Undercoat paint for plating, substrate with coating layer, and method for manufacturing plated product using these

Abstract

To provide primer paint for plating that enables thin-wire printing of 50 μm or less in wire width and eliminates breaking of a plating primer coating layer even if a base material with a coating layer is drawn after the thin-wire printing of 50 μm or less in wire width.SOLUTION: There is provided primer paint for plating used to form a metal plating film on a base material by an electroless plating method, and the primer paint for plating includes electrically conductive or reducible polymer fine particles, synthetic resin and an inorganic filler, wherein the primer paint contains 5 to 19 mass pts. of the electrically conductive or reducible polymer fine particles for 100 mass pts. of the synthetic resin in terms of solid content rate, and 11 to 45 mass pts. of the inorganic filler for 100 mass pts. of the synthetic resin in terms of solid content rate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a primer coating for plating, a substrate with a coating layer, and a method for producing a plated product using these. [Background technology]

[0002] In recent years, fine-line printing of electrode materials for printed circuit boards, touch sensors, and the like has progressed in order to achieve higher integration and reduce visibility. Touch sensors are also increasingly being made three-dimensional, rather than just flat. A known method for providing electrode materials on substrates with complex three-dimensional shapes is to form the electrode materials on the substrate and then shaping them three-dimensionally by vacuum forming or other methods. Metal materials such as copper, silver, and gold, or non-flexible metal oxide materials such as indium tin oxide, are generally used for electrode materials used in printed circuit boards and touch sensors. However, when a substrate having an electrode member made of such a non-flexible material is three-dimensionally molded, the non-flexible material cannot follow the deformation of the substrate, resulting in a problem of breakage. On the other hand, it is known to use flexible materials such as conductive paste as electrode members, but even flexible materials such as conductive paste lack extensibility, and when attempting to form three-dimensional shapes after printing fine lines on a substrate, problems arise such as broken lines or increased resistance.

[0003] To address these issues, Patent Document 1 describes a three-dimensionally molded plated product using a specific coating layer. Specifically, the coating layer (plating base coating layer) is formed on a substrate and is composed of reducible or conductive polymer microparticles, a binder (synthetic resin), and an inorganic filler. The binder (synthetic resin) content is 0.1 to 60 parts by weight per 1 part by weight of the reducible or conductive polymer microparticles, and the inorganic filler content is 0.05 to 1.5 parts by weight per 1 part by weight of the synthetic resin. The coating layer is then screen-printed to form a straight line with a line width of 1.0 mm. The substrate on which the coating layer is formed is then biaxially stretched to a stretching ratio of 200 to 800% relative to its original size, followed by plating, to obtain a three-dimensional plated product having a plating film on the coating layer.

[0004] Patent Document 2 also describes a plating undercoat layer that exhibits excellent plating deposition and adhesion without cracking. Specifically, the plating undercoat layer is composed of conductive or reducing polymer microparticles, a synthetic resin, and an inorganic filler. The synthetic resin content is 0.1 to 60 parts by mass per part by mass of the polymer microparticles, and the inorganic filler content is 0.1 to 0.7 parts by mass per part by mass of the synthetic resin, in terms of solid content. The synthetic resin in the plating undercoat layer contains a synthetic resin with a Tg of 30°C or less in an amount of 15% by mass or more in terms of solid content. The document proposes that a straight line with a line width of 1.0 mm is formed by screen printing using the plating undercoat layer, and the substrate with the coating layer is stretched and then plated, resulting in a plated product with excellent plating deposition and adhesion on the plating undercoat layer without cracking. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2011-74407 A [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-241208 Summary of the Invention [Problem to be solved by the invention]

[0006] However, with the changing times, there is a demand for thinner lines in electrode members, specifically line widths of 50 μm or less. However, although it is shown that the use of the plating undercoat layer described in Patent Documents 1 and 2 makes it possible to print and draw fine lines with a line width of 1.0 mm, it is not possible to print fine lines with a line width of 50 μm or less, and no undercoat coating for plating that can print and draw fine lines with a line width of 50 μm or less is known yet.

