CN115735022A

CN115735022A - Catalyst imparting liquid for electroless plating

Info

Publication number: CN115735022A
Application number: CN202180046353.3A
Authority: CN
Inventors: 瀬户宽生; 桥爪佳; 田中克幸; 河崎佳奈; 长尾敏光
Original assignee: Okuno Chemical Industries Co Ltd
Current assignee: Okuno Chemical Industries Co Ltd
Priority date: 2020-07-03
Filing date: 2021-06-16
Publication date: 2023-03-03
Also published as: WO2022004367A1; KR20230005394A; JP2022013121A; TW202212628A; JP6841462B1

Abstract

The present invention provides a catalyst-imparting solution used for pretreatment in electroless plating of a metal material, which is useful for forming an electroless plating film having excellent plating deposition properties, selective deposition properties, barrier properties, adhesion properties, and the like, and has excellent bath stability. The electroless plating catalyst-imparting liquid contains a cobalt compound and a reducing agent.

Description

Catalyst imparting liquid for electroless plating

Technical Field

The present invention relates to a catalyst-imparting liquid for electroless plating, and the like.

Background

In the field of electronic related products such as printed wiring boards, semiconductor packages, and electronic components, there are cases where, in one of the final steps in the production, conductor circuits, terminal portions, and the like are subjected to electroless nickel plating and further to electroless gold plating. The electroless nickel/gold plating film formed by this method is used for preventing oxidation of the copper circuit surface, exhibiting good solder connection performance, improving wire bondability between a semiconductor package and an electronic component mounted thereon, and the like. When the electroless nickel plating film is formed and then the displacement gold plating film is formed, there is a problem that the nickel is partially dissolved and the corrosion of the nickel, so-called black pad (black pad), and the Au surface is contaminated by the extension of the base metal due to the heat treatment, depending on the state of the nickel plating film of the base. As a method for solving such problems, electroless nickel plating, palladium plating, and electroless nickel plating/palladium/gold plating are added as barrier films between electroless nickel plating and gold plating. In order to cope with the miniaturization of copper wiring accompanying the increase in density of printed wiring boards, an electroless palladium/gold plating process has been developed in which an electroless nickel plating film having the highest film thickness is omitted (see patent document 1 below).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 5-327187

Disclosure of Invention

Technical problems to be solved by the invention

In the case of performing electroless plating on a metal material of a substrate, a catalyst-applying treatment for depositing palladium metal serving as a catalyst core on the metal material by a substitution reaction may be performed in order to improve plating deposition properties and the like. The inventors of the present invention have studied and found that when the catalyst-applying treatment is performed, the plating deposition property is good, but the barrier property and the adhesion property are insufficient. As a result of studies on the cause of this, it has been found that excessive dissolution of the metal material may occur when the above-mentioned catalyst application treatment is performed, and that minute voids (voids) may be formed between the deposited plating film and the metal material when the electroless plating (nickel, palladium, or the like) is performed thereafter.

Therefore, the inventors of the present invention tried a catalyst-imparting treatment in which palladium metal is precipitated by a reduction reaction without a substitution reaction. However, some of the properties such as plating deposition property, selective deposition property, bath stability, barrier property, and adhesion property are not sufficient.

Therefore, the technical problem to be solved by the invention is as follows: provided is a catalyst-imparting solution for use in pretreatment when electroless plating is performed on a metal material, which is useful for forming an electroless plating film having excellent plating deposition properties, selective deposition properties, barrier properties, adhesion properties, and the like, and which has excellent bath stability.

Technical solution for solving technical problem

The present inventors have intensively studied in view of the above-mentioned problems, and as a result, they have found that the above-mentioned problems can be solved if the catalyst-applying liquid for electroless plating contains a cobalt compound and a reducing agent. The inventors of the present invention have further studied based on this finding and, as a result, have completed the present invention. That is, the present invention includes the following embodiments.

Item 1. A catalyst-imparting liquid for electroless plating, which contains a cobalt compound and a reducing agent.

The catalyst-providing liquid for electroless plating according to item 2, wherein the reducing agent comprises an amine compound.

The catalyst-imparting liquid for electroless plating according to claim 2, wherein the amine compound contains at least 1 selected from the group consisting of amine borane, hydrazine, and hydrazine derivative.

The catalyst-imparting liquid for electroless plating according to any one of claims 1 to 3, which contains a complexing agent.

The electroless plating catalyst-imparting liquid according to item 5. Above, wherein the complexing agent contains a carboxylic acid.

The catalyst-imparting liquid for electroless plating according to item 6, wherein the carboxylic acid comprises a hydroxycarboxylic acid or a dicarboxylic acid.

