TW202212628A - Catalyst-imparting solution for electroless plating - Google Patents

Abstract

To provide a catalyst-imparting solution used for pretreatment when electroless plating is performed on a metal material, the catalyst-imparting solution having superior bath stability, as well as being useful for forming an electroless plating film having superior plating deposition, selective deposition, barrier properties, bondability, etc. A catalyst-imparting solution for electroless plating contains a cobalt compound and a reducing agent.

Description

Catalyst imparting solution for electroless plating

The present invention relates to a catalyst imparting solution for electroless plating and the like.

In the electronic related fields such as printed wiring boards, semiconductor packages, electronic parts, etc., one of the last steps in manufacturing is to apply electroless nickel plating on conductor circuits, terminal parts, etc., and further perform electroless gold plating. . The electroless nickel/gold plated film formed in this way is used for the following purposes: to prevent oxidation of the copper circuit surface so that it can exert good solder connection performance, and to improve the soldering between the semiconductor package and the electronic parts mounted thereon. wire bondability, etc. After the electroless nickel plating film is formed, when the gold plating film is to be formed in place of the gold plating film, there is a problem that, depending on the state of the nickel plating film of the base, the nickel is partially dissolved and nickel corrosion occurs, that is, a black pad. (Black pad); Au surface is polluted due to the diffusion of base metal due to heat treatment. As a means to solve such a problem, an electroless nickel/palladium/gold plating process in which electroless palladium plating is performed between electroless nickel plating and gold plating as a barrier film has been added. Furthermore, in order to cope with the miniaturization of copper wiring accompanying the increase in the density of printed wiring boards, electroless palladium/gold plating treatment has been developed that omits the electroless nickel plating film with the largest film thickness (refer to the following patent documents). 1).

[Prior Art Literature] [Patent Literature] [Patent Document 1] Japanese Patent Application Laid-Open No. 5-327187

Summary of Invention [The problem to be solved by the invention] When electroless plating is performed on a metal material of a substrate, for the purpose of improving plating precipitation and the like, a catalyst imparting treatment is performed in which palladium metal, which becomes a catalyst nucleus, is deposited on the metal material by a substitution reaction. The inventors of the present invention have found that, in the course of their studies, when this catalyst imparting treatment is performed, although the plating precipitation properties are good, the barrier properties and bonding properties are insufficient. In the process of investigating the cause, it was found that during the above-mentioned catalyst application treatment, the metal material may be excessively dissolved. There are tiny voids everywhere between the plating film and the metal material.

Therefore, the inventors of the present invention tried to provide a catalyst treatment for precipitating palladium metal not by a substitution reaction but by a reduction reaction. However, some properties such as plating precipitation properties, selective precipitation properties, bath stability, barrier properties, and bonding properties are insufficient.

Therefore, the present invention has an object to provide a catalyst-imparting liquid that is used in a pretreatment when electroless plating is performed on a metal material, which contributes to the formation of The electroless plating film is more excellent in plating precipitation, selective precipitation, barrier properties, and bonding properties, and the catalyst imparting solution is more excellent in bath stability.

[means to solve the problem] The inventors of the present invention have found that the above-mentioned problems can be solved by using a catalyst-imparting solution for electroless plating containing a cobalt compound and a reducing agent as a result of earnest research in view of the above-mentioned problems. The present inventors completed the present invention as a result of further studies based on this knowledge. That is, the present invention includes the following aspects.

Item 1. A catalyst-imparting solution for electroless plating, comprising a cobalt compound and a reducing agent.

Item 2. The catalyst-imparting solution for electroless plating according to Item 1, wherein the reducing agent contains an amine compound.

Item 3. The catalyst-imparting solution for electroless plating according to Item 2, wherein the amine compound contains at least one selected from the group consisting of boraneamine, hydrazine, and hydrazine derivatives.

Item 4. The catalyst-imparting solution for electroless plating according to any one of Items 1 to 3, which contains a complexing agent.

Item 5. The catalyst-imparting solution for electroless plating according to Item 4, wherein the complexing agent contains a carboxylic acid.

