JP5930525B2 - Electroless plating pretreatment agent and electroless plating pretreatment method using the pretreatment agent - Google Patents

Description

  The present invention relates to an electroless plating pretreatment agent and an electroless plating pretreatment method using the pretreatment agent.

  Electroless plating is used industrially as a method for obtaining films of nickel, nickel alloys, copper, silver, etc. Nickel alloy and cobalt plating are used as magnetic recording materials, etc., and copper plating is a conductive film for printed circuits. For example, silver plating is used for mirror reflectors.

  In the electroless plating process, first, in order to improve the adhesion between the resin substrate and the conductive film, a resin swelling process using a treatment liquid containing a solvent as a main component, followed by a treatment containing a permanganate as a main ingredient. The anchor is formed in a series of desmear / roughening steps in which the resin is oxidized and decomposed by a liquid roughening step to form a roughened shape, and then manganese is removed in a neutralization (reduction) treatment step. Subsequently, an electroless plating treatment is performed through an electroless plating pretreatment agent, a catalyst application / activation step, and a conductive film having adhesion is formed. As the electroless plating catalyst, palladium having excellent catalytic activity is mainly used.

  For example, Patent Document 1 discloses a pretreatment method for electroless plating using an aqueous treatment liquid containing a cationic polymer, a resin having an electron-donating group, and a surfactant. Patent Document 2 discloses a pretreatment agent for electroless plating containing at least one nonionic surfactant, at least one cationic resin, and at least one metal ion complexing agent. It is disclosed. Further, Patent Document 3 discloses a conditioner used as a pretreatment liquid for performing electroless plating containing a cationic polymer, a nonionic surfactant and water and further containing ammonium hydrogen fluoride.

JP 2004-91877 A JP 2006-249520 A JP 2010-106337 A

  In any of the pretreatment methods described in Patent Documents 1 to 3, the adhesion strength between the object to be plated and the plating film may not reach the desired adhesion strength and may be insufficient. In particular, when the roughness of the anchor formed on the object to be plated is low, the adhesion strength between the object to be plated and the plating film is lowered, so that it is very possible to obtain a plating film having high adhesion strength. It was difficult.

  Accordingly, an object of the present invention is to provide an electroless plating pretreatment agent and an electroless plating pretreatment method capable of obtaining an electroless plating film having high adhesion.

As a result of repeated studies, the present inventors have found that the above problems can be solved by treating the substrate with an electroless plating pretreatment agent comprising an aqueous solution containing a specific amine compound, and the present invention. Reached.
That is, the present invention, L - (+) - lysine, using an electroless plating pretreatment agent Do that from an aqueous solution containing at least one selected from m- xylylenediamine and p- xylylenediamine, epoxy The present invention provides a pretreatment method for electroless plating , characterized in that a pretreatment is applied to a resin-based object to be plated .

Furthermore, the present invention applies the pretreatment method described above to the epoxy resin- plated body, and further from copper, silver, gold, zinc, nickel, tin, cobalt, chromium, palladium, tungsten, platinum, rhodium and ruthenium. The present invention provides a method for producing an electroless plating film, which forms an electroless plating film by applying one or two or more kinds of electroless plating selected from the group consisting of:

  According to the present invention, an electroless plating film with high adhesion can be obtained by using the electroless plating pretreatment agent and the electroless plating pretreatment method of the present invention.

Hereinafter, the electroless plating pretreatment agent and the electroless plating pretreatment method of the present invention will be described.
The electroless plating pretreatment agent of the present invention comprises an aqueous solution containing a neutral or basic primary to tertiary amine compound. The neutral or basic primary to tertiary amine compound is reactive with the neutral or basic primary to tertiary amine compound present on the surface of the object to be plated, or is bonded to an affinity group. Affinity is improved by improving the surface of the object to be plated, thereby improving the adhesion strength between the object to be plated and the electroless plating film.

  As the group having reactivity or affinity with the neutral or basic primary to tertiary amine compound, a carboxyl group is a particularly preferable group, and a particularly preferable example is desmear as an object to be plated. Treated organic synthetic resin substrate, neutral or basic primary or secondary amine compound is used as neutral or basic primary or secondary amine compound, and is generated on the surface of the substrate by desmear process By reacting with the carboxyl group and amidating the substrate surface, the surface of the object to be plated can be modified, and the adhesion strength between the object to be plated and the plating film can be greatly improved.