[0007] Furthermore, as wires become thinner, the area where the substrate with a coating layer and the metal plating film come into contact with each other decreases. Therefore, the adhesion between the substrate with a coating layer and the metal plating film described in Patent Documents 1 and 2 is not sufficient for drawing thin wires of 50 μm or less, and further improvement in adhesion is required.

[0008] The present invention aims to provide an undercoat paint for plating that enables fine line printing with a line width of 50 μm or less and prevents the plating undercoat layer from breaking even when the substrate with the coating layer is stretched after printing of fine lines with a line width of 50 μm or less. Another object of the present invention is to provide a substrate with a coating layer that has excellent adhesion to a metal plating film and plating deposition even when the line width is 50 μm or less, by using the undercoat coating for plating of the present invention. A further object of the present invention is to provide a method for producing plated articles using the undercoat coating for plating of the present invention. [Means for solving the problem]

[0009] The plating primer coating according to claim 1 of the present invention is a plating primer coating for forming a plated object having a three-dimensional shape, and the plating primer coating contains conductive or reducing polymer particles, a synthetic resin, and an inorganic filler, the polymer fine particles are polypyrrole fine particles, the synthetic resin is a polyester-based resin, and the inorganic filler is one of silica particles, carbon black, and titanium oxide;The content of the conductive or reducing polymer fine particles is 5 parts by mass or more and 19 parts by mass or less, in terms of solid content, relative to 100 parts by mass of synthetic resin, and the content of the inorganic filler is 11 parts by mass or more and 45 parts by mass or less, in terms of solid content, relative to 100 parts by mass of synthetic resin. It is possible to form a plating base coating layer with a line width of 50 μm or less. It is characterized by: The substrate with a coating layer according to claim 2 of the present invention comprises a substrate on which a plating undercoat layer made of the undercoat paint for plating according to claim 1 is formed. and the line width of the plating base coating layer is 50 μm or less. It is characterized by: A method for producing a plated product according to a third aspect of the present invention is characterized in that the substrate with a coating layer according to the second aspect is three-dimensionally formed, and then electroless plating is carried out. [Effects of the Invention]

[0010] The present invention provides a primer coating for plating that enables fine line printing with a line width of 50 μm or less and prevents the plating primer coating layer from breaking even when the substrate with the coating layer is stretched after printing fine lines with a line width of 50 μm or less. Furthermore, by using the primer coating for plating of the present invention, a substrate with a coating layer that has excellent adhesion to the metal plating film and plating deposition even with a line width of 50 μm or less and that does not break even when three-dimensionally molded can be provided. It is also possible to provide a method for producing a plated product using the undercoat paint for plating. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention provides a primer coating for plating containing conductive or reducing polymer microparticles, synthetic resin, and inorganic filler, characterized in that the content of the conductive or reducing polymer microparticles is, in terms of solid content, 5 to 19 parts by mass per 100 parts by mass of synthetic resin, and the content of the inorganic filler is, in terms of solid content, 11 to 45 parts by mass per 100 parts by mass of synthetic resin.

[0012] <Plating primer> (Conductive or reducing polymer particles) The conductive or reducing polymer fine particles used in the present invention are not particularly limited as long as they are a polymer having a conductive or reducing π-conjugated double bond, and examples thereof include pyrrole, N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N-methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-n-propoxypyrrole, 3-n-butoxypyrrole, 3-phenylpyrrole, 3-toluylpyrrole, 3-naphthylpyrrole, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3-dimethylaminopyrrole, 3-diethylaminopyrrole, 3-diphenylaminopyrrole, 3-methylphenylaminopyrrole, and 3-phenylnaphthylaminopyrrole. aniline derivatives such as aniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, o-ethoxyaniline, m-ethoxyaniline, p-ethoxyaniline, o-methylaniline, m-methylaniline, and p-methylaniline; and thiophene derivatives such as thiophene, 3-methylthiophene, 3-n-butylthiophene, 3-n-pentylthiophene, 3-n-hexylthiophene, 3-n-heptylthiophene, 3-n-octylthiophene, 3-n-nonylthiophene, 3-n-decylthiophene, 3-n-undecylthiophene, 3-n-dodecylthiophene, 3-methoxythiophene, 3-naphthoxythiophene, and 3,4-ethylenedioxythiophene, of which pyrrole, aniline, thiophene, and 3,4-ethylenedioxythiophene are preferred, and pyrrole is more preferred.

