WO2021014599A1

WO2021014599A1 - Method for manufacturing plated part, and pretreatment liquid for applying electroless plating catalyst

Info

Publication number: WO2021014599A1
Application number: PCT/JP2019/028940
Authority: WO
Inventors: 遊佐　敦; 美由喜土畑; 朗子鬼頭; 直樹臼杵; 吟孫
Original assignee: マクセルホールディングス株式会社
Priority date: 2019-07-24
Filing date: 2019-07-24
Publication date: 2021-01-28
Also published as: JPWO2021014599A1; JP6666529B1; CN114127334A

Abstract

Provided is a method for manufacturing a plated part in which an electroless plating catalyst can be applied to a base material by a simple method using a stable treatment liquid, the reactivity and selectivity of electroless plating are high, and precipitation of a plating film on a jig can be suppressed. The method for manufacturing a plated part comprises: irradiating a part of the surface of a base material with a laser beam; bringing a pretreatment liquid that includes a nitrogen-containing polymer having a weight average molecular weight of 1000 or more and has a surface tension of 20-60 mN/m into contact with the base material irradiated with the laser light; washing the base material which has been brought into contact with the pretreatment liquid; bringing a plating catalyst solution including a metal salt into contact with the washed base material; and bringing an electroless plating solution into contact with the base material that has been brought into contact with the plating catalyst solution and forming an electroless plated film on the laser beam irradiation portion.

Description

Manufacturing method of plated parts and pretreatment liquid for applying electroless plating catalyst

The present invention relates to a method for manufacturing plated parts and a pretreatment liquid for applying an electroless plating catalyst.

Three-dimensional circuit molded parts (MID: Molded Integrated Device), in which circuits are three-dimensionally formed on a three-dimensional resin molded product, are expanding the market centered on built-in antennas for smartphones. MID has merits such as reduction of printed circuit boards and flexible substrates and reduction of the number of manufacturing processes, and various manufacturing methods have been developed.

It has been proposed that the MID circuit formed on the insulating base material (resin molded product) be formed by electroless plating. In electroless plating, an electroless plating catalyst is first applied to the surface of the base material, and then an electroless plating process is performed. Two main methods for applying electroless plating catalysts are known: the sensitizer-activator method and the catalyst-accelerator method. In the sensitizer-activator method, a tin colloid is adsorbed on a substrate (sensitizer), then 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. Therefore, in the conventional catalyst addition treatment, it has been required to reduce the number of steps.

Furthermore, the conventional catalyst addition treatment also has the following problems. In the catalyst accelerator method, since the catalyst palladium is a colloid, it is unstable and easily precipitates and aggregates. Therefore, the amount of catalyst used increases. Further, in the sensitizer-activator method, continuous treatment is difficult because the sensitizer solution is an unstable colloidal solution in which tin is self-reduced. 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.

Patent Document 1 proposes a method for manufacturing a molded circuit component using an electroless plating catalyst application treatment different from the sensitizer activator method and the catalyst accelerator method. In the method disclosed in Patent Document 1, the base material is irradiated with a laser beam having a specific wavelength, partially roughened and surface-modified, and the surface-modified portion of the laser beam irradiation portion is a catalyst composed of metal ions. Is adsorbed and the ion catalyst is reduced, and then electroless plating is performed. Since the catalyst composed of metal ions selectively adheres to the laser beam irradiation portion, an electroless plating film is selectively formed on the laser beam irradiation portion.

Further, Patent Document 2 discloses a plating method that does not deposit a plating film on a jig that holds a base material, although it is not a method for manufacturing a circuit component. In the plating method of Patent Document 2, the base material (plastic) is subjected to etching treatment, addition of a catalyst-imparting enhancer, application of an electroless plating catalyst, and electroless plating in this order. The catalyst-imparting enhancer contains a nitrogen atom-containing compound having selective adsorption on functional groups exposed on the surface of the base material (plastic).

Japanese Patent No. 5022501 Japanese Unexamined Patent Publication No. 2008-31513

However, in the method for manufacturing a molded circuit component of Patent Document 1, the adhesion of the electroless plating catalyst to the base material is controlled only by irradiating or not irradiating the laser beam. Therefore, the selectivity of plating (contrast with or without plating film) may be insufficient. Further, according to the study by the present inventors, it is necessary to optimize the combination of the laser and the resin base material in order to control the adhesion of the electroless plating catalyst only by irradiating or not irradiating the laser beam. I understood. Therefore, the selection range of the resin base material that can be practically applied is narrowed. Further, in the method for manufacturing a molding circuit component of Patent Document 1, it is essential to reduce the electroless plating catalyst before the electroless plating treatment in order to suppress the desorption of the electroless catalyst during the electroless plating treatment. is there. Further, in order to strengthen the adsorption force of the electroless plating catalyst to the base material, it has been proposed that the base material is treated with an alkali or a surfactant after irradiation with a laser beam. Therefore, the manufacturing method of the molded circuit component of Patent Document 1 requires a long manufacturing process.

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, problems in the conventional catalyst application treatment such as a large number of steps and instability of the treatment liquid have not been solved yet. Further, according to the study by the present inventors, the plating method using the catalyst-imparting enhancer disclosed in Patent Document 2 has insufficient plating selectivity (contrast with or without plating film), and MID and antenna. It was found that it is difficult to form the fine plating pattern (circuit pattern, antenna pattern) required for the member.

The present invention solves these problems, an electroless plating catalyst can be applied to a substrate by a simple method using a stable treatment liquid, the electroless plating has high reactivity and selectivity, and further. Provided is a method for manufacturing a plated part capable of suppressing precipitation of a plated film on a jig.

According to the first aspect of the present invention, in the method for manufacturing a plated part, a part of the surface of a base material is irradiated with a laser beam, and the base material irradiated with the laser light is subjected to a weight average molecular weight. Contacting a pretreatment liquid containing 1,000 or more nitrogen-containing polymers and having a surface tension of 20 mN / m to 60 mN / m, cleaning the base material contacted with the pretreatment liquid, and the cleaning. The plating catalyst solution containing a metal salt is brought into contact with the base material, and the electroless plating solution is brought into contact with the base material contacted with the plating catalyst solution to form an electroless plating film on the laser beam irradiation portion. A method of manufacturing a plated part including what to do is provided.