The electroless plating catalyst-imparting solution according to any one of claims 1 to 6, wherein the reducing agent contains at least 1 selected from a boron-containing compound and a phosphorus-containing compound.

The electroless plating catalyst-imparting liquid according to any one of claims 1 to 7, further comprising a metal salt.

The electroless plating catalyst-applying liquid according to any one of claims 1 to 8, wherein the cobalt content is 50 mass% or more based on 100 mass% of the metal.

The electroless plating catalyst-imparting liquid according to any one of claims 1 to 9, wherein,

the reducing agent contains at least 1 kind selected from a boron-containing compound and a phosphorus-containing compound, and,

the electroless plating is electroless plating of at least 1 selected from the group consisting of electroless palladium plating, electroless nickel plating, and electroless gold plating of a material having copper and/or a copper alloy exposed on the surface.

Item 11. A method of producing an electroless plating object material containing a catalyst core, comprising:

(1) A step of bringing a material to be electroless plated into contact with the electroless plating catalyst-imparting liquid according to any one of claims 1 to 10.

A method of manufacturing a material comprising an electroless plating film, comprising:

(1) A step of bringing an object to be electroless plated into contact with the electroless plating catalyst application liquid according to any one of items 1 to 10; and

(2) And (2) performing electroless plating after the step (1).

Item 13. A material comprising a material having a metal exposed on the surface thereof, a catalyst core 1 on the metal, and a coating film 2 on the catalyst core 1, and,

the above-mentioned catalyst core 1 contains cobalt,

the coating 2 is an electroless plating coating.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a catalyst-imparting liquid used for pretreatment in electroless plating of a metal material, which is useful for forming an electroless plating film having more excellent plating deposition properties, selective deposition properties, barrier properties, adhesion properties, and the like, and has more excellent bath stability.

Detailed Description

In the present specification, expressions of "including" and "including" include concepts of "including", "consisting essentially of … …" and "consisting of … … only".

1. Catalyst imparting liquid

In one embodiment, the present invention relates to a catalyst-applying liquid for electroless plating containing a cobalt compound and a reducing agent (which may be referred to as "the catalyst-applying liquid of the present invention" in the present specification). This will be explained below.

The cobalt compound is not particularly limited as long as it is soluble in the plating solution. Examples of the cobalt compound include organic or inorganic cobalt salts, and more specifically, examples thereof include cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt bromide, cobalt iodide, cobalt hypophosphite, cobalt phosphate, cobalt ammonium sulfate, cobalt ammonium chloride, cobalt potassium sulfate, cobalt sulfamate, cobalt acetate, cobalt carbonate, cobalt acetylacetonate, cobalt formate, cobalt oxalate, cobalt stearate, cobalt citrate, cobalt tartrate, and cobalt lactate. Among these, from the viewpoint of the effect of the present invention, inorganic cobalt salts are preferably used, cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt phosphate, cobalt hypophosphite, and the like are more preferably used, and cobalt sulfate and cobalt chloride are still more preferably used.

The cobalt compounds may be used alone in 1 kind or in combination of 2 or more kinds.

The cobalt concentration in the catalyst-providing liquid of the present invention is, for example, 0.05g/L or more. From the viewpoint of the effect of the present invention, the cobalt concentration is preferably 0.05 to 50g/L, more preferably 0.1 to 30g/L, still more preferably 0.2 to 20g/L, yet more preferably 0.4 to 15g/L, particularly preferably 0.6 to 10g/L, and particularly preferably 0.7 to 6g/L.

The cobalt content in the catalyst-applying liquid of the present invention is, for example, 50 mass% or more, preferably 60 mass% or more, more preferably 70 mass%, or 80 mass% or more, or 90 mass% or more, with respect to 100 mass% of the content of the transition metal element containing cobalt.

The reducing agent is not particularly limited as long as it is a reducing agent capable of precipitating cobalt metal, and a reducing agent that can be used for reduction plating can be used. Examples of the reducing agent include amine compounds, boron-containing compounds, and phosphorus-containing compounds. There are also substances belonging to these. For example, reducing agents that are amine compounds and are boron-containing compounds are also present. In this case, when the reducing agent is contained, it can be said that the reducing agent contains an amine compound and a boron-containing compound.

Examples of the amine compound include amine borane, hydrazine, and hydrazine derivatives.

