layer on the metal layer (D) by electrolytic plating. Then, an etching resist is formed on a portion to be a circuit, Further, an etching process may be performed to form a circuit on the surface of the substrate (A) (subtractive method).

In addition, examples of the patterning method applicable to the present invention (a method of forming the metal layer (D) on a part of the surface of the substrate (A)) include the following methods:
The conductive polymer layer (B) is uniformly formed on the substrate (A), a mask having a predetermined patterning image is pasted on the conductive polymer layer (B) without any gap, and a metal catalyst is adhered, thereby partially A method of obtaining a patterned metal layer (D) by forming a conductive polymer layer (C) having a catalyst attached thereto and forming the metal layer (D) by electroless plating;
A conductive polymer layer (B) is uniformly formed on the substrate (A), and a metal catalyst is attached to form a conductive polymer layer (C) to which the catalyst is attached, and then a mask having a predetermined patterning image. A method of obtaining a patterned metal layer (D) by pasting the catalyst on the conductive polymer layer (C) to which the catalyst is adhered without gaps and partially forming the metal layer (D) by electroless plating;
The conductive polymer layer (B) is uniformly formed on the substrate (A), and the conductive polymer layer (B) is formed into a conductive polymer layer (B) patterned by a known technique such as etching or a lift-off method. A method of obtaining a patterned metal layer (D) by depositing a metal catalyst to form a conductive polymer layer (C) to which the catalyst is adhered, and forming a metal layer (D) by electroless plating;
A negative or positive resist conductive polymer layer (B) is formed on the substrate (A), light is irradiated through a mask having a predetermined patterning image, unnecessary portions are peeled off, and patterned conductive Metal obtained by patterning by obtaining a polymer layer (B), attaching a metal catalyst to form a conductive polymer layer (C) to which the catalyst is attached, and forming a metal layer (D) by electroless plating Method for obtaining layer (D).

According to such a method for producing a plated product of the present invention, a plated product in which a metal layer is formed on the surface of a substrate can be suitably produced.
A plated product produced using the method for producing a plated product of the present invention is also one aspect of the present invention.

Examples of the plated product include circuit components, electromagnetic wave shielding members, and ornaments. Examples of the circuit components include printed circuit boards such as single-sided boards, double-sided boards, multilayer boards, and build-up boards, and molded circuit parts (MID) such as antennas, optical pickups, and board-to-board connecting parts. In particular, according to the manufacturing method of the present invention, a molded circuit component (MID) can be preferably manufactured.
Examples of the electromagnetic wave shielding member include those in which a metal layer is formed on the surface of a flexible film, and those in which a metal layer is formed on the surface of a box-shaped substrate.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. Hereinafter, “parts” or “%” means “parts by weight” or “% by weight”, respectively, unless otherwise specified.

(Preparation of conductive polymer composition A)
An aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) is added to 15 parts as a binder. Acrylic resin aqueous dispersion (manufactured by Nippon Pure Chemicals Co., Ltd .: Jurimer AT-613, solid content 23.5%), 4.7 parts of dimethyl sulfoxide (manufactured by Kanto Chemical Co., Ltd.) as a conductivity improver, 5.0 parts of interface An activator (solid content 100%), 33 parts of water, and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition A.

(Preparation of conductive polymer composition B)
An aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) was added to 100 parts as a binder. Polyester aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content 25.0%), 4.7 parts of dimethyl sulfoxide (manufactured by Kanto Chemical Co., Ltd.) as a conductivity improver, 5.0 parts of surface activity Agent (solid content 100%), 33 parts of water, and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition B.

(Preparation of conductive polymer composition C)
100 parts of a polypyrrole dispersion (Polymerits: PES-E10, solid content: 1.0%) and 15 parts of an acrylic resin water dispersion (Nippon Pure Chemicals: Jurimer AT-613, solids: 23.5) as a binder %), 4.7 parts dimethyl sulfoxide (manufactured by Kanto Chemical Co., Inc.), 5.0 parts surfactant (solid content 100%), 33 parts water, and 32 parts ethanol as a conductivity improver Stir for 1 hour. This was filtered with a 400 mesh SUS sieve to obtain a conductive polymer composition C.