In this embodiment, the surface of the base material may be roughened and / or modified by irradiating the laser beam. The nitrogen-containing polymer may be polyethyleneimine. The weight average molecular weight of the nitrogen-containing polymer may be 1,000 to 100,000, 10,000 to 100,000, or 50,000 to 100,000. The blending amount of the nitrogen-containing polymer in the pretreatment liquid may be 0.01 g / L to 100 g / L or 2 g / L to 50 g / L. The pretreatment liquid may contain a surfactant.

It may further include applying a catalytic deactivator to the surface of the base material before irradiating the base material with laser light. The catalytic deactivator may be a hyperbranched polymer. The metal salt of the plating catalyst solution may be palladium chloride, and the blending amount of palladium chloride in the plating catalyst solution may be 0.01 g / L to 1.0 g / L. The electroless plating solution may contain sodium hypophosphite. By contacting the plating catalyst solution, the metal ions derived from the metal salt may be adsorbed on the base material, and the electroless plating solution may be brought into contact with the base material on which the metal ions are adsorbed. The electroless plating film may form an electric circuit or an antenna pattern.

According to the second aspect of the present invention, it is a pretreatment liquid for applying an electroless plating catalyst, which contains water, a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more, and a surfactant, and has a surface tension. A pretreatment solution is provided in which is 20 mN / m to 60 mN / m.

In this embodiment, the nitrogen-containing polymer may be polyethyleneimine. The blending amount of the nitrogen-containing polymer in the pretreatment liquid may be 0.01 g / L to 100 g / L.

In the method for manufacturing a plated part of the present invention, an electroless plating catalyst can be applied to a base material by a simple method using a stable treatment liquid, and the reactivity and selectivity of electroless plating are high. Further, precipitation of the plating film on the jig holding the base material can be suppressed.

FIG. 1 is a flowchart showing a method for manufacturing a plated component according to the first embodiment. FIG. 2 is a flowchart showing a method of manufacturing the plated parts of the second embodiment.

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

(1) Laser Light Irradiation First, a part of the surface of the base material is irradiated with laser light (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, semi-aromatic polyamides such as nylon 6T (PA6T), nylon 9T (PA9T), polyamide MXD6 (MXD6PA), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polybutylene terephthalate (PBT), syndiotac polystyrene ( A thermoplastic resin (heat-resistant resin) having heat resistance such as SPS), polyetheretherketone (PEEK), and polyetherimide can be used. Further, a crystalline resin such as an epoxy resin or a silicone resin can also be used. The base material containing these heat-resistant resins and / or crystalline resins has solder reflow resistance, and also has high durability, high heat resistance, and chemical resistance. If the plated parts are not required to have solder reflow resistance, use general-purpose engineering plastics such as ABS resin, polycarbonate (PC), polymer alloy of ABS resin and PC (ABS / PC), polypropylene, aliphatic polyamide, etc. Can be done. 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, a heat-dissipating metal or ceramic may be used for at least a part of the base material. Examples of the metal (conductor) include iron, copper, aluminum, titanium, magnesium, stainless steel (SUS) and the like. Examples of ceramics (non-conductors) include ceramics such as zirconia, alumina, and aluminum nitride. These metals and ceramics may be used alone or in combination of two or more.

In the present embodiment, the surface of the base material can be roughened and / or modified by irradiating the base material with laser light. Here, the fact that the surface of the base material is roughened means that the surface roughness or the size of the unevenness on the surface of the base material becomes larger than that before the laser irradiation. Further, modifying the surface of the base material means that, for example, a functional group is generated on the surface of the base material by breaking the chemical bond of the material constituting the base material with laser light. Only one of the roughening and the modification of the surface of the base material may occur, or both may occur. Further, before and / or after irradiation of the base material with laser light, surface treatment such as roughening, modification, swelling, and etching of the base material may be further performed by chemical or physical etching or the like. It does not have to be.

The laser used for laser light irradiation is not particularly limited, and may be appropriately selected based on the intended use of the plated parts. For example, YV0 ₄ laser emitting a laser beam in the infrared region (λ = 1064nm), a fiber laser (λ = 1090nm), may be used a CO ₂ laser (lambda = 10 [mu] m) and the like. When laser light in the infrared region is used, the surfaces of resins and metals are cut and the base material is roughened. In particular, when the base material is a resin base material containing a filler, the contained filler is exposed to the laser beam irradiation portion, and the anchoring (anchoring) effect improves the adhesion strength of the electroless plating film formed on the base material. .. Further, for example, a green laser (λ = 532 nm), a UV laser (λ = 355 nm), an excimer laser (λ = 193 nm), or the like that emits a laser beam having a short wavelength may be used. When a short wavelength laser beam is used, the spot diameter is narrowed down, excessive heat or damage is not given to the base material, and fine processing and surface modification of the base material are possible. As a result, an electroless plating film can be formed on a smooth base material surface without significantly roughening the base material surface.

(2) Pretreatment for Catalysis Next, as a pretreatment for applying the electroless plating catalyst to the base material, the pretreatment liquid is brought into contact with the base material (step S2 in FIG. 1). The pretreatment liquid contains a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more, and may further contain water and a surfactant. The surface tension of the pretreatment liquid is 20 mN / m to 60 mN / m.

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. Polyethylenimine is a highly reactive polymer containing primary, secondary, and tertiary amines and having 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 laser-irradiated portion of the substrate, i.e., the roughened and / or modified portion of the substrate, but the nitrogen-containing polymer has a weight average molecular weight of less than 1,000. If there is, it becomes easy to be separated from the base material in the cleaning step (step S3 in FIG. 1) which is a subsequent step. As a result, the reactivity of electroless plating decreases. By setting the weight average molecular weight of the nitrogen-containing polymer to 1,000 or more, desorption of the nitrogen-containing polymer in the washing step can be suppressed, and the reactivity of electroless plating can be enhanced. From the viewpoint of further suppressing the desorption of the nitrogen-containing polymer, the weight average molecular weight of the nitrogen-containing polymer is preferably 10,000 or more, or 50,000 or more, for example. It should be noted that even if the base material is gently washed in the washing step, the desorption of the nitrogen-containing polymer from the base material can be suppressed, but the washing of the base material becomes insufficient and the selectivity of electroless plating is lowered. There is a risk. This tendency is remarkable when the shape of the base material is complicated.

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 laser beam irradiation portion. This phenomenon is remarkable when the plating pattern is a fine pattern such as a fine line. As a result, there is a possibility that the plating film is not deposited in the laser beam irradiation portion, and conversely, the plating film may be deposited between the fine lines of the fine pattern. That is, the reactivity and / or selectivity of electroless plating may decrease. From the above viewpoint, the weight average molecular weight of the nitrogen-containing polymer is preferably 100,000 or less, 80,000 or less, or 70,000 or less, for example.