Item 6. The catalyst-imparting solution for electroless plating according to Item 5, wherein the carboxylic acid contains a hydroxycarboxylic acid or a dicarboxylic acid.

Item 7. The catalyst-imparting solution for electroless plating according to any one of Items 1 to 6, wherein the reducing agent contains at least one selected from the group consisting of a boron-containing compound and a phosphorus-containing compound.

Item 8. The catalyst-imparting solution for electroless plating according to any one of Claims 1 to 7, which further contains a metal salt.

Item 9. The catalyst-imparting solution for electroless plating according to any one of Items 1 to 8, wherein the cobalt content is 50 mass % or more relative to 100 mass % of the metal.

Item 10. The catalyst-imparting solution for electroless plating according to any one of Items 1 to 9, wherein the reducing agent contains at least one selected from the group consisting of a boron-containing compound and a phosphorus-containing compound, and The aforementioned electroless plating refers to a material having copper and/or copper alloy exposed on the surface, and is at least one selected from the group consisting of electroless palladium plating, electroless nickel plating, and electroless gold plating 1 type of electroless plating.

Item 11. A method for producing an electroless plating target material comprising a catalyst core, comprising the steps of: (1) contacting the electroless plating target material with the electroless plating target material according to any one of Items 1 to 10 The step of mediator imparting liquid contact.

Item 12. A method for producing a material comprising an electroless plating film, comprising the steps of: (1) making the electroless plating target material and the catalyst-imparting solution for electroless plating according to any one of items 1 to 10 The step of contacting; and (2) the step of performing electroless plating treatment after step (1).

Item 13. A material comprising: a material with exposed metal on the surface, 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 electroless plating Apply a skin film.

[Inventive effect] According to the present invention, it is possible to provide a catalyst-imparting liquid that is used in a previous treatment when electroless plating is performed on a metal material, which contributes to the formation of plating precipitation properties , Select the electroless plating film which is more excellent in precipitation, barrier properties, bonding, etc., and the bath stability of the catalyst imparting solution is more excellent.

Form for carrying out the invention In this specification, the expressions of "contains" and "includes" include the concepts of "contains", "includes", "substantially consists of" and "consists only of".

1. Catalyst imparting solution One aspect of the present invention relates to a catalyst-imparting solution for electroless plating containing a cobalt compound and a reducing agent (also referred to as "catalyst-imparting solution of the present invention" in this specification). This will be described 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, cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt bromide, cobalt iodide, cobalt hypophosphite, cobalt phosphate, cobalt sulfate Ammonium, cobalt ammonium chloride, cobalt potassium sulfate, cobalt sulfamate, cobalt acetate, cobalt carbonate, cobalt acetylacetonate, cobalt formate, cobalt oxalate, cobalt stearate, cobalt citrate, cobalt tartrate, cobalt lactate, etc. Among these, from the viewpoint of the effect of the present invention, inorganic cobalt salts are preferably mentioned, preferably cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt phosphate, cobalt hypophosphite, etc., and more preferably, cobalt sulfate ,Cobalt chloride.

Cobalt compounds may be used alone or in combination of two or more.

The cobalt concentration in the catalyst imparting solution of the present invention is, for example, 0.05 g/L or more. From the viewpoint of the effect of the present invention, the cobalt concentration is preferably 0.05~50g/L, preferably 0.1~30g/L, more preferably 0.2~20g/L, still more preferably 0.4~15g/L, especially It is 0.6~10g/L, and 0.7~6g/L is particularly good.

The content of cobalt in the catalyst imparting solution of the present invention is, for example, 50% by mass or more, preferably 60% by mass, preferably 70% by mass, or 80% by mass relative to 100% by mass of the transition metal element containing cobalt. % or more, or 90% by mass or more.

