JP7005363B2 - Manufacturing method of plating film coating and pretreatment liquid - Google Patents

Description

The present invention relates to a method for producing a plating film coating and a pretreatment liquid for imparting an electroless plating catalyst to a base material.

Electroless plating is known as an inexpensive method for forming a metal film on an insulating base material. In electroless plating, the surface of the base material is first roughened, and then the electroless plating catalyst is applied to the surface of the base material by a catalyst application treatment. Then, the base material to which the electroless plating catalyst is applied is immersed in the electroless plating solution to form an electroless plating film on the surface of the base material.

Two types are known as the main method of the catalyst application treatment, the sensitizer activator method and the catalyst accelerator method. In the sensitizer-activator method, tin colloid is adsorbed on a substrate (sensitizer), immersed in a palladium chloride solution (activator), and palladium chloride is reduced with stannous chloride to precipitate metallic palladium. In the catalyst / accelerator method, palladium tin colloid is adsorbed on a substrate (catalyst) and then reduced with concentrated sulfuric acid or the like to precipitate metallic palladium (accelerator). These conventional catalyst application treatments actually require more steps. For example, in the catalyst accelerator method, post-etching for improving the surface property of a base material and post-accelerator for removing tin that cannot be completely removed by the accelerator are performed. Therefore, in the conventional catalyst application treatment, it has been required to reduce the number of steps.

Further, the conventional catalyst applying treatment also has the following problems. In the catalyst accelerator method, palladium, which is a catalyst, is a colloid, so that it is unstable and easily settles and aggregates. Therefore, the amount of catalyst used increases. On the other hand, in the sensitizer-activator method, palladium, which is a catalyst, is stable because it is ionized in the liquid. However, since the sensitizer solution is an unstable colloidal solution, continuous treatment is difficult. Furthermore, the tin colloid in the sensitizer solution has a strong adsorptive power. For example, when electroless plating is performed using the sensitizer-activator method while the base material is held by a metal jig coated with vinyl chloride, not only the base material on which the plating film is formed but also the base material is formed. The plating film also precipitates on the jig holding the material. Therefore, it is necessary to replace the jig that holds the base material between the catalyst application treatment and the plating treatment, which hinders the improvement of throughput.

In Patent Document 1, in order to reduce the number of steps in the catalyst application treatment, a first solution containing an inorganic acid-containing corrosive agent such as hydrochloric acid, an ionogen activator such as palladium ion, and an organic acid such as acetic acid is used as a base material. A method of processing is proposed. According to Patent Document 1, a good plating film is formed on the substrate by pretreating the polyamide substrate with the first solution.

Further, in Patent Document 2, the base material (plastic) is sufficiently adhered to the plastic surface by performing the etching treatment, the application of the catalyst-imparting enhancer, the application of the electroless plating catalyst, and the electroless plating in this order. A method is disclosed in which a plated film can be formed and the plating film is not deposited on a jig. The catalyst-imparting enhancer contains a compound containing a nitrogen atom, which is selectively adsorbable to the functional group exposed on the surface of the substrate (plastic).

Patent No. 4109615 Japanese Unexamined Patent Publication No. 2008-31513

Since the first solution disclosed in Patent Document 1 contains a catalyst as palladium ions, it is presumed to be a stable solution. However, according to the studies by the present inventors, it is known that palladium ions have low adsorptivity to a substrate. For example, the surface of a molded product (base material) such as polyamide may have different crystallinity and resin density depending on the location. In this case, uneven adsorption of palladium ions on the substrate and further unevenness in the reaction of electroless plating due to this occur. As a result, it becomes difficult to obtain a uniform plating film having high adhesion strength. This phenomenon is particularly remarkable in a substrate having a complicated shape or a large shape. Further, when electroless plating is performed on a substrate having a complicated shape or a large shape, electroless plating is performed while violently stirring the electroless plating solution by air bubbling or the like in order to suppress the reaction unevenness of the electroless plating. However, in this method, palladium ions, which are catalysts, are shed from the substrate, and rather, the reaction unevenness of electroless plating is promoted.

Further, Patent Document 2 discloses a plating method in which a plating film is not deposited on a jig holding a base material, but a conventional catalyst accelerator method is used for the catalyst application treatment. Therefore, the problems in the conventional catalyst-imparting treatment such as the large number of steps and the instability of the treatment liquid have not been solved yet.

The present invention solves these problems, and the catalyst application treatment is performed by a simple method using a stable treatment liquid, and even on a substrate having a complicated shape or a large shape, there is no uniform and high adhesion strength. Provided is a method for manufacturing a plating film coating film which can form an electrolytic plating film and does not require replacement of a jig.

According to the first aspect of the present invention, there is a method for producing a plating film coating, in which at least a part of the surface of a base material is roughened and / or swelled, and a roughened and / or swollen base material is used. A pretreatment liquid containing a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more is brought into contact with the base material, the base material to which the pretreatment liquid is brought into contact is washed, and a metal salt is added to the washed base material. Electroless plating is performed on the base material to which the metal ions derived from the metal salt are adsorbed by contacting the containing plating catalyst liquid and the metal ions adsorbing to the base material to which the plating catalyst liquid is in contact. A method for producing a plating film coating including contacting a liquid is provided.

In this embodiment, at least a part of the surface of the base material may be roughened by irradiating at least a part of the surface of the base material with a laser beam. When the base material contains an aliphatic polyamide, at least a part of the surface of the base material may be roughened and / or swelled by contacting at least a part of the surface of the base material with hydrochloric acid. .. When the base material contains ABS resin, at least a part of the surface of the base material is roughened and / or by contacting at least a part of the surface of the base material with permanganate or chromic acid. Alternatively, it may be inflated.

The nitrogen-containing polymer may be polyethyleneimine. The weight average molecular weight of the nitrogen-containing polymer may be 1,000 to 100,000 or 70,000 to 100,000. Further, the blending amount of the nitrogen-containing polymer in the pretreatment liquid may be 0.01 g / L to 100 g / L.

According to the second aspect of the present invention, in the method for producing a plating film coating, at least a part of the surface of the base material is roughened and / or swelled, and the roughened and / or swollen base material is used. A pretreatment liquid containing a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more is brought into contact with the base material, the base material to which the pretreatment liquid is brought into contact is washed, and a metal salt is added to the washed base material. The pretreatment liquid further contains a reducing agent which is calcium hypophosphite. , A method for manufacturing a plating film coating is provided.
In this embodiment, the blending amount of the reducing agent in the pretreatment liquid may be 1 g / L to 100 g / L.

The metal salt of the plating catalyst solution may be palladium chloride. Further, the electroless plating solution may be an electroless nickel plating solution containing sodium hypophosphite.

The electroless plating solution may be brought into contact with the base material while being stirred. With the base material held by a jig, the pretreatment liquid is brought into contact with both the base material and the jig to perform the cleaning, and the plating catalyst liquid is brought into contact with the electroless plating liquid. May be contacted.

According to the third aspect of the present invention, it is a pretreatment liquid for imparting an electroless plating catalyst to a substrate, and is composed of a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more, water, and calcium hypophosphite. A pretreatment solution containing a reducing agent is provided.