The amine borane being a borane (e.g. BH) ₃ ) Amine borane complexes with amines. The amine constituting the amine borane may be any of a chain amine (non-cyclic amine) and a cyclic amine, and is preferably a chain amine, and among the chain amines, more preferably a chain amine represented by the general formula (1):

[ in the formula, R ¹ 、R ² And R ³ The same or different, represent a hydrogen atom or an alkyl group.]。

The alkyl group also includes any of linear, branched and cyclic groups. The alkyl group is preferably linear or branched, and more preferably linear. The number of carbon atoms of the alkyl group is not particularly limited, and is, for example, 1 to 8, preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2, and still more preferably 1. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a n-pentyl group, a neopentyl group, a n-hexyl group, a 3-methylpentyl group, and a cyclohexyl group.

In a preferred embodiment of the present invention, R is ¹ 、R ² And R ³ Any 2 or all (more preferably 2) of them are alkyl groups,the remainder being hydrogen atoms.

Specific examples of the amine constituting the borane complex include dimethylamine, diethylamine, trimethylamine, triethylamine, methoxyethylamine, dicyclohexylamine, tert-butylamine, aminopyridine, ethylenediamine, morpholine, pyridine, piperidine, and imidazole. Among these, dimethylamine, diethylamine, trimethylamine, methoxyethylamine, dicyclohexylamine and the like are preferable, and dimethylamine and the like are more preferable.

Suitable examples of the amine borane include dimethylamine borane, diethylamine borane, and trimethylamine borane.

The hydrazine derivative is not particularly limited as long as it can be used as a reducing agent for electroless plating.

Examples of the boron-containing compound include hydrogen boride compounds, more specifically, for example, the above-mentioned amine boranes which are also amine compounds, borane complexes other than amine boranes (complexes of borane and other compounds), alkali metal salts of hydrogen boride (for example, sodium salts, etc.), and the like.

Examples of the phosphorus-containing compound include hypophosphorous acid, hypophosphites (for example, sodium salt, potassium salt, ammonium salt, etc.), phosphorous acid, phosphites (for example, sodium salt, potassium salt, ammonium salt, etc.), and hydrates thereof.

From the viewpoint of the effect of the present invention, the reducing agent preferably contains an amine compound. In this case, the amine compound more preferably contains at least 1 selected from the group consisting of amine borane, hydrazine, and hydrazine derivatives, still more preferably contains at least 1 selected from the group consisting of amine borane and hydrazine, and still more preferably contains amine borane. When the reducing agent contains an amine compound, the reducing agent more preferably further contains a phosphorus-containing compound.

From the viewpoint of the effect of the present invention, the reducing agent preferably contains at least 1 selected from the group consisting of a boron-containing compound and a phosphorus-containing compound.

The reducing agent may be used alone in 1 kind or in combination of 2 or more kinds.

The concentration of the reducing agent in the catalyst-providing liquid of the present invention is, for example, 0.05g/L or more. From the viewpoint of the effect of the present invention, the concentration is preferably 0.05 to 100g/L, more preferably 0.2 to 50g/L, and still more preferably 0.5 to 30g/L. When the reducing agent contains an amine compound, the concentration of the amine compound in the catalyst-providing liquid of the present invention is preferably 0.05 to 25g/L, more preferably 0.1 to 20g/L, even more preferably 0.2 to 15g/L, even more preferably 0.4 to 10g/L, and particularly preferably 0.6 to 8g/L, from the viewpoint of the effect of the present invention. When the reducing agent contains a phosphorus-containing compound, the concentration of the phosphorus-containing compound in the catalyst-imparting liquid of the present invention is preferably 1 to 200g/L, more preferably 5 to 150g/L, still more preferably 10 to 100g/L, and still more preferably 20 to 80g/L, from the viewpoint of the effect of the present invention.

From the viewpoint of the effect of the present invention, the catalyst-imparting liquid of the present invention preferably further contains a complexing agent.

The complexing agent is not particularly limited, and complexing agents that can be used in electroless plating (particularly, reduction plating) can be used. Examples of the complexing agent include monocarboxylic acids such as acetic acid and formic acid, and ammonium salts, potassium salts, and sodium salts thereof; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid, and ammonium salts, potassium salts, and sodium salts thereof; hydroxycarboxylic acids such as malic acid, lactic acid, glycolic acid, gluconic acid, citric acid, and tartaric acid, and ammonium salts, potassium salts, and sodium salts thereof; ethylenediamine diacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ammonium salts, potassium salts, sodium salts thereof, and the like; aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, and their sodium salts, potassium salts, and ammonium salts; phosphoric acids such as pyrophosphoric acid, sodium salts, potassium salts, and ammonium salts thereof; amino acids such as glycine and glutamic acid.