  The neutral or basic primary to tertiary amine compound used in the electroless plating pretreatment agent of the present invention is not particularly limited. For example, alanine, arginine, asparagine, cysteine, glutamine, glycine, histidine. , Isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine and other amino acids, methylamine, dimethylamine, ethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, diisopropyl Alkanoamines such as amines, alkano such as monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N, N-dimethylethanolamine Amines such as ruamines, ethylamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, tris (hydroxymethyl) aminomethane, m-xylylenediamine, p-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, taurine And heterocyclic compounds having one nitrogen atom in the ring, such as aminosulfonic acids such as 2-aminoethanethiol, 3-picolylamine, 3-pyridinemethanol and the like. Neutral or base having one or more nucleophilic groups such as amino group, imino group, carboxyl group, amide group, hydroxyl group, thiol group, sulfonic acid group, etc. from the viewpoint of improving adhesion and in-plane uniformity Of these, neutral or basic primary amine compounds having one or more nucleophilic groups are preferred because of their high adhesion-improving effect. Neutral or basic amino acids having one or more nucleophilic groups are particularly preferred because of their ease.

  The concentration of the neutral or basic primary to tertiary amine compound used in the electroless plating pretreatment agent of the present invention may be adjusted as appropriate depending on the object to be plated. For example, 0.001 to 10 mass %, Preferably in the range of 0.005 to 5 mass%. Here, when it is less than 0.001% by mass, the effect of improving the adhesion is not exhibited, which is not preferable, and when it exceeds 10% by mass, the improvement of the compounding effect due to the increase of the compounding amount is not observed.

  What is necessary is just to adjust suitably the preferable pH value in the electroless-plating pretreatment agent of this invention so that it may become pH 5-14. The pH of the electroless plating pretreatment agent of the present invention is particularly preferably pH 6-13. In adjusting the pH, a pH buffer solution can also be used.

  The pH buffer solution is not particularly limited, and a well-known general pH buffer solution may be used. Examples thereof include an acetate buffer solution, a phosphate buffer solution, a citrate buffer solution, and a borate buffer solution. .

  The electroless plating pretreatment agent of the present invention can be mixed with other known additives as necessary as long as the effects of the present invention are not impaired. Examples of such other additives include a surfactant.

  Said surfactant is used in order to improve the wettability of the electroless-plating pretreatment agent. For example, surfactants such as cationic, nonionic, anionic, and betaine are listed, and cationic, nonionic, or anionic surfactants are preferably used. As for the usage-amount in the case of using surfactant, 0.01-5 mass% is preferable.

  Examples of the cationic surfactant that may be used in the electroless plating pretreatment agent of the present invention include alkyl (or alkenyl) trimethylammonium salt, dialkyl (or alkenyl) dimethylammonium salt, and alkyl (or alkenyl) quaternary. Ammonium salt, mono- or dialkyl (or alkenyl) quaternary ammonium salt, ether (or alkenyl) pyridinium salt, alkyl (or alkenyl) dimethylbenzylammonium salt, alkyl (or alkenyl) isoquinolinium containing ether group or ester group or amide group Salts, dialkyl (or alkenyl) morphonium salts, polyoxyethylene alkyl (or alkenyl) amines, alkyl (or alkenyl) amine salts, polyamine fatty acid derivatives, amino acids Alcohol fatty acid derivatives, benzalkonium chloride, etc. benzethonium chloride and the like, may contain fluorine atoms in these structures.

  Nonionic surfactants that may be used in the electroless plating pretreatment agent of the present invention include, for example, polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers (ethylene oxide and propylene). The addition form of oxide may be random or block), polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid ester or its ethylene oxide adduct, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid Esters, alkylpolyglucosides, fatty acid monoethanolamides or their ethylene oxide adducts, fatty acid-N-methylmonoethanolamide Is its ethylene oxide adduct, fatty acid diethanolamide or its ethylene oxide adduct, sucrose fatty acid ester, alkyl (poly) glycerin ether, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, fatty acid methyl ester ethoxylate, N-long chain alkyl Examples thereof include dimethylamine oxide, and these structures may contain a fluorine atom.

