Catalyst application liquid for electroless plating, catalyst application method, and electroless plating method

Abstract

Provided is a catalyst-imparting liquid for forming an electroless plating film having excellent plating deposition properties and patterning properties on a metal material. Specifically provided is a catalyst-imparting liquid for electroless plating, which contains (A) at least one cationic compound selected from the group consisting of cationic polymers and cationic surfactants, and (B) a metal catalyst that contains at least one compound selected from the group consisting of Pd, Au, Ag and Pt, and which has a pH of 5 or less. The content of the cationic compound (A) is 0.01 mg / L to 1000 mg / L, and the content of the metal catalyst (B) is 0.01 mg / L to 100 mg / L.

Description

Technical Field

[0001] The present invention relates to a catalyst-imparting solution for electroless plating, a catalyst-imparting method, and an electroless plating method. Background Art

[0002] In the fields related to electronics such as printed circuit boards, semiconductor packages, and electronic components, one of the final processes in manufacturing involves electroless plating of conductor circuits, terminal portions, etc. Further, when performing electroless plating on the metal material of a substrate, a catalyst-imparting treatment is sometimes carried out for the purpose of improving plating deposition properties, etc. Among them, metal catalysts such as palladium that form catalyst nuclei are deposited on the metal material by a displacement reaction (for example, refer to Patent Document 1).

[0003] When performing electroless plating treatment on a metal material such as a copper circuit, for example, it is necessary to immerse the material to be plated in a catalyst-imparting solution containing 10 to 100 mg / L of palladium. However, in recent years, due to the soaring prices of metal catalysts represented by palladium, there has been a demand to reduce the concentration of the metal catalyst in the catalyst-imparting solution.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2011-058062 Summary of the Invention

[0007] Technical Problem to be Solved by the Invention

[0008] The inventors of the present invention found that when the palladium concentration is reduced, since sufficient catalyst nuclei are not formed on the copper circuit, it cannot fully function as a catalyst for electroless plating deposition, and there is a problem of low plating deposition properties.

[0009] In addition, the inventors of the present invention found that when the immersion time in the palladium catalyst-imparting solution is extended in order to improve plating deposition properties, although sufficient palladium catalyst can be adsorbed on the copper circuit, at the same time, the palladium catalyst is also easily adsorbed on the surface of the insulator, and there is a problem of difficulty in obtaining sufficient patterning due to plating spread.

[0010] Thus, when using the existing catalyst-imparting solution, when the concentration of the metal catalyst in the catalyst-imparting solution is low, both the plating deposition properties and the plating patternability on the metal material are insufficient.

[0011] The present invention has been made in view of the above-described state of the prior art, and its main object is to provide a catalyst-imparting solution for forming an electroless plating film having excellent plating deposition properties and patternability on a metal material.

[0012] Technical solution for solving technical problems

[0013] The inventors of the present invention have repeatedly conducted in-depth research in order to achieve the above object. As a result, it has been found that by using an electroless plating catalyst-imparting liquid containing (A) at least one cationic compound selected from cationic polymers and cationic surfactants, and (B) a metal catalyst, an electroless plating film excellent in plating deposition properties and pattern properties can be formed on a metal material. Based on such findings, the inventors of the present invention have further repeatedly studied, and thus completed the present invention. That is, the present invention includes the following solutions.

[0014] Item 1. An electroless plating catalyst-imparting liquid, comprising:

[0015] (A) At least one cationic compound selected from cationic polymers and cationic surfactants, and

[0016] (B) A metal catalyst,

[0017] The above-mentioned (B) metal catalyst includes at least one selected from Pd, Au, Ag, and Pt,

[0018] The pH of the electroless plating catalyst-imparting liquid is 5 or less,

[0019] The content of the above-mentioned (A) cationic compound is 0.01 mg / L to 1000 mg / L,

[0020] The content of the above-mentioned (B) metal catalyst is 0.01 mg / L to 100 mg / L.