From the viewpoint of the effect of the present invention, the complexing agent preferably contains a carboxylic acid. In this case, the carboxylic acid more preferably includes hydroxycarboxylic acid or dicarboxylic acid from the viewpoint of the effect of the present invention. Among hydroxycarboxylic acids and dicarboxylic acids, malic acid, citric acid, tartaric acid, lactic acid, adipic acid, succinic acid, malonic acid, gluconic acid, and the like are more preferable, and malic acid, citric acid, tartaric acid, and the like are still more preferable.

The complexing agents may be used alone in 1 kind or in combination of 2 or more kinds.

When the catalyst-providing liquid of the present invention contains a complexing agent, the concentration of the complexing agent in the catalyst-providing liquid of the present invention is, for example, 0.5g/L or more. From the viewpoint of the effect of the present invention, the cobalt concentration is preferably 1 to 200g/L, more preferably 2 to 150g/L, still more preferably 4 to 120g/L, yet more preferably 6 to 100g/L, and particularly preferably 7 to 70g/L.

From the viewpoint of the effect of the present invention, the catalyst-providing liquid of the present invention preferably further contains a metal salt.

The metal salt is not particularly limited, and examples thereof include salts containing transition metal elements other than cobalt. Examples of the transition metal element include metal elements such as gold, palladium, nickel, tungsten, molybdenum, and rhenium. More specifically, examples of the metal salt include nickel sulfate, nickel chloride, palladium sulfate, palladium chloride, sodium tungstate, disodium molybdate, gold potassium cyanide, gold sodium sulfite, and ammonium perrhenate.

The metal salts may be used alone in 1 kind or in combination of 2 or more kinds.

When the catalyst-applying liquid of the present invention contains a metal salt, the concentration of the metal contained in the metal salt in the catalyst-applying liquid of the present invention is, for example, 0.005g/L or more. From the viewpoint of the effect of the present invention, the concentration is preferably 0.005 to 5g/L, more preferably 0.01 to 3g/L, still more preferably 0.02 to 2g/L, and yet more preferably 0.03 to 1g/L. The concentration is, for example, 0.8/1 or less, preferably 0.6/1 or less, or 0.5/1 or less, 0.3/1 or less, 0.2/1 or less, or 0.15/1 or less of the cobalt concentration in the catalyst-providing liquid of the present invention.

The catalyst-imparting liquid of the present invention mainly contains water as a solvent. When a solvent other than water is further contained, the content thereof is, for example, 10% by mass or less, 5% by mass or less, 1% by mass or less, or 0.1% by mass or less with respect to 100% by mass of the solvent containing water.

Various additives can be added to the catalyst-imparting liquid of the present invention as needed. Examples of the additive include a stabilizer, a pH buffer, and a surfactant.

As the stabilizer, for example, lead salts such as lead nitrate and lead acetate; bismuth salts such as bismuth nitrate and bismuth acetate; 1 kind of sulfur compound such as sodium thiosulfate, etc. or 2 or more kinds of sulfur compound are added in a mixed manner. When the stabilizer is added, the amount of the stabilizer added is not particularly limited, and may be, for example, about 0.01 to 100 mg/L.

As the pH buffer, for example, 1 kind of acetic acid, boric acid, phosphoric acid, phosphorous acid, carbonic acid, sodium salts, potassium salts, ammonium salts thereof, and the like, alone or 2 or more kinds thereof may be mixed and added. When the pH buffer is added, the amount of the pH buffer added is not particularly limited, and may be about 0.002 to 1mol/L from the viewpoint of bath stability and the like.

Examples of the surfactant include nonionic, anionic, cationic, and electrostatic surfactants. For example, alkali salts of aromatic or aliphatic sulfonic acids, alkali salts of aromatic or aliphatic carboxylic acids, and the like can be mentioned. The surfactant may be used singly or in combination of two or more. When the surfactant is added, the amount of the surfactant added is not particularly limited, and may be, for example, about 0.01 to 1000 mg/L.

The pH of the electroless plating solution of the present invention may be usually about 2 to 12, preferably about 6 to 10, more preferably about 6.5 to 9, and still more preferably about 6.9 (or 7.0) to 8.5.

2. Catalyst imparting method

In one embodiment, the present invention relates to a method for producing an electroless plating target material containing catalyst nuclei, which includes (1) a step of bringing an electroless plating target material into contact with the catalyst-imparting liquid of the present invention, or a method for subjecting an electroless plating target material to a catalyst-imparting treatment (which may be referred to as "method 1 of the present invention" in the present specification). This will be explained below.