  Examples of the anionic surfactant that may be used in the electroless plating pretreatment agent of the present invention include higher fatty acid salts, higher alcohol sulfate esters, sulfurized olefin salts, higher alkyl sulfonates, α-olefin sulfonic acids. Salt, sulfated fatty acid salt, sulfonated fatty acid salt, phosphate ester salt, sulfate ester salt of fatty acid ester, glyceride sulfate ester, sulfonate salt of fatty acid ester, α-sulfo fatty acid methyl ester salt, polyoxyalkylene alkyl ether sulfate Ester salt, polyoxyalkylene alkyl phenyl ether sulfate, polyoxyalkylene alkyl ether carboxylate, acylated peptide, sulfate ester of fatty acid alkanolamide or its alkylene oxide adduct, sulfosuccinate, alkyl base Benzene sulfonate, alkyl naphthalene sulfonate, alkyl benzimidazole sulfonate, polyoxyalkylene sulfosuccinate, N-acyl-N-methyl taurine salt, N-acyl glutamic acid or salt thereof, acyloxyethane sulfonate, Alkoxyethanesulfonate, N-acyl-β-alanine or a salt thereof, N-acyl-N-carboxyethyltaurine or a salt thereof, N-acyl-N-carboxymethylglycine or a salt thereof, acyl lactate, N-acyl Examples thereof include sarcosine salts and alkyl or alkenylaminocarboxymethyl sulfates, and these structures may contain a fluorine atom.

  The pretreatment method of electroless plating using the electroless plating pretreatment agent of the present invention is by bringing the electroless plating pretreatment agent of the present invention into contact with the object to be plated.

  The method for bringing the electroless plating pretreatment agent of the present invention into contact with the object to be plated is not particularly limited, and a known general pretreatment method may be used. For example, a pretreatment method using a dip method, a spray method, or a spin method can be used.

  The pretreatment method of electroless plating using the electroless plating pretreatment agent of the present invention can be incorporated in the desmear treatment step.

  For example, when electroless copper plating is carried out by incorporating a process by a pretreatment method using an electroless plating pretreatment agent of the present invention into a desmear treatment process on an epoxy resin substrate, (1) smear swelling process (2) Microetching step, (3) Reduction step, (4) Step by electroless plating pretreatment method using electroless plating pretreatment agent of the present invention, (5) Drying step, (6) Catalyst application step (7) An electroless copper plating film can be formed on an object to be plated by going through a process called an electroless copper plating process. A water washing step may be added between or during each step.

  Specifically, the surface of the epoxy resin substrate is in a state in which the carboxyl group is exposed on the substrate surface by the steps (1) to (3), and (4) the electroless plating pretreatment agent of the present invention In the step of the electroless plating pretreatment method using, the substrate is brought into contact with the electroless plating pretreatment agent of the present invention under appropriate conditions to amidate the carboxyl group on the substrate surface, An electroless copper plating film having excellent adhesion can be obtained through the steps 5) to (7).

   (4) In the electroless plating pretreatment step using the electroless plating pretreatment agent of the present invention, the conditions for bringing the electroless plating pretreatment agent of the present invention into contact with the object to be plated are not particularly limited. It can be arbitrarily set according to the shape and film thickness of the substrate to be electrolessly plated. For example, when making it contact by immersing, 10 to 90 degreeC is preferable and, as for temperature, 30 to 80 degreeC is especially preferable. Since the temperature of the pretreatment agent may be increased by the heat of reaction, the temperature may be controlled by a known means so as to maintain it within the above temperature range if necessary. Further, the time is not particularly limited because it is sufficient to make the time sufficiently necessary for the surface of the object to be plated to be completely processed. For example, when an epoxy resin substrate is processed, pretreatment may be performed by contacting for about 1 to 30 minutes within the above temperature range.

  The object to be plated to be pretreated by the method of the present invention can be applied to a synthetic resin or the like. For example, polysiloxane polyethylene, polypropylene, polybutene-1, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polystyrene, acrylonitrile butadiene styrene, polycarbonate, polyhexamethylene adipamide, Synthetic resins such as norbornene resin, nitrocellulose, urethane resin, phenol resin, urea resin, melamine resin, amide resin, acrylic resin, epoxy resin, acrylonitrile butadiene rubber, silicone rubber, etc., these resins contain fillers Or two or more types may be mixed. In particular, since the effect of improving the adhesion between the object to be plated and the plating layer after electroless plating is high, an epoxy resin is particularly preferable as the object to be plated. The surface of the object to be plated may be roughened or not roughened, and the degree of roughening may be high or low.

  The method for producing an electroless plating film of the present invention is based on applying electroless plating to an object to be plated that has been subjected to pretreatment of electroless plating using the electroless plating pretreatment agent of the present invention.

  As the electroless plating solution used in the method for producing an electroless plating film of the present invention, a known one can be used. For example, copper, silver, gold, zinc, nickel, tin, cobalt, chromium, palladium In order to plate one or more selected from the group consisting of tungsten, platinum, rhodium, and ruthenium, and particularly for plating copper, nickel, and silver from the viewpoint of high effect of improving adhesion The electroless plating solution is preferable.