The reducing agent is not particularly limited as long as it can precipitate cobalt metal, and a reducing agent that can be used for reduction plating can be used. As a reducing agent, an amine compound, a boron-containing compound, a phosphorus-containing compound, etc. are mentioned, for example. Reducing agents also exist and belong to several of them. For example, there are also reducing agents that are both amine compounds and boron-containing compounds. In this case, when the reducing agent is contained, it can be said that an amine compound is contained, and it can also be said that a boron-containing compound is contained.

As an amine compound, a borane amine, a hydrazine, a hydrazine derivative, etc. are mentioned, for example.

Boraneamine is a complex of borane (eg, BH ₃ ) and an amine, that is, a boraneamine complex. As the amine constituting the borane amine, either a chain amine (acyclic amine) or a cyclic amine may be used, but a chain amine is preferable, and among the chain amines, the general formula is preferred. Chain amine shown in (1):

[Chemical formula 1]

[In the formula, R ¹ , R ² and R ³ are the same or different, and represent a hydrogen atom or an alkyl group].

The alkyl group includes any of linear, branched, and cyclic. The alkyl group is preferably straight-chain or branched, preferably straight-chain. The carbon number of the alkyl group is not particularly limited, for example, it is 1-8, preferably 1-6, preferably 1-4, more preferably 1-2, and more preferably 1. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, Neopentyl, n-hexyl, 3-methylpentyl, cyclohexyl, etc.

In a preferred aspect of the present invention, among R ¹ , R ² and R ³ , any two or all (preferably two) are alkyl groups, and the rest are hydrogen atoms.

Specific examples of the amine constituting the borane complex include dimethylamine, diethylamine, trimethylamine, triethylamine, methoxyethylamine, dicyclohexylamine, t- Butylamine, amine pyridine, ethylenediamine, mofolin, pyridine, piperidine, imidazole, etc. Among these, dimethylamine, diethylamine, trimethylamine, methoxyethylamine, dicyclohexylamine, etc. are also preferably used, and dimethylamine and the like are preferably used.

Suitable specific examples of borane amine include dimethyl borane amine, diethyl borane amine, trimethyl borane amine, and the like.

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 boron hydride compounds, and more specifically, the above-mentioned borane amine, which is also an amine compound, and borane complexes other than borane amine (complex complexes of borane and other compounds) compounds), boron hydride alkali metal salts (such as sodium salts, etc.).

Examples of the phosphorus-containing compound include hypophosphorous acid, hypophosphite (for example, sodium salt, potassium salt, ammonium salt, etc.), phosphorous acid, phosphite (for example, sodium salt, potassium salt, ammonium salt, etc.), and the like. Hydrate etc.

The reducing agent preferably contains an amine compound from the viewpoint of the effect of the present invention. In addition, in this case, the amine compound preferably contains at least one selected from the group consisting of boraneamine, hydrazine, and hydrazine derivatives, and more preferably contains at least one selected from the group consisting of boraneamine and hydrazine derivatives. At least one of the group consisting of hydrazine is more preferably boraneamine. Moreover, when the reducing agent contains an amine compound, it is preferable that the reducing agent further contains a phosphorus-containing compound.

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

The reducing agent may be used alone or in combination of two or more.

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

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 a complexing agent that can be used for electroless plating (especially reduction plating) can be used. Examples of complexing agents include monocarboxylic acids such as acetic acid and formic acid, and ammonium salts, potassium salts, and sodium salts thereof; and dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid. And these ammonium salts, potassium salts, sodium salts, etc; Diacetic acid, 1-hydroxyethylene-1,1-diphosphonic acid and their ammonium salts, potassium salts, sodium salts, etc.; Sodium, potassium and ammonium salts of acids and the like; phosphonic acids such as pyrophosphoric acid and their sodium salts, potassium salts, ammonium salts, etc.; amino acids such as glycine and glutamic acid, etc.

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

A complex agent can be used individually by 1 type or in combination of 2 or more types.