[0013] The conductive or reducing polymer microparticles contained in the undercoat paint for plating of the present invention are capable of reducing and adsorbing a catalytic metal such as palladium onto the conductive or reducing polymer microparticles when forming a metal plating film by electroless plating, and then forming a metal plating film starting from the conductive or reducing polymer microparticles to which the catalytic metal such as palladium is adsorbed. When forming a plating undercoat layer by applying a plating undercoat to a substrate, either conductive polymer fine particles or reducing polymer fine particles can be used as the conductive or reducing polymer fine particles. When forming a plating undercoat layer by applying a plating undercoat containing conductive polymer fine particles and a synthetic resin to a substrate, it is preferable to then carry out a dedoping treatment described below before reducing and adsorbing the catalytic metal. In addition, when a metal plating film is formed on a plated product by electroless plating, catalytic metals such as palladium are reduced and adsorbed onto conductive or reducing polymer particles, so the plated product becomes conductive polymer particles.

[0014] (Conductive polymer fine particles) The conductive polymer fine particles are particles having electrical conductivity, specifically, fine particles having a conductivity of 0.01 S / cm or more. The conductive polymer fine particles may be spherical fine particles, and the average particle size (measured by a laser diffraction / scattering method) is preferably 10 to 100 nm.

[0015] As the conductive polymer fine particles, for example, polypyrrole or polypyrrole derivatives having conductive π-conjugated double bonds can be used. In addition, they can be synthesized from pyrrole monomers having π-conjugated double bonds, but commercially available conductive polypyrrole fine particles can also be used.

[0016] (reducible polymer particles) As the reducing polymer fine particles, for example, polypyrrole or polypyrrole derivatives having π-conjugated double bonds and a conductivity of less than 0.01 S / cm can be used. As the reducing polymer fine particles, polypyrrole fine particles having a conductivity of 0.005 S / cm or less are preferred. The reducible polymer fine particles can be synthesized from a monomer having a π-conjugated double bond, but commercially available reducible polypyrrole fine particles can also be used. The reducing polymer fine particles include spherical fine particles, and the average particle size (measured by a laser diffraction / scattering method) is preferably 10 to 100 nm.

[0017] <Synthetic resin> Examples of synthetic resins that can be used in the present invention include polycarbonate resins, polyvinyl chloride resins, polystyrene resins, polymethyl methacrylate resins, polyester resins, polysulfone resins, polyphenylene oxide resins, polybutadiene resins, poly(N-vinylcarbazole) resins, hydrocarbon resins, ketone resins, phenoxy resins, polyamide resins, ethyl cellulose resins, vinyl acetate resins, ABS resins, polyurethane resins, melamine resins, acrylic resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicone resins.

[0018] Furthermore, it is preferable that the synthetic resin in the undercoat layer for plating described below contains 15% by mass or more of a synthetic resin with a glass transition temperature (Tg) of 30°C or lower. If the content is less than 15% by mass, cracks may occur in the undercoat layer for plating after it is formed. Furthermore, the adhesion between the substrate with the coating layer and the metal plating film may decrease, and the stretchability of the substrate with the coating layer may decrease.

[0019] (inorganic filler) Examples of inorganic fillers used in the present invention include silica particles, carbon black, and titanium oxide.