In the method for producing a plating film coating film of the present invention, a catalyst is applied by a simple method using a stable treatment liquid, and even on a substrate having a complicated shape or a large shape, electroless plating with uniform and high adhesion strength is performed. A film can be formed. Further, since it is not necessary to replace the jig for holding the base material between the catalyst application treatment and the plating treatment, the throughput can be improved.

FIG. 1 is a flowchart showing a method for manufacturing a plating film covering body according to the first embodiment. FIG. 2 is a flowchart showing a method of manufacturing the plating film covering body of the second embodiment.

[First Embodiment]
As the first embodiment, a method for manufacturing the plating film coating body will be described according to the flowchart shown in FIG. The plating film covering body of the present embodiment is a member (part) in which an electroless plating film is formed on at least a part of the surface of the base material.

(1) Roughening and / or swelling of the base material First, at least a part of the surface of the base material is roughened and / or swelled (step S1 in FIG. 1).

As the base material, a commercially available product may be used, or the material constituting the base material may be molded into a desired shape by a general-purpose method. The material of the base material is not particularly limited, and for example, resin, glass, metal, ceramic, wood and the like can be used. Examples of the resin include thermoplastic resins and thermosetting resins. For example, since the aliphatic polyamide has high water absorption, it has an advantage that the electroless plating solution easily permeates and the plating film grows stably. Furthermore, the present inventors have found that the aliphatic polyamide easily adsorbs metal ions derived from a metal salt used as an electroless plating catalyst in the present embodiment. The aliphatic polyamide is not particularly limited as long as it does not have an aromatic ring, and for example, nylon 6 (PA6), nylon 66 (PA66), nylon 12 (PA12), nylon 11 (PA11), and nylon 6.66 co-weight. Combined materials, composite materials obtained by copolymerizing or alloying these, amorphous nylon, and the like can be used. Of these, nylon 6 and nylon 66, which have high water absorption and easily swell, are preferable, and nylon 6 is more preferable, from the viewpoint of easily forming a plating film. Further, a composite material obtained by copolymerizing or alloying the above-mentioned aliphatic polyamide with a thermoplastic resin other than polyamide may be used. Examples of such a composite material include a polymer alloy of nylon and polypropylene (PA / PP) and a polymer alloy of ABS resin, polycarbonate and the like with nylon. These resins may be used alone or in combination of two or more.

Further, as the base material, for example, semi-aromatic polyamide such as nylon 6T (PA6T) and nylon 9T (PA9T), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polyetheretherketone (PEEK), polyimide and the like can be used. A thermoplastic resin having heat resistance (heat resistant resin) can be used. The base material containing these heat-resistant resins has solder reflow resistance, and also has high durability, high heat resistance, and chemical resistance. When the plating film coating is not required to have solder reflow resistance, general-purpose engineering plastics such as ABS resin, polycarbonate (PC), polymer alloy of ABS resin and PC (ABS / PC), polypropylene and the like can be used. .. From the viewpoint of improving dimensional stability and rigidity, these resins may contain an inorganic filler such as a glass filler or a mineral filler. Further, these resins may be used alone or in combination of two or more. Further, the base material may be a foam molded product of these resins. Further, as the base material, a metal having heat dissipation can be used, and examples thereof include iron, copper, aluminum, titanium, magnesium, and stainless steel (SUS). Above all, it is preferable to use magnesium and aluminum from the viewpoint of weight reduction, heat dissipation and cost. These metals may be used alone or in combination of two or more.

Roughening and / or swelling of the substrate causes, for example, fine irregularities to be formed on the surface of the substrate, chemical bonds of the material forming the substrate to be broken, or molecules of the material forming the substrate. Changes such as a decrease in hardness occur due to an increase in the distance. This promotes the adsorption and permeation of the nitrogen-containing polymer, water, and electroless plating catalyst used in the subsequent step into the substrate, and as a result, the roughening and / or the plating reactivity of the swollen portion of the substrate is improved. .. The roughening and swelling of the base material may occur independently or at the same time.

The roughening and / or swelling of the substrate can be performed by any method, for example, a slurry-like liquid containing laser light irradiation (laser drawing), chemical etching, dry etching, acid treatment, sandblasting, and polishing particles. Can be performed by wet blasting or the like in which is jetted at high speed. Further, UV irradiation or plasma irradiation may be used to break the chemical bond of the material forming the base material. When forming fine plated wiring such as a circuit, it is preferable to roughen the base material by irradiating with laser light.

Further, the method for roughening and / or swelling the base material is preferably selected according to the type of the base material. For example, when the base material contains a polyamide resin, an acid such as hydrochloric acid, sulfuric acid, or nitric acid may be brought into contact with the base material. As the acid, hydrochloric acid is preferable, and 1 to 3N hydrochloric acid is more preferable. Further, for example, when the base material contains ABS resin or PC / ABS resin (polymer alloy of PC and ABS resin), the base material may be chemically etched with permanganic acid or chromic acid. The butadiene component is dissolved and fine irregularities can be formed on the surface of the base material. Further, for example, when the base material is an inorganic material such as metal or ceramic, or wood, the base material may be roughened by sandblasting, wet blasting, or the like.

Roughening and / or swelling may be performed on the entire surface of the substrate or only on a part of the surface of the substrate. When the entire surface of the substrate is roughened and / or swollen, an electroless plating film can be formed on the entire surface of the substrate. When only a part of the surface of the base material is roughened and / or swollen, an electroless plating film can be selectively formed only on the roughened and / or swollen part. For example, only a part of the surface of the base material can be roughened by laser light irradiation. Further, for example, a base material which is a two-color molded body composed of a first portion formed of polypropylene (PP) and a second portion formed of a polymer alloy (PA / PP) of polyamide and polypropylene is prepared. , Hydrochloric acid may be brought into contact with the substrate. Since the first portion formed of polypropylene is not roughened and swollen by hydrochloric acid, only the second portion can be roughened and / or swollen.

(2) Pretreatment for catalyst application Next, as a pretreatment for imparting an electroless plating catalyst to the substrate, a pretreatment liquid containing a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more is brought into contact with the substrate (). Step S2 in FIG. 1).

The nitrogen-containing polymer is a polymer capable of adsorbing metal ions derived from a metal salt which is a electroless plating catalyst used in a subsequent step. For example, polyacrylamide, polyallylamine, polyethyleneimine and the like can be used, among which polyethyleneimine is used. preferable. Polyethyleneimine contains primary, secondary and tertiary amines, is a highly reactive polymer with a branched structure, and has a high ability to adsorb electroless plating catalysts, which are metal ions.