(Preparation of conductive polymer composition D)
An aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) was added to 100 parts as a binder. Polyester aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content 25.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts polyether-modified siloxane-based A leveling agent (BYK-345 manufactured by Big Chemie, solid content 90%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition D.

(Preparation of conductive polymer composition E)
An aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) was added to 100 parts as a binder. Polyester aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content 25.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts carboxyl group-containing acrylic polymer system Leveling agent (Kyoeisha Chemical Co., Ltd. polyflow WS-30, solid content 50%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition E.

(Preparation of conductive polymer composition F)
An aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) was added to 100 parts as a binder. Polyester aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content 25.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts fluorine-containing group / hydrophilicity A base / lipophilic group-containing oligomer-based leveling agent (Megafac F-477 manufactured by DIC Corporation, solid content: 100%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition F.

(Preparation of conductive polymer composition G)
An aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) was added to 100 parts as a binder. Polyester aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content 25.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts fluorine leveling agent ( AGC Surflon, solid content 100%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition G.

(Preparation of conductive polymer composition H)
An aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) was added to 100 parts as a binder. Polyester aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content 25.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts Fluorocarbon Modified Polyacrylate leveling Agent (BAKA EFKA3772, solid content 60%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition H.

(Preparation of conductive polymer composition I)
An aqueous dispersion of a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) was added to 100 parts as a binder. Polyester aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content 25.0%), 5.0 parts surfactant (solid content 100%), 20 parts polyether-modified siloxane leveling agent (BYK-345 manufactured by Big Chemie, solid content 90%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400-mesh SUS sieve to obtain a conductive polymer composition I.

(Preparation of conductive polymer composition J)
An aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) is added to 40 parts as a binder. Acrylic resin aqueous dispersion (manufactured by Nippon Pure Chemicals Co., Ltd .: Jurimer AT-613, solid content 23.5%), 5.0 parts surfactant (solid content 100%), 5.0 parts polyether-modified siloxane Leveling agent (BYK-345 manufactured by Big Chemie, solid content 90%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered with a 400 mesh SUS sieve to obtain a conductive polymer composition J.

(Preparation of conductive polymer composition K)
An aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) is added to 40 parts as a binder. Polyester aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content 25.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts polyether-modified siloxane-based A leveling agent (BYK-345 manufactured by Big Chemie, solid content 90%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition K.

(Preparation of conductive polymer composition L)
An aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) is added to 40 parts as a binder. Polyurethane aqueous dispersion (manufactured by DIC: Hydran WLS-213, solid content 35.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts polyether-modified siloxane leveling agent (BYK-345 manufactured by Big Chemie, solid content 90%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition L.

(Preparation of conductive polymer composition M)
An aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) is added to 40 parts as a binder. Polyurethane aqueous dispersion (Daiichi Kogyo Seiyaku Co., Ltd .: Superflex 300, solid content 30.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts polyether-modified siloxane-based A leveling agent (BYK-345 manufactured by Big Chemie, solid content 90%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition M.

(Preparation of conductive polymer composition N)
An aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) is added to 40 parts as a binder. Acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: U-4HA, solid content 100.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts polyether-modified siloxane leveling agent (BYK-345 manufactured by Big Chemie, solid content 90%), 33 parts of water and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400-mesh SUS sieve to obtain a conductive polymer composition N.

(Preparation of conductive polymer composition O)
An aqueous dispersion of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (HC Starck Co., Ltd .: CleviosP, solid content: 1.0%) is added to 40 parts as a binder. Epoxy resin (manufactured by Nagase ChemteX: Denacol EX-314, solid content 100.0%), 5.0 parts surfactant (solid content 100%), 5.0 parts polyether-modified siloxane leveling agent ( BYK-345 manufactured by Big Chemie, solid content 90%), 33 parts of water, and 32 parts of ethanol were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain a conductive polymer composition O.

Example 1
(Step 1-1): Conductive polymer composition A is placed on one side of a substrate made of conductive polymer-coated polybutylene terephthalate (PBT) with wire bar No. 8 (wet film thickness 18 μm) was applied by a bar coating method and dried at 130 ° C. for 15 minutes to obtain a laminate in which a conductive polymer layer was formed on a PBT substrate.