[0020] (solvent) The undercoat for plating of the present invention may contain a solvent in addition to the conductive or reducing polymeric fine particles, synthetic resin, and inorganic filler. Examples of solvents that can be contained in the primer coating include aliphatic esters such as butyl acetate, aromatic solvents such as toluene and xylene, ketones such as methyl ethyl ketone and cyclohexanone, cyclic saturated hydrocarbons such as cyclohexane, chain saturated hydrocarbons such as n-octane, chain saturated alcohols such as methanol, ethanol and n-octanol, aromatic esters such as methyl benzoate, aliphatic ethers such as diethyl ether, and mixtures thereof. When a dispersion liquid in which conductive or reducing polymer fine particles are dispersed in an organic solvent in advance is used, the organic solvent used in the dispersion liquid can be used as part or all of the solvent for the primer coating for plating.

[0021] Furthermore, the primer coating may contain dispersion stabilizers, thickeners, pigments, dyes, inorganic fillers, etc., depending on the application and the object to be coated.

[0022] (Various contents) The content of the conductive or reducing polymer fine particles is, in terms of solids ratio, 5 to 19 parts by mass, preferably 7 to 11 parts by mass, of the conductive or reducing polymer fine particles per 100 parts by mass of the synthetic resin. If the content exceeds 19 parts by mass, peeling between the substrate with the coating layer and the metal plating film (described later) becomes extremely likely, and good adhesion cannot be obtained. In addition, there is a risk of wire breakage when the substrate with the coating layer is stretched. If the content is less than 5 parts by mass, there is a risk of significant deterioration in plating deposition properties. If the content of the conductive or reducing polymer fine particles is 7 to 11 parts by mass, the adhesion between the substrate with the coating layer and the metal plating film and the plating deposition properties of the substrate with the coating layer are superior. In addition, the substrate with the coating layer can be stretched without wire breakage even when stretched at a high ratio. The content of the inorganic filler is, in terms of solid content, 11 to 45 parts by mass, preferably 16 to 27 parts by mass, per 100 parts by mass of synthetic resin. If the content exceeds 45 parts by mass, peeling between the substrate with the coating layer and the metal plating film (described later) becomes extremely likely, and good adhesion cannot be obtained. In addition, there is a risk of wire breakage when the substrate with the coating layer is stretched. If the content is less than 11 parts by mass, there is a risk of significant deterioration in plating deposition properties. If the content is 16 to 27 parts by mass, the adhesion between the substrate with the coating layer and the metal plating film and the plating deposition properties of the substrate with the coating layer are superior. In addition, the substrate with the coating layer can be stretched without wire breakage even when stretched at a high ratio.

[0023] <Plating base coating layer> The plating undercoat layer of the present invention can be obtained by printing a plating undercoat containing conductive or reducing polymer particles, a synthetic resin, and an inorganic filler onto a substrate. Printing methods include gravure printing, screen printing, flexographic printing, offset printing, dry offset printing, pad printing, and inkjet printing. For printing fine lines of 50 μm or less, gravure offset printing and screen printing are preferred, with screen printing being more preferred. Furthermore, when the undercoat for plating is printed on a substrate, it is preferable that it be in a pattern with a line width of 50 μm or less.

[0024] <Base material> The substrate is not particularly limited, but examples thereof include polycarbonate resin, polyester resin such as polyethylene terephthalate, acrylic resin such as polymethyl methacrylate, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyamide resin, polyimide resin, and glass, and may be appropriately selected when three-dimensional molding is performed.

[0025] The thickness of the plating undercoat layer is not particularly limited, but is preferably in the range of 0.1 μm to 100 μm. If the thickness of the plating undercoat layer is less than 0.1 μm, there is a risk that the adhesion between the substrate provided with the plating undercoat layer (substrate with a coating layer) and the metal plating film will decrease, and that the plating deposition properties will also decrease. If the thickness of the plating undercoat layer exceeds 100 μm, there is a risk that the adhesion between the substrate with a coating layer and the metal plating film will decrease.