[0021] Item 2. The catalyst-imparting liquid according to Item 1, wherein the above-mentioned (A) cationic compound includes at least one selected from polyethyleneimine, diallyldimethylammonium chloride sulfur dioxide copolymer, methyldiallylamine hydrochloride polymer, diallyldimethylammonium chloride polymer, dicyandiamide-polyalkylenepolyamine condensate, dicyandiamide type cation resin, allylamine hydrochloride-diallylamine hydrochloride polymer, allylamine hydrochloride polymer, allylamine polymer, O-[2-hydroxy-3-(trimethylammonio)propyl] hydroxyethyl cellulose chloride, polylysine, cationized guar gum, coconut oil amine acetate, myristylamine acetate, stearylamine acetate, didecyldimethylammonium chloride, coconut alkyltrimethylammonium chloride, cetyltrimethylammonium chloride, and stearyltrimethylammonium chloride.

[0022] Item 3. The catalyst-imparting liquid according to Item 1 or 2, wherein the above-mentioned (B) metal catalyst includes Pd.

[0023] Item 4. The catalyst-imparting liquid according to any one of Items 1 to 3, further containing (C) at least one acid selected from organic acids and inorganic acids.

[0024] Item 5. The catalyst-imparting liquid according to Item 4, wherein the above-mentioned (C) acid includes at least one selected from acetic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, glycolic acid, lactic acid, malic acid, gluconic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, methanesulfonic acid, glutamic acid, aspartic acid, and boric acid.

[0025] Item 6. The catalyst-imparting liquid according to any one of Items 1 to 5, further containing (D) a chloride.

[0026] Item 7. The catalyst-imparting liquid according to Item 6, wherein the above-mentioned (D) chloride includes at least one selected from potassium chloride, sodium chloride, ammonium chloride, calcium chloride, magnesium chloride, lithium chloride, chloral hydrate, and chlorine dioxide.

[0027] Item 8. The catalyst-imparting liquid according to Item 6 or 7, wherein the content of the above-mentioned (D) chloride is 0.01 to 200 g / L.

[0028] Item 9. The catalyst-imparting liquid according to any one of Items 1 to 8, wherein the electroless plating is at least one selected from electroless palladium plating, electroless palladium alloy plating, electroless nickel plating, electroless nickel alloy plating, electroless silver plating, electroless silver alloy plating, electroless gold plating, and electroless gold alloy plating.

[0029] Item 10. The catalyst-imparting liquid according to any one of Items 1 to 9, wherein the electroless plating is plating on a substrate having an insulating region and a conductive region on its surface.

[0030] Item 11. A method for imparting a catalyst for electroless plating, comprising: (1) a step of bringing the catalyst-imparting liquid according to any one of Items 1 to 10 into contact with an object to be plated.

[0031] Item 12. An electroless plating method, successively comprising: (1) a step of bringing the catalyst-imparting liquid according to any one of Items 1 to 10 into contact with an object to be plated; and

[0032] (2) a step of performing electroless plating treatment.

[0033] Item 13. A substrate imparted with a catalyst by the catalyst-imparting method according to Item 11.

[0034] Item 14. A substrate subjected to electroless plating treatment by the electroless plating method according to Item 12.

[0035] Effects of the Invention

[0036] The catalyst-imparting liquid for electroless plating of the present invention is useful for forming an electroless plating film having excellent plating precipitation properties and patterning properties on a metal material. Detailed Description

[0037] In this specification, the expressions "containing" and "comprising" include any one of the meanings of "containing", "comprising", "consisting only of", "substantially consisting only of", and "consisting only of".

[0038] In this specification, the notation of the numerical range of "A to B" means "A or more and B or less".

[0039] 1. Catalyst-imparting liquid

[0040] The catalyst-imparting liquid for electroless plating of the present invention (hereinafter, in this specification, sometimes also referred to as "the catalyst-imparting liquid of the present invention" or "the catalyst-imparting liquid") contains (A) at least one cationic compound selected from a cationic polymer and a cationic surfactant (hereinafter, sometimes also simply referred to as "(A) cationic compound") and (B) a metal catalyst. The catalyst-imparting liquid of the present invention having the above configuration contains, in addition to (B) the metal catalyst, (A) at least one cationic compound selected from a cationic polymer and a cationic surfactant, and thus can sufficiently impart a catalyst to the surface of the object to be plated. Therefore, it can exhibit excellent plating precipitation properties, can suppress the adsorption of the palladium catalyst on the surface of the insulator, can thus suppress the spread of plating, can exhibit sufficient patterning properties, and can suppress the corrosion of the copper surface. Hereinafter, the present invention will be described in detail.