(Step 1-2): Catalyst support This laminate was immersed in a catalyst bath containing 0.2 g / l palladium chloride-200 ml aqueous hydrochloric acid adjusted to 30 ° C. for 5 minutes, the laminate was taken out, washed with water, By drying, the laminated body which carry | supported the palladium catalyst on the electroconductive polymer layer was obtained.

(Step 1-3): A laminate carrying electroless plated palladium is immersed in a container containing a copper plating bath ATS add copper IW bath (Okuno Seiyaku Kogyo Co., Ltd.) adjusted to 32 ° C. to form a metal layer film When the thickness reached 0.5 μm, the laminate was pulled up, washed with water and dried.
By passing through (Process 1-1)-(Process 1-3), the plating thing in which the copper plating layer was formed in the single side | surface of the board | substrate made from PBT was obtained.

(Example 2)
(Step 2-1): Conductive polymer composition A was placed on one side of a substrate made of conductive polymer-coated polybutylene terephthalate (PBT). 8 (wet film thickness 18 μm) was applied by a bar coating method and dried at 130 ° C. for 15 minutes to obtain a laminate in which a conductive polymer layer was formed on a PBT substrate.

(Step 2-2): The dedope-treated laminate was immersed in a 10 w% NaOH aqueous solution (pH 10) adjusted to 45 ° C. for 10 minutes, and the laminate was taken out, washed with water, and dried to conduct the conductivity. A laminate having a conductive polymer layer was obtained.

(Step 2-3): Catalyst support This laminate was immersed in a catalyst bath containing 0.2 g / l palladium chloride-200 ml hydrochloric acid solution adjusted to 30 ° C. for 5 minutes, the laminate was taken out, washed with water, By drying, the laminated body which carry | supported the palladium catalyst on the electroconductive polymer layer was obtained.

(Step 2-4): The laminate carrying the electroless plating palladium is immersed in a container containing a copper plating bath ATS add-copper IW bath (Okuno Pharmaceutical Co., Ltd.) adjusted to 32 ° C., and a metal layer film When the thickness reached 0.5 μm, the laminate was pulled up, washed with water and dried.
By passing through (Process 2-1)-(Process 2-4), the plating thing in which the copper plating layer was formed in the single side | surface of the board | substrate made from PBT was obtained.

(Example 3)
In step 1-1, steps 1-1 to 1-3 are performed in the same manner as in Example 1 except that a substrate made of polyamide (manufactured by Polyplastics Co., Ltd.) is used instead of the PBT substrate. A plated product having a copper plating layer formed thereon was obtained.

Example 4
In step 1-1, steps 1-1 to 1-3 are performed in the same manner as in Example 1 except that a substrate made of polycarbonate is used instead of the PBT substrate, and a copper plating layer is formed on one surface of the polycarbonate substrate. A plated product was obtained.

(Example 5)
In step 1-1, steps 1-1 to 1-3 are performed in the same manner as in Example 1 except that a substrate made of ABS resin is used instead of the PBT substrate, and a copper plating layer is formed on one surface of the ABS resin substrate As a result, a plated product was obtained.

(Example 6)
In Step 1-1, Step 1-1 to Step 1-3 were performed in the same manner as in Example 1 except that a substrate made of polyphthalamide (manufactured by Kuraray Co., Ltd.) was used instead of the PBT substrate. A plated product having a copper plating layer formed on one side of the substrate was obtained.

(Example 7)
In Step 1-1, Step 1-1 to Step 1-3 were performed in the same manner as in Example 1 except that a substrate made of syndiotactic polystyrene (made by Idemitsu Kosan Co., Ltd.) was used instead of the PBT substrate. A plated product in which a copper plating layer was formed on one side of a tic polystyrene substrate was obtained.

(Example 8)
In Step 1-1, Step 1-1 to Step 1-3 were performed in the same manner as in Example 1 except that a substrate made of polycarbonate / ABS resin alloy (manufactured by Techno Polymer Co., Ltd.) was used instead of the PBT substrate. / A plated product having a copper plating layer formed on one side of an ABS resin alloy substrate was obtained.