From the above, the weight average molecular weight of the nitrogen-containing polymer is preferably, for example, 1,000 to 100,000, 10,000 to 100,000, 50,000 to 100,000, or 10,000 to 70,000.

The blending amount of the nitrogen-containing polymer in the pretreatment liquid is preferably, for example, 0.01 g / L to 100 g / L, 2 g / L to 50 g / L, or 5 g / L to 50 g / L. Since the specific gravities of the nitrogen-containing polymer and the pretreatment liquid are almost the same, the blending amounts are, for example, 0.001% by weight to 10% by weight, 0.2% by weight to 5% by weight, and 0.5% by weight to 5. Weight% is preferred. Since the metal ions used as the electroless plating catalyst are stable in water, they are not easily adsorbed on the surface of the base material. By setting the blending amount of the nitrogen-containing polymer in the pretreatment liquid to be equal to or higher than the lower limit of the above range, a sufficient amount of nitrogen-containing polymer for adsorbing metal ions on the base material can be applied to the base material, and the cleaning step Even after passing through (step S3 in FIG. 1), a sufficient amount of nitrogen-containing polymer can remain in the laser beam irradiation portion. Further, if the blending amount of the nitrogen-containing polymer is too large, the nitrogen-containing polymer may be precipitated in the pretreatment liquid, and the plating film may be precipitated on the jig holding the base material. By setting the blending amount of the nitrogen-containing polymer in the pretreatment liquid to be equal to or less than the upper limit of the above range, it is possible to suppress the precipitation of the nitrogen-containing polymer in the pretreatment liquid and keep the pretreatment liquid stable. In addition, precipitation of the plating film on the jig holding the base material can be suppressed.

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 solvents; examples of these mixed solvents. 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, the main component of the solvent may be water, and a water-soluble organic solvent such as alcohol may be contained.

The surface tension of the pretreatment liquid is 20 mN / m to 60 mN / m, preferably 30 mN / m to 50 mN / m. If the surface tension is smaller than the above range, the pretreatment liquid tends to adhere to the jig holding the base material, and it becomes difficult to remove it even through the cleaning step (step S3 in FIG. 1). As a result, a plating film may be deposited on the jig surface. On the other hand, if the surface tension is larger than the above range, it becomes difficult for the pretreatment liquid to sufficiently wet the roughened region and fine irregularities on the surface of the base material. This phenomenon is remarkable when the plating pattern is a fine pattern such as a fine line. As a result, there is a possibility that the plating film is not deposited in the laser beam irradiation portion, and conversely, the plating film may be deposited between the fine lines of the fine pattern. That is, the reactivity and / or selectivity of electroless plating is reduced. Further, if the surface tension is larger than the above range, the adhesion strength of the plating film may decrease. The surface tension of the pretreatment liquid can be adjusted by using, for example, a surfactant or a surface conditioner.

The type of the surfactant is not particularly limited, and an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, a silicone-based surfactant, a fluorine-based surfactant, etc. are appropriately selected. Can be used. The amount of the surfactant blended in the pretreatment liquid is not particularly limited as long as the surface tension of the pretreatment liquid is adjusted to be within the above range. For example, the blending amount of the surfactant in the pretreatment liquid is 0.01% by weight to 5% by weight and 0.05% by weight to 1% by weight. According to the study by the present inventors, when the solvent of the pretreatment liquid is water or the main component of the solvent is water and the pretreatment liquid does not contain a surfactant, the surface tension of the pretreatment liquid is as described above. It is likely to be larger than the range, in which case it has been found that the reactivity and selectivity of electroless plating is reduced (see Experiment 16 in Examples below).

The pretreatment liquid may further contain general-purpose additives such as preservatives, if necessary. The pretreatment liquid can be prepared by mixing a nitrogen-containing polymer, a solvent, and if necessary, a surfactant and a general-purpose additive by any method. The pretreatment liquid may or may not further contain a reducing agent.

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 laser beam irradiation portion of the base material. 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 in contact with the pretreatment liquid is washed (step S3 in FIG. 1). The nitrogen-containing polymer is adsorbed and / or permeated into the laser-irradiated portion of the substrate, that is, the roughened and / or modified portion of the substrate. On the other hand, the nitrogen-containing polymer is not adsorbed on the non-irradiated portion of the laser beam, or is adsorbed with a relatively weak force. Therefore, by cleaning the base material, the nitrogen-containing polymer adhering to the laser light non-irradiated portion, that is, the portion where the electroless plating film is not formed can be removed, and the nitrogen-containing polymer can be left only in the laser light irradiated portion. it can. In addition, the nitrogen-containing polymer adhering to the jig holding the base material can be removed, and the precipitation of the plating film on the jig can be suppressed.

Cleaning can be performed, for example, by immersing the base material in a liquid (cleaning solution) 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, as cleaning of the base material, it is preferable to wash the base material with water. 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, the stirring of the cleaning liquid means, for example, stirring, circulating, flowing, etc. the cleaning liquid by air bubbling, a pump, or the like. Alternatively, the base material and the jig may be shaken in the cleaning liquid. In order to suppress an increase in the concentration of the nitrogen-containing polymer eluted in the cleaning liquid, it is preferable to pass the cleaning liquid through a filter, activated carbon or the like and circulate it to maintain the cleaning effect.

The temperature of the cleaning liquid and the cleaning time (time during which the base material 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 80 ° C., and the cleaning time is, for example, 1 to 20 minutes. In order to enhance the cleaning effect, the substrate may be washed a plurality of times.

(4) Application of Electroless Plating Catalyst Next, a plating catalyst solution 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 laser beam irradiation portion of the base material, that is, the roughened and / or swollen portion.

In conventional catalyst application treatments such as the sensitizer activator method and the catalyst accelerator method, metal ions, which are catalysts, are reduced and adsorbed on the substrate as a metal state with an oxidation number of 0 (zero). The reason will be explained below. First, metal ions are difficult to adsorb on the surface of the substrate. Even if it is adsorbed, it has a weak adsorption force, so that it may be detached from the base material during the electroless plating process. In the conventional catalyst application treatment, the metal ion is reduced to a metallic state to enhance the adsorption force to the base material. Second, electroless plating catalysts usually exhibit catalytic activity in a metallic state with an oxidation number of 0 (zero). It does not show catalytic activity in the ionic state. In the conventional catalyst application treatment, metal ions are reduced and adsorbed on the base material, so that the base material adsorbed by the electroless plating catalyst in a metallic state showing catalytic activity is brought into contact with the electroless plating solution in the electroless plating step. I'm letting you.