[0041] (A) Cationic compound

[0042] (A) The cationic compound is not particularly limited as long as it can be adsorbed on the insulating portion via electrostatic interaction. As the (A) cationic compound, specific examples include, for example: polyethyleneimine, diallyldimethylammonium chloride sulfur dioxide copolymer, methyldiallylamine hydrochloride polymer, diallyldimethylammonium chloride polymer, dicyandiamide-polyalkylenepolyamine condensate, dicyandiamide-type cationic resin, allylamine hydrochloride-diallylamine hydrochloride polymer, allylamine hydrochloride polymer, allylamine polymer, O-[2-hydroxy-3-(trimethylammonio)propyl] hydroxyethyl cellulose chloride, polylysine, cationized guar gum, coconut oil amine acetate, myristyl amine acetate, stearyl amine acetate, dicetyldimethylammonium chloride, coconut alkyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, etc. Among these, from the viewpoint of forming an electroless plating film with more excellent plating precipitation properties and pattern properties on the metal material, cationic polymers are preferred, and diallyldimethylammonium chloride sulfur dioxide copolymer, methyldiallylamine hydrochloride polymer, diallyldimethylammonium chloride polymer, allylamine hydrochloride-diallylamine hydrochloride polymer, allylamine hydrochloride polymer, allylamine polymer are more preferred.

[0043] Specific examples of the (A) cationic compound include compounds represented by the following general formula, etc.

[0044]

[0045] [In the formula, n represents an integer of 10 to 1500, l represents an integer of 1 or more, and m represents an integer of 2 or more. The upper limit of the numerical range of l and m is not particularly limited as long as it does not conflict with the numerical range of the preferred weight average molecular weight of the cationic polymer described later. In addition, R represents an alkyl group having 8 to 18 carbon atoms.]

[0046] (A) The molecular weight of the cationic compound is not particularly limited. When the (A) cationic compound is a cationic polymer, the weight average molecular weight is preferably 1000 to 1000000.

[0047] (A) The cationic compound can be used alone or in combination of two or more.

[0048] The content of the (A) cationic compound in the catalyst-imparting liquid of the present invention is 0.01 mg / L to 1000 mg / L. By making the content of the (A) cationic compound within the above range, the catalyst-imparting liquid of the present invention can suppress the foaming of the plating solution and can also reduce the manufacturing cost. From the viewpoint of forming an electroless plating film having more excellent plating deposition properties and patterning properties on a metal material, the content of the (A) cationic compound is preferably 0.05 mg / L to 1000 mg / L, more preferably 0.1 mg / L to 1000 mg / L, and further preferably 1 mg / L to 1000 mg / L.

[0049] (B) Metal catalyst

[0050] (B) The metal contained in the metal catalyst includes at least one selected from Pd, Au, Ag, and Pt. Among these, from the viewpoint of forming an electroless plating film having more excellent plating deposition properties and patterning properties on a metal material, Pd is preferred.

[0051] (B) The metal catalyst can be used alone or in combination of two or more.

[0052] The content of the (B) metal catalyst in the catalyst-imparting liquid of the present invention is 0.01 mg / L to 100 mg / L. As the content of the (B) metal catalyst, from the viewpoint of forming an electroless plating film having more excellent plating deposition properties and patterning properties on a metal material, it is preferably 0.05 mg / L to 100 mg / L, and more preferably 0.1 mg / L to 100 mg / L. By using the catalyst-imparting liquid of the present invention, even when the amount of the metal catalyst used is small (for example, the content in the catalyst-imparting liquid is 20 mg / L or less), an electroless plating film having more excellent plating deposition properties and patterning properties on a metal material can be formed, and thus the formation cost of the electroless plating film can be reduced.

[0053] From the viewpoint of forming an electroless plating film having more excellent plating deposition properties and patterning properties on a metal material, the content of the (B) metal catalyst in the catalyst-imparting liquid of the present invention is preferably 0.001 part by mass to 100 parts by mass, more preferably 0.005 part by mass to 50 parts by mass, and further preferably 0.01 part by mass to 10 parts by mass, relative to 1 part by mass of the (A) cationic compound.