The material to be electroless-plated is not particularly limited as long as it is a material having a metal exposed on the surface. For example, as the raw material, 1 kind or a combination of materials such as glass fiber reinforced epoxy, polyimide, and PET plastics, and glass, ceramics, metal oxide, metal, paper, synthetic or natural fibers can be used, and the shape thereof may be any of a plate, a film, a cloth, a fiber, and a tube. Examples of the metal exposed on the surface include copper, copper alloy, silver alloy, gold alloy, platinum alloy, molybdenum, and tungsten. Among these, as the copper alloy, silver alloy, gold alloy, and platinum alloy, for example, an alloy containing 50 wt% or more of copper, silver, gold, or platinum can be used. Specific examples of the material to be electroless plated include printed wiring boards, semiconductor packages, electronic components, and ceramic substrates. Among these materials, the metal exposed on the surface may constitute a wiring.

The material to be electroless-plated is preferably subjected to a pretreatment such as degreasing treatment or soft etching treatment.

The specific method for bringing the catalyst-applying liquid of the present invention into contact with the material to be electroless plated is not particularly limited, and the material to be treated may be immersed in the catalyst-applying liquid of the present invention. Further, the surface of the electroless plating target material can be subjected to a catalyst-applying treatment by a method of spraying the catalyst-applying liquid, or the like.

When the catalyst-applying liquid of the present invention is carried out by the immersion method, the liquid temperature of the catalyst-applying liquid of the present invention is usually preferably about 10 to 90 ℃, more preferably about 40 to 80 ℃, and still more preferably 60 to 80 ℃.

The treatment time is preferably about 30 seconds to 20 minutes, and more preferably about 1 minute to 5 minutes.

By the method 1 of the present invention, a catalyst core containing cobalt is formed on the surface metal of the electroless plating object material. The catalyst core has a composition corresponding to the components in the electroless plating solution of the invention. For example, when the reducing agent in the catalyst-imparting liquid of the present invention contains a boron-containing compound and/or a phosphorus-containing compound, the catalyst core contains Co, and B and/or P. When the catalyst-imparting liquid of the present invention contains a compound containing a metal element, the catalyst core contains Co and the metal.

The Co content in the catalyst core is, for example, 50 mass% or more, preferably 60 mass% or more, and more preferably 70 mass%, or 80 mass% or more, or 90 mass% or more.

When the catalyst core contains B, the content thereof is, for example, 2 mass% or less, preferably 1 mass% or less, more preferably 0.5 mass% or less, and further preferably 0.2 mass% or less. The lower limit of the content is, for example, 0.01 mass%, 0.05 mass%, or 0.07 mass%.

When the catalyst core contains P, the content thereof is, for example, 0.5 to 20% by mass, preferably 1.5 to 15% by mass, and more preferably 3 to 10% by mass.

The content of each element in the catalyst core can be identified by measurement using an energy dispersive X-ray analyzer (EDX, EMAX-act manufactured by HORIBA) or a dissolution method using an Inductively Coupled Plasma (ICP) emission spectrometer (PS 3500DDII manufactured by hitachi high and new technology).

By subjecting the material to electroless plating containing the catalyst core to electroless plating, an electroless plating film having more excellent plating deposition properties, selective deposition properties, barrier properties, adhesion properties, and the like can be formed. The catalyst core is intended to be surface-activated, and therefore, the thickness thereof may be, for example, 0.05 μm or less, or 0.005 to 0.05. Mu.m.

3. Electroless plating method

In one embodiment, the present invention relates to a method for producing a material including an electroless plating film, or a method for electroless plating an electroless plating target material (in this specification, it may be referred to as "method 2 of the present invention"), including (1) a step of bringing the electroless plating target material into contact with the catalyst-applying liquid of the present invention and (2) a step of performing an electroless plating treatment after the step (1). This will be explained below.

The step (1) is the step described in "2. Catalyst application method" above.

The electroless plating treatment can be performed by contacting the electroless plating object material containing the catalyst nuclei obtained in the step (1) with an electroless plating solution.

The electroless plating solution is not particularly limited, and an autocatalytic electroless plating solution can be used. For example, an electroless palladium plating solution, an electroless palladium alloy plating solution, an electroless copper alloy plating solution, an electroless Jie Yin plating solution, an electroless silver alloy plating solution, an electroless nickel alloy plating solution, an electroless gold alloy plating solution, or the like can be used. Specific compositions of these electroless plating solutions are not particularly limited, and an autocatalytic electroless plating solution of a known composition containing a reducing agent component may be used. The plating conditions may be normal plating conditions depending on the type of plating solution used.