On the other hand, in the present embodiment, it is not necessary to reduce the metal ion as a catalyst in the catalyst application treatment (step S4 in FIG. 1). A nitrogen-containing polymer capable of adsorbing metal ions is present in the laser beam irradiation portion of the base material of the present embodiment. The nitrogen-containing polymer allows metal ions to be adsorbed on the laser beam irradiation portion of the base material. Since the nitrogen-containing polymer enhances the adsorption force of the electroless plating catalyst on the substrate, it is possible to suppress the detachment of the electroless plating catalyst during the electroless plating treatment. In the present embodiment, in the catalyst application treatment, metal ions are adsorbed on the base material. Therefore, in the electroless plating step (step S5 in FIG. 1), an ionic electroless plating catalyst (oxidation number of metal) showing no catalytic activity. The base material to which is positive) is brought into contact with the electroless plating solution. However, in the present embodiment, the electroless plating catalyst can be present on the surface of the substrate at a sufficient concentration even in the ionic state, and is reduced by the reducing agent contained in the electroless plating solution to exhibit catalytic activity. it can. As a result, an electroless plating film can be formed on the laser beam irradiation portion of the base material.

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 is improved. Further, in the present embodiment, the unstable colloidal solution used in the conventional catalyst application treatment is unnecessary. The plating catalyst solution containing the metal salt used in the present embodiment is stable and easy to manage and store.

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 amount of the metal salt blended in the plating catalyst solution is not particularly limited, and is based on conditions such as the temperature of the plating catalyst solution, the contact time between the plating catalyst solution and the base material, or the electroless plating step described later (FIG. It can be appropriately adjusted based on the type of electroless plating solution used in step S5) of 1. For example, the blending amount of the metal salt in the plating catalyst solution is 0.01 g / L to 1.0 g / L, 0.05 g / L to 0.5 g / L, or 0.1 g / L to 0.3 g / L. It is L. If the amount of the metal salt blended is less than the above range, the amount of the metal salt adsorbed on the base material may be uneven, and the plating film may be defective. On the other hand, if the blending amount 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, 0.1N to 12N, preferably 0.1N to 5N, and more preferably 1.0N to 4.0N. Further, in the present embodiment, an alkaline plating catalyst solution may be used.

The plating catalyst solution may be composed of only a metal salt and a solvent, or may contain a general-purpose additive, if necessary. The plating catalyst solution may contain, for example, a stabilizer, a complexing agent, and a surfactant.

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 sensitizer (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 using the colloidal solution is not necessary. Therefore, in the electroless plating catalyst application treatment of the present embodiment, the throughput is improved as compared with the sensitizer-activator method.

The method of bringing the plating catalyst solution into contact with the base material is arbitrary, and for example, the entire base material may be immersed in the plating catalyst solution. Further, the plating catalyst solution may be brought into contact with only a part of the base material, but in this case, the plating catalyst solution is brought into contact with the region including the laser beam irradiation portion of the base material. Further, the temperature of the plating catalyst solution and the time for contacting the plating catalyst solution with the base material are not particularly limited. The temperature of the plating catalyst solution is, for example, room temperature or 20 ° C. to 40 ° C., and the contact time of the plating catalyst solution is preferably, for example, 30 seconds to 10 minutes. When the temperature of the plating catalyst solution and the contact time are within the above ranges, the electroless plating catalyst can be uniformly adsorbed on the laser beam irradiation portion. In addition, deterioration of the base material due to permeation of the plating catalyst solution and adhesion of the catalyst to the laser light non-irradiated portion can be suppressed. After immersing the base material in the plating catalyst solution, it is preferable to wash the base material with water.

(5) Electroless plating Next, the electroless plating solution is brought into contact with the base material that has been brought into contact with the plating catalyst solution (step S5 in FIG. 1). In the present embodiment, it is not necessary to reduce the electroless plating catalyst (metal ions) after applying the electroless plating catalyst (metal ions) to the base material (step S4 in FIG. 1). That is, the electroless plating solution may be brought into contact with the base material on which the metal ions are adsorbed. As a result, an electroless plating film can be formed on the laser beam irradiation portion of the base material.

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 hypophosphate, formalin, and dimethylamine borane. As the electroless plating solution, an electroless nickel plating solution (electroless nickel phosphorus plating solution), an electroless copper nickel plating solution, an electroless copper plating solution, an electroless palladium plating solution, etc. can be used, and among them, electroless plating. An electroless nickel plating solution and an electroless copper nickel plating solution containing sodium hypophosphite having a high reducing effect of a catalyst (metal ion) as a reducing agent are preferable. Further, the electroless copper nickel plating solution containing sodium hypophosphite as a reducing agent further has the following advantages. Unlike general electroless copper plating, it is not necessary to use formalin as a reducing agent, which is highly harmful to the human body and easily vaporizes naturally. The electroless copper nickel plating film to be formed can form an electroless or electrolytic copper plating film directly above it with good adhesion, and has high electrical conductivity close to that of pure copper.

When sodium hypophosphate is used as a reducing agent, the blending amount of sodium hypophosphate in the electroless plating solution is preferably 5 g / L to 50 g / L. When the blending amount of the reducing agent is within the above range, the metal ions (electroless plating catalyst) adsorbed on the substrate can be sufficiently reduced.

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.

Alternatively, electroless plating may be performed by bringing the electroless plating solution into contact with the base material while stirring or shaking it. By stirring or shaking the electroless plating solution, the temperature and plating reactivity of the electroless plating solution can be made uniform. As a result, 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. In the present embodiment, the electroless plating catalyst is relatively strongly adsorbed on the laser beam irradiation portion of the base material by the nitrogen-containing polymer. Therefore, even if the electroless plating solution is stirred or shaken, the electroless plating catalyst does not separate from the base material, and unevenness of the plating reaction is unlikely to occur. Here, stirring or rocking the electroless plating solution means, for example, stirring, circulating, or flowing the electroless plating solution by 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 plated parts, or the electroless plating film may be formed by electrolytic plating. Good. 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 for natural drying. Further, the following steps 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 plated component 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. Further, when the base material has a three-dimensional surface including a spherical surface or the like, the electroless plating film may be formed three-dimensionally along the three-dimensional surface. When the electroless plating film is formed three-dimensionally over a plurality of surfaces of the molded product 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 plated component having such a predetermined pattern plating film functions as a three-dimensional circuit molded component (MID: Molded Interconductor Device).