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

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

Although it does not specifically limit as a metal salt, For example, the salt containing the transition metal element other than cobalt is mentioned. Examples of the transition metal element include metal elements such as gold, palladium, nickel, tungsten, molybdenum, and rhenium. More specific examples of the metal salt include nickel sulfate, nickel chloride, palladium sulfate, palladium chloride, sodium tungstate, 2 sodium molybdate, potassium gold cyanide, sodium gold sulfite, and ammonium perrhenate. Wait.

Metal salts may be used alone or in combination of two or more.

When the catalyst imparting liquid of the present invention contains a metal salt, the concentration of the metal contained in the metal salt in the catalyst imparting liquid of the present invention is, for example, 0.005 g/L or more. From the viewpoint of the effect of the present invention, the concentration is preferably 0.005-5 g/L, preferably 0.01-3 g/L, more preferably 0.02-2 g/L, still more preferably 0.03-1 g/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 imparting 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 also contained, the content thereof is, for example, 10% by mass or less, 5% by mass or less, 1% by mass, or 0.1% by mass or less with respect to 100% by mass of the solvent containing water.

The catalyst imparting liquid of the present invention can be mixed with various additives according to other requirements. As an additive, a stabilizer, pH buffer, surfactant, etc. are mentioned, for example.

As a stabilizer, one of the following can be added alone, or two or more of the following can be mixed and added, for example: lead salts such as lead nitrate and lead acetate; bismuth salts such as bismuth nitrate and bismuth acetate; sulfur compounds such as sodium thiosulfate, etc. When adding a stabilizer, the addition amount is not particularly limited, but can be, for example, about 0.01 to 100 mg/L.

As a pH buffer, one of the following can be added alone, or two or more of the following can be mixed and added, for example: acetic acid, boric acid, phosphoric acid, phosphorous acid, carbonic acid and their sodium salts, potassium salts, ammonium salts, etc. When adding a pH buffer, the addition amount is not particularly limited, but from the viewpoint of bath stability and the like, it can be set to about 0.002 to 1 mol/L.

As a surfactant, various surfactants, such as nonionic, anionic, cationic, and amphoteric, can be used, for example. For example, an aromatic or aliphatic sulfonic acid alkali salt, an aromatic or aliphatic carboxylic acid alkali metal salt, etc. are mentioned. Surfactant can be used individually by 1 type or in mixture of 2 or more types. When adding a surfactant, the addition amount thereof is not particularly limited, but may be, for example, about 0.01 to 1000 mg/L.

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

2. Catalyst giving method One aspect of the present invention relates to a method for producing a material for electroless plating including a catalyst core, or a method for applying a catalyst to the material for electroless plating (in this specification, it is also expressed as "Method 1 of the present invention"), the aforementioned method includes the following steps: (1) The step of bringing the electroless plating object material into contact with the catalyst imparting liquid of the present invention. Hereinafter, this will be described.

The material to be subjected to electroless plating is not particularly limited as long as the metal is exposed on the surface. For example, the material is one or a combination of the following materials: glass fiber reinforced epoxy, polyimide, PET and other plastics; glass, ceramics, metal oxides, metals, paper, synthetic or Natural fiber, etc.; its shape can be any of plate, film, cloth, fiber, tube, and the like. Examples of metals exposed on the surface include copper, copper alloys, silver, silver alloys, gold, gold alloys, platinum, platinum alloys, molybdenum, and tungsten. Among them, as copper alloys, silver alloys, gold alloys, and platinum alloys, for example, each can be applied to an alloy containing copper, silver, gold, or platinum in an amount of 50% by weight or more. As an electroless-plating object material, a printed wiring board, a semiconductor package, an electronic component, a ceramic substrate, etc. are mentioned specifically, for example. Among these materials, the metal exposed on the surface can constitute wiring.

The material to be subjected to electroless plating is preferably one that has been subjected to pretreatment such as degreasing treatment and soft etching treatment.

The specific method for bringing the catalyst application liquid of the present invention into contact with the material to be electroless-plating is not particularly limited, but generally, the object to be treated may be immersed in the catalyst application liquid of the present invention. In addition, the catalyst imparting treatment may be performed by a method of spraying the catalyst imparting liquid on the surface of the material to be electroless plating, or the like.

