JP5422812B2 - Coating composition for electroless plating - Google Patents

Description

  The present invention relates to a coating composition for electroless plating.

  The technology for forming metal plating (hereinafter also simply referred to as plating) on non-conductive substrates such as polyethylene terephthalate (PET) and polycarbonate (PC) is to provide conductive films such as electromagnetic wave seals; Decorative plating for the purpose of: Electronic components such as integrated circuits and resistors; In particular, when an electronic component is manufactured, a technique for forming the plating is used when forming a conductive wiring pattern on a non-conductive substrate.

  A non-conductive substrate cannot obtain a metal bond at the interface with the plating. Therefore, in order to obtain excellent adhesion between the nonconductive substrate and the plating, by performing etching (roughening) to form fine irregularities on the surface of the nonconductive substrate, It is necessary to give an anchor effect (throwing effect). This etching has a problem that the process is complicated and a chemical having a high environmental load such as chromic acid has to be used.

  On the other hand, Patent Documents 1 to 4 describe a technique for forming a plating on a non-conductive substrate by performing a treatment aiming at the same effect as etching without using chromic acid. . In both Patent Documents 1 and 2, there is a method in which a chemical bond is generated between the base material, the adhesive layer, and the catalyst by forming an adhesive layer having a binding property with the catalyst on the base material. Have been described. Patent Document 3 describes a technique for imparting an anchor effect by etching a substrate with UV or ozone. Patent Document 4 describes a method for forming an underlayer for electroless plating by applying an ink having an electroless plating catalyst onto a substrate.

JP 2010-031318 A JP 2008-050541 A JP 2010-270389 A JP 2010-171045 A

  However, all of Patent Documents 1 to 3 require a catalyst application step and a catalyst activation step between the pretreatment step for imparting adhesion and the electroless plating step. That is, there is a problem that the number of steps is not different from the conventional etching with chromic acid, and the steps are complicated. Moreover, in patent document 4, before performing electroless plating, it calls an activation process, and the reduction process by a boron type compound and the washing | cleaning process which removes the said boron type compound are required. When such an ink is used, the process becomes complicated, and there is also a problem of environmental burden due to the boron-based compound.

  Therefore, development of a coating composition that can easily perform electroless plating treatment, has little adverse effect on the environment, is highly safe, and can impart excellent plating adhesion Is desired.

  The present invention is a coating composition that enables an electroless plating process to be easily performed, has a small adverse effect on the environment, has high safety, and can impart excellent plating adhesion. The purpose is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present invention has found that a coating composition capable of achieving the above object can be obtained by using specific components, and the present invention is completed here. It came.

That is, the present invention relates to the following electroless plating coating composition.
1. The following (1) to (3):
(1) a composite of palladium particles and a dispersant,
(2) solvent, and
(3) A coating composition for electroless plating containing a binder resin,
The complex is obtained by reducing palladium ions in the presence of a dispersant,
The solvent includes at least one selected from the group consisting of N-methylpyrrolidone, dimethylformamide, and dimethylacetamide,
The binder resin, characterized in that at least one member selected from the group consisting of polyester resins, Polyurethane resins, polyamide resins and polyimide resins, for electroless plating coating composition.
2. The coating composition for electroless plating according to Item 1, wherein the content of the binder resin is 10 ² to 10 ⁴ parts by mass with respect to 100 parts by mass of the composite.
3. Item 3. The coating composition for electroless plating according to Item 1 or 2, wherein the content of the solvent is 10 ² to 10 ⁶ parts by mass with respect to 100 parts by mass of the composite.
4). Item 4. The coating composition for electroless plating according to any one of Items 1 to 3, wherein the dispersant is a block copolymer type polymer dispersant having a hydroxyl group and / or a carboxyl group.
5. A method for producing a coating composition for electroless plating containing a solvent and a binder resin,
The binder resin is at least one selected from the group consisting of polyester resins, Polyurethane resins, polyamide resins and polyimide resins,
The solvent includes at least one selected from the group consisting of N-methylpyrrolidone, dimethylformamide, and dimethylacetamide,
The following (i) and (ii):
(i) Step 1 in which a palladium ion and a dispersant are present in a solvent, and
(ii) Step 2 of reducing the palladium ions by reacting the palladium ions with a reducing agent;
In order, The manufacturing method of the coating composition for electroless plating characterized by the above-mentioned.
6). The to-be-plated object obtained by apply | coating the coating composition for electroless plating in any one of said claim | item 1-4 with respect to a base material, and giving electroless plating.
7). Item 7. The plated object according to Item 6, wherein the application is pattern printing by an inkjet printing method, a gravure offset printing method, or a flexographic printing method.
8). A method for forming an electroless plating film by applying a coating composition for electroless plating according to any one of Items 1 to 4 to a substrate to form a coating film, and then contacting the electroless plating solution. .