The weight average molecular weight of the nitrogen-containing polymer is 1,000 or more. The nitrogen-containing polymer adsorbs and / or penetrates the roughened and / or swollen portion of the substrate. Then, according to the study by the inventors, by setting the weight average molecular weight of the nitrogen-containing polymer to 1,000 or more, roughening and / or roughening and / or even through a washing step (step S3 in FIG. 1) which is a subsequent step. It became clear that the nitrogen-containing polymer was difficult to desorb from the swollen portion. On the other hand, if the weight average molecular weight of the nitrogen-containing polymer is less than 1,000, the nitrogen-containing polymer may be desorbed in the subsequent cleaning step (step S3 in FIG. 1), resulting in uneven plating reaction. .. From the viewpoint of further suppressing the desorption of the nitrogen-containing polymer from the substrate, the weight average molecular weight of the nitrogen-containing polymer is preferably 70,000 or more, for example. Further, if the weight average molecular weight of the nitrogen-containing polymer is too large, it becomes difficult for the nitrogen-containing polymer to be adsorbed and / or permeated into the roughened and / or swollen portion of the base material, and the plating reactivity of the base material may decrease. However, a nitrogen-containing polymer having a weight average molecular weight of about 100,000, which is generally commercially available, is effective in this embodiment. Therefore, from a substantial point of view, the weight average molecular weight of the nitrogen-containing polymer is, for example, 100,000 or less.

The blending amount (P) of the nitrogen-containing polymer in the pretreatment liquid is, for example, 0.01 g / L to 100 g / L, 2 g / L to 50 g / L, 10 g / L to 50 g / L. Since the specific gravity of the nitrogen-containing polymer and the pretreatment liquid are almost the same, the blending amount (P) is, for example, 0.001% by weight to 10% by weight, 0.2% by weight to 5% by weight, 1% by weight to 5. It is% by weight. Since the metal ions used as the electroless plating catalyst are stable in water, they are not easily adsorbed on the surface of the substrate. By setting the blending amount (P) of the nitrogen-containing polymer in the pretreatment liquid within the above range, a sufficient amount of nitrogen-containing polymer can be imparted to the substrate to adsorb the metal ions on the substrate. Further, by setting the blending amount (P) of the nitrogen-containing polymer in the pretreatment liquid within the above range, a sufficient amount for the roughened and / or swollen portion even after the washing step (step S3 in FIG. 1). Nitrogen-containing polymer can be retained. Further, it is possible to suppress the precipitation of the nitrogen-containing polymer in the pretreatment liquid and keep the pretreatment liquid stable.

The solvent of the pretreatment liquid for dissolving the nitrogen-containing polymer is not particularly limited and can be selected depending on the type of the nitrogen-containing polymer. For example, water; ethanol, propanol, isopropanol, butanol, isobutanol, acetone, ethyl methyl ketone and the like. Organic solvent; examples thereof include a mixed solvent thereof. Above all, the solvent of the pretreatment liquid is preferably water. In this case, the nitrogen-containing polymer is preferably a water-soluble polymer, and the pretreatment liquid is preferably an aqueous solution of the nitrogen-containing polymer. Further, all of the solvent may be water, or the main component of the solvent may be water and may further contain a water-soluble organic solvent such as alcohol.

The pretreatment liquid may further contain a reducing agent. The reducing agent in the pretreatment liquid, together with the nitrogen-containing polymer, adsorbs and / or permeates the roughened and / or swollen portion of the substrate. Then, it is presumed that the electroless plating catalyst, which is a metal ion used in the subsequent process, is reduced and the adsorption to the substrate is promoted. As the reducing agent, for example, calcium hypophosphite and sodium hypophosphite can be used, and calcium hypophosphite is particularly preferable. Since calcium hypophosphite has a relatively low solubility in water, it is presumed that it easily adsorbs and / or permeates into the roughened and / or swollen portion of the substrate.

When the pretreatment liquid contains a reducing agent, the blending amount (R) of the reducing agent in the pretreatment liquid is, for example, 1 g / L to 100 g / L, 10 g / L to 100 g / L, 10 g / L to 50 g /. It is L. When the blending amount (P) of the nitrogen-containing polymer in the pretreatment liquid is within the above range, a sufficient amount of the reducing agent can be applied to the substrate, and the precipitation of the reducing agent in the pretreatment liquid is suppressed. , The pretreatment liquid can be kept stable.

The pretreatment liquid may further contain a general-purpose additive such as a surfactant, if necessary. The pretreatment liquid can be prepared by mixing a nitrogen-containing polymer, a solvent, and if necessary, a reducing agent and a general-purpose additive by any method.

The method of bringing the pretreatment liquid into contact with the base material is arbitrary, and for example, the entire base material may be immersed in the pretreatment liquid. Further, the pretreatment liquid may be brought into contact with only a part of the base material, but in this case, the pretreatment liquid is brought into contact with the region including the roughened and / or swollen part of the base material. Further, the temperature of the pretreatment liquid and the pretreatment time (time for bringing the pretreatment liquid into contact with the substrate) are not particularly limited. The temperature of the pretreatment liquid is, for example, room temperature or 10 ° C to 50 ° C, and the pretreatment time is, for example, 1 to 10 minutes. When the temperature of the pretreatment liquid and the pretreatment time are within the above ranges, a sufficient amount of nitrogen-containing polymer can be adsorbed on the base material, and deterioration of the base material due to permeation of the pretreatment liquid can be suppressed.

(3) Cleaning of the base material Next, the base material to which the pretreatment liquid is in contact is washed (step S3 in FIG. 1). By cleaning the substrate, the nitrogen-containing polymer adhering to the portion of the substrate that has not been roughened and / or swelled, that is, the portion that does not form the electroless plating film can be removed. In addition, the nitrogen-containing polymer adhering to the jig holding the base material can be removed, and the formation of a plating film on the jig can be suppressed.

The cleaning can be performed, for example, by immersing the base material in a liquid (cleaning liquid) capable of dissolving the nitrogen-containing polymer contained in the pretreatment liquid. As the cleaning liquid, those listed as the solvent of the above-mentioned pretreatment liquid can be used, and water is preferable. That is, it is preferable to wash the base material with water as the washing of the base material. Further, in order to improve the cleaning effect, the cleaning liquid in which the substrate is immersed may be stirred during the cleaning of the substrate. Here, stirring the cleaning liquid means, for example, stirring, circulating, flowing, etc. the cleaning liquid by air bubbling, a pump, or the like.

The temperature of the cleaning liquid and the cleaning time (time during which the substrate is immersed in the cleaning liquid) are not particularly limited. The temperature of the cleaning liquid is, for example, room temperature or 10 ° C. to 40 ° C., and the cleaning time is, for example, 1 to 20 minutes.

(4) Addition of electroless plating catalyst Next, a plating catalyst liquid containing a metal salt is brought into contact with the base material (step S4 in FIG. 1). As a result, metal ions derived from the metal salt, which is an electroless plating catalyst, are adsorbed on the roughened and / or swollen portion of the base material.

Metal ions such as palladium, which is an electroless plating catalyst, are difficult to be adsorbed on the surface of a substrate such as resin as it is. Therefore, in the conventional catalyst application treatment such as the sensitizer activator method and the catalyst accelerator method, the palladium ion is reduced and adsorbed on the substrate as metallic palladium having an oxidation number of 0 (zero). In this embodiment, a nitrogen-containing polymer capable of adsorbing metal ions is present in the roughened and / or swollen portion of the substrate. With this nitrogen-containing polymer, metal ions can be adsorbed on the roughened and / or swollen portion of the substrate.