[0054] In the catalyst-imparting liquid of the present invention, the (B) metal catalyst preferably exists in an ionic state. Further, the (B) metal catalyst preferably does not form a colloid. In this case, adsorption of the (B) metal catalyst on the insulating region of the object to be plated is suppressed, and the (B) metal catalyst is easily and efficiently deposited on the conductive region of the object to be plated by a displacement reaction. Therefore, an electroless plating film having more excellent plating deposition properties and pattern properties on the metal material can be formed.

[0055] (C) Acid

[0056] The catalyst-imparting liquid of the present invention is preferably acidic. By making the catalyst-imparting liquid of the present invention acidic, the cationicity of the (A) cationic compound can be utilized more effectively. Specifically, adsorption (deposition) of the (B) metal catalyst on the insulator can be suppressed, and thus an electroless plating film having excellent plating deposition properties and pattern properties on the metal material can be easily formed. In the present specification, being acidic means that the pH is less than 7, preferably the pH is 6.9 or less or 6.8 or less.

[0057] The pH of the catalyst-imparting liquid of the present invention is 5 or less. From the viewpoint of forming an electroless plating film having excellent plating deposition properties and pattern properties on the metal material, the pH is preferably 3 or less, more preferably 1 or less. By making the pH of the catalyst-imparting liquid of the present invention 5 or less, the cationicity of the (A) cationic compound can be effectively utilized. Specifically, adsorption of the (B) metal catalyst on the insulator can be suppressed, and thus it is useful for forming an electroless plating film having excellent plating deposition properties and pattern properties on the metal material.

[0058] From the viewpoint of making the catalyst-imparting liquid of the present invention acidic as described above, the catalyst-imparting liquid of the present invention may further contain at least one acid selected from organic acids and inorganic acids (in the present specification, also simply referred to as "(C) acid") in addition to the (A) cationic compound and the (B) metal catalyst. By making the catalyst-imparting liquid of the present invention contain the (C) acid, the cationicity of the (A) cationic compound can be effectively utilized. Specifically, adsorption of the (B) metal catalyst on the insulating region can be suppressed, and thus an electroless plating film having excellent plating deposition properties and pattern properties on the metal material can be easily formed.

[0059] (C) acid is not particularly limited as long as it is soluble in the catalyst-imparting liquid. Specific examples of (C) acid include acetic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, glycolic acid, lactic acid, malic acid, gluconic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, methanesulfonic acid, glutamic acid, aspartic acid, and boric acid. Among these, from the viewpoint of forming an electroless plating film excellent in plating deposition properties and patternability on a metal material, glycolic acid, sulfuric acid, hydrochloric acid, and methanesulfonic acid are also preferred.

[0060] (C) acid may be used alone or in combination of two or more.

[0061] When (C) acid is included, its content is not particularly limited as long as the pH is within the above range.

[0062] (D) Chloride

[0063] In addition to the above compounds, the catalyst-imparting liquid of the present invention may further contain (D) chloride. Usually, when a metal material is immersed in the catalyst-imparting liquid for a long time, corrosion caused by the metal catalyst occurs. However, when the catalyst-imparting liquid of the present invention contains (D) chloride, it is possible to form an electroless plating film excellent in plating deposition properties and patternability on the metal material while further suppressing the corrosion of the metal material in the treatment process. Furthermore, when using a catalyst-imparting liquid containing (D) chloride, the patternability of the electroless plating film on the metal material can be further improved as compared with the case where (D) chloride is not used.

[0064] (D) chloride is not particularly limited as long as it is soluble in the catalyst-imparting liquid. Examples of (D) chloride include potassium chloride, sodium chloride, ammonium chloride, calcium chloride, magnesium chloride, lithium chloride, chloral, and chlorine dioxide. Among these, from the viewpoint of forming an electroless plating film excellent in plating deposition properties and patternability on a metal material, sodium chloride, potassium chloride, and ammonium chloride are also preferred.

[0065] (D) chloride may be used alone or in combination of two or more.

[0066] When the catalyst-imparting liquid of the present invention contains (D) chloride, its content is not particularly limited, preferably 0.01 g / L to 200 g / L, more preferably 1 g / L to 100 g / L, and still more preferably 3 g / L to 50 g / L. When there is too much chloride, the metal material itself becomes easily soluble, which instead promotes the progress of corrosion, or chloride is formed on the metal material, thus hindering the displacement reaction of the metal catalyst. On the other hand, when there is too little chloride, since the chloride ions in the catalyst-imparting liquid are insufficient, it is difficult to sufficiently inhibit the corrosion of the metal material.

