KR20160140455A - Replacement nickel plating bath for the copper surface treatment, manufacturing method of the copper parts of using the plating bath and the copper parts - Google Patents

Abstract

According to a copper component such as a multi-layer wiring substrate and a lead frame, adhesion between a copper base material and an insulating resin is improved. According to the copper component, nickel plating bath forms a nickel film improving adhesion between the copper base material and a resin material on a surface of the copper base material, and replacement nickel plating bath for copper surface treatment contains a complexing agent without containing a reducing agent and additionally contains a specific hydrophilic polymer compound and a silane coupling agent. The replacement plating bath enables a replacement nickel film to be interposed and enables the copper base material and the insulating resin material to be laminated thereon, thereby significantly improving adhesion between the copper base material and the resin material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a replacement nickel plating bath for copper surface treatment, a method of manufacturing a copper component using the plating bath, and a copper component,

The present invention relates to a replacement nickel plating bath for copper surface treatment, a process for producing a copper component using the plating bath, and a copper component having a copper base coated with a resin for insulation, A multilayer wiring substrate is provided with a nickel film using a substitution nickel bath interposed between a copper substrate and a resin material to improve the adhesion between the nickel substrate and the multilayer wiring substrate.

Conventionally, a general multilayer wiring board (build-up wiring board) is manufactured by laminating an inner layer substrate having a conductive layer made of copper on its surface portion with an insulating resin material interposed therebetween and another innerlayer substrate. Between the conductive layers, the air holes are electrically connected by copper-plated through holes.

Here, with respect to the wiring of the multilayer wiring board, the copper layer used for the surface portion of the innerlayer substrate is required to have adhesion with a resin material. Therefore, in order to improve the adhesion between the surface of the copper layer and the resin material, the surface treatment of the copper layer is generally performed.

Examples of the surface treatment method of the copper layer include a method in which the surface of the copper layer is etched with copper chloride, hydrogen sulfide / hydrogen peroxide or the like to roughen the surface of the copper layer to form an irregular oxide film. According to this method, when the oxide film of irregular shape is pierced into the resin material, an anchor effect is generated, and the adhesion between the copper layer and the resin material is improved.

Another method for improving the adhesion between the copper layer and the resin material is to treat the roughened surface of the copper layer with a tin or silane coupling agent.

On the other hand, in recent years, it is required to reduce the thickness of the multilayer wiring board in response to the miniaturization and thinning of electronic devices and electronic parts. In addition, in response to high frequency and high density of electronic devices and electronic components, fine) is also required.

In such a situation, when the surface of the copper layer of the multilayer wiring board is roughened, there is a problem that the surface current flowing to the multilayer wiring board causes electrical loss and signal delay.

Hereinafter, a method for improving the adhesion between the copper layer and the resin material, such as the multilayer wiring board, without performing the roughing treatment such as etching is listed below.

(1) Patent Document 1

In order to improve adhesion between the copper layer and the insulating resin, a plating solution containing a first tin salt is immersed on the surface of the copper layer to form a copper alloy layer containing copper and tin, and then a coating of a silane coupling agent is formed (Claim 2, Example 1 (paragraphs 25 to 26)).

(2) Patent Document 2

A tin plating layer is formed on the surface of the copper layer in order to adhere the copper layer and the insulating resin layer such as a multilayer wiring board (claims 1 to 6, paragraphs 9 and 11).

An aqueous solution containing an acid, a second tin salt, a complexing agent (thiourea, etc., paragraph 15), a stabilizer (ethylene glycol etc., paragraph 16), a complex formation inhibitor (phosphoric acids, hypophosphoric acids, Forming liquid can suppress deterioration with time of the formation performance of the adhesive layer and ensure smoothness of the surface of the adhesive layer (claim 1, paragraph 11).

(3) Patent Document 3

This is a similar technique of Patent Document 2.

Wherein the adhesive layer forming liquid is an aqueous solution containing an acid, a first tin salt, a second tin salt, a complexing agent, and a stabilizer, wherein the mass% ratio of the first tin salt and the second tin salt is specified (claims 1 to 5, 8, 11).

(4) Patent Document 4

This is an extension technique of Patent Document 2.

The adhesive layer-forming liquid is preferably a mixture of an acid, a tin salt (or a tin oxide), a third metal salt or an oxide (silver, nickel, zinc), a reaction promoter (thiourea etc.) ), And a resin adhesive layer composed of an alloy of tin and a third metal is formed on the surface of the copper to improve the adhesion between the copper and the resin (claims 1, 10, 12, paragraph 8).