[0026] <Stretching of substrate with coating layer> The substrate with a coating layer of the present invention can be stretched to form a three-dimensional shape. The substrate with a coating layer in the present invention is a substrate on which a plating primer coating layer made of the plating primer of the present invention is formed. Stretching in the present invention refers to stretching the substrate with a coating layer to a predetermined ratio. The stretching ratio in the present invention is expressed as (thickness of substrate with coating layer before stretching / thickness of substrate with coating layer after stretching by vacuum forming)×100[%]. Specifically, the substrate with the coating layer is stretched by vacuum molding using a mold, and the thickness of the substrate with the coating layer after stretching is measured, and the stretching ratio can be calculated. The three-dimensional molding in the present invention refers to three-dimensional molding (making the substrate with a coating layer into a three-dimensional shape) by vacuum molding, press molding, pressure molding or the like. Furthermore, by using the undercoat coating for plating of the present invention, the substrate with the coating layer can be stretched without breaking even at a stretch ratio of 100% or more but less than 1000%.

[0027] <Method of manufacturing plated items> The present invention provides a plated article having a metal plating film formed on the above-mentioned plating undercoat layer by electroless plating. When the plated article has a three-dimensional shape, the substrate with the coating layer may be three-dimensionally formed and then plated. In a method for producing a plated product, first, a substrate with a coating layer is treated with an alkaline dedoping treatment solution as needed. Then, the dedoped substrate is immersed in a catalyst solution for imparting a catalytic metal such as palladium chloride. Then, the substrate to which the catalytic metal such as palladium chloride has been imparted is immersed in a plating solution for depositing the metal, thereby obtaining a plated product.

[0028] (undoped) The method for producing a plated product when using conductive polymer fine particles will be described below. Note that when using reducing polymer fine particles, the dedoping step is not required. First, the substrate with the coating layer is treated with an alkaline dedoping solution. Note that "alkaline" refers to a value of 10 measured with a personal pH meter (manufactured by Yokogawa Electric Corporation). Specifically, the plating primer coating layer formed by applying a plating primer containing conductive polypyrrole microparticles and a synthetic resin to the substrate is dedoped from reducing to conductive. An example of the dedoping treatment is a method in which the substrate with the coating layer is immersed in a dedoping solution. For example, the treatment is carried out in an alkaline dedoping solution with a pH of 10 at a temperature of 20°C to 70°C, preferably 30°C to 40°C, for 1 minute to 30 minutes, preferably 3 minutes to less than 10 minutes.

[0029] (Catalyst addition) The substrate with the dedoped coating layer is then immersed in a catalyst solution to impart a catalytic metal such as palladium chloride. The catalyst solution is a solution containing a precious metal (catalytic metal) that has catalytic activity for electroless plating. Examples of the catalytic metal include palladium, gold, platinum, and rhodium. These metals may be in the form of a single metal or a compound. Palladium compounds are preferred due to their stability, and palladium chloride is particularly preferred. A specific example of the catalyst solution is a 0.05 wt% palladium chloride-0.005 wt% hydrochloric acid aqueous solution (pH 3). The treatment temperature is 20 to 50°C, preferably 30 to 40°C, and the treatment time is 0.1 to 20 minutes, preferably 1 to 10 minutes. Through the above procedure, the reducing polypyrrole microparticles in the plating undercoat layer adsorb the catalytic metal, thereby becoming conductive polypyrrole microparticles.

[0030] (metal precipitation) The substrate with the coating layer provided with a catalytic metal such as palladium chloride is then immersed in a plating solution for depositing the metal, resulting in a plated product with a metal plating film. The plating solution is not particularly limited as long as it is a plating solution typically used in electroless plating. That is, any metal usable for electroless plating, such as copper, gold, silver, or nickel, can be used, although copper is preferred. A specific example of an electroless copper plating solution is ATS Add Copper IW Bath (manufactured by Okuno Chemical Industries, Ltd.). The treatment temperature is 20 to 50°C, preferably 30 to 40°C, and the treatment time is 1 to 60 minutes, preferably 10 to 30 minutes. The resulting plated product is preferably aged for several hours or more, e.g., 2 hours or more, at a temperature lower than the Tg of the substrate used.