<< Coating composition for electroless plating of the present invention >>
The electroless plating coating composition of the present invention includes the following (1) to (2):
(1) a composite of palladium particles and a dispersant, and
(2) A coating composition for electroless plating containing a solvent, wherein the composite is obtained by reducing palladium ions in the presence of a dispersant. The coating composition for electroless plating of the present invention (hereinafter also referred to as the coating composition of the present invention) can form a coating film for electroless plating more easily and efficiently than the conventional method, Moreover, there are few adverse effects on the environment, and safety is high. Moreover, the said electroless-plating coating film can form the electroless-plating film excellent in adhesiveness and an external appearance film | membrane, and is excellent also in the precipitation rate of the said electroless-plating film | membrane.

  Hereinafter, each component of the coating composition for electroless plating of the present invention will be described. In the present invention, indications such as parts and% are used, and unless otherwise specified, parts by mass or mass% (wt%) are expressed.

(1) Composite of palladium particles and dispersant The coating composition for electroless plating of the present invention contains a composite of palladium particles (Pd particles) and a dispersant (hereinafter, this composite is referred to as a Pd composite). Also called body).

  The Pd complex can be produced as follows. That is, it can be obtained by reducing palladium ions (Pd ions) in the presence of a dispersant. For example, after making a dispersing agent and palladium ion exist in a solvent, it can obtain by reducing the said palladium ion.

As the dispersant, the shape of the Pd composite satisfies the condition that (i) the dispersants are intertwined with each other and (ii) at least some of the dispersants are in contact with each other. Is preferred. For example, polycarboxylic acid polymer dispersants such as polycarboxylic acid ammonium salt, polycarboxylic acid sodium salt, polycarboxylic acid triethylamine salt, polycarboxylic acid triethanolamine salt; polyoxyethylene alkyl ether carboxylate, alkyl hydroxy ether Block copolymer type polymer dispersant having hydroxyl group such as carboxylate; Block having carboxyl group such as acrylic acid-maleic acid copolymer, styrene-maleic acid copolymer, acrylic acid-sulfonic acid copolymer Copolymer type polymer dispersants; and the like can be used. A dispersing agent can be used 1 type or in combination of 2 or more types. Among the dispersants, a block copolymer type polymer dispersant having a hydroxyl group and / or a carboxyl group is preferable.
Polycarboxylic acid-based polymer dispersants are Nopco Santo K, R, RFA, Nop Cosperth 44-C, SN Dispersant 5020, 5027, 5029, 5034, 5045, 5468 manufactured by San Nopco Co., Ltd., Demole P, manufactured by Kao Co., Ltd. It is sold as EP, Poise 520, 521, 530, 532A, etc. The block copolymer type polymer dispersant having a carboxyl group is sold as DISPERBYK 180, 187, 191, 194, Nippon Kayaku Co., Ltd. Aquaric TL, GL, LS. Moreover, as a block copolymer type polymer dispersing agent having a hydroxyl group, it is sold as DISPERBYK190, 2010, etc. manufactured by BYK Japan Japan Co., Ltd.

  Examples of the compound that supplies palladium ions include palladium chloride, palladium sulfate, palladium nitrate, palladium acetate, palladium benzoate, palladium salicylate, palladium paratoluenesulfonate, palladium perchlorate, and palladium benzenesulfonate. The compound which supplies palladium ion can be used 1 type or in combination of 2 or more types.