[0067] The catalyst-imparting liquid of the present invention preferably mainly contains water as a solvent. The catalyst-imparting liquid of the present invention may also contain solvents other than water. The solvents other than water that the catalyst-imparting liquid of the present invention may contain are not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include alcohols such as methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, and glycerol; ethers such as ethylene glycol dimethyl ether, 1,4-dioxane, and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone. When it also contains solvents other than water, its content is not particularly limited, and relative to 100% by mass of the solvent, it is preferably 5% by mass or less, and more preferably 0.5% by mass or less. By setting the upper limit of the content of the solvent other than water within the above range, the reduction in the effect of the cationic compound due to the hydrophobicity of the solvent can be further suppressed.

[0068] Various additives can also be appropriately incorporated into the catalyst-imparting liquid of the present invention. Examples of the additives include stabilizers, pH buffers, surfactants, and the like.

[0069] As the stabilizer, 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 can be added singly or in combination of two or more. When a stabilizer is added, its addition amount is not particularly limited, and can be set to, for example, about 0.01 mg / L to about 100 mg / L.

[0070] As the pH buffer, for example, sodium salts, potassium salts, ammonium salts of acetic acid, boric acid, phosphoric acid, phosphorous acid, carbonic acid, phthalic acid, oxalic acid, etc. can be added singly or in combination of two or more. When a pH buffer is added, its addition amount is not particularly limited, and from the viewpoint of bath stability and the like, it can be set to about 0.002 mol / L to about 1 mol / L.

[0071] As the surfactant, in addition to the above-mentioned cationic surfactants, various surfactants such as nonionic, anionic, and amphoteric surfactants can also be used. Examples thereof include alkali metal salts of aromatic or aliphatic sulfonic acids, alkali metal salts of aromatic or aliphatic carboxylic acids, etc. The surfactant can be used alone or in combination of two or more. When adding the surfactant, its addition amount is not particularly limited, and can be set to, for example, about 0.01 mg / L to about 1000 mg / L.

[0072] The catalyst-imparting liquid of the present invention preferably does not contain a reducing agent. In this case, by suppressing the formation of colloids of the (B) metal catalyst, adsorption of the (B) metal catalyst on the insulating region of the object to be plated can be suppressed, and the (B) metal catalyst can be easily and efficiently deposited on the conductive region of the object to be plated by a displacement reaction. Therefore, an electroless plating film having more excellent plating deposition properties and patterning properties on the metal material can be formed.

[0073] 2. Catalyst-imparting method

[0074] In one aspect of the present invention, it relates to a method for manufacturing an electroless plating target material containing a catalyst core or a method for performing a catalyst-imparting treatment on an electroless plating target material, which includes a step of bringing the catalyst-imparting liquid of the present invention into contact with the object to be plated (in this specification, sometimes also referred to as "the method 1 of the present invention"). Hereinafter, this will be described.

[0075] The object to be plated is not particularly limited as long as it is a material in which metal is exposed on the surface. For example, as the raw material, it can be one or a combination of materials such as plastics such as glass fiber-reinforced epoxy resin, polyimide, and PET, glass, ceramics, metal oxides, metals, paper, synthetic or natural fibers, and as its shape, it can be any shape such as a plate, a film, a cloth, a fiber, or a tube.

[0076] Specific examples of the object to be plated include printed circuit boards, semiconductor packages, electronic components, ceramic substrates, etc. Among these materials, the metal exposed on the surface can form wiring.

[0077] Examples of the metal exposed on the surface include copper, copper alloy, nickel, nickel alloy, silver, silver alloy, gold, gold alloy, platinum, platinum alloy, molybdenum, tungsten, etc. Among these, as the copper alloy, silver alloy, gold alloy, and platinum alloy, alloys containing 50 mass% or more of copper, nickel, silver, gold, or platinum can be respectively applied.