In step (2) of method 2 of the present invention, as the electroless plating solution, an electroless palladium alloy plating solution, an electroless nickel alloy plating solution, or the like, an electroless gold plating solution, and an electroless gold alloy plating solution are preferably used. When an electroless palladium plating solution or an electroless palladium alloy plating solution is used in step (2), it is preferable to further perform electroless gold plating or electroless gold alloy plating. When an electroless nickel plating solution or an electroless nickel alloy plating solution is used in step (2), it is preferable to further perform electroless palladium plating or electroless palladium alloy plating, and more preferable to further perform electroless gold plating or electroless gold alloy plating next. In the case where an electroless nickel plating solution or an electroless nickel alloy plating solution is used in step (2), electroless gold plating or electroless gold alloy plating can be further performed subsequently. In the step (2), only the electroless gold plating solution or the electroless gold alloy plating solution may be performed.

The method 2 of the present invention can form an electroless plating film having more excellent plating deposition properties, selective deposition properties, barrier properties, adhesion properties, and the like. The method 2 of the present invention can provide a material capable of providing such an electroless plating film, specifically, a material comprising a material having a metal exposed on the surface thereof, a catalyst core 1 on the metal, and a film 2 on the catalyst core 1, wherein the catalyst core 1 contains cobalt, and the film 2 is an electroless plating film.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

(1) Preparation of catalyst imparting solution

An electroless plating catalyst-imparting solution having the following composition was prepared. Water was used as the solvent.

(1-1) examples 1 to 8: containing Co

Example 1 Co-B

Cobalt sulfate 7 hydrate 5g/L (1 g/L in cobalt)

DL-malic acid 10g/L

Dimethylamine borane 3.0g/L

pH 7.5, bath temperature 70 ℃.

Example 2 Co-Ni-B

Cobalt sulfate 7 hydrate 5g/L (1 g/L in cobalt)

Nickel sulfate 6 hydrate 0.45g/L (calculated as nickel 0.1 g/L)

DL-malic acid 10g/L

Dimethylamine borane 3.0g/L

pH 7.5, bath temperature 70 ℃.

Example 3 Co-Pd-B

Cobalt sulfate 7 hydrate 5g/L (1 g/L in cobalt)

Palladium chloride 0.08g/L (0.05 g/L calculated as palladium)

Citric acid 50g/L

Dimethylamine borane 1.0g/L

pH 7.5, bath temperature 70 ℃.

Example 4 Co-W-B

Cobalt sulfate 7 hydrate 5g/L (1 g/L in cobalt)

Sodium tungstate.2 hydrate 1g/L (0.55 g/L in terms of tungsten)

Citric acid 50g/L

Dimethylamine borane 1.0g/L

pH 7.5, bath temperature 70 ℃.

Example 5 Co-Mo-B

Cobalt sulfate 7 hydrate 20g/L (calculated as cobalt 4 g/L)

Sodium 2 molybdate 2 hydrate 0.5g/L (calculated as molybdenum 0.2 g/L)

Citric acid 50g/L

Dimethylamine borane 1.0g/L

pH 7.5, bath temperature 70 ℃.

Example 6 Co-B-P

Cobalt sulfate 7 hydrate 20g/L (calculated as cobalt, 4 g/L)

Citric acid 50g/L

Dimethylamine borane 1.0g/L

60g/L sodium hypophosphite

pH 7.5, bath temperature 70 ℃.

Example 7 Co-B-P

Cobalt sulfate 7 hydrate 20g/L (calculated as cobalt 4 g/L)

Citric acid 50g/L

Boric acid 10g/L

Dimethylamine borane 1.0g/L

Sodium phosphite 20g/L

pH 8.0 and bath temperature 70 ℃.

Example 8 Co-P

Cobalt sulfate 7 hydrate 20g/L (calculated as cobalt, 4 g/L)

Citric acid 50g/L

Boric acid 10g/L

Hydrazine 2.0g/L

Sodium hypophosphite 20g/L

pH 8.0 and bath temperature 70 ℃.

(1-2) comparative examples 1 to 5: does not contain Co

Comparative example 1 Ni-B

Nickel sulfate 6 hydrate 4.5g/L (calculated as nickel 1.0 g/L)

DL-malic acid 10g/L

Dimethylamine borane 5.0g/L

pH 7.5 and bath temperature 60 ℃.

Comparative example 2 Ni-B

Nickel sulfate 6 hydrate 0.45g/L (calculated as nickel 0.1 g/L)

DL-malic acid 10g/L

Dimethylamine borane 5.0g/L

pH 7.5 and bath temperature 60 ℃.

Comparative example 3 Ni-B-P

Nickel sulfate 6 hydrate 0.45g/L (calculated as nickel 0.1 g/L)

DL-malic acid 10g/L

Dimethylamine borane 5.0g/L

Sodium hypophosphite 10g/L

pH 7.5 and bath temperature 60 ℃.