[0031] (resistance value) In order to check whether the thin wire of the plated product of the present invention was broken, the resistance value was measured. 3 Preferably less than 5.0×10 Ω / cm 1 More preferably, the resistance is less than 1.0×10 Ω / cm. 3With a resistance of less than 5.0×10 Ω / cm, it can be used as an electrode material for sensors, etc. 1 When the resistance is less than Ω / cm, the sensitivity as an electrode material for a sensor or the like is good.

[0032] (peel strength) In the plated product of the present invention, the peel strength between the substrate with a coating layer and the metal plating film is preferably 0.3 N / mm or more, more preferably 0.6 N / mm or more. If the peel strength is 0.3 N / mm or more, when fine line printing with a line width of 50 μm or less is performed, the adhesion between the substrate with a coating layer and the metal plating film is excellent, so that the substrate with a coating layer can be stretched without breaking. Furthermore, if the peel strength is 0.6 N / mm or more, when fine line printing with a line width of 50 μm or less is performed, the adhesion between the substrate with the coating layer and the metal plating film is better, and the substrate with the coating layer can be stretched without breakage. [Example]

[0033] The present invention will be described below based on examples. The reducing polymer fine particles, synthetic resin, and inorganic filler, which are components of the plating primer coating in Table 1, are as shown in the following examples. The numerical values ​​showing the composition of the materials in Table 1 are in parts by mass.

[0034] Manufacturing Example 1: Preparation of plating primer A 0.42 mmol of the anionic surfactant Pelex OT-P (Kao Corporation), 2.1 mmol of the polyoxyethylene alkyl ether-based nonionic surfactant Emulgen 409P (Kao Corporation), 10 mL of toluene, and 100 mL of ion-exchanged water were added and stirred at 20°C until emulsified. 21.2 mmol of pyrrole monomer was added to the resulting emulsion and stirred for 1 hour. 6.0 mmol of ammonium persulfate was then added and the polymerization reaction was carried out for 2 hours. After the reaction was completed, the organic phase was recovered and washed several times with ion-exchanged water to obtain reducible polypyrrole microparticles with reducing properties dispersed in toluene. The solids content of the reducible polypyrrole microparticles in the resulting toluene dispersion was 5.0%. Separately, a synthetic resin [VYLON23CS: polyester-based (manufactured by Toyobo Co., Ltd.)] and an inorganic filler [Black #5500: carbon black (manufactured by Tokai Carbon Co., Ltd.)] were mixed so that the solid content ratio was 45 parts by mass of inorganic filler to 100 parts by mass of synthetic resin, and after pre-mixing, the mixture was dispersed using a three-roll mill. Next, the previously prepared dispersion liquid containing synthetic resin and inorganic filler was mixed with the previously prepared dispersion liquid of reducing polypyrrole microparticles so that the solids ratio was synthetic resin:conductive or reducing polymer microparticles:inorganic filler = 100:19:45, and the mixture was stirred and degassed to prepare primer coating A for plating.

[0035] Manufacturing Example 2: Preparation of plating primer B Undercoat coating B for plating was prepared in the same manner as in Production Example 1, except that the solid content ratio of synthetic resin:conductive or reducing polymer fine particles:inorganic filler was 100:14:34.

[0036] Manufacturing Example 3: Preparation of plating primer C Undercoat coating C for plating was prepared in the same manner as in Production Example 1, except that the solid content ratio of synthetic resin:conductive or reducing polymer fine particles:inorganic filler was mixed at 100:11:27.

[0037] Manufacturing Example 4: Preparation of plating primer D Undercoat coating D for plating was prepared in the same manner as in Production Example 1, except that the solid content ratio of synthetic resin:conductive or reducing polymer fine particles:inorganic filler was 100:9:22.

[0038] Manufacturing Example 5: Preparation of plating primer E A plating primer coating E was prepared in the same manner as in Production Example 1, except that the solid content ratio of synthetic resin:conductive or reducing polymer fine particles:inorganic filler was 100:7:16.