When the catalyst imparting liquid of the present invention is carried out by the immersion method, the liquid temperature of the catalyst imparting liquid of the present invention is usually set to about 10 to 90° C., preferably about 40 to 80° C., more preferably 60~80℃.

The processing time is preferably about 30 seconds to 20 minutes, preferably about 1 minute to 5 minutes.

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

The Co content in the catalyst core is, for example, 50 mass % or more, preferably 60 mass % or 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, preferably 0.5 mass % or less, and more 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 mass %, preferably 1.5 to 15 mass %, and preferably 3 to 10 mass %.

The content of each element in the catalyst core is measured by an energy dispersive X-ray analyzer (EDX, EMAX X-act manufactured by HORIBA), or by using a high-frequency inductively coupled plasma (ICP) emission spectrometer ( It was identified by the dissolution method of Hitachi High tech science PS3500DDII).

By subjecting the electroless-plating target material including the catalyst core to electroless-plating treatment, an electroless-plating film having more excellent plating precipitation properties, selective precipitation properties, barrier properties, and bonding properties can be formed. Since the catalyst core is for the purpose of surface activation, its thickness may be, for example, 0.05 μm or less, and 0.005 to 0.05 μm.

3. Electroless plating method One aspect of the present invention relates to a method for producing a material comprising an electroless plating film, or a method for performing electroless plating on a material to be electroless plating (in this specification, it is also referred to as "the present invention"). Method 2"), the aforementioned method comprises the following steps: (1) the step of contacting the electroless plating object material with the catalyst imparting solution of the present invention; and (2) after step (1), performing electroless plating The steps of applying treatment. Hereinafter, this will be described.

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

The electroless plating treatment can be performed by bringing the electroless plating object material containing the catalyst core obtained in the step (1) into contact with the electroless plating solution.

It does not specifically limit as an electroless plating liquid, A self-catalytic electroless plating liquid can be used. For example, electroless palladium plating solution, electroless palladium alloy plating solution, electroless copper plating solution, electroless copper alloy plating solution, electroless silver plating solution, electroless silver alloy plating solution, Electrolytic nickel plating solution, electroless nickel alloy plating solution, electroless gold plating solution, electroless gold alloy plating solution, etc. The specific composition of these electroless plating solutions is not particularly limited, and an autocatalytic electroless plating solution having a known composition containing a reducing agent component may be used. Regarding the plating conditions, it is sufficient to follow the usual plating conditions depending on the type of the plating solution to be used.

In the step (2) of the method 2 of the present invention, as the electroless plating solution, it is suitable to use an electroless palladium plating solution, an electroless palladium alloy plating solution, an electroless nickel plating solution, and an electroless nickel alloy plating solution. etc., electroless gold plating solution, electroless gold alloy plating solution. When using an electroless palladium plating solution or an electroless palladium alloy plating solution in step (2), it is preferable to further perform electroless gold plating or electroless gold alloy plating. Also, when using an electroless nickel plating solution or an electroless nickel alloy plating solution in step (2), it is advisable to further carry out electroless palladium plating or electroless palladium alloy plating, preferably further carry out electroless gold plating or electroless gold alloy plating. Moreover, when 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 may be further performed. In addition, in step (2), only the electroless gold plating solution and the electroless gold alloy plating solution may be performed.

According to the method 2 of the present invention, an electroless plating film having more excellent plating precipitation properties, selective precipitation properties, barrier properties, bonding properties, and the like can be formed. A material capable of providing such an electroless plating film can be obtained by the method 2 of the present invention. Specifically, a material can be obtained, which includes: a material with exposed metal on the surface, the catalyst core 1 on the metal, and the catalyst. The film 2 on the catalyst core 1, the catalyst core 1 contains cobalt, and the film 2 is an electroless plating film.

[Example] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.

(1) Preparation of catalyst imparting solution A catalyst application solution for electroless plating having the composition shown below was prepared. Water was used as solvent.