  The electroless plating production conditions used in the electroless plating film production method of the present invention are not particularly limited, and well-known general conditions and methods can be used according to the electroless plating solution used. .

  As an electroless copper plating condition when producing a 1 μm electroless copper plating film by the method for producing an electroless plating film of the present invention, the plating bath temperature is preferably 10 to 60 ° C., particularly preferably 20 to 40 ° C. . The electroless plating time is preferably 1 to 60 minutes, particularly preferably 1 to 30 minutes.

  The plated product manufactured using the pretreatment method of electroless plating of the present invention is not particularly limited. For example, automotive industrial materials (heat sinks, carburetor parts, fuel injectors, cylinders, various valves, Engine internals, etc., electronics industry materials (contacts, circuits, semiconductor packages, printed circuit boards, thin film resistors, capacitors, hard disks, magnetic materials, lead frames, nuts, magnets, resistors, stems, computer components, electronic components, laser oscillation) Element, optical memory element, optical fiber, filter, thermistor, heating element, high temperature heating element, varistor, magnetic head, various sensors (gas, temperature, humidity, light, speed, etc.), MEMS, etc., precision equipment (copier parts, Optical equipment parts, watch parts, etc.), aviation and ship materials (hydraulic equipment, screws, engines, Turbines, etc.), chemical industrial materials (ball, gate, plug, check, etc.), various molds, machine tool parts, vacuum equipment parts like, include those extensive. The electroless plating pretreatment method of the present invention is particularly preferably used for electronic industrial materials that require adhesion between the electroless plating and the object to be plated. In particular, the plating process is used in the manufacture of semiconductor packages and printed circuit boards. More preferably, the semiconductor package is more preferable.

Hereinafter, the present invention will be described in more detail with reference to examples and the like. However, the present invention is not limited by the following examples.
Example 1: Preparation of pretreatment agent According to the compounds and blending amounts shown in Table 1, Example Composition No. 1 to 25 were prepared so that the total mass was 500 g.

Comparative Example 1
Comparative compositions 1 to 5 were prepared according to the compounds and blending amounts shown in Table 1 so that the total mass was 500 g.

Example 2: Pretreatment 1
As an object to be plated, an aromatic epoxy resin composition (roughness: Ra = 0.1 μm, shape: 50 mm × 130 mm × 1 mm) subjected to a smear swelling process, a microetching process, and a reduction process was used. After immersing this object to be plated in each composition prepared above at 30 ° C. for 3 minutes, it was washed with water at room temperature for 1 minute and dried at 130 ° C. for 15 minutes to perform a pretreatment for electroless plating.

Evaluation Example 1: Adhesion evaluation 1
After applying a Pd catalyst to the object to be plated pretreated by the method described in Example 2, the object to be plated is immersed in an electroless copper plating bath adjusted to 32 ° C., and electroless copper plating is performed for 20 minutes with air stirring. Went. The electroless copper plating solution used was Atotech Co., Ltd., product name: MSK-DK. The obtained plating thickness is 1 μm. This was washed with water at 25 ° C. for 1 minute, dried in a constant temperature bath at 150 ° C. for 30 minutes, and immersed in 10% sulfuric acid for 1 minute. Then, 20 μm of electrolytic copper plating was formed on the electroless copper plating, washed with water at 25 ° C. for 1 minute, and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product. About the obtained plating object, peel strength was measured using the Shimadzu Corporation desk test machine EZ-S. The measurement conditions are a peel speed of 50 mm / min and a width of 5 mm. The results are shown in Table 2.

When the peel strength is higher than the strength of the body to be plated, or when the strength of the body to be plated is almost the same as the peel strength, the phenomenon that the body to be plated completely breaks when measuring the peel strength of the coating is defined as cohesive failure. Further, the phenomenon in which the coating peels off at the interface between the object to be plated and the coating and the phenomenon in which cohesive failure coexists is defined as partial cohesive failure.
From the results shown in Table 2, in Comparative Examples 1-1 to 1-5, the Cu peel strength was almost unchanged. When Comparative Examples 1-1 to 1-5 and Evaluation Examples 1-1 to 1-25 are compared, Evaluation Examples 1-1 to 1-25 are significantly more Cu peeled than Comparative Examples 1-1 to 1-5. It was found that a plating film with improved strength and high adhesion could be obtained. Moreover, as a result of observation by an electron microscope, it was confirmed that all of Comparative Examples 1-1 to 1-5 were partially cohesive failure, and that of Evaluation Examples 1-1 to 1-24 were all cohesive failure. . In Evaluation Example 1-25, it was confirmed that partial cohesive failure occurred locally.