[0078] As described above, the object to be plated is preferably an object having an insulating region and a conductive region on its surface. In this case, by Method 1 of the present invention, (A) a cationic compound is pre-adsorbed on the insulating region, and a part or all of the (B) metal catalyst used is efficiently deposited on the conductive region by a displacement reaction. That is, by Method 1 of the present invention, a catalyst core containing the (B) metal catalyst can be efficiently formed on the conductive region (especially the surface metal) of the object to be plated. Therefore, according to Method 1 of the present invention, in the subsequent electroless plating treatment step, it is possible to ensure both the plating deposition property on the metal material and easily form an electroless plating film with excellent patterning properties.

[0079] By Method 1 of the present invention, a material provided with a catalyst can be obtained. Specifically, a substrate having an insulating region and a conductive region on its surface and a material (substrate) having the metal catalyst 1 on the above-mentioned conductive region and suppressing the adhesion of the above-mentioned metal catalyst 1 to the insulating region. By subjecting the object to be plated, which is such a material provided with a catalyst, to an electroless plating treatment, an electroless plating film with more excellent plating deposition properties and patterning properties (selective deposition properties) can be formed. The catalyst core containing the metal catalyst is for the purpose of surface activation, and thus its thickness is, for example, set to 0.05 μm or less, 0.005 μm to 0.05 μm.

[0080] The object to be plated is preferably subjected to pretreatment such as degreasing treatment and soft etching treatment.

[0081] Regarding the specific method for bringing the catalyst-imparting liquid of the present invention into contact with the object to be plated, there is no particular limitation, and generally, the object to be plated may be immersed in the catalyst-imparting liquid of the present invention. In addition, the catalyst-imparting treatment can also be carried out by a method such as coating or spraying the catalyst-imparting liquid on the surface of the object to be plated.

[0082] In the case of using the impregnation method for the catalyst-imparting liquid of the present invention, the liquid temperature of the catalyst-imparting liquid of the present invention is generally preferably about 10°C to 90°C, more preferably about 20°C to 40°C, and further preferably 25°C to 35°C.

[0083] Regarding the treatment time, it is preferably about 10 seconds to 20 minutes, more preferably about 30 seconds to 5 minutes, and further preferably 1 minute to 3 minutes.

[0084] 3. Electroless plating method

[0085] In one aspect of the present invention, there is provided a method for manufacturing a material having an electroless plating film or for electroless plating an object to be plated, which sequentially includes (1) a step of bringing a catalyst-imparting liquid of the present invention into contact with the object to be plated, and (2) a step of performing electroless plating treatment (in this specification, sometimes also referred to as "the method 2 of the present invention"). Hereinafter, this will be described.

[0086] Regarding step (1), as described in the above "2. Catalyst-imparting method".

[0087] (2) The electroless plating treatment in the step of performing electroless plating treatment can be carried out by bringing the catalyst-imparted material (object to be plated) obtained in step (1) into contact with an electroless plating solution.

[0088] Before the electroless plating treatment, a part or all of the (A) cationic compound on the object to be plated can be removed. The removal of the (A) cationic compound can be carried out by ordinary water washing treatment.

[0089] The electroless plating solution is not particularly limited, and a self-catalytic electroless plating solution can be used. For example, an electroless palladium plating solution, an electroless palladium alloy plating solution, an electroless copper plating solution, an electroless copper alloy plating solution, an electroless nickel plating solution, an electroless nickel alloy plating solution, an electroless silver plating solution, an electroless silver alloy plating solution, an electroless gold plating solution, an electroless gold alloy plating solution, etc. can be used. Regarding the specific composition of these electroless plating solutions, there is no particular limitation, and a self-catalytic electroless plating solution having a known composition containing a reducing agent component can be used. Regarding the plating conditions, they can also be according to the type of plating solution used and the usual plating conditions.