Furthermore, electroless plating catalysts usually exhibit catalytic activity in a metallic state with an oxidation number of 0 (zero). Therefore, in the conventional catalyst application treatment, palladium is reduced while being adsorbed on the substrate. Therefore, conventionally, it has been difficult to use it as an electroless plating catalyst because it does not exhibit catalytic activity even if palladium ions that are not in a metallic state are applied to the substrate. However, the present inventors have found that an electroless plating reaction occurs in the electroless plating step without performing the reduction treatment of metal ions. Although the reason for this is not clear, in the present embodiment, it is presumed that the metal ions are reduced by the reducing agent contained in the electroless plating solution in the electroless plating step to exhibit the electroless plating catalytic ability. Therefore, in the present embodiment, the reduction treatment of the electroless plating catalyst (metal ion) can be omitted before the electroless plating step. Therefore, the manufacturing cost can be reduced and the throughput can be improved.

As the metal salt contained in the plating catalyst solution, any metal salt having electroless catalytic ability can be used. For example, salts of Pd, Pt, Cu, Ni and the like can be mentioned, and among them, Pd having high catalytic ability is preferable. Examples of the salt of Pd include palladium chloride, palladium acetate, and a palladium complex, and among them, inexpensive and stable palladium chloride is preferable.

The blending amount (M) of the metal salt in the plating catalyst solution can be appropriately adjusted based on conditions such as the temperature of the plating catalyst solution and the contact time between the plating catalyst solution and the substrate, and can be adjusted appropriately, for example, from 0.05 mg / L. It is 100 g / L, preferably 1 mg / L to 20 g / L, and more preferably 5 mg / L to 10 g / L. If the concentration of the metal salt is lower than the above range, the amount of the metal salt adsorbed on the substrate may be uneven, and the plating film may be defective. Further, if the concentration of the metal salt exceeds the above range, the plating reaction on the outermost surface of the base material becomes dominant, and the adhesion strength of the plating film may decrease.

The solvent of the plating catalyst solution for dissolving the metal salt is not particularly limited and can be selected depending on the type of the metal salt. For example, water; ethanol, propanol, isopropanol, butanol, isobutanol, acetone, ethyl methyl ketone and the like. Organic solvent; examples thereof include a mixed solvent thereof. Further, in order to increase the solubility of the metal salt, hydrochloric acid, nitric acid, ammonia, sodium hydroxide and the like may be added to adjust the pH of the liquid. For example, when the plating catalyst solution contains hydrochloric acid, the concentration of hydrochloric acid in the plating catalyst solution is, for example, 0.1 to 12N, preferably 0.1 to 5N, and more preferably 1.0 to 4.0N. When the base material contains minerals that are soluble in acids such as calcium carbonate and calcium silicate, by using an acid in the plating catalyst solution, the minerals in the base material are dissolved and irregularities are formed on the surface of the base material. , Can promote the adsorption of metal salts to the substrate.

The plating catalyst liquid may be composed only of a metal salt and a solvent, or may contain a general-purpose additive, if necessary. The plating catalyst liquid may contain, for example, a surfactant. By containing the surfactant, the surface tension of the plating catalyst liquid is lowered, the wettability to the surface of the base material is improved, and the metal salt easily penetrates into the inside of the base material. As the surfactant, a general-purpose surfactant such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.

The plating catalyst solution may be prepared by mixing a metal salt, a solvent, and if necessary, a general-purpose additive or the like, or a commercially available product may be used. As a commercially available product, for example, a catalytic treatment agent (activator) used in the sensitizer-activator method can be used. In the usual sensitizer-activator method, a sensitizer treatment using a sensitivity-imparting agent (sensitizer), which is an unstable colloidal solution, is performed before the activator treatment using a catalytic treatment agent (activator) containing Pd ²⁺ . However, in this embodiment, the treatment with the colloidal solution is not necessary. Therefore, the electroless plating catalyst application treatment of the present embodiment can improve the throughput as compared with the sensitizer activator method.

The method of bringing the plating catalyst liquid into contact with the base material is arbitrary, and for example, the entire base material may be immersed in the plating catalyst liquid. Further, the plating catalyst liquid may be brought into contact with only a part of the base material, but in this case, the plating catalyst liquid is brought into contact with the region including the roughened and / or swollen part of the base material. Further, the temperature of the plating catalyst liquid and the time for contacting the plating catalyst liquid with the substrate are not particularly limited. The temperature of the plating catalyst liquid is, for example, room temperature or 40 ° C. to 85 ° C., and the contact time of the plating catalyst liquid is preferably, for example, 5 seconds to 30 minutes. If the temperature of the plating catalyst liquid and the contact time are within the above ranges, the electroless plating catalyst can be uniformly adsorbed on the base material, and the base material is deteriorated due to the permeation of the plating catalyst liquid, and the base material is rough. It is possible to suppress the adhesion of the catalyst to other than the plated and / or swollen portion.

(5) Electroless plating Next, the electroless plating solution is brought into contact with the base material which has been brought into contact with the plating catalyst solution (step S5 in FIG. 1). As described above, metal ions are adsorbed on the roughened and / or swollen portion of the base material by the nitrogen-containing polymer. By bringing the electroless plating solution into contact with such a base material, an electroless plating film can be formed on the roughened and / or swollen portion of the base material, and a plating film coating film can be obtained.

As the electroless plating solution, any general-purpose electroless plating solution can be used depending on the purpose. The electroless plating solution contains, for example, a reducing agent such as sodium hypophosphite and formalin. As the electroless plating solution, an electroless nickel plating solution, an electroless nickel phosphorus plating solution, an electroless copper plating solution, an electroless palladium plating solution, or the like can be used, and among them, the reducing effect of the electroless plating catalyst (metal ion). An electroless nickel plating solution containing a high sodium hypophosphite as a reducing agent and having a stable plating solution is preferable.

The temperature of the electroless plating solution and the electroless plating time (time for contacting the electroless plating solution with the base material) can be appropriately determined according to the type of the electroless plating solution and the base material. For example, the temperature of the electroless plating solution is 50 ° C. to 80 ° C., and the electroless plating time is 1 minute to 1 hour.

Further, the electroless plating may be performed by contacting the base material with the electroless plating solution while stirring. By stirring the electroless plating solution, the temperature and plating reactivity of the electroless plating solution can be made uniform. This makes it possible to form an electroless plating film that is uniform and has high adhesion strength even on a substrate having a complicated shape or a large shape. In the present embodiment, the electroless plating catalyst is relatively strongly adsorbed on the substrate by the nitrogen-containing polymer. Therefore, even if the electroless plating solution is stirred, the electroless plating catalyst does not separate from the base material, and unevenness of the plating reaction is unlikely to occur. Here, the stirring of the electroless plating solution means that the electroless plating solution is stirred, circulated, flowed, etc. by, for example, air bubbling, a pump, or the like.