As described above, in the production method of the present embodiment, the base material irradiated with the laser beam is brought into contact with a pretreatment liquid containing a nitrogen-containing polymer having a specific weight average molecular weight and having a specific surface tension. Pretreatment for catalysis is performed. As a result, 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, and the reactivity and selectivity of electroless plating are improved. In the present embodiment, an electroless plating film can be selectively formed on the laser beam irradiation portion of the base material.

Further, in the present embodiment, the formation of the plating film on the jig can be suppressed. Therefore, while the base material is held by the jig, the pretreatment liquid is brought into contact with both the base material and the jig to perform cleaning, the plating catalyst liquid is brought into contact with the plating catalyst liquid, and the electroless plating liquid is brought into contact with the base material and the jig. May be good. That is, it is not necessary to replace the jig that holds the base material between the catalyst application treatment and the plating treatment. This improves throughput.

Further, in the production method of the present embodiment, the reduction treatment of the electroless plating catalyst (metal ion), which has been conventionally performed, can be omitted. 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. By omitting the reduction treatment of the electroless plating catalyst (metal ion), the manufacturing cost can be reduced and the throughput can be improved. In the production method of the present embodiment, after the electroless plating catalyst (metal ion) is applied to the base material (step S4 in FIG. 1) and before the electroless plating treatment (step S5 in FIG. 1), A reduction treatment of the electroless plating catalyst (metal ion) may be provided. The reduction treatment of electroless plating is not an essential step, but the reduction treatment of electroless plating improves the proportion of electroless plating that is metallized. This may widen the range of choices for the type of electroless plating solution.

[Second Embodiment]
As a second embodiment, a method of manufacturing a plated part will be described with reference to the flowchart shown in FIG. In the present embodiment, a catalyst deactivating agent (catalytic activity interfering agent) is applied to the surface of the base material before irradiating the base material with laser light (step S11 in FIG. 2). Other than that, the plated parts are 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 deactivator, 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 deactivator either reacts directly 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 react directly with the electroless plating catalyst. It is presumed. Examples of such catalyst deactivators 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 and an oxidizing agent such as a peroxide. 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 because it has high permeability to the base material. These catalytic deactivators can be applied to the substrate by, for example, the method disclosed in International Patent Publication No. WO2016 / 013464. It is presumed that these catalytic deactivators applied to the base material permeate the base material or strongly adsorb to the base material.

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 base material, the catalytic deactivating agent is applied to the surface of the base material. May be good. For example, an interfering layer containing the above-mentioned catalytic deactivator such as iodine and a resin serving as a binder is formed. By using a resin that serves as a binder, the catalyst deactivating agent can be retained on the surface of the base material that is difficult for the catalyst deactivating agent to directly adsorb or permeate.

Further, as the catalyst deactivating agent, a resin that interferes with the catalytic activity may be used. The catalyst deactivator, which is a resin, can be applied onto the substrate as an interfering layer. As the catalyst deactivator 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 to prevent the catalyst from exerting its catalytic ability. Further, as the catalyst deactivator 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 International Patent Publication No. WO2017 / 154470 or WO2018 / 131492 can be used, and the surface of the base material can be used by the method disclosed in the same publication. A disturbing layer can be formed on the surface.

The dendritic polymer is represented by the following formula (1) disclosed in, for example, International Patent Publication No. WO2017 / 154470 or WO2018 / 131492, and has a weight average molecular weight of 1,000 to 1,000. A hyperbranched polymer of 000 is preferred.

In the formula (1), A ¹ is a group containing an aromatic ring, A ² is a group containing an amide group, A ³ is a group containing sulfur, and R ⁰ is hydrogen or 1 to 1 to carbon atoms. There are 10 substituted or unsubstituted hydrocarbon groups, m1 is 0.5 to 11, and n1 is 5 to 100.

Next, as shown in FIG. 2, the following steps similar to those in the first embodiment are performed. First, a part of the surface of the base material to which the catalyst deactivator is applied is irradiated with laser light (step S1 in FIG. 2). By laser light irradiation, a laser light irradiation part and a laser light non-irradiation part are formed on the surface of the base material. In the laser light irradiation unit, the catalyst deactivating agent is removed or modified or altered so that it does not act as the catalyst deactivating agent. Further, the laser light irradiation unit is roughened and / or modified in the same manner as in the first embodiment.

Next, as in the first embodiment, pretreatment for catalyst application (step S2 in FIG. 2), cleaning of the base material (step S3 in FIG. 2), 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 plated component having an electroless plating film formed on the laser beam irradiation 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 an electroless plating film can be selectively formed on the laser beam irradiation portion of the base material. Further, in the present embodiment, the catalyst deactivator remaining in the laser light non-irradiated portion can more reliably suppress the precipitation of the plating film in the laser light non-irradiated portion. This improves the selectivity of electroless plating.

[Third Embodiment]
As a third embodiment, a set of a base material treatment agent for electroless plating will be described. The set of the base material treatment agent for electroless plating of the present embodiment includes a pretreatment liquid for applying an electroless plating catalyst and a catalyst deactivator. The pretreatment liquid for applying the electroless plating catalyst contains water, a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more, and a surfactant, and has a surface tension of 20 mN / m to 60 mN / m. As the pretreatment liquid of the present embodiment, the same pretreatment liquid as that of the first embodiment can be used. Catalytic deactivators include hyperbranched polymers. As the catalyst deactivating agent of the present embodiment, the same catalyst deactivating agent as that of the second embodiment can be used.

By using the pretreatment liquid for applying the electroless plating catalyst and the catalyst deactivator together as a set of the base material treatment agent for electroless plating, the reactivity and selectivity of electroless plating are further improved. be able to. The set of the base material treatment agent for electroless plating of the present embodiment is particularly effective for forming a fine plating pattern (circuit pattern, antenna pattern) required for the MID and the antenna member.

In the set of the present embodiment, it is preferable to use a pretreatment liquid containing polyethyleneimine as a nitrogen-containing polymer and a hyperbranched polymer represented by the formula (1) as a catalyst deactivator in combination.