Comparative example 4 Pd-B

Palladium chloride 0.83g/L (0.5 g/L calculated as palladium)

Ethylene diamine 10g/L

Dimethylamine borane 1.0g/L

pH 7.5 and bath temperature 40 ℃.

Comparative example 5 Pd

Palladium chloride 0.83g/L (0.5 g/L calculated as palladium)

Ethylene diamine 10g/L

Hydrazine 1.0g/L

pH 7.5 and bath temperature 40 ℃.

(1-3) comparative examples 6 to 7: pd catalyst imparting treatment by metathesis (prior art)

Comparative example 6

Palladium chloride 0.17g/L (0.1 g/L calculated as palladium)

35% hydrochloric acid 100ml/L

The bath temperature was 30 ℃.

Comparative example 7

0.19g/L palladium sulfate (0.1 g/L calculated as palladium)

98% sulfuric acid 20ml/L

The bath temperature was 30 ℃.

(2) Evaluation test

In the following evaluation test, after pretreatment (acid degreasing and soft etching) of a material to be subjected to electroless plating, catalyst nuclei are formed on the metal surface by the above-mentioned catalyst-imparting solution, and then electroless palladium plating and electroless gold plating are performed in this order. The details of each process are as follows, unless otherwise specified. The treatment was carried out for 1 minute by washing with running water between the steps.

(a) Acid degreasing

The resulting film was immersed in an acidic degreasing solution (trade name: ICP Clean S-135K) containing sulfuric acid and a surfactant at 40 ℃ for 5 minutes.

(b) Soft etching

The resulting mixture was immersed in an aqueous solution containing 100g/L of sodium persulfate and 10ml/L of 98% sulfuric acid at room temperature for 1 minute.

(c) Catalyst imparting treatment

In examples 1 to 8 and comparative examples 1 to 5, the catalyst cores were immersed in the catalyst-applying solution for 1 to 5 minutes so that the thickness of the catalyst cores became 0.01. Mu.m. For comparative examples 6 and 7, the immersion was carried out for 1 minute.

(d) Electroless palladium plating

The resultant was immersed in an electroless palladium plating solution (trade name: top Pallas PD, australian pharmaceutical industries, ltd.) at 65 ℃ for 5 minutes to obtain a plating film having a thickness of about 0.1. Mu.m.

(e) Electroless gold plating

The plate was immersed in electroless gold plating (trade name: top Pallas AU, austrian pharmaceutical industry (manufactured)) at 80 ℃ for 10 minutes. A plated coating film having a thickness of about 0.05 μm was obtained.

(2-1) measurement of composition of catalyst core

After acidic degreasing, soft etching, and catalyst application treatment were performed on a copper-coated epoxy substrate used as an electroless plating target material, the composition was identified by measurement using an energy dispersive X-ray analyzer (EDX, EMAX-act manufactured by HORIBA), or a dissolution method using an Inductively Coupled Plasma (ICP) emission spectrometer (PS 3500DDII manufactured by hitachi high tech).

(2-2) evaluation of plating deposition Property

As a material to be electroless plated, a BGA (Ball Grid Array) resin substrate having an over-resist type (over-resist type) fine copper pad (diameter 0.2mm, pad number 30) on a resin substrate was used. The electroless plating object material is sequentially subjected to acid degreasing, soft etching, catalyst imparting treatment, electroless palladium plating, and electroless gold plating. The presence or absence of plating deposition in each pad was judged by Microscope (VHX-1000 manufactured by KEYENCE), and evaluated according to the following evaluation criteria.

< evaluation Standard of plating deposition Property >

Good: all pads were precipitated normally.

X: there was a pad with no plating precipitated.

(2-3) evaluation of Selective precipitation Properties

As an object material for electroless plating, a resin substrate having a copper wiring pattern with a wiring width/wiring interval (L/S) =20/20 μm manufactured by an SAP method was used. The electroless plating object material is treated in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. The presence or absence of plating deposition between wiring patterns (resin portions) was determined by a scanning electron microscope (SEM, S-3400N, hitachi Seisakusho technologies), and evaluated according to the following evaluation criteria.

< evaluation criterion for Selectivity precipitation >

Good: no plating deposition occurs between the wiring patterns.

And (delta): plating between wiring patterns is slightly precipitated.

X: deposited on the entire surface between wiring patterns.

(2-4) evaluation of bath stability

The catalyst-imparting solution used for evaluating plating deposition properties was heated to a bath temperature of +5 ℃ in the catalyst-imparting treatment, and left to stand for 72 hours. Whether or not the bath decomposition occurred was visually judged, and evaluation was performed according to the following evaluation criteria.