Example 3: Pretreatment 2
As the object to be plated, a filler-containing aromatic epoxy resin composition (roughness: Ra = 1.3 μm, shape: 50 mm × 130 mm × 1 mm) subjected to a smear swelling process, a microetching process, and a reduction process was used. After immersing this object to be plated in each composition prepared above at 30 ° C. for 3 minutes, it was washed with water at room temperature for 1 minute and dried at 130 ° C. for 15 minutes to perform a pretreatment for electroless plating.

Evaluation example 2: Adhesion evaluation 2
After the Pd catalyst was applied to the object to be plated pretreated by the method described in Example 3, the object to be plated was immersed in an electroless nickel plating bath adjusted to 60 ° C., and electroless nickel was stirred for 15 minutes under air stirring. Plating was performed. As the electroless nickel plating solution, an electroless nickel bath containing the components shown in Table 3 was used. The obtained plating thickness is 2.0 μm. This was washed with water at 25 ° C. for 1 minute, dried in a constant temperature bath at 180 ° C. for 30 minutes, and immersed in 10% sulfuric acid for 1 minute. Then, 20 μm of electrolytic copper plating was formed on the electroless nickel plating, washed with water at 25 ° C. for 1 minute, and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product. About the obtained plating object, peel strength was measured using the Shimadzu Corporation desk test machine EZ-S. The measurement conditions are a peel speed of 50 mm / min and a width of 5 mm. The results are shown in Table 4.

  From the results of Table 4, when Comparative Example 2, Evaluation Example 2-1 and Evaluation Example 2-2 are compared, Evaluation Example 2-1 and Evaluation Example 2-2 are greatly improved in peel strength as compared with Comparative Example 2. I found out. From this, it was found that even when the electroless plating is nickel, the pretreatment agent of the present invention has an effect of improving adhesion. Moreover, as a result of observation with an electron microscope, it was confirmed that in Comparative Example 2, Evaluation Example 2-1, and Evaluation Example 2-2, the coating was peeled off at the interface between the substrate and the coating.

Evaluation Example 3: Adhesion evaluation 3
After the Pd catalyst was applied to the substrate pretreated by the method described in Example 3, the object to be plated was immersed in an electroless silver bath adjusted to 25 ° C., and 10% glucose was stirred while stirring the bath in an air atmosphere. The aqueous solution was added dropwise over 7 minutes. After completion of dropping, the mixture was stirred for 30 minutes and electroless silver plating was performed. As the electroless silver plating solution, an electroless silver plating bath containing the components shown in Table 5 was used. The obtained plating thickness is 0.5 μm. This was washed with water at 25 ° C. for 1 minute, dried in a constant temperature bath at 180 ° C. for 30 minutes, and immersed in 10% sulfuric acid for 1 minute. Then, 20 μm of electrolytic copper plating was formed on this electroless silver plating, washed with water at 25 ° C. for 1 minute, and then dried at 180 ° C. for 30 minutes in a thermostatic bath to obtain a plated product. About the obtained plating object, peel strength was measured using the Shimadzu Corporation desk test machine EZ-S. The measurement conditions are a peel speed of 50 mm / min and a width of 5 mm. The results are shown in Table 6.

  From the results of Table 6, when Comparative Example 3, Evaluation Example 3-1 and Evaluation Example 3-2 are compared, Evaluation Example 3-1 and Evaluation Example 3-2 have larger peel strength than Comparative Example 3-1. It turns out that it is improving. From this, it was found that even when the electroless plating was silver, the pretreatment agent of the present invention had an effect of improving adhesion. Moreover, as a result of observation with an electron microscope, it was confirmed that in Comparative Example 3, Evaluation Example 3-1, and Evaluation Example 3-2, the coating film was peeled off at the interface between the substrate and the coating film.

Claims (2)

L - (+) - lysine, using an electroless plating pretreatment agent comprising an aqueous solution containing at least one selected from m- xylylenediamine and p- xylylenediamine, Previous epoxy resin plated body A pretreatment method for electroless plating, characterized by applying a treatment. The pretreatment method according to claim 1 is applied to the epoxy resin plated body, and further from the group consisting of copper, silver, gold, zinc, nickel, tin, cobalt, chromium, palladium, tungsten, platinum, rhodium and ruthenium. The manufacturing method of the electroless-plating film which forms an electroless-plating film by performing the 1 type (s) or 2 or more types of electroless-plating selected.