A plurality of different types of electroless plating films may be formed on the electroless plating film for the purpose of improving the use and design of the plating film coating, or the electroless plating film may be formed by electrolytic plating. You may. Further, the base material on which the electroless plating film is formed may be annealed after electroless plating, or may be left at room temperature to be naturally dried. Further, the next step such as continuously forming an electrolytic plating film may be performed without performing annealing treatment or natural drying.

The electroless plating film may have conductivity. In this case, the electroless plating film can function as a wiring pattern, an electric circuit, an antenna, or the like, and the plating film coating film functions as an electronic component. Further, the electroless plating film may be formed flatly on only one surface of the base material, or may be formed three-dimensionally over a plurality of surfaces of the base material. When the base material has a three-dimensional surface including a spherical surface, the electroless plating film may be formed three-dimensionally along the three-dimensional surface. When the electroless plating film is three-dimensionally formed over a plurality of surfaces of the molded body or along the surface of a three-dimensional shape including a spherical surface and has conductivity, the electroless plating film functions as a three-dimensional electric circuit. However, the plating film coating body having such a plating film having a predetermined pattern functions as a three-dimensional circuit molding component (MID: Molded Interconductor Device).

As described above, in the production method of the present embodiment, the roughened and / or swollen substrate is brought into contact with a pretreatment liquid containing a nitrogen-containing polymer having a specific weight average molecular weight to pretreat the catalyst. I do. Thereby, the electroless plating catalyst can be applied to the base material by using the plating catalyst solution containing a metal salt, which is a stable plating catalyst solution. In the present embodiment, the reduction treatment of the electroless plating catalyst (metal ion), which has been conventionally performed, can be omitted. Therefore, the manufacturing cost can be reduced and the throughput can be improved. Further, in the present embodiment, electroless plating may be performed while stirring the electroless plating solution. Therefore, an electroless plating film having a uniform shape and high adhesion strength can be formed even on a base material having a complicated shape or a large shape. Further, in the present embodiment, since the formation of the plating film on the jig can be suppressed, the pretreatment liquid is brought into contact with both the base material and the jig while the base material is held by the jig to perform cleaning. , The plating catalyst solution may be contacted, and the electroless plating solution may be contacted. That is, it is not necessary to replace the jig that holds the base material between the catalyst application treatment and the plating treatment. Therefore, the throughput can be further improved. Further, in the present embodiment, only a part of the surface of the base material may be roughened and / or swelled. This makes it possible to selectively form an electroless plating film only on the roughened and / or swollen portion.

As described above, in the production method of the present embodiment, it is not necessary to separately provide a reduction treatment (reduction step) of the electroless plating catalyst (metal ion). In other words, in the production method of the present embodiment, of the liquids in contact with the base material, only the electroless plating solution may contain a reducing agent, or only the electroless plating solution and the pretreatment liquid are reducing agents. May be contained.

[Second Embodiment]
As a second embodiment, a method for manufacturing the plating film coating body will be described according to the flowchart shown in FIG. In this embodiment, a catalytic deactivating agent is applied to the surface of the substrate before roughening and / or swelling at least a part of the surface of the substrate (step S11 in FIG. 2). Other than that, the plating film coating body is manufactured by the same method as in the first embodiment.

As the base material, the same material as in the first embodiment can be used. As the catalyst deactivating agent, any substance can be used as long as it is a substance that prevents the electroless plating catalyst from exerting its catalytic ability and, as a result, suppresses the reaction of electroless plating. The catalyst deactivating agent directly reacts with the electroless plating catalyst to poison the electroless plating catalyst, or prevents the electroless plating catalyst from exerting its catalytic ability even if it does not directly react with the electroless plating catalyst. It is presumed. Examples of such catalyst deactivating agents include heavy metals such as zinc (Zn), lead (Pb), tin (Sn), bismuth (Bi), antimony (Sb) and other heavy metals and compounds thereof, iodine and the like. Examples thereof include the compound, an oxidizing agent such as a peroxide, and the like. Among them, zinc (Zn), lead (Pb), tin (Sn), bismuth (Bi), antimony (Sb) and their compounds are preferable in that they are highly toxic to electroless plating catalysts, and iodine is preferable. , It is preferable in that it has high permeability to the base material. These catalytic deactivating agents can be applied to the substrate by, for example, the method disclosed in Japanese Patent No. 5902853. It is presumed that these catalytic deactivating agents applied to the substrate permeate the substrate or strongly adsorb to the substrate.

Further, by forming a catalytic activity interfering layer containing a catalytic deactivating agent (hereinafter, appropriately simply referred to as “interfering layer”) on the surface of the substrate, the catalytic deactivating agent is applied to the surface of the substrate. May be good. For example, it forms an interfering layer containing the above-mentioned catalytic deactivating agent such as iodine and a resin serving as a binder. By using a resin that serves as a binder, the catalyst deactivating agent can be retained even on the surface of the substrate on which the catalyst deactivating agent is difficult to directly adsorb or permeate.

Further, as the catalyst deactivating agent, a resin that interferes with the catalytic activity may be used. The catalyst deactivating agent, which is a resin, can be applied onto the substrate as an interfering layer. As the catalyst deactivating agent which is a resin, a polymer having an amide group and a dithiocarbamate group in the side chain is preferable. It is presumed that the amide group and dithiocarbamate group of the side chain act on the metal ion serving as the electroless plating catalyst and hinder the exertion of the catalytic ability. Further, as the catalyst deactivating agent which is a resin, a dendritic polymer such as a dendrimer or a hyperbranched polymer is preferable. As the resin that interferes with the catalytic activity, for example, the polymer disclosed in JP-A-2017-160518 can be used, and the interfering layer is formed on the surface of the substrate by the method disclosed in JP-A. can.

Next, as shown in FIG. 2, the following steps similar to those of the first embodiment are performed. First, at least a part of the surface of the substrate to which the catalyst deactivating agent is applied is roughened and / or swelled (step S1 in FIG. 2). In this embodiment, laser drawing (laser light irradiation) is performed on the surface of the base material. By laser drawing, a laser drawing portion and a non-laser drawing portion are formed on the surface of the base material. In the laser drawing portion, the surface of the substrate is roughened, and the catalyst deactivating agent is removed or modified or denatured so as not to act as the catalyst deactivating agent.

Next, as in the first embodiment, pretreatment for applying the catalyst (step S2 in FIG. 2), cleaning of the substrate (step S3 in FIG. 2), and application of the electroless plating catalyst (step S4 in FIG. 2). And electroless plating (step S5 in FIG. 2) is performed in this order. As a result, a plating film covering body in which an electroless plating film is formed on the laser drawing portion can be obtained.

In the manufacturing method of the present embodiment, the same effect as that of the first embodiment can be obtained, and the electroless plating film is selectively formed only on the laser drawing portion of the base material. Further, in the present embodiment, the catalyst deactivating agent remaining in the non-laser drawing portion can more reliably suppress the formation of the plating film in the non-laser drawing portion. Thereby, on the surface of the base material, the contrast between the portion where the electroless plating film is formed and the portion where the electroless plating film is not formed can be made clearer. In particular, when the catalytic activity of the electroless plating solution is high, it is preferable to add a catalytic deactivating agent to the base material in order to more reliably suppress the formation of the plating film in the non-laser drawing portion. For example, when the concentration of the reducing agent in the electroless plating solution, the temperature of the electroless plating solution is high, or the bath load is low, the catalytic activity of the electroless plating solution becomes high. Further, in general, the electroless nickel phosphorus plating solution contains a stronger reducing agent than the electroless copper plating solution, and therefore has higher catalytic activity.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples and Comparative Examples.