[0090] In step (2) of the method 2 of the present invention, preferred electroless plating solutions include: an electroless palladium plating solution, an electroless palladium alloy plating solution, an electroless nickel plating solution, an electroless nickel alloy plating solution, an electroless silver plating solution, an electroless silver alloy plating solution, an electroless gold plating solution, and an electroless gold alloy plating solution, etc. When an electroless nickel plating solution or an electroless nickel alloy plating solution is used in step (2), it is preferred to further perform electroless silver plating, electroless silver alloy plating, electroless gold plating, or electroless gold alloy plating. In addition, when an electroless nickel plating solution or an electroless nickel alloy plating solution is used in step (2), it is preferred to further perform electroless palladium plating or electroless palladium alloy plating, and more preferably to continue further performing electroless gold plating or electroless gold alloy plating after that. In addition, when an electroless palladium plating solution or an electroless palladium alloy plating solution is used in step (2), it is preferred to further perform electroless gold plating or electroless gold alloy plating. In addition, in step (2), only an electroless palladium plating solution, an electroless palladium alloy plating solution, an electroless nickel plating solution, an electroless nickel alloy plating solution, an electroless silver plating solution, an electroless silver alloy plating solution, an electroless gold plating solution, or an electroless gold alloy plating solution can also be used.

[0091] By the method 2 of the present invention, an electroless plating film with more excellent plating precipitation property and patterning property (selective precipitation property) can be formed. By the method 2 of the present invention, a material for providing such an electroless plating film can be obtained. Specifically, a substrate having an insulating region and a conductive region on the surface, a material (substrate) having a metal catalyst 1 on the conductive region and a film 2 on the metal catalyst 1 and suppressing the formation of the metal catalyst 1 and / or the film 2 on the insulating region.

[0092] Examples

[0093] Examples and comparative examples are shown below to illustrate the present invention in more detail. However, the present invention is not limited to the examples.

[0094] (Preparation of catalyst-imparting solution)

[0095] The raw materials shown in Table 1 were sequentially added in the proportions shown in Table 1 to water as a solvent to prepare 500 mL of the catalyst-imparting solution for each example and comparative example.

[0096] (Evaluation test)

[0097] In the following evaluation test, after the object to be plated was pretreated (acid degreasing, soft etching), a catalyst core was formed on the metal surface by the prepared catalyst-imparting solution, and then, electroless nickel plating or electroless palladium plating was carried out first, and finally electroless gold plating was carried out in this order. The details of each treatment are as follows unless otherwise specified. A 1-minute running water washing treatment was carried out between each process.

[0098] (a) Acid degreasing

[0099] It was immersed in an acid degreasing solution (trade name: ICP Clean S-135K) containing sulfuric acid and a surfactant at 40 °C for 5 minutes.

[0100] (b) Soft etching

[0101] It was immersed 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.

[0102] (c) Catalyst-imparting treatment

[0103] Impregnate in the above catalyst-imparting liquid under the conditions shown in Table 1. Specifically, as the pH, 1 or less was used in Examples 1 to 41 and Comparative Examples 1 to 5, and 6.8 was used in Examples 42 to 48 and Comparative Example 6. In addition, as the impregnation time, 1 minute was used in Examples 1 to 34 and Comparative Examples 1 to 4, and 3 minutes was used in Examples 35 to 48 and Comparative Examples 5 and 6. As the treatment temperature, 30 °C was used in any of the catalyst-imparting liquids.

[0104] (d-1) Electroless nickel plating

[0105] Impregnate in an electroless nickel plating solution (trade name: ICP NICORON FPF, manufactured by Okuno Pharmaceutical Co., Ltd.) at 84 °C for 25 minutes to obtain a plating film with a film thickness of 4 μm.

[0106] (d-2) Electroless palladium plating

[0107] Impregnate 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 with a film thickness of 0.1 μm.

[0108] (e) Electroless gold plating

[0109] Impregnate in an electroless gold plating solution (trade name: TOP PALLAS AU, manufactured by Okuno Pharmaceutical Co., Ltd.) at 80 °C for 1 minute to obtain a plating film with a film thickness of 0.05 μm.

[0110] Test Example 1: Evaluation of plating deposition property

[0111] As the object to be plated, prepare a BGA resin substrate having micro copper pads with a resist pattern ([ (number of pads: 30) on a resin substrate. Perform electroless plating on this BGA resin substrate using the above treatment process. For the micro pads after electroless plating, observe the precipitation state of the electroless plating by microscopic observation (300 times). Evaluate according to the following evaluation criteria.

[0112] 〇: No precipitation was observed at all.

[0113] △: Only a slight amount of non-precipitation was confirmed.

[0114] ×: A large amount of non-precipitation occurred.