< evaluation criterion of bath stability >

Good component: the bath is not decomposed.

X: the bath is decomposed.

(2-5) confirmation of voids (voids)

As a material to be electroless plated, a BGA (Ball Grid Array) resin substrate having a copper pad of an over-resist type on a resin base material is used. The electroless plating object material is treated in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. Next, the cross section was processed using a beam focused ion beam processing and observation apparatus, and the presence or absence of a void was observed using a scanning ion microscope (FIB/SIM, hitachi high tech FB 2200).

Evaluation criteria for voids

Good: no void is present.

X: with a void.

(2-6) evaluation of Barrier Properties

As a material to be electroless plated, a BGA (Ball Grid Array) resin substrate having a copper pad of an over-resist type on a resin base material is used. The electroless plating object material is treated in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. Subsequently, the treated substrate was heat-treated at 175 ℃ for 16 hours, and then the elemental composition of the Au-plated surface was measured with an X-ray photoelectron spectrometer (ULVAC-PHI Co., ltd., PHI5000Versa Probe III). The presence or absence of the base metal (Cu, co, ni, pd) on the surface of the Au coating was detected, and evaluated according to the following evaluation criteria.

< evaluation Standard of Barrier Property >

Good: no base metal (Cu, co, ni, pd) was detected on the Au coating surface.

X: the base metals (Cu, co, ni, pd) were detected on the surface of the Au coating.

(2-7) evaluation of bondability

As the material to be subjected to electroless plating, a BGA resin substrate having a resist-type fine copper pad (diameter: 0.6mm, number of pads: 20) on a resin base material was used. The material to be electrolessly plated was treated in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. Thereafter, solder balls of Sn-3Ag-0.5Cu are mounted

After heating (peak temperature 250 ℃ C.) with a reflow apparatus, a solder ball pull-off test was carried out at a pull-off speed of 5000 μm/sec with a solder ball pull-off test apparatus (product #4000 of Dage corporation). The mode in which the solder was broken or the base material was broken was judged as good, and the mode in which the bonding interface between the solder ball and the plating film was broken was judged as bad, and the evaluation was performed based on the following evaluation criteria.

< evaluation criterion of bondability >

Good: the good mode is 50% or more.

And (delta): good mode is more than 0% and less than 50%.

X: all are bad mode (good mode 0%).

(3) As a result, the

The results are shown in Table 1.

TABLE 1

Claims

1. A catalyst-imparting liquid for electroless plating, characterized in that:

contains cobalt compound and reducing agent.

2. The electroless plating catalyst-imparting liquid according to claim 1, characterized in that:

the reducing agent comprises an amine compound.

3. The electroless plating catalyst-imparting liquid according to claim 2, characterized in that:

the amine compound comprises at least 1 selected from the group consisting of amine boranes, hydrazines, and hydrazine derivatives.

4. The electroless plating catalyst-imparting liquid according to any one of claims 1 to 3, characterized in that:

contains a complexing agent.

5. The electroless plating catalyst-imparting liquid according to claim 4, characterized in that:

the complexing agent comprises a carboxylic acid.

6. The electroless plating catalyst-imparting liquid according to claim 5, characterized in that:

the carboxylic acid comprises a hydroxycarboxylic acid or a dicarboxylic acid.

7. The electroless plating catalyst-imparting liquid according to any one of claims 1 to 6, characterized in that:

the reducing agent comprises at least 1 selected from a boron-containing compound and a phosphorus-containing compound.

8. The electroless plating catalyst-imparting liquid according to any one of claims 1 to 7, characterized in that:

also contains metal salt.

9. The electroless plating catalyst-imparting liquid according to any one of claims 1 to 8, characterized in that:

the cobalt content is 50 mass% or more relative to 100 mass% of the metal.

10. The electroless plating catalyst-imparting liquid according to any one of claims 1 to 9, characterized in that:

the reducing agent contains at least 1 selected from a boron-containing compound and a phosphorus-containing compound, and,

11. A method for producing an electroless plating object material containing a catalyst core, characterized by comprising:

(1) A step of bringing an electroless plating target material into contact with the electroless plating catalyst-imparting liquid according to any one of claims 1 to 10.

12. A method for producing a material containing an electroless plating film, comprising:

(1) A step of bringing an electroless plating target material into contact with the electroless plating catalyst-imparting liquid according to any one of claims 1 to 10; and

(2) And (2) performing electroless plating after the step (1).

13. A material characterized by:

comprising a material having a metal exposed on the surface thereof, a catalyst core 1 on the metal, and a coating film 2 on the catalyst core 1, and,

the catalyst core 1 contains cobalt and is,

the coating 2 is an electroless plating coating.