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 experiments 1 to 17 described below, samples 1 to 17 which are plated parts were prepared. Tables 1 and 2 show the types of the base material and the laser used in each experiment, the presence or absence of the catalyst deactivator, the composition of the pretreatment liquid, the amount of the metal salt mixed in the catalyst liquid, and the types of the electroless plating liquid. Experiments 1 to 12 correspond to Examples, and Experiments 13 to 17 correspond to Comparative Examples.

[Experiment 1]
(1) Base material Polyphenylene sulfide (PPS) (manufactured by DIC, Z230) was injection-molded to obtain a flat plate-shaped base material of 80 mm × 80 mm × 2 mm. The mold temperature was 150 ° C. The molded base material was held by a copper jig coated with vinyl chloride, and in that state, each step described below was carried out.

(2) Application of catalyst deactivating agent A catalytic activity interfering layer containing a hyperbranched polymer represented by the following formula (A), which is a catalytic deactivating agent, was formed on the surface of the base material. The hyperbranched polymer represented by the following formula (A) was synthesized by the method disclosed in International Patent Publication No. WO2018 / 131492. In the formula (A), R ⁰ is a vinyl group or an ethyl group.

The synthesized polymer represented by the formula (A) was dissolved in methyl ethyl ketone to prepare a polymer solution having a polymer content 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 catalytic activity interfering layer having a film thickness of about 100 nm was formed on the surface of the base material.

(3) Laser light irradiation (laser drawing)
YVO ₄ laser to a substrate to form a catalytically active interference layer (manufactured by Keyence, MD-V9929WA, wavelength 1064 nm) was used to laser writing the following wiring patterns A and B. The power at the time of laser drawing was 80%, the frequency was 40 kHz, and the linear velocity was 600 mm / s. After the laser drawing, the base material was degreased and washed.
Wiring pattern A (line / space: 0.5 mm / 0.5 mm): Five lines (0.5 mm × 5 mm) formed by a grid pattern with a 0.1 mm pitch are drawn with a space of 0.5 mm.
Wiring pattern B (line / space: 0.2 mm / 0.2 mm): Five lines (0.2 mm × 5 mm) formed by a grid pattern with a pitch of 0.05 mm are drawn with a space of 0.2 mm.

(4) Pretreatment for catalysis In water, polyethyleneimine (PEI) having a weight average molecular weight of 70,000 (manufactured by Wako Pure Chemical Industries, Ltd., 30 wt% concentration solution) as a nitrogen-containing polymer, and sodium lauryl sulfate as a surfactant (4) SLS) was mixed, and a pretreatment solution was prepared so that the blending amount (solid content concentration) of polyethyleneimine was 10 g / L and the blending amount of sodium lauryl sulfate was 0.1 g / L. The surface tension of the pretreatment liquid was 34.5 mN / m. The substrate was immersed in the pretreatment liquid adjusted to 30 ° C. for 5 minutes.

(5) 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 washing was performed once more.

(6) Addition of Electroless Plating Catalyst First, an aqueous palladium chloride solution was prepared. After dissolving 0.1 g of palladium chloride in 1 mL of 12N hydrochloric acid, it was diluted with water to make 1 L. From this, a palladium chloride aqueous solution having a blending amount of 0.1 g / L was prepared. The substrate was immersed in a palladium chloride aqueous solution adjusted to 30 ° C. for 5 minutes. After removing the base material from the aqueous solution of palladium chloride, it was washed by immersing it in water at room temperature stirred by air bubbling for several seconds. The same washing was performed twice more.

(7) Electroless plating The base material was immersed in an electroless nickel plating solution (manufactured by Okuno Pharmaceutical Co., Ltd., ICP Nicolon LTN-NP, reducing agent: sodium hypophosphite) adjusted to 65 ° C. for 5 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 base material by about 1 μm to obtain a plated part (Sample 1).

[Experiment 2]
In the pretreatment for catalyst application, the plated parts (made by Wako Pure Chemical Industries, Ltd., 30 wt% concentration solution) were used in the same manner as in Experiment 1 except that polyethyleneimine having a weight average molecular weight of 10,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the nitrogen-containing polymer. Sample 2) was produced.

[Experiment 3]
In the pretreatment for catalyst application, the plated parts (produced by Wako Pure Chemical Industries, Ltd., 30 wt% concentration solution) were used in the same manner as in Experiment 1 except that polyethyleneimine having a weight average molecular weight of 1,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the nitrogen-containing polymer. Sample 3) was produced.

[Experiment 4]
In the pretreatment for catalyst application, the plated parts (made by Wako Pure Chemical Industries, Ltd., 30 wt% concentration solution) were used in the same manner as in Experiment 1 except that polyethyleneimine having a weight average molecular weight of 100,000 was used as the nitrogen-containing polymer. Sample 4) was produced.

[Experiment 5]
A plated part (sample 5) was produced by the same method as in Experiment 1 except that the blending amount of the nitrogen-containing polymer was 0.01 g / L in the pretreatment for applying the catalyst.

[Experiment 6]
A plated part (Sample 6) was produced by the same method as in Experiment 1 except that the blending amount of the nitrogen-containing polymer was 2 g / L in the pretreatment for applying the catalyst.

[Experiment 7]
A plated part (Sample 7) was produced by the same method as in Experiment 1 except that the blending amount of the nitrogen-containing polymer was 50 g / L in the pretreatment for applying the catalyst.

[Experiment 8]
A plated part (Sample 8) was produced by the same method as in Experiment 1 except that the blending amount of the nitrogen-containing polymer was 100 g / L in the pretreatment for applying the catalyst.

[Experiment 9]
As the surfactant of the pretreatment liquid, a silicone-based surfactant (polyether-modified siloxane) was used instead of SLS, and the surface tension of the pretreatment liquid was 22.0 mN / m, which was the same as in Experiment 1. A plated part (Sample 9) was produced by the method.

[Experiment 10]
As the surfactant of the pretreatment liquid, a nonionic surfactant (manufactured by Kao Corporation, Emargen (registered trademark) A500, polyoxyethylene distyrene phenyl ether) is used instead of SLS, and the surface tension of the pretreatment liquid is used. A plated part (sample 10) was produced by the same method as in Experiment 1 except that the value was 52.7 mN / m.