[0115] Test Example 2: Evaluation of patterning

[0116] As the object to be plated, a BGA resin substrate having fine wirings (L / S = 50 / 50 μm) on a resin base material was prepared. Electroless plating was performed on this BGA resin substrate using the above-described treatment process. For the wiring pattern portion with L / S = 50 / 50 μm after electroless plating, the presence or absence of plating expansion of the electroless plating was observed by microscopic observation (1000 times). Evaluation was performed according to the following evaluation criteria.

[0117] 〇: There is no plating expansion at all.

[0118] △: Plating expansion was slightly confirmed only.

[0119] ×: A large amount of plating expansion occurred.

[0120] The results are shown in Tables 1 to 7.

[0121] [Table 1]

[0122]

[0123] [Table 2]

[0124]

[0125] [Table 3]

[0126]

[0127] [Table 4]

[0128]

[0129] [Table 5]

[0130]

[0131] [Table 6]

[0132]

[0133] [Table 7]

[0134]

Claims

1. A catalyst-applying liquid for electroless plating, characterized in that: contain: (A) at least one cationic compound selected from cationic polymers and cationic surfactants, and (B) a metal catalyst, The (B) metal catalyst comprises at least one selected from the group consisting of Pd, Au, Ag and Pt, The pH of the electroless plating catalyst application liquid is 5 or less, The content of the cationic compound (A) is 0.01 mg / L to 1000 mg / L, The content of the (B) metal catalyst is 0.01 mg / L to 100 mg / L.

2. The catalyst imparting liquid according to claim 1, characterized in that: The (A) cationic compound comprises at least one selected from polyethyleneimine, diallyldimethylammonium chloride sulfur dioxide copolymer, methyldiallylamine hydrochloride polymer, diallyldimethylammonium chloride polymer, dicyandiamide-polyalkylene polyamine condensation product, dicyandiamide type cationic resin, allylamine hydrochloride-diallylamine hydrochloride polymer, allylamine hydrochloride polymer, allylamine polymer, O-[2-hydroxy 3-(trimethylammonium)propyl]hydroxyethylcellulose chloride, polylysine, cationized guar gum, coconut amine acetate, tetradecylamine acetate, octadecylamine acetate, didecyldimethylammonium chloride, coconut alkyltrimethylammonium chloride, hexadecyltrimethylammonium chloride and stearyltrimethylammonium chloride.

3. The catalyst imparting liquid according to claim 1, characterized in that: The (B) metal catalyst comprises Pd.

4. The catalyst imparting liquid according to claim 1, characterized in that: The composition further contains (C) at least one acid selected from the group consisting of organic acids and inorganic acids.

5. The catalyst imparting liquid according to claim 4, characterized in that: The (C) acid includes at least one selected from acetic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, glycolic acid, lactic acid, malic acid, gluconic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, methanesulfonic acid, glutamic acid, aspartic acid and boric acid.

6. The catalyst imparting liquid according to claim 1, characterized in that: It also contains (D) chloride.

7. The catalyst imparting liquid according to claim 6, characterized in that: The (D) chloride includes at least one selected from the group consisting of potassium chloride, sodium chloride, ammonium chloride, calcium chloride, magnesium chloride, lithium chloride, chloral and chlorine dioxide.

8. The catalyst imparting liquid according to claim 6, characterized in that: The content of the (D) chloride is 0.01 g / L to 200 g / L.

9. The catalyst imparting liquid according to claim 1, characterized in that: The electroless plating is at least one selected from the group consisting of electroless palladium plating, electroless palladium alloy plating, electroless nickel plating, electroless nickel alloy plating, electroless silver plating, electroless silver alloy plating, electroless gold plating, and electroless gold alloy plating.

10. The catalyst imparting liquid according to claim 1, characterized in that: The electroless plating is performed on a substrate having an insulating region and a conductive region on its surface.

11. A method for imparting a catalyst for electroless plating, characterized in that: include: (1) A step of bringing the catalyst-imparting liquid according to any one of claims 1 to 10 into contact with an object to be plated.

12. An electroless plating method, characterized in that: Including in order: (1) a step of bringing the catalyst imparting liquid according to any one of claims 1 to 10 into contact with an object to be plated; and (2) A step of performing an electroless plating treatment.

13. A substrate to which a catalyst is imparted by the catalyst imparting method according to claim 11.

14. A substrate subjected to electroless plating by the electroless plating method according to claim 12.

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