[0039] Manufacturing Example 6: Preparation of plating primer F Undercoat coating F for plating was prepared in the same manner as in Production Example 1, except that the solid content ratio of synthetic resin:conductive or reducing polymer fine particles:inorganic filler was 100:5:11.

[0040] Manufacturing Example 7: Preparation of plating primer G A plating primer coating G was prepared in the same manner as in Production Example 1, except that the solid content ratio of synthetic resin:conductive or reducing polymer fine particles:inorganic filler was 100:33:80.

[0041] Manufacturing Example 8: Preparation of Undercoat Coating H for Plating Undercoat coating H for plating was prepared in the same manner as in Production Example 1, except that the solid content ratio of synthetic resin:conductive or reducing polymer fine particles:inorganic filler was mixed at 100:4:10.

[0042] The coating materials A to H obtained in the production examples were evaluated for plating deposition property and adhesion by the methods described below. The evaluation results are shown in Table 1. Furthermore, since the plating deposition property of coating material H was evaluated as "x", adhesion was not evaluated.

[0043] (Plating Deposition Properties) Using a 0.5 mm thick PC film (Teijin Chemical Co., Ltd., Panlite PC1151: polycarbonate film), the above-prepared plating primer coatings A to H were printed using a screen printer in a fine line pattern with a thickness of 3.0 μm and an L / S = 50 μm / 50 μm. The resulting substrate with the coating layer was then immersed in an electroless copper plating bath (ATS Add Copper IW) at 35°C for 20 minutes, resulting in a plated product with a metal plating film (copper plating film) with a line width of 50 μm. The proportion of the metal plating film formed relative to the plating primer coating layer of the resulting plated product was visually confirmed to evaluate plating deposition properties. Plating was deposited on the entire surface of the plating base coating layer... There were some areas where plating did not deposit in the undercoat layer...△ - There were areas where plating did not deposit in most of the plating base coating layer... ×

[0044] (adhesion) Each of the above-prepared plating primers A to H was applied to a 0.5 mm thick PC film (Teijin Chemical Co., Ltd., Panlite PC1151: polycarbonate film) to a thickness of 0.30 μm. The resulting substrate with the coating layer was then immersed in an electroless copper plating bath (ATS Add Copper IW) at 35°C for 20 minutes, followed by electroplating to obtain a plated product with a 30 μm thick metal plating film (copper plating film). The resulting metal plating film was cut into a 5.0 × 12.0 cm rectangular test piece. A 5.0 mm wide cut was made in the test piece with a utility knife, and the peel strength was measured in accordance with JIS C 6471-1995 using a tensile tester (Imada Seisakusho: SV-52NA-5HH) at a pulling rate of 50 mm / min and a 180° peel angle to determine the stress (N / mm). In the present invention, a coating having a peel strength of 0.3 N / mm or more was used as a primer coating for plating with excellent adhesion.

[0045] Example 1 A 0.5 mm thick PC film (Panlite PC1151: polycarbonate film manufactured by Teijin Chemical Co., Ltd.) was used as the substrate, and the above-prepared plating primer coating A was printed with a fine line pattern of L / S = 50 μm / 50 μm using a screen printing machine. The substrate was then heated and dried in a hot air oven at 100°C for 10 minutes to obtain a substrate with a coating layer having a thickness of 3.0 μm.

[0046] Subsequently, the substrate with the coating layer was vacuum molded using various molds designed to give stretch ratios of 140%, 250%, 330%, and 530%.

[0047] The formed substrate with the coating layer was then immersed in a 0.05% palladium chloride-0.005% hydrochloric acid aqueous solution at 35°C for 5 minutes, then rinsed with cleaning water. Next, the film was immersed in an electroless copper plating bath, ATS Add Copper IW bath (manufactured by Okuno Chemical Industries Co., Ltd.), at 35°C for 20 minutes, rinsed with cleaning water, and then dried to obtain a plated product with a metal plating film formed thereon.

[0048] Example 2 A plated product having a metal plating film formed thereon was obtained in the same manner as in Example 1, except that undercoat paint B for plating was used.