(1-1) Examples 1 to 8: Co-containing (Example 1) Co-B Cobalt Sulfate Hexahydrate 5g/L (Cobalt 1g/L) DL-malic acid 10g/L Dimethylboraneamine 3.0g/L pH 7.5, bath temperature 70°C.

(Example 2) Co-Ni-B Cobalt Sulfate Hexahydrate 5g/L (Cobalt 1g/L) Nickel sulfate hexahydrate 0.45g/L (Nickel 0.1g/L) DL-malic acid 10g/L Dimethylboraneamine 3.0g/L pH 7.5, bath temperature 70°C.

(Example 3) Co-Pd-B Cobalt Sulfate Hexahydrate 5g/L (Cobalt 1g/L) Palladium chloride 0.08g/L (palladium 0.05g/L) Citric acid 50g/L Dimethylboraneamine 1.0g/L pH 7.5, bath temperature 70°C.

(Example 4) Co-W-B Cobalt Sulfate Hexahydrate 5g/L (Cobalt 1g/L) Sodium Tungstate・Dihydrate 1g/L (Tungsten 0.55g/L) Citric acid 50g/L Dimethylboraneamine 1.0g/L pH 7.5, bath temperature 70°C.

(Example 5) Co-Mo-B Cobalt Sulfate Hexahydrate 20g/L (Cobalt 4g/L) Disodium Molybdate Dihydrate 0.5g/L (Molybdenum 0.2g/L) Citric acid 50g/L Dimethylboraneamine 1.0g/L pH 7.5, bath temperature 70°C.

(Example 6) Co-B-P Cobalt Sulfate Hexahydrate 20g/L (Cobalt 4g/L) Citric acid 50g/L Dimethylboraneamine 1.0g/L Sodium hypophosphite 60g/L pH 7.5, bath temperature 70°C.

(Example 7) Co-B-P Cobalt Sulfate Hexahydrate 20g/L (Cobalt 4g/L) Citric acid 50g/L Boric acid 10g/L Dimethylboraneamine 1.0g/L Sodium phosphite 20g/L pH 8.0, bath temperature 70°C.

(Example 8) Co-P Cobalt Sulfate Hexahydrate 20g/L (Cobalt 4g/L) Citric acid 50g/L Boric acid 10g/L Hydrazine 2.0g/L Sodium hypophosphite 20g/L pH 8.0, bath temperature 70°C.

(1-2) Comparative Examples 1 to 5: Co is not contained (Comparative Example 1) Ni-B Nickel sulfate hexahydrate 4.5g/L (Nickel 1.0g/L) DL-malic acid 10g/L Dimethylboraneamine 5.0g/L pH 7.5, bath temperature 60°C.

(Comparative Example 2) Ni-B Nickel sulfate hexahydrate 0.45g/L (Nickel 0.1g/L) DL-malic acid 10g/L Dimethylboraneamine 5.0g/L pH 7.5, bath temperature 60°C.

(Comparative Example 3) Ni-B-P Nickel sulfate hexahydrate 0.45g/L (Nickel 0.1g/L) DL-malic acid 10g/L Dimethylboraneamine 5.0g/L Sodium hypophosphite 10g/L pH 7.5, bath temperature 60°C.

(Comparative Example 4) Pd-B Palladium chloride 0.83g/L (palladium 0.5g/L) Ethylenediamine 10g/L Dimethylboraneamine 1.0g/L pH 7.5, bath temperature 40°C.

(Comparative Example 5) Pd Palladium chloride 0.83g/L (palladium 0.5g/L) Ethylenediamine 10g/L Hydrazine 1.0g/L pH 7.5, bath temperature 40°C.

(1-3) Comparative Examples 6 to 7: Pd catalyst application treatment by substitution reaction (conventional technology) (Comparative Example 6) Palladium chloride 0.17g/L (palladium 0.1g/L) 35% hydrochloric acid 100 ml/L Bath temperature 30°C.

(Comparative Example 7) Palladium sulfate 0.19g/L (palladium 0.1g/L) 98% sulfuric acid 20 ml/L Bath temperature 30°C.