  Examples of the method for reducing Pd ions include a method in which a dispersing agent and Pd ions are present in a solvent and then the reducing agent is added to the solvent. Thereby, Pd ion and a reducing agent contact and react. Examples of the reducing agent include secondary or tertiary amines such as hydrazine hydrate (hydrazine monohydrate), sodium borohydride, N, N dimethylethanolamine and diethanolamine.

  As the solvent used for the reduction (the solvent for allowing the dispersant and Pd ions to exist), the same solvent as the solvent described in the following (2) can be used. A solvent can be used 1 type or in combination of 2 or more types.

  As shown in FIG. 2, the shape of the Pd composite is such that (i) the dispersing agents are intertwined with each other, (ii) at least some of the dispersing agents are joined to each other, and (iii) It is thought that the structure has Pd particles attached to the dispersant. Specifically, the shape of the Pd complex may be a random coil shape, a dense spherical shape, or a spherical structure.

  Most of the Pd particles are considered to be attached to the outside of the dispersant. For example, when the shape of the Pd complex (the shape of the dispersant) is a dense sphere, it is considered that most of the Pd particles are attached to the spherical surface side (outside).

  The mass ratio between the Pd particles and the dispersant in the Pd composite is about Pd particles: dispersant = 50: 50 to 95: 5, and Pd particles: dispersant = 65: 35 to 85:15 is preferable.

  The average particle diameter of the Pd particles alone is not particularly limited, but is preferably 2 to 10 nm. In the present specification, the particle diameter of the Pd particles is measured by a transmission electron microscope described later. Further, in this specification, the average particle diameter of Pd particles is calculated by randomly selecting 10 Pd particles, measuring the particle diameter of the Pd particles with the transmission electron microscope, and averaging the number. (Number-based average diameter).

  On the other hand, the average particle diameter of the Pd composite is not particularly limited, but preferably has a spherical structure (FIG. 2 in this specification) having an average particle diameter of about 40 to 300 nm as a whole. In the present specification, the average particle size of the Pd complex is measured with a particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-1000) (mass standard average diameter). It can also be measured with a scanning electron microscope.

The reason why the coating film for electroless plating of the present invention can form an electroless plating film excellent in adhesion and appearance film, and is excellent in the deposition rate of the electroless plating film is based on the following principle. It is considered a thing.
(Principle) The inside of the structure formed by the Pd complex is included to adsorb the solvent. The solvent inside the Pd composite has a lower drying rate than the solvent in the coating composition of the present invention. Therefore, when the coating composition of the present invention is applied to the substrate, the solvent in the coating composition is first dried to form the entire coating film, and then the solvent inside the Pd complex present in the coating film is dried. By doing so, crater-like irregularities are formed on the surface of the coating film. Thereby, a coating film for electroless plating (hereinafter also simply referred to as a coating film) is formed. There are many Pd particles on the uneven surface. Since the coating film is formed on such a principle, the following (a) and (b):
(a) Since there are many Pd particles so as to be concentrated on the coating film surface, the reactivity between the coating film surface and the electroless plating solution is excellent,
(b) Since the unevenness is formed on the coating film surface, the anchor effect between the plating film and the coating film is excellent.
It is thought that the effect is played.

(2) Solvent The coating composition of the present invention contains a solvent (dispersion medium). The solvent disperses the Pd complex.

The solvent (dispersion medium) of the Pd complex is not particularly limited as long as the Pd complex is dispersed.
From the viewpoint of imparting dispersibility of the Pd complex in the coating composition for electroless plating, it is preferable to include water and / or an aprotic polar solvent. In addition, a solvent can be used 1 type or in combination of 2 or more types.

  Examples of the aprotic polar solvent include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and the like. The solvent can also be converted after the reduction reaction of palladium ions (for example, the solvent is converted from water to NMP).

  In addition to water and / or aprotic polar solvents, alcohols such as methanol and ethanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; methyl benzoate Aromatic carboxylic acid esters such as ethyl benzoate and methyl salicylate; aromatic hydrocarbons such as toluene and xylene; glycols such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, and butyl carbitol acetate Ether esters; alkanol esters such as ethyl acetate and butyl acetate; When using these solvents, the content is preferably 1 to 5000 parts by mass with respect to 100 parts by mass of water and / or aprotic polar solvent.

Although content of a solvent is not specifically limited, About 10 < ² > -10 < ⁶ > mass part is preferable with respect to 100 mass parts of the above-mentioned Pd composite_body, and 10 < ³ > -10 < ⁵ > mass part is more preferable.

(3) Binder resin The coating composition of the present invention may contain a binder resin. By using the binder resin, the coating film for electroless plating can be more firmly adhered to the substrate.

  As the binder resin, a resin that is dispersed or dissolved in the solvent (2) can be used. Specific examples of the binder resin include epoxy resin, polyester resin, acrylic resin, polyurethane resin, polyamide resin, polyimide resin, shellac resin, melamine resin, urea resin, and the like. Especially, at least 1 sort (s) chosen from the group which consists of a polyester resin, a polyamide resin, and a polyimide resin is preferable. Binder resin can be used 1 type or in combination of 2 or more types.

When the binder resin is used, the content of the resin is preferably 10 ² to 10 ⁴ parts by mass and more preferably 500 to 2000 parts by mass with respect to 100 parts by mass of the Pd composite.

≪Method for producing coating composition for electroless plating of the present invention≫
The method for producing the coating composition of the present invention comprises:
(I) Step 1 in which palladium ions and a dispersant are present in the solvent, and (ii) Step 2 in which the palladium ions are reacted with the reducing agent.
including. According to the said manufacturing method, the coating composition for electroless plating which can form the coating film for electroless plating can manufacture easily and efficiently with little bad influence with respect to an environment. The coating composition for electroless plating can form a coating film for electroless plating more easily and efficiently than the conventional method, and has little adverse effect on the environment and high safety. The coating film for electroless plating can form an electroless plating film excellent in adhesion and appearance film, and is excellent in the deposition rate of the electroless plating film.

  In step 1, palladium ions and a dispersant are present in a solvent. As the palladium ion, the above-mentioned compound supplying the palladium ion can be used as a supply source. As the dispersant, the above-described dispersants can be used.

  The use ratio (mass ratio) of the palladium ions and the dispersant in Step 1 is usually about 10 to 200 parts by mass with respect to 100 parts by mass of the palladium ions. The dispersant is preferably 30 to 150 parts by mass, more preferably 50 to 100 parts by mass with respect to 100 parts by mass of palladium ions.

As the solvent used in Step 1, the same solvent as the solvent of (2) above can be used. The amount of the solvent used is not particularly limited as long as the palladium ions and the dispersant can be uniformly present, but is preferably 10 ² to 2 × 10 ⁶ parts by mass with respect to 100 parts by mass of palladium ions, and 10 ³ to 2 ×. 10 ⁵ parts by mass is more preferred. The said solvent can be used 1 type or in combination of 2 or more types.

  In step 2, palladium ions are reduced by the reducing agent by reacting the palladium ions with the reducing agent. That is, in Step 2, a palladium ion reduction reaction occurs, and as a result, the above-mentioned Pd complex (1) can be obtained. As the reducing agent in step 2, the reducing agent used for preparing the Pd complex of (1) described above can be used. Although the usage-amount of a reducing agent is not specifically limited, It is about 100-800 mass parts with respect to 100 mass parts of palladium ions, and 200-600 mass parts is preferable.

  Regarding step 2, the reaction temperature is about 35 to 45 ° C, and the temperature is raised to about 50 to 60 ° C. The reaction time is not particularly limited, but may be about 1 to 5 hours. The pressure and atmosphere during the reaction are not particularly limited, and may be carried out under atmospheric pressure and air (air) atmosphere. The reaction can be performed in an open system such as a beaker. As a reaction method, a solution containing palladium ions, a dispersant and a reducing agent may be stirred with a bladed stirring rod.

  The coating composition for electroless plating of the present invention can be obtained by the procedure of only step 1 and step 2, but after step 2, for example, (addition) of (2) solvent, (3) binder resin, etc .; Pd Other operations such as separation of the complex-containing liquid may be performed. This point will be described below.

  After the step 2, the above-mentioned (2) solvent and / or (3) binder resin can be contained. In addition, the solvent is converted after the reduction reaction of palladium ions (for example, water is used as the solvent in Step 1 and the water is converted into NMP after Step 2 so that the electroless plating paint composition using NMP as the solvent is used. It is also possible that

After step 2, the Pd complex-containing liquid obtained in step 2 can be separated by ultrafiltration. By this operation, it is possible to remove inorganic salts, excess dispersants, and the like contained in the Pd complex-containing liquid. More specifically, filtration operation and water, solvent, etc. (especially water) supplementation operations can be repeated for the Pd complex-containing liquid.
<< Substance to be plated of the present invention >>
The object to be plated of the present invention is obtained by applying the coating composition of the present invention to a substrate and then performing electroless plating to form an electroless plating film. The electroless plating film formed on the object to be plated is excellent in adhesion.

  Although it does not specifically limit as a base material, For example, resin, a nonwoven fabric (or woven fabric), ceramics, etc. are mentioned. Specific resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyester resin such as polylactic acid ester, acrylic resin such as polymethyl methacrylate (PMMA), polycarbonate resin (PC), polystyrene resin, polychlorinated resin. Vinyl resin, polyamide resin, polyimide resin, polyetherimide resin, polyacetal resin, polyether ether ketone resin, cyclic polyolefin resin, polyethylene resin, polyphenylene sulfide resin, liquid crystal polymer, modified polyphenyl ether resin, polysulfone resin, phenol resin, etc. Is mentioned. Specific examples of the nonwoven fabric (or woven fabric) include nonwoven fabric (or woven fabric) made of wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, and the like. Specific ceramics include glass and alumina.

  The method for applying the coating composition to the substrate is not particularly limited. For example, a gravure printing machine (gravure offset), flexographic printing machine, ink jet printing machine, dipping, spraying, spin coater, roll coater, reverse coater. It can be printed or coated using a screen printer or the like.

  After applying the coating composition of the present invention, a drying treatment can be performed. The drying step can efficiently remove an unnecessary solvent when performing electroless plating, and can improve the adhesion between the coating film and the substrate and the surface strength of the coating film.

  The temperature of the drying treatment is preferably about 60 to 400 ° C. More preferably, it is 80-150 degreeC. Although depending on the drying temperature, the drying time is usually about 0.1 minute (6 seconds) to 60 minutes. More preferably, it is about 10 to 30 minutes.

  The electroless plating coating includes a Pd composite. The Pd complex exists in a state of being uniformly dispersed in the coating film. Therefore, electroless plating can be more efficiently performed on the coating film.

  The thickness of the coating film before drying can be appropriately selected depending on the intended use. Before drying, it is usually about 1 to 30 μm, preferably 2 to 20 μm.

  The thickness of the coating film after drying is usually about 0.05 to 3 μm, preferably 0.1 to 1 μm. If the thickness of the coating film after drying is within the above range, the adhesion between the substrate and the coating film and the adhesion between the electroless plating film (metal film) and the coating film are particularly excellent.

  The base material on which the coating film is formed by the above method comes into contact with a plating solution for depositing a metal, thereby forming an electroless plating film. Electroless plating has good reactivity, and the obtained electroless plating film has no unevenness and is excellent in adhesion and appearance film.

  The plating solution is not particularly limited as long as it is a plating solution usually used for electroless plating, and examples thereof include copper, gold, silver, nickel, and chromium. In particular, copper or nickel is preferable from the relationship with the coating film formed by the coating composition of the present invention. About these plating conditions, what is necessary is just to follow a conventional method.

  For example, the electroless plating temperature is usually about 25 to 45 ° C. in the electroless copper plating bath, the processing time is about 10 to 20 minutes, and the deposited film thickness is about 0.3 to 0.4 μm. In the electroless nickel boron bath, the treatment temperature is about 55 to 70 ° C., and the deposition rate is usually about 5 μm / hr (60 ° C.). In an electroless nickel phosphorus bath, it is usually about 85 to 95 ° C., and the deposition rate is usually about 20 μm / hr (90 ° C.).

  The coating composition for electroless plating of the present invention can form a coating film for electroless plating more easily and efficiently than the conventional method, and has less adverse effects on the environment and high safety. Moreover, the said electroless-plating coating film can form the electroless-plating film excellent in adhesiveness and an external appearance film | membrane, and is excellent also in the precipitation rate of the said electroless-plating film | membrane.

It is the schematic of the coating composition for electroless plating of this invention. It is the schematic of the Pd complex of this invention. It is the schematic of the to-be-plated object of this invention. The SEM image of the coating film for electroless plating used by this invention is shown. The TEM image of Pd composite_body | complex used by this invention is shown. The particle size distribution of the Pd composite in the coating composition for electroless plating of Reference Example 1 of the present application is shown. The particle size distribution is measured with a particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-1000).

  The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Production Example 1: Preparation of Pd complex-containing liquid A 944.5 g of ion-exchanged water was placed in a 3 liter flask, and 5.0 g of palladium nitrate was added to the ion-exchanged water, followed by stirring. Thereby, palladium nitrate was dissolved in water. To the aqueous solution, 3.8 g of a block copolymer type polymer dispersant having a carboxyl group (DISPERBYK194, manufactured by Big Chemie Japan, nonvolatile content 53 wt%) was further added and dissolved in the aqueous solution. This solution was heated to 42 ° C., and 10.0 g of hydrazine monohydrate was added with stirring. Thereafter, the solution was stirred at room temperature (23 ° C.) for 1 hour. The temperature of the solution rose to 53 ° C. after the addition of hydrazine monohydrate, but the temperature of the solution after stirring for 1 hour was 40 ° C. By this operation, palladium ions in the aqueous solution were reduced. This solution was subjected to ultrafiltration filter AHP-1010 (manufactured by Asahi Kasei Corporation) to separate the reduced Pd complex-containing liquid and the inorganic salt-containing liquid. To the Pd complex-containing liquid obtained by this operation, ion-exchanged water having the same mass as that of the separated inorganic salt-containing liquid was added, and the separation operation was again performed using an ultrafiltration filter. This ion exchange water supplementing operation and separation operation were repeated 5 times. The electrical conductivity (conductivity) of the Pd complex-containing liquid obtained after the operation was 28 μS · cm ⁻¹ . That is, since the electrical conductivity was 30 μS · cm ⁻¹ or less, it was confirmed from this result that the inorganic salt could be removed from the Pd complex-containing liquid. Regarding the obtained Pd complex-containing liquid, the Pd complex content was examined by TG / DTA analysis, and it was found from the residual solid content at 550 ° C. that the Pd complex content was 1.2 wt%. It was. Further, the average particle diameter of the Pd particles was in the range of 2 to 10 nm, and the mass ratio of the Pd particles and the dispersant in the Pd composite was Pd particles: dispersant = 75: 25.

Production Example 2: Preparation of Pd complex-containing liquid B
In place of DISPERBYK194, a Pd complex-containing liquid B was prepared in the same manner as in Production Example 1 except that the block copolymer type polymer dispersant DISPERBYK2010 having a hydroxyl group (non-volatile content: 40 wt%) was used. Got. In addition, the Pd complex content rate of the Pd complex containing liquid B was 1.4 wt%. Further, the average particle diameter of the Pd particles was in the range of 2 to 10 nm, and the mass ratio of the Pd particles and the dispersant in the Pd composite was Pd particles: dispersant = 75: 25.

Production Example 3 Production of Pd Complex-Containing Liquid C The Pd complex-containing liquid A was rotated at a rotational speed of 13000 G load for 16 hours in a centrifuge to precipitate the solid content. After removing the supernatant by decantation, N-methylpyrrolidone having the same mass as that of the removed supernatant was added. Thereafter, the N-methylpyrrolidone-containing liquid was stirred to disperse the Pd complex so that there was no undissolved residue at the bottom of the circular tube. This liquid was rotated in a centrifuge for 16 hours at a rotation speed of 13000 G load. By this operation, the solid content was settled and the supernatant was removed. This operation was performed 4 times. Then, after confirming that the water content of the precipitated solid content was 1 wt% or less by Karl Fischer method, by adding N-methylpyrrolidone to the solid content, Pd complex containing A Pd complex-containing liquid C (dispersion medium: N-methylpyrrolidone (NMP)) having a rate of 8 wt% was obtained. The average particle size of the Pd particles was in the range of 2 to 10 nm, and the mass ratio of Pd particles to dispersant in the Pd composite was Pd particles: dispersant = 80: 20.

Production Example 4: Preparation of Pd ion aqueous solution D 936.8 g of ion-exchanged water was placed in a 3 liter flask, and 21.6 g of palladium nitrate was added to the ion-exchanged water, followed by stirring. Thereby, palladium nitrate was dissolved in water. To this aqueous solution, 40.0 g of DISPERBYK194 (Bic Chemie Japan, nonvolatile content 53 wt%) was added and dissolved in the aqueous solution. To this aqueous solution, 1.6 g of sodium hydroxide was added so that pH = 9. Thereby, Pd ion aqueous solution D was obtained. The concentration of Pd ions was 1 wt%.

Reference example 1
As shown in Table 1 below, Pd complex-containing liquid A 8.3 wt%, polyester resin aqueous solution (RZ-570, solid content 25 wt%, manufactured by Kyoyo Chemical Co., Ltd.) 4.0 wt%, and ion-exchanged water 87.7 wt% Thus, a coating composition a for electroless plating was produced. The coating composition a was applied onto a polyethylene terephthalate (PET) film (SL-50, manufactured by Teijin DuPont Films Ltd.) using a bar coater # 12 and dried in an oven for drying at 105 ° C. for 5 minutes. . Thereby, the coating composition-coated film of Reference Example 1 was obtained.

Reference example 2
As shown in Table 1 below, Pd complex-containing liquid B 7.1 wt%, polyester resin aqueous solution (RZ-570, solid content 25 wt%, manufactured by Kyoyo Chemical Co., Ltd.) 4.0 wt%, and ion-exchanged water 88.9 wt% are mixed Thus, a coating composition b for electroless plating was produced. Then, it replaced with the said coating composition a, and obtained the coating composition coating film of the reference example 2 like the said reference example 1 except using the said coating composition b.

Reference example 3
As shown in Table 1 below, in the same manner as in Reference Example 1, a coating composition a for electroless plating was produced. The black ink was extracted from a black ink cartridge of an inkjet printer (PX-A550, manufactured by Seiko Epson Corporation), washed, and then filled with the coating composition a. The cartridge filled with the coating composition a was set in the printer (PX-A550), and a line and space pattern of 300 μm / 300 μm was printed on a PET film (SL-50, manufactured by Teijin DuPont Films Ltd.) . Thereafter, the coating composition-coated film of Reference Example 3 was obtained by drying at room temperature (23 ° C.) for 30 minutes.

Example 4
As shown in Table 1 below, Pd complex containing liquid C1.25wt%, polyimide ink (Q-IP-X0897, made by PI Engineering Laboratory, solid content 32wt%) 3.13wt% and cyclohexanone 95.62wt% were mixed. Thus, a coating composition c for electroless plating was produced. The coating composition c was applied onto a polyimide film (Kapton 200H, manufactured by Toray Industries, Inc.) using a bar coater # 12 and dried in an oven for drying at 105 ° C. for 5 minutes. Thereafter, it was further dried at 300 ° C. for 5 minutes in a drying oven. This obtained the coating composition application film of Example 4.

Example 5
As shown in Table 1 below, Pd complex-containing liquid C 25.0 wt%, polyimide ink (Q-IP-X0897, manufactured by PI Engineering Laboratory, solid content 32 wt%) 46.88 wt%, cyclohexanone 14.06 wt% and butyl cellosolve acetate A coating composition d for electroless plating was prepared by mixing 14.06 wt%. The coating composition d was filled in the pores of the gravure intaglio formed at a pitch of 100 μm using a doctor blade. A transfer blanket rubber roll (A (0.6) SP11-1, manufactured by Kinyo Co., Ltd.) was brought into close contact with the portion filled with the coating composition d, and the coating composition d was transferred onto the roll. Thereafter, the coating composition d was transferred onto the PET film by bringing the blanket rubber roll into close contact with the PET film (SL-50, manufactured by Teijin DuPont Films Ltd.). This obtained the coating composition coating film of Example 5.

Example 6
As shown in Table 1 below, Pd complex-containing liquid C25.0wt%, polyamide resin (Tomide 558, T & K TOKA Corporation) 15.0wt%, toluene 15.0wt%, isopropanol 15.0wt%, and cyclohexanone 30.0wt% are mixed Thus, a coating composition e for electroless plating was produced. Then, it replaced with the said coating composition d, and obtained the coating composition application film of Example 6 like the said Example 5 except using the said coating composition e.

Comparative Example 1
As shown in Table 1 below, Pd ion aqueous solution D10.0 wt%, polyester resin aqueous solution (RZ-570, solid content 25 wt%, manufactured by Kyoyo Chemical Co., Ltd.) 4.0 wt%, and ion-exchanged water 86.0 wt% are mixed. A coating composition f was prepared. Then, it replaced with the said coating composition a, and obtained the coating composition coating film of the comparative example 1 like the said reference example 1 except using the said coating composition f.

Test Example: Evaluation of Electroless Plating Property A plating film is deposited by immersing the coating composition-coated films of Examples 4 to 6 , Reference Examples 1 to 3 and Comparative Example 1 obtained above in an electroless plating bath. It was evaluated whether or not. The electroless copper plating bath is Urumura Kogyo Sulcup PSY (initial Cu concentration 2.5g / l, bath volume 500ml, 30 ° C 15min), the electroless nickel plating bath is Uemura Kogyo BEL801 (initial Ni concentration 6g / l, bath volume 500 ml 65 ° C. 15 minutes).

  In addition, the electroless plating property was evaluated as follows. That is, a case where good metal deposition occurred immediately after immersion in the plating bath and a copper or nickel plating film could be formed was evaluated as ◯. The case where no metal deposition reaction occurred and a plating film could not be formed was evaluated as x evaluation.

  The results are shown in Table 1 below. The upper part of Table 1 shows the mass% of each sample used in preparing each coating composition, and the middle part of Table 1 shows the mass% of each component in each coating composition. The lower part in 1 shows the results of the coating method and test examples.

Claims (8)

The following (1) to (3):
(1) a composite of palladium particles and a dispersant,
(2) solvent, and
(3) A coating composition for electroless plating containing a binder resin,
The complex is obtained by reducing palladium ions in the presence of a dispersant,
The solvent includes at least one selected from the group consisting of N-methylpyrrolidone, dimethylformamide, and dimethylacetamide,
The binder resin, characterized in that at least one member selected from the group consisting of polyester resins, Polyurethane resins, polyamide resins and polyimide resins, for electroless plating coating composition. The coating composition for electroless plating according to claim 1, wherein the content of the binder resin is 10 ² to 10 ⁴ parts by mass with respect to 100 parts by mass of the composite. The coating composition for electroless plating according to claim 1 or 2, wherein the content of the solvent is 10 ² to 10 ⁶ parts by mass with respect to 100 parts by mass of the composite.   The coating composition for electroless plating according to any one of claims 1 to 3, wherein the dispersant is a block copolymer type polymer dispersant having a hydroxyl group and / or a carboxyl group. A method for producing a coating composition for electroless plating containing a solvent and a binder resin,
The binder resin is at least one selected from the group consisting of polyester resins, Polyurethane resins, polyamide resins and polyimide resins,
The solvent includes at least one selected from the group consisting of N-methylpyrrolidone, dimethylformamide, and dimethylacetamide,
The following (i) and (ii):
(i) Step 1 in which a palladium ion and a dispersant are present in a solvent, and
(ii) Step 2 of reducing the palladium ions by reacting the palladium ions with a reducing agent;
In order, The manufacturing method of the coating composition for electroless plating characterized by the above-mentioned.   The to-be-plated object obtained by apply | coating the coating composition for electroless plating in any one of Claims 1-4 with respect to a base material, and then applying electroless plating.   The to-be-plated object of Claim 6 whose said application | coating is pattern printing by an inkjet printing system, a gravure offset printing system, or a flexographic printing system.   A method for forming an electroless plating film by applying a coating composition for electroless plating according to any one of claims 1 to 4 to a substrate to form a coating film, and then contacting the electroless plating solution. .

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