[0049] Example 3 A plated product having a metal plating film formed thereon was obtained in the same manner as in Example 1, except that undercoat coating C for plating was used.

[0050] Example 4 A plated product having a metal plating film formed thereon was obtained in the same manner as in Example 1, except that undercoat paint D for plating was used.

[0051] Example 5 A plated product having a metal plating film formed thereon was obtained in the same manner as in Example 1, except that undercoat paint E for plating was used.

[0052] Example 6 A plated product having a metal plating film formed thereon was obtained in the same manner as in Example 1, except that undercoat coating F for plating was used.

[0053] (Comparative Example 1) A plated product having a metal plating film formed thereon was obtained in the same manner as in Example 1, except that undercoat coating G for plating was used.

[0054] (Comparative Example 2) The same method as in Example 1 was carried out except that undercoat paint H for plating was used, but no plating was deposited and no plated product was obtained.

[0055] The resistance values ​​of the plated products obtained in Examples 1 to 6 and Comparative Example 1 were measured, and the results are shown in Table 2. In Comparative Example 1, the substrate with the coating layer was split, and the resistance value was 1.0 × 10 6 As a result, the resistance value was evaluated as "X." In addition, in Comparative Example 2, a plated product could not be obtained, and therefore the resistance value after stretching could not be measured, and therefore "-" was shown for "resistance value after stretching."

[0056] (resistance value) The plated products obtained in Examples 1 to 6 and Comparative Example 1 were measured for resistance value within 1.0 cm of the metal plating film using a digital multimeter (Custom Co., Ltd., CDM-2000D). Resistance is 5.0×10 1 Less than Ω / cm...OK Resistance is 5.0×10 1 Ω / cm or more 1.0×10 6 Less than Ω / cm...△ Resistance is 1.0×10 6 Ω / cm or more…×

[0057] [Table 1]

[0058] [Table 2]

[0059] From the examples, it was confirmed that the plating primer of the present invention enables printing of fine lines with a line width of 50 μm or less, and also has excellent plating deposition properties and adhesion after printing of fine lines with a line width of 50 μm or less. Furthermore, the plating primer of the present invention is such that the resistance of the plated product obtained by electroless plating after three-dimensional molding of the substrate with the coating layer is 5.0 × 10 1 Ω / cm or less than 5.0 x 10 1 Ω / cm or more 1.0×10 6 The resistance was "less than Ω / cm," which confirmed that the undercoat paint for plating can be provided without causing disconnection of the undercoat paint layer even when the substrate with the coating layer is stretched. In addition, it has been possible to provide a method for producing a substrate with a coating layer and a plated product that do not break even when formed into a three-dimensional shape. [Industrial Applicability]

[0060] The plating primer of the present invention can be used for flat touch sensors, metal mesh, fine circuits, antennas, coils, etc. In addition, by combining it with three-dimensional molding, it can be used for curved touch sensors, three-dimensional circuits, etc.

Claims

1. It is a base coating for plating to form three-dimensional plated objects, The undercoat for plating contains conductive or reducing polymer particles, synthetic resin, and inorganic filler, the polymer fine particles are polypyrrole fine particles, the synthetic resin is a polyester-based resin, the inorganic filler is made of any one of silica particles, carbon black, and titanium oxide; the content of the conductive or reducing polymer fine particles is, in terms of solid content, 5 parts by mass or more and 19 parts by mass or less per 100 parts by mass of the synthetic resin; The content of the inorganic filler is, in terms of solid content ratio, 11 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the synthetic resin, A primer coating for plating, capable of forming a plating primer coating layer having a line width of 50 μm or less.

2. A plating undercoat layer made of the undercoat paint for plating according to claim 1 is formed on a substrate, A substrate with a coating layer, characterized in that the line width of the plating undercoat layer is 50 μm or less.

3. 3. A method for producing a plated product, comprising three-dimensionally forming the substrate with the coating layer according to claim 2, and then subjecting it to electroless plating.

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