[Experiment 11]
Liquid crystal polymer (LCP) (manufactured by Ueno Pharmaceutical Co., Ltd., 5030G) is used as the base material, UV laser (manufactured by Keyence, MD-U1000C) is used as the laser, and sodium hypophosphite is used as the reducing agent as the electroless plating solution. The copper-nickel alloy plating solution (electroless copper nickel plating solution) (manufactured by JCU Co., Ltd., AISL) was used. Further, the concentration of the palladium chloride aqueous solution was set to 0.2 g / L. Other than that, the plated parts (sample 11) were manufactured by the same method as in Experiment 1.

[Experiment 12]
A plated part (sample 12) was produced by the same method as in Experiment 11 except that the catalyst deactivator was not applied to the base material.

[Experiment 13]
A plated part (Sample 13) was produced by the same method as in Experiment 1 except that the weight average molecular weight of the nitrogen-containing polymer was set to 500.

[Experiment 14]
As the surfactant of the pretreatment liquid, a fluorine-based surfactant (Surflon S-242 manufactured by AGC Seimi Chemical Co., Ltd.) was used instead of SLS, and the surface tension of the pretreatment liquid was set to 18.0 mN / m. Produced a plated part (sample 14) by the same method as in Experiment 1.

[Experiment 15]
As the surfactant of the pretreatment liquid, sodium alkylsuccinate sulfonate was used instead of SLS, and the plating parts were plated by the same method as in Experiment 1 except that the surface tension of the pretreatment liquid was 67.9 mN / m. (Sample 15) was produced.

[Experiment 16]
A plated part (sample 16) was produced by the same method as in Experiment 1 except that no surfactant was used in the pretreatment liquid and the surface tension of the pretreatment liquid was 73.0 mN / m.

[Experiment 17]
In Experiment 17, no pretreatment liquid for applying the catalyst was applied to the base material, and no catalyst deactivator was applied. Further, by the same method as in Example 1 of Patent Document 1, the base material is subjected to alkali treatment and surface activator treatment after laser light irradiation (laser drawing), and electroless plating catalyst is applied and then electroless plating treatment is performed. Before, a reduction treatment was performed using sodium borohydride. Other than that, a plated part (sample 17) was manufactured in the same manner as in Experiment 1. Therefore, the main difference between Experiment 17 and Example 1 of Patent Document 1 is the type of base material and the type of laser. In Experiment 17, the base material of polyphenylene sulfide (PPS), while using a YVO ₄ laser (wavelength 1064 nm), in Example 1 of Patent Document 1, the absorptive high aromatic polyamide electroless plating catalyst A base material and a shorter wavelength green laser are used.

[Evaluation of samples 1 to 17]
(1) Reactivity and selectivity of electroless plating The surfaces of samples (plated parts) 1 to 17 were visually observed and microscopically observed, and the reactivity and selectivity of electroless plating were evaluated according to the following evaluation criteria. .. The results are shown in Tables 1 and 2.

<Evaluation criteria for electroless plating reactivity>
◯: There is no region (film missing, unprecipitated portion) in which the electroless plating film is not formed in the laser drawing portion, and the electroless plating film is stably formed.
Δ: There is a film omission in a part of the laser drawing part. However, when the electroless plating time was extended, the electroless plating reaction proceeded and the film loss disappeared.
X: There is a film omission in a part of the laser drawing part. Even if the electroless plating time was extended, the electroless plating reaction did not proceed any further.

<Evaluation criteria for electroless plating selectivity>
◯: In both wiring patterns A and B, there is no short circuit (connection) between adjacent wirings.
Δ: In the wiring pattern A (line / space: 0.5 mm / 0.5 mm), there is no short circuit (connection) between the wirings, but in the wiring pattern B (0.2 mm / 0.2 mm), some of them are adjacent to each other. A short circuit is observed between the wires.
X: In both wiring patterns A and B, a short circuit (connection) is observed between some adjacent wirings.

(2) Precipitation of plating film on the jig After manufacturing the plated parts, visually observe the surface (vinyl chloride) of the jig holding the base material, and check the presence or absence of the electroless plating film on the jig as follows. It was evaluated according to the evaluation criteria of. The results are shown in Tables 1 and 2.

<Evaluation criteria for precipitation of plating film on jig>
◯: No electroless plating film was deposited on the jig.
Δ: A plating film is deposited on a part of the jig.
X: An electroless plating film is deposited on the entire surface of the jig.

As shown in Tables 1 and 2, in Experiments 1 to 12, both the responsiveness and selectivity of the electroless plating reaction were good, and the precipitation of the plating film on the jig was suppressed. On the other hand, in Experiments 13 to 17, the selectivity or reactivity of the electroless plating was poor, or the electroless plating film was deposited on the entire surface of the jig.

Experiments 1 to 4 and 13 in which the weight average molecular weight of the nitrogen-containing polymer (PEI) contained in the pretreatment liquid is different and other conditions are the same are compared. In Experiments 1 to 4 in which the weight average molecular weight of the nitrogen-containing polymer (PEI) was 1,000 to 100,000, the reactivity and selectivity of electroless plating were good, and the plating was performed on a jig. The film did not precipitate. In particular, in Experiments 1 to 3 in which the weight average molecular weight of the nitrogen-containing polymer (PEI) is 70,000 or less, the selectivity of electroless plating is better, and the weight average molecular weight of the nitrogen-containing polymer (PEI) is 10. In Experiments 1, 2 and 4 where it is 000 or more, the reactivity of electroless plating is better, and in Experiments 1 and 2 where the weight average molecular weight of the nitrogen-containing polymer (PEI) is 10,000 to 70,000. The reactivity and selectivity of electroless plating were better, and the plating film did not precipitate on the jig. On the other hand, in Experiment 13 (weight average molecular weight: 500) in which the weight average molecular weight of the nitrogen-containing polymer (PEI) was less than 1,000, the reactivity of electroless plating was extremely low, and the plating film was hardly precipitated. Therefore, the selectivity of electroless plating could not be evaluated.

Experiments 5 to 8 in which the amount of the nitrogen-containing polymer (PEI) blended in the pretreatment liquid is different and other conditions are the same are compared. In Experiments 5 to 8 in which the blending amount of the nitrogen-containing polymer (PEI) was 0.01 g / L to 100 g / L, the selectivity and reactivity of electroless plating were good, and plating on a jig was performed. The precipitation of the film was suppressed. In particular, in Experiments 5 to 7 in which the blending amount of the nitrogen-containing polymer (PEI) was 0.01 g / L to 50 g / L, the plating film did not precipitate on the jig, and the blending amount of the nitrogen-containing polymer (PEI) was not deposited. In Experiments 6-8, where is 2 g / L-100 g / L, the reactivity of the electroless plating is better, and the amount of the nitrogen-containing polymer (PEI) blended is 2 g / L-50 g / L. In Nos. 6 and 7, the reactivity and selectivity of the electroless plating were better, and the plating film did not precipitate on the jig.