In Examples 1 to 9 and Comparative Examples 1 to 4, plating film coatings were produced. Table 1 shows the types of the base material used in each Example and Comparative Example, the method of roughening and / or swelling of the base material, the composition of the pretreatment liquid for applying the catalyst, the electroless plating catalyst or the method of applying the catalyst. ..

[Example 1]
In this example, a molded product made of polyamide 6 (PA6) containing glass fiber was used as the base material. Further, while the base material was held by a copper jig coated with vinyl chloride, each step described below was carried out to manufacture a plating film coating body.

(1) Molding of base material Polyamide 6 (Glamide T-402 manufactured by Toyobo Co., Ltd.) containing 30% by weight of glass fiber was injection-molded to obtain a plate-shaped base material having a size of 100 mm × 200 mm × 2 mm. In injection molding, the resin temperature was 280 ° C. and the mold temperature was 80 ° C.

(2) Roughening and / or swelling treatment of the base material The base material was immersed in 3.0 N hydrochloric acid adjusted to 35 ° C. for 5 minutes. After the immersion, the surface of the substrate was cloudy. From this, it was confirmed that the surface of the substrate was roughened and / or swollen by hydrochloric acid. After the substrate was taken out from hydrochloric acid, it was washed by immersing it in water at room temperature stirred by air bubbling for 5 minutes. The same wash was performed once more.

(3) Pretreatment for catalysis In water, polyethyleneimine (PEI) (manufactured by Wako Pure Chemical Industries, Ltd., 30 wt% concentration solution) having a weight average molecular weight of 70,000 as a nitrogen-containing polymer, and calcium hypophosphite (road) as a reducing agent. (Pharmaceutical) was mixed, and a pretreatment solution was prepared so that the blending amount (solid content concentration) of polyethyleneimine was 30 g / L and the blending amount of calcium hypophosphite was 50 g / L. The substrate was immersed in the prepared pretreatment liquid at room temperature for 5 minutes.

(4) Cleaning of the base material The base material was washed by immersing the base material in water at room temperature stirred by air bubbling for 5 minutes. The same wash was performed once more.

(5) Addition of electroless plating catalyst The substrate was immersed in a commercially available aqueous solution of palladium chloride (PdCl ₂ ) adjusted to 35 ° C. (manufactured by Okuno Pharmaceutical Co., Ltd., activator, palladium chloride concentration: 150 ppm) for 3 minutes. After the substrate was taken out from the aqueous solution of palladium chloride, it was washed by immersing it in water at room temperature stirred by air bubbling for 5 minutes. The same wash was performed once more.

(6) Substrate swelling treatment The substrate was immersed in water (warm water) adjusted to 65 ° C. for 5 minutes. The swelling treatment of the base material was performed in order to enhance the penetration of the electroless plating solution into the aliphatic polyamide in the electroless plating treatment in the subsequent step.
(7) Electroless plating The substrate was immersed in an electroless nickel plating solution (manufactured by Okuno Pharmaceutical Industry Co., Ltd., Top Nicolon HMB) adjusted to 65 ° C. for 10 minutes. During the electroless plating, the electroless plating solution was vigorously stirred by air bubbling and a pump. An electroless nickel plating film was grown on the surface of the substrate by about 1 μm to obtain a plating film coating film of this example.

[Example 2]
In this example, the same as in Example 1 except that polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., 30% by weight solution) having a weight average molecular weight of 100,000 was used as the nitrogen-containing polymer in the pretreatment for applying the catalyst. A plating film coating was produced by the method.

[Example 3]
In this example, the same as in Example 1 except that polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., 30% by weight solution) having a weight average molecular weight of 1,000 was used as the nitrogen-containing polymer in the pretreatment for applying the catalyst. A plating film coating was produced by the method.

[Example 4]
In this example, in the pretreatment for applying the catalyst, a plating film coating was produced by the same method as in Example 1 except that the pretreatment liquid did not contain a reducing agent.

[Example 5]
In this example, in the pretreatment for applying the catalyst, the plating film coating was carried out by the same method as in Example 1 except that the blending amount (solid content concentration) of the nitrogen-containing polymer in the pretreatment liquid was 2 g / L. Manufactured.

[Example 6]
In this embodiment, as a base material, a first portion formed of polypropylene (PP) containing 20% by weight of talc (manufactured by Prime Polymer Co., Ltd., J105G), and a polymer alloy of polyamide and polypropylene containing an inorganic filler (PA6). / PP) (Toyobo, Glamide NB777-03) was used as a two-color polymer composed of a second portion. Further, 2.0N hydrochloric acid was used for roughening and / or swelling treatment of the base material. Other than that, a plating film coating was produced by the same method as in Example 1.

In this example, in the base material which is a two-color molded product, only the second portion of the base material containing polyamide was roughened and / or swollen with hydrochloric acid. In addition, the inorganic filler mixed in the second portion was dissolved in hydrochloric acid. Therefore, even in the region where the polypropylene (PP) domain is abundant in the second portion and it is difficult to roughen and / or swell, the inorganic filler is extracted with hydrochloric acid to promote the roughening.

[Example 7]
In this embodiment, a molded body made of a polymer alloy (ABS / PC) (manufactured by Teijin, MK-1000A, plating grade) of ABS resin and polycarbonate is used as the base material, and the base material is prepared by the method described below. Roughening and / or swelling treatment was performed. Moreover, the swelling treatment of the base material was not performed before the electroless plating treatment. Other than that, a plating film coating was produced by the same method as in Example 1.

(1) Roughening and / or swelling treatment of the base material The base material was subjected to degreasing, chromic acid etching, and neutralization in this order as a general pretreatment for plating ABS resin. In the chromic acid etching, first, 400 g / L of chromic acid, 400 g / L of concentrated sulfuric acid, and 10 g / L of trivalent chromium were mixed with water to prepare an etching solution. Then, the base material was immersed in the etching solution adjusted to 60 ° C. for 10 minutes. By the plating pretreatment (etching) described above, the butadiene component in the substrate was dissolved and fine irregularities were formed on the substrate.

(2) Pretreatment for applying catalyst, cleaning of base material, application of electroless plating catalyst and electroless plating For the etched base material, pretreatment for applying catalyst and base material by the same method as in Example 1. Cleaning, electroless plating catalyst application and electroless plating were performed in this order.

[Example 8]
In this example, a molded product made of polyphenylene sulfide (PPS) (manufactured by DIC, Z230) was used as the base material. Further, as described below, a catalytic activity interfering layer containing a catalytic deactivating agent was formed on the surface of the substrate, and then the substrate was roughened by laser light irradiation (laser drawing). Moreover, the swelling treatment of the base material was not performed before the electroless plating treatment. Other than that, a plating film coating was produced by the same method as in Example 1.