(5) Patent Document 5

An adhesive layer is formed between the copper layer and the insulating resin layer by using a surface treatment agent containing a tin compound and a hydrophilic polymer compound having an epoxy group and a carboxyl group (claim 1).

The hydrophilic polymer compound having an epoxy group and a carboxyl group can be produced by, for example, reacting a silane coupling agent having an epoxy group with a hydrophilic polymer having a carboxyl group (poly (meth) acrylate, (meth) acrylate copolymer, (Claim 2, paragraphs 36-39).

The hydrophilic polymer compound is incorporated in the tin layer deposited on the copper surface to form a crosslinked structure (functional group (carboxyl group) of the tin layer and the polymer compound and is firmly bonded (paragraph 17). Further, (Or hydrogen bond) to the insulating resin layer (paragraph 15).

In Example 1, a copper surface treatment agent is prepared by mixing an epoxy silane-modified polyacrylate as a hydrophilic polymer compound with stannous sulfate, thiourea and methanesulfonic acid (paragraphs 98 to 101 and 107).

(6) Patent Document 6

The adhesive layer is formed between the copper layer and the insulating resin layer using a surface treatment agent containing a tin compound and a hydrophilic polymer compound having a functional group such as an epoxy group, silanol group or amino group One).

The hydrophilic polymer is a polyacrylate, an acrylate copolymer, an epoxy silane modified acrylate, or the like (paragraphs 55 to 56 of claims, examples 14 to 16)

The polymer compound forms a crosslinked structure with the tin deposited on the copper surface and is incorporated into the tin, and the functional group of the polymer compound forms a hydrogen bond or a covalent bond with the resin layer (insulating layer) to provide sufficient adhesion to the copper and the resin layer It is possible to treat the copper surface smoothly without roughing treatment (paragraphs 14 to 15, 17).

The surface treating agent of Example 1 includes stannous sulfate, thiourea, and polyacrylate. In Example 15, it includes stannous sulfate, thiourea, epoxy silane-modified polyacrylate, and hydrogen fluoride.

As a technique similar to that of Patent Document 6, there are Patent Documents 7 to 9.

Japanese Patent Laid-Open No. 2009-019266 Japanese Patent Laid-Open No. 2010-013516 Japanese Patent Laid-Open No. 2010-111748 Japanese Patent Application Laid-Open No. 2005-023301 Japanese Patent Laid-Open No. 2011-168888 Japanese Re-publication 2010/010716 Bulletin Japanese Patent Publication No. 2009/110364 Japanese Patent Application Laid-Open No. 2009-235565 Japanese Patent Laid-Open No. 2010-150613

Patent Document 1 discloses that a silane coupling agent coating film is laminated after forming a substitutional tin coating for adhesion on the surface of a copper substrate in order to improve the adhesion between the copper substrate and the insulating resin (Example 1, 2). Patent Documents 2 to 4 are to form a tin or tin alloy coating film for bonding on the copper substrate surface in order to increase the adhesion between the copper substrate and the insulating resin.

Patent Documents 5 to 9 disclose a method for increasing the adhesion between a copper substrate and an insulating resin

(1) a coating film comprising a tin compound and a hydrophilic polymer compound having an epoxy group and a carboxyl group (for example, an epoxy silane-modified polyacrylate or the like)

or

(2) A coating film of a tin compound and a surface treatment agent containing a hydrophilic polymer compound such as polyacrylate is formed on the copper base surface.

However, in Patent Document 1, since the coating of the silane coupling agent is laminated after the tin coating is formed on the copper substrate, the treatment is complicated and not only the productivity is poor, but also the adhesion between the copper base and the insulating resin is sufficient There is no problem. Patent Documents 2 to 4 are also similar in that the adhesion is not sufficient.

With respect to Patent Documents 5 to 9, although the complication of the same treatment as in Patent Document 1 can be solved, the adhesiveness between the copper base and the insulating resin still remains insufficient.

It is a technical object of the present invention to improve the adhesion between a copper substrate such as a multilayer wiring board and a resin for insulation by means different from the above-described Patent Documents 1 to 9.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The inventors of the present invention have found that, by using the above-described Patent Documents 1 to 9, particularly Patent Documents 5 to 6 as