(2) Evaluation test In the following evaluation tests, after pre-treatment (acidic degreasing, soft etching) of the target material for electroless plating, catalyst nuclei were formed on the metal surface with the above-mentioned catalyst imparting solution, followed by electroless palladium plating. , The order of electroless gold plating is processed. The details of each processing are as follows unless otherwise stated. Between each step, a 1-minute process of washing with running water was performed.

(a) Acid degreasing It was immersed in an acidic degreasing solution (trade name: ICP CLEAN S-135K) containing sulfuric acid and a surfactant at 40° C. for 5 minutes.

(b) Soft etching Immerse in an aqueous solution containing 100 g/L of sodium persulfate and 10 ml/L of 98% sulfuric acid at room temperature for 1 minute.

(c) Catalyst application treatment Examples 1 to 8 and Comparative Examples 1 to 5 were immersed in the catalyst imparting liquid for 1 to 5 minutes so that the thickness of the catalyst core was 0.01 μm. It was immersed for 1 minute with respect to the comparative examples 6 and 7 series.

(d) Electroless Palladium Plating It was immersed in an electroless palladium plating solution (trade name: TOP PALLAS PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 65° C. for 5 minutes to obtain a plating film having a thickness of about 0.1 μm.

(e) Electroless gold plating It was immersed in electroless gold plating (trade name: TOP PALLAS AU, manufactured by Okuno Pharmaceutical Co., Ltd.) at 80° C. for 10 minutes. A plated film with a thickness of about 0.05 μm was obtained.

(2-1) Composition measurement of catalyst core Using a copper-clad epoxy substrate as the target material for electroless plating, after performing acid degreasing, soft etching, and catalyst application treatment, it is measured by an energy dispersive X-ray analyzer (EDX, EMAX X-act manufactured by HORIBA), or The composition was identified by the dissolution method using a high-frequency inductively coupled plasma (ICP) emission spectroscopic analyzer (PS3500DDII manufactured by Hitachi High Tech Science).

(2-2) Evaluation of Plating Precipitation Properties As a material for electroless plating, a BGA (Ball Grid Array) resin substrate having over-resist type copper pads (0.2 mm in diameter, 30 pads) on a resin substrate was used. The electroless plating target material was processed in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. The presence or absence of plating precipitation on each pad was judged by a microscope (VHX-1000 manufactured by KEYENCE), and the evaluation was performed according to the following evaluation criteria.

<Evaluation Criteria for Plating Precipitation Properties> ○: All the pads were deposited normally. ×: There is a pad without plating precipitation.

(2-3) Evaluation of selective precipitation As a material for electroless plating, a resin substrate having a copper wiring pattern produced by the SAP method and having wiring width/wiring spacing (L/S)=20/20 μm was used. The electroless plating target material was processed in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. The presence or absence of plating precipitation between the wiring patterns (resin part) was determined by a scanning electron microscope (SEM, S-3400N manufactured by Hitachi High Technologies), and evaluated according to the following evaluation criteria.

<Evaluation criteria for selecting precipitation properties> ○: No plating precipitation between wiring patterns. △: There is a little plating precipitation between the wiring patterns. ×: The entire surface was deposited between the wiring patterns.

(2-4) Evaluation of bath stability The catalyst application liquid used for the evaluation of the plating precipitation was heated to +5°C of the bath temperature of the catalyst application treatment, and left to stand for 72 hours. The presence or absence of bath decomposition was judged by visual observation, and the evaluation was performed according to the following evaluation criteria.

<Evaluation criteria for bath stability> ○: No bath decomposition. ×: Bath decomposition.

(2-5) Confirmation of void As a material for electroless plating, a BGA (Ball Grid Array) resin substrate having an over-solder resist type copper pad on a resin substrate was used. The electroless plating target material was processed in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. Next, cross-section processing was performed using a focused ion beam processing observation apparatus, and the presence or absence of voids was observed by a scanning ion microscope (FIB/SIM, FB2200 manufactured by Hitachi High Technologies). <Evaluation criteria for voids> ○: No gap. ×: There are voids.