(1) Application of catalyst deactivating agent A catalytic activity blocking layer containing a hyperbranched polymer represented by the following formula (1), which is a catalytic deactivating agent, was formed on the surface of the substrate. The hyperbranched polymer represented by the following formula (1) was synthesized by the method disclosed in JP-A-2017-160518.

The synthesized polymer represented by the formula (1) was dissolved in methyl ethyl ketone to prepare a polymer solution having a polymer concentration of 0.3% by weight. The substrate was immersed in a polymer solution at room temperature for 5 seconds and then dried in an 85 ° C. dryer for 5 minutes. As a result, a catalytically active interfering layer having a film thickness of about 100 nm was formed on the surface of the substrate.

(2) Laser drawing A line (1 mm × 50 mm) formed by a 0.2 mm square lattice pattern using a _YVO4 laser (manufactured by KEYENCE, MD-V9929WA, wavelength 1064 nm) on a substrate on which a catalytically active interfering layer is formed. Was drawn with a space of 0.5 mm. After drawing with the laser, the substrate was degreased and washed.

(3) Pretreatment for applying catalyst, cleaning of base material, application of electroless plating catalyst and electroless plating For the base material drawn by laser, pretreatment for applying catalyst and base material by the same method as in Example 1. Cleaning, electroless plating catalyst application, and electroless plating were performed in this order.

[Example 9]
In this example, a ceramic base material of aluminum nitride (AlN) (a disk-shaped plate material having a diameter of 50 cm) was used as the base material. Similar to Example 8, a catalytically active interfering layer containing a catalytic deactivating agent was formed on the surface of the substrate, and then the substrate was roughened by laser light irradiation (laser drawing). Moreover, the swelling treatment of the base material was not performed before the electroless plating treatment. Other than that, a plating film coating was produced by the same method as in Example 1.

(1) Application of catalyst deactivating agent and laser drawing By the same method as in Example 8, a catalytic activity interfering layer containing a hyperbranched polymer represented by the formula (1), which is a catalytic deactivating agent, on the surface of the substrate. Was formed, and then laser drawing was performed.

(2) Pretreatment for applying catalyst, cleaning of base material, application of electroless plating catalyst and electroless plating For the base material drawn by laser, pretreatment for applying catalyst and base material by the same method as in Example 1. Cleaning, electroless plating catalyst application, and electroless plating were performed in this order.

[Comparative Example 1]
In this comparative example, the pretreatment for applying the catalyst, that is, the treatment for contacting the base material with the pretreatment liquid containing the nitrogen-containing polymer was not performed. Other than that, a plating film coating was produced by the same method as in Example 1.

[Comparative Example 2]
In this comparative example, polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., 30 wt% concentration solution) having a weight average molecular weight of 300 was used as the nitrogen-containing polymer in the pretreatment for applying the catalyst. Other than that, a plating film coating was produced by the same method as in Example 1.

[Comparative Example 3]
In this comparative example, an electroless plating catalyst was applied to the substrate by the conventional catalyst accelerator method (C / A method). Other than that, a plating film coating was produced by the same method as in Example 1.

[Comparative Example 4]
In this comparative example, the plating film coating is produced by the same method as in Example 8 except that the pretreatment for applying the catalyst, that is, the treatment for contacting the base material with the pretreatment liquid containing the nitrogen-containing polymer is not performed. did. That is, in this comparative example, a molded body made of polyphenylene sulfide (PPS) (manufactured by DIC, Z230) is used as the base material, and a catalytic activity interfering layer containing a catalytic deactivating agent is formed on the surface of the base material, and then The substrate was roughened by laser light irradiation (laser drawing).

[Evaluation of Plated Film Covers Obtained in Examples 1-9 and Comparative Examples 1-4]
(1) Plating reactivity The surfaces of the plating film coatings obtained in Examples 1 to 9 and Comparative Examples 1 to 4 were visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 1.

<Evaluation criteria for plating reactivity>
◯: A plating film is uniformly formed on the entire surface of the roughened and / or swollen portion of the base material.
Δ: There is unevenness in the plating film in the roughened and / or swollen portion of the base material.
X: No plating film is formed on the roughened and / or swollen portion of the base material.

(2) Adhesion strength of plating film Adhesion strength of plating film is formed by forming 40 μm electrolytic copper plating on the electroless plating film of the plating film coatings obtained in Examples 1 to 9 and Comparative Examples 1 to 4. A sample for measurement was prepared. The adhesion strength of the plating film of the measurement sample was measured by a vertical tensile test. The results are shown in Table 1.

(3) Presence or absence of growth of the plating film on the jig In Examples 1 to 9 and Comparative Examples 1 to 4, the surface of the jig holding the base material was visually observed after the plating film coating was manufactured. The presence or absence of the electroless plating film on the jig was evaluated according to the following evaluation criteria. The results are shown in Table 1.

<Evaluation criteria for the presence or absence of growth of the plating film on the jig>
◯: The electroless plating film has not grown on the jig.
X: An electroless plating film is growing on the jig.

As shown in Table 1, in Examples 1 to 9, the plating reactivity was good. In Examples 1 to 5 and 7, since the entire surface of the substrate was roughened and / or swollen, an electroless plating film was uniformly formed on the entire surface of the substrate. In Example 6, in the substrate which is a two-color molded product, only the second portion of the substrate containing the polyamide was roughened and / or swollen by hydrochloric acid, so that the electroless plating film was selectively formed only on the second portion. Been formed. Further, in Examples 8 and 9, an electroless plating film was selectively formed only on the laser-drawn portion.

Further, in Examples 1 to 9, the adhesion strength of the plating film was at a level at which there was no particular problem in practical use. Examples 1 to 3 in which only the weight average molecular weight of the nitrogen-containing polymer in the catalyst-imparted pretreatment liquid is different and the other conditions are the same are compared. The adhesion strengths of the plating films of Examples 1 to 3 are all 10 N / cm or more, which is a target value for general resin plating, but the weight average molecular weight is 70,000 or more of Examples 1 and 2. The adhesion strength was higher. Further, comparing Examples 1 and 4 in which the conditions other than the presence or absence of the reducing agent in the catalyst-imparted pretreatment liquid are the same, the adhesion strength of the plating film of Example 1 containing the reducing agent in the pretreatment liquid is higher. It was higher. Further, the general target value for resin plating of thin wires as in Example 8 is 5 N / cm. In Example 8, a high adhesion strength exceeding the target value was obtained. Further, in the ninth embodiment, the electric wiring by the plating film can be directly formed on the ceramic base material which is a high thermal conductivity and insulating material, and the formed wiring (plating film) can be used as the minimum wiring. It was confirmed that it has the adhesion strength of.

Further, in Examples 1 to 9, despite the electroless plating treatment being performed while vigorously stirring the electroless plating solution, the plating reactivity was good and the adhesion strength shown in Table 1 was obtained. From this result, it is presumed that an electroless plating film having a uniform shape and high adhesion strength can be formed even on a substrate having a complicated shape or a large shape by the same manufacturing method as in Examples 1 to 9.