Compare Experiments 9-10 and 14-16 with different surface tensions of the pretreatment solution and similar other conditions. In Experiments 9 and 10 in which the surface tension of the pretreatment liquid was in the range of 20 to 60 mN / m, the selectivity and reactivity of electroless plating were good, and the plating film did not precipitate on the jig. On the other hand, in Experiment 14 (18.0 mN / m) in which the surface tension of the pretreatment liquid was less than 20 mN / m, an electroless plating film was deposited on the entire surface of the jig. Further, in Experiment 15 (67.9 mN / m) in which the surface tension of the pretreatment liquid was higher than 60 mN / m, the reactivity of electroless plating was poor, and in Experiment 16 (73.0 mN / m), electroless plating was performed. The selectivity and reactivity were poor. The pretreatment liquid used in Experiment 16 has a solvent of water and does not contain a surfactant. It was found that the surface tension of such a pretreatment liquid was higher than 60 mN / m, and the reactivity and selectivity of electroless plating were lowered.

Consider experiments 11 and 12. In Experiments 11 and 12, a liquid crystal polymer was used as a base material, and a short wavelength laser (UV laser) was used as a laser. It has been clarified by the present inventors that the surface modification effect of the UV laser is large for the liquid crystal polymer. Therefore, in Experiments 11 and 12, it is presumed that the adsorption of the electroless plating catalyst could be enhanced by surface modification without significantly roughening the laser beam irradiation portion. In Experiment 12, it was confirmed that the selectivity of electroless plating was good even without applying a catalyst deactivator to the base material. Further, in Experiment 11, it was confirmed that the selectivity of electroless plating was further improved by applying the catalyst deactivator to the base material.

Further, in Experiments 11 and 12, it was confirmed that electroless plating having good reactivity and selectivity can be performed by using an electroless copper nickel plating solution containing sodium hypophosphite as a reducing agent. In addition, electroless plating using electroless copper nickel plating solution requires more electroless plating catalyst than electroless plating using electroless nickel plating. Therefore, in Experiments 11 and 12, the amount of the electroless plating catalyst (PdCl ₂ ) in the catalyst solution was larger than that in Experiment 1.

Consider Experiment 17. In Experiment 17, in which the pretreatment liquid was not applied to the base material, the reactivity of electroless plating was extremely low, and the plating film was hardly precipitated. Therefore, the selectivity of electroless plating could not be evaluated. Further, as described above, the main difference from the first embodiment of Patent Document 1 is the type of the base material and the type of the laser. From this result, in order to control the adhesion of the electroless plating catalyst only by irradiating or not irradiating the laser light without applying the pretreatment liquid to the base material, it is necessary to combine the types of the laser light source and the resin base material. It was confirmed that optimization is necessary.

According to the method for manufacturing plated parts of the present invention, an electroless plating catalyst can be applied to a base material by a simple method using a stable treatment liquid, and plated parts such as MID that require a fine plating pattern can be manufactured. 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 is improved.

Claims

It is a manufacturing method of plated parts.
Irradiating a part of the surface of the base material with laser light and
The base material irradiated with the laser beam is brought into contact with a pretreatment liquid containing a nitrogen-containing polymer having a weight average molecular weight of 1,000 or more and having a surface tension of 20 mN / m to 60 mN / m.
Cleaning the base material that has been brought into contact with the pretreatment liquid, and
Contacting the washed substrate with a plating catalyst solution containing a metal salt
A method for manufacturing a plated component, which comprises contacting an electroless plating solution with a base material which has been brought into contact with the plating catalyst solution to form an electroless plating film on the laser beam irradiation portion.
The method for manufacturing a plated part according to claim 1, wherein the surface of the base material is roughened and / or modified by irradiating the laser beam.
The method for producing a plated part according to claim 1 or 2, wherein the nitrogen-containing polymer is polyethyleneimine.
The method for producing a plated part according to any one of claims 1 to 3, wherein the nitrogen-containing polymer has a weight average molecular weight of 1,000 to 100,000.
The method for producing a plated part according to claim 4, wherein the nitrogen-containing polymer has a weight average molecular weight of 10,000 to 100,000.
The method for producing a plated part according to claim 4, wherein the nitrogen-containing polymer has a weight average molecular weight of 50,000 to 100,000.
The method for producing a plated part according to any one of claims 1 to 6, wherein the amount of the nitrogen-containing polymer blended in the pretreatment liquid is 0.01 g / L to 100 g / L.
The method for producing a plated part according to claim 7, wherein the blending amount of the nitrogen-containing polymer in the pretreatment liquid is 2 g / L to 50 g / L.
The method for manufacturing a plated part according to any one of claims 1 to 8, wherein the pretreatment liquid contains a surfactant.
The method for manufacturing a plated part according to any one of claims 1 to 9, further comprising applying a catalytic deactivator to the surface of the base material before irradiating the base material with laser light.
The method for manufacturing a plated part according to claim 10, wherein the catalytic deactivator is a hyperbranched polymer.
Any one of claims 1 to 11, wherein the metal salt of the plating catalyst solution is palladium chloride, and the blending amount of palladium chloride in the plating catalyst solution is 0.01 g / L to 1.0 g / L. The method for manufacturing plated parts according to.
The method for manufacturing a plated part according to any one of claims 1 to 12, wherein the electroless plating solution contains sodium hypophosphite.
By bringing the plating catalyst solution into contact, the metal ions derived from the metal salt are adsorbed on the base material, and the metal ions are adsorbed on the base material.
The method for manufacturing a plated component according to any one of 1 to 13, wherein the electroless plating solution is brought into contact with the base material on which the metal ions are adsorbed.
The method for manufacturing a plated component according to any one of claims 1 to 14, wherein the electroless plating film forms an electric circuit or an antenna pattern.
A pretreatment liquid for applying electroless plating catalyst,
water and,
Nitrogen-containing polymers with a weight average molecular weight of 1,000 or more,
Contains surfactants
A pretreatment liquid having a surface tension of 20 mN / m to 60 mN / m.
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 amount of the nitrogen-containing polymer blended in the pretreatment liquid is 0.01 g / L to 100 g / L.