(2-6) Evaluation of barrier properties As a material for electroless plating, a BGA (Ball Grid Array) resin substrate having an over-solder resist type copper pad on a resin substrate was used. The electroless plating target material was processed in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. Next, the treated substrate was heat-treated at 175° C. 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., PHI5000VersaProbe III). Based on the presence or absence of detection of the base metal (Cu, Co, Ni, and Pd) on the surface of the Au film, the evaluation was performed according to the following evaluation criteria.

<Evaluation Criteria for Barrier Characteristics> ○: No base metal (Cu, Co, Ni, Pd) was detected on the surface of the Au film. ×: Base metals (Cu, Co, Ni, Pd) were detected on the surface of the Au film.

(2-7) Evaluation of bondability As a material for electroless plating, a BGA resin substrate having over-solder resist type micro-copper pads (0.6 mm in diameter, 20 pads) on a resin substrate was used. The electroless plating target material was processed in the order of acid degreasing, soft etching, catalyst application treatment, electroless palladium plating, and electroless gold plating. Then, after mounting Sn-3Ag-0.5Cu solder balls (φ0.76mm) and heating with a reflow device (peak temperature 250°C), a solder ball tensile tester (#4000 manufactured by Dage) was used at a pulling speed of 5000 μm/ Perform the solder ball pull test in seconds. The mode in which the inside of the solder was broken or the base material was destroyed was judged to be good, and the mode in which the bonding interface between the solder ball and the plated film was destroyed was judged to be poor, and the evaluation was performed according to the following evaluation criteria.

<Evaluation Criteria for Bondability> 〇: The good mode is 50% or more. △: Good mode is higher than 0% and lower than 50%. ×: All are bad patterns (good patterns 0%).

(3) Results The results are shown in Table 1.

[Table 1]

Claims (13)

A catalyst imparting solution for electroless plating containing a cobalt compound and a reducing agent. The catalyst imparting solution for electroless plating according to claim 1, wherein the reducing agent contains an amine compound. The catalyst imparting solution for electroless plating according to claim 2, wherein the amine compound contains at least one selected from the group consisting of boraneamine, hydrazine, and hydrazine derivatives. The catalyst imparting solution for electroless plating according to any one of claims 1 to 3, which contains a complexing agent. The catalyst-imparting solution for electroless plating according to claim 4, wherein the complexing agent contains a carboxylic acid. The catalyst imparting solution for electroless plating according to claim 5, wherein the carboxylic acid contains a hydroxycarboxylic acid or a dicarboxylic acid. The catalyst imparting solution for electroless plating according to any one of claims 1 to 6, wherein the reducing agent contains at least one selected from the group consisting of a boron-containing compound and a phosphorus-containing compound. The catalyst imparting solution for electroless plating according to any one of claims 1 to 7, which further contains a metal salt. The catalyst imparting solution for electroless plating according to any one of claims 1 to 8, wherein the cobalt content is 50 mass % or more relative to 100 mass % of the metal. The catalyst imparting solution for electroless plating according to any one of claims 1 to 9, wherein the reducing agent contains at least one selected from the group consisting of boron-containing compounds and phosphorus-containing compounds, and none of the above Electrolytic plating refers to a material having copper and/or copper alloy exposed on the surface, and is at least one selected from the group consisting of electroless palladium plating, electroless nickel plating, and electroless gold plating Electroless plating. A method of manufacturing an electroless plating object material comprising a catalyst core, comprising the steps of: (1) A step of bringing the electroless-plating object material into contact with the catalyst-imparting liquid for electroless-plating according to any one of claims 1 to 10. A method of manufacturing a material comprising an electroless plated film, comprising the steps of: (1) the step of bringing the electroless plating object material into contact with the catalyst imparting solution for electroless plating according to any one of claims 1 to 10; and (2) After step (1), a step of electroless plating treatment is performed. A material comprising: a material with exposed metal on the surface, 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.