Example 9
In Step 1-1, except that the conductive polymer composition B was used in place of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 10)
In Step 1-1, except that the conductive polymer composition D was used in place of the conductive polymer composition A, Step 1-1 to Step 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 11)
In Step 1-1, except that the conductive polymer composition E was used instead of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 12)
In Step 1-1, except that the conductive polymer composition F was used in place of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 13)
In Step 1-1, except that the conductive polymer composition G was used in place of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 14)
In Step 1-1, except that the conductive polymer composition H was used in place of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 15)
In Step 1-1, except that the conductive polymer composition I was used in place of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 16)
In Step 1-1, except that the conductive polymer composition J was used in place of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 17)
In Step 1-1, except that the conductive polymer composition K was used in place of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 18)
In Step 1-1, Step 1-1 to Step 1-3 were performed in the same manner as in Example 1 except that the conductive polymer composition L was used in place of the conductive polymer composition A to obtain a plated product. .

(Example 19)
In Step 1-1, except that the conductive polymer composition M was used in place of the conductive polymer composition A, Step 1-1 to Step 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 20)
In Step 1-1, except that the conductive polymer composition N was used in place of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 21)
In Step 1-1, except that the conductive polymer composition O was used in place of the conductive polymer composition A, Step 1-1 to Step 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Example 22)
In step 1-1, steps 1-1 to 1-3 are performed in the same manner as in Example 10 except that a substrate made of polyethersulfone (manufactured by Sumitomo Chemical Co., Ltd.) is used instead of the PBT substrate. A plated product having a copper plating layer formed on one side was obtained.

(Example 23)
In Step 1-1, Step 1-1 to Step 1-3 were performed in the same manner as in Example 10 except that a substrate made of polyphenylene sulfide (made by Idemitsu Kosan Co., Ltd.) was used instead of the PBT substrate. A plated product on which a plated layer was formed was obtained.

(Example 24)
In Step 1-1, Step 1-1 to Step 1-3 were performed in the same manner as in Example 10 except that a substrate made of liquid crystal polymer (manufactured by Sumitomo Chemical) was used instead of the PBT substrate, and copper was formed on one side of the substrate. A plated product on which a plated layer was formed was obtained.

(Comparative Example 1)
In Step 1-1, except that the conductive polymer composition C was used in place of the conductive polymer composition A, the steps 1-1 to 1-3 were performed in the same manner as in Example 1 to obtain a plated product. .

(Comparative Example 2)
(Step 3-1): Surface treatment 1
The PBT substrate was immersed in an OPC-1050 conditioner (Okuno Pharmaceutical Co., Ltd.) at 60 ° C. for 5 minutes, then washed with water and dried (surface treatment 1).

(Step 3-2): Surface treatment 2
Next, the PBT substrate subjected to the surface treatment 1 was immersed in ATS precondition PIW-1 (Okuno Pharmaceutical Co., Ltd.) at 45 ° C. for 2 minutes, then washed with water and dried (surface treatment 2). It was.

(Step 3-3): Surface treatment 3
Next, the PBT substrate subjected to the surface treatments 1 and 2 was immersed in an ATS Condicrine CIW-2 bath (Okuno Pharmaceutical Co., Ltd.) at 60 ° C. for 5 minutes, then washed with water and dried (surface treatment 3). )

(Step 3-4): Pre-dip Next, after the PBT substrate subjected to the surface treatments 1 to 3 is immersed in a pre-dip solution (OPC-SALM bath (Okuno Pharmaceutical Co., Ltd.)) at 20 ° C. for 2 minutes. It was washed with water and dried to obtain a pre-dip treated substrate.

(Step 3-5): Catalyst support Next, the pre-dip substrate was immersed in a catalyst liquid (OPC-80 catalyst bath (Okuno Pharmaceutical Co., Ltd.)) at 25 ° C. for 6 minutes, washed with water, and then activated. In order to give the agent, the substrate on which the catalyst was supported was obtained by immersing in an OPC-500 accelerator MX bath (Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 5 minutes, followed by washing with water and drying.

(Step 3-6): Electroless Plating Next, the substrate carrying the catalyst is immersed in an electroless copper plating bath ATS add copper IW bath (Okuno Pharmaceutical Co., Ltd.) for 10 minutes at 35 ° C., and the film thickness of the metal layer When the thickness became 0.5 μm, the laminate was pulled up, washed with water and dried.
By passing through (Process 3-1)-(Process 3-6), the plating thing in which the copper plating layer was formed on both surfaces of the board | substrate made from PBT was obtained.