Further, in Examples 1 to 9, no plating film growth was confirmed on the jig holding the base material. Therefore, in the manufacturing methods of Examples 1 to 9, it is not necessary to replace the jig that holds the base material between the catalyst application treatment and the plating treatment.

On the other hand, in Comparative Example 1 in which the pretreatment for applying the catalyst was not performed, the plating reactivity was low, and the plating film did not precipitate on about 10% of the surface of the substrate. The unprecipitated plating film was concentrated on the edge portion of the base material (molded body) and the portion corresponding to the vicinity of the gate of the mold. Since these portions have high crystallinity of the base material and low water permeability, the electroless plating catalyst is difficult to adsorb. Therefore, it is presumed that the electroless plating catalyst was desorbed around the edge portion of the molded product by cleaning the base material. Further, in Comparative Example 2 in which a nitrogen-containing polymer having a weight average molecular weight of less than 1000 was used in the pretreatment for applying the catalyst, the plating reactivity was low and the plating film did not precipitate on about 5% of the surface of the substrate. It is presumed that the nitrogen-containing polymer having a low weight average molecular weight did not have sufficient adsorption power to the roughened and / or swollen portion of the base material, and was desorbed from the base material by washing the base material. Further, in Comparative Example 3 in which the electroless plating catalyst was applied by the catalyst accelerator method (C / A method), the electroless plating film grew on the jig. In the catalyst accelerator method, palladium colloid is used as the electroless plating catalyst instead of metal ions, and a reduction step is performed separately. Therefore, it is presumed that the electroless plating catalyst was strongly adsorbed on the jig and the electroless plating film was generated.

Further, in Comparative Example 4 in which polyphenylene sulfide (PPS) was used as a base material and no pretreatment for catalyst application was performed, an electroless plating film was not formed on the laser drawing portion. It is presumed that this is because the electroless plating catalyst (metal ion) is difficult to adsorb to non-polar materials such as PPS. On the other hand, as described above, in Example 8 using the PPS substrate, an electroless plating film having sufficient adhesion strength could be formed on the laser drawing portion. From the comparison between Example 8 and Comparative Example 4, the adsorption amount of the electroless plating catalyst (metal ion) is increased by the pretreatment for applying the catalyst even to the base material of the non-polar material such as PPS, and the electroless plating catalyst (metal ion) is not electrolyzed. It was confirmed that a plating film could be formed.

According to the method for producing a plating film coating film of the present invention, the catalyst application treatment is performed by a simple method using a stable treatment liquid, and even on a substrate having a complicated shape or a large shape, there is no uniform and high adhesion strength. An electrolytic plating film can be formed. Further, since it is not necessary to replace the jig for holding the base material between the catalyst application treatment and the plating treatment, the throughput can be improved.

Claims (20)

It is a method of manufacturing a plating film coating,
Roughening and / or swelling at least a portion of the surface of the substrate,
Contacting the roughened and / or swollen substrate with a pretreatment solution containing a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more.
Cleaning the base material that has been brought into contact with the pretreatment liquid, and
A plating catalyst solution containing a metal salt is brought into contact with the washed base material to adsorb metal ions derived from the metal salt to the base material .
A method for producing a plating film coating body, which comprises contacting an electroless plating solution with a substrate on which the metal ions are adsorbed, which is in contact with the plating catalyst solution. The method for producing a plating film coating according to claim 1, wherein at least a part of the surface of the base material is roughened by irradiating at least a part of the surface of the base material with a laser beam. The substrate contains an aliphatic polyamide and contains
The plating film coating material according to claim 1, wherein at least a part of the surface of the base material is brought into contact with hydrochloric acid to roughen and / or swell at least a part of the surface of the base material. Production method. The base material contains ABS resin and contains
The first aspect of claim 1, wherein at least a part of the surface of the base material is brought into contact with permanganate or chromic acid to roughen and / or swell at least a part of the surface of the base material. A method for manufacturing a plated film coating. The method for producing a plating film coating according to any one of claims 1 to 4, wherein the nitrogen-containing polymer is polyethyleneimine. The method for producing a plating film coating according to any one of claims 1 to 5, wherein the nitrogen-containing polymer has a weight average molecular weight of 1,000 to 100,000. The method for producing a plating film coating according to claim 6, wherein the nitrogen-containing polymer has a weight average molecular weight of 70,000 to 100,000. The production of the plating film coating body according to any one of claims 1 to 7, wherein the blending amount of the nitrogen-containing polymer in the pretreatment liquid is 0.01 g / L to 100 g / L. Method. It is a method of manufacturing a plating film coating,
Roughening and / or swelling at least a portion of the surface of the substrate,
Contacting the roughened and / or swollen substrate with a pretreatment solution containing a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more.
Cleaning the base material that has been brought into contact with the pretreatment liquid, and
By contacting the washed substrate with a plating catalyst solution containing a metal salt,
Including contacting the electroless plating liquid with the base material to which the plating catalyst liquid has been brought into contact, including contacting the electroless plating liquid.
A method for producing a plating film coating, wherein the pretreatment liquid further contains a reducing agent which is calcium hypophosphite. The method for producing a plating film coating according to claim 9, wherein the blending amount of the reducing agent in the pretreatment liquid is 1 g / L to 100 g / L. The method for producing a plating film coating according to any one of claims 1 to 10 , wherein the metal salt of the plating catalyst solution is palladium chloride. The method for producing a plating film coating according to any one of claims 1 to 11 , wherein the electroless plating solution is an electroless nickel plating solution containing sodium hypophosphite. The method for producing a plating film coating according to any one of claims 1 to 12 , wherein the electroless plating solution is brought into contact with the base material while being stirred. With the base material held by a jig, the pretreatment liquid is brought into contact with both the base material and the jig to perform the cleaning, and the plating catalyst liquid is brought into contact with the electroless plating liquid. The method for producing a plating film coating according to any one of claims 1 to 13 , wherein the plating film coating is brought into contact with each other. Further comprising applying a catalytic deactivating agent to the surface of the substrate.
The method for producing a plating film coating according to any one of claims 1 to 14 , wherein at least a part of the surface of the base material to which the catalyst deactivating agent is applied is roughened. A pretreatment liquid for applying an electroless plating catalyst to a substrate.
Nitrogen-containing polymers with a weight average molecular weight of 1,000 or more,
With water
A pretreatment liquid containing a reducing agent which is calcium hypophosphite . The pretreatment liquid according to claim 16 , wherein the nitrogen-containing polymer is polyethyleneimine. The pretreatment liquid according to claim 16 or 17 , wherein the nitrogen-containing polymer has a weight average molecular weight of 1,000 to 100,000. The pretreatment liquid according to any one of claims 16 to 18 , wherein the blending amount of the nitrogen-containing polymer in the pretreatment liquid is 0.01 g / L to 100 g / L. The pretreatment liquid according to any one of claims 16 to 19, wherein the blending amount of the reducing agent in the pretreatment liquid is 1 g / L to 100 g / L.

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