The following evaluation was performed on Examples 1 to 24 and Comparative Examples 1 and 2. The results are shown in Table 1.

(Evaluation of plating appearance)
The state of the metal coating (electroless plating film) after electroless plating was visually observed and evaluated according to the following criteria. In Comparative Example 2, only one side was observed.
(Circle): The area of the part coat | covered with the metal is 95% or more of the area of the whole substrate surface in the board | substrate surface by which the metal film was formed.
(Triangle | delta): The area of the part coat | covered with the metal is 50% or more and less than 95% of the area of the whole substrate surface in the board | substrate surface by which the metal film was formed.
X: On the substrate surface on the side where the metal coating is formed, the area of the portion covered with metal is less than 50% of the total area of the substrate surface.

(Evaluation of plating uniformity)
The state of the metal coating (electroless plating film) after electroless plating was visually observed and evaluated according to the following criteria. In Comparative Example 2, only one side was observed.
○: 95% or more of the area of the entire surface of the metal coating is a mirror surface.
Δ: On the entire surface of the metal coating, 50% or more and less than 95% of the area is a mirror surface.
X: Less than 50% of the area of the entire surface of the metal coating is a mirror surface.

(Plating deposition start time)
The time from when the substrate was immersed in the electroless plating bath to when the metal deposition started was defined as the plating deposition start time. Here, the deposition of the plating was visually confirmed.

(Plating deposition finish time)
The time required from when the substrate was immersed in the electroless plating bath until the substrate was lifted when the metal film thickness was 0.5 μm or more was measured.

From the results of Examples and Comparative Examples, the method for producing a plated product of the present invention can form an electroless plating film in a shorter time than when polypyrrole is used as a conductive polymer (Comparative Example 1). And it became clear that the plating appearance is favorable. In addition, it is clear that an electroless plating film can be formed in a short time and the number of steps can be reduced as compared with a conventionally used method that does not use a conductive polymer (Comparative Example 2). It became.
In addition, it was revealed that a more uniform metal film (electroless plating film) can be formed by using a composition containing a leveling agent when forming the conductive polymer layer.

The present invention is used for the manufacture of plated products such as circuit components, electromagnetic wave shielding members, and ornaments.

Claims (7)

at least,
(1) A step of applying a composition containing a polythiophene-based conductive polymer to part or all of the surface of the substrate (A) to form a conductive polymer layer (B),
(2) A step of attaching a metal catalyst to the conductive polymer layer (B) to form a conductive polymer layer (C) containing the metal catalyst, and
(3) forming a metal layer (D) by electroless plating on the conductive polymer layer (C);
It is a manufacturing method of the plated product characterized by passing through,
In the step (1), before applying the composition containing the polythiophene-based conductive polymer and after applying the composition containing the polythiophene-based conductive polymer, a dedoping treatment is performed on the polythiophene-based conductive polymer. The manufacturing method of the plated product which is not applied The method for producing a plated product according to claim 1, wherein the composition containing the polythiophene-based conductive polymer further contains a leveling agent. The plating according to claim 1 or 2, wherein the polythiophene-based conductive polymer is composed of poly (3,4-disubstituted thiophene) or a composite of poly (3,4-disubstituted thiophene) and polyanion. Manufacturing method. The composition containing the said polythiophene type conductive polymer contains the compound containing an acrylic group, the compound which has an epoxy group, polyester, a polyurethane, an acrylic resin, or an epoxy resin in any one of Claims 1-3. The manufacturing method of the plated material of description. The said base | substrate (A) is a resin base | substrate, The manufacturing method of the plated article of any one of Claims 1-4. The resin base material resin is epoxy resin, polyacetal, polyamide, polyphthalamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, syndiotactic polystyrene, polyacrylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyether The method for producing a plated product according to claim 5, which is at least one selected from the group consisting of ketone, polyimide, polyetherimide, fluororesin, liquid crystal polymer, polyethylene terephthalate, ABS resin, and nylon. The method for producing a plated product according to any one of claims 1 to 6, wherein the plated product is a circuit component, an electromagnetic wave shielding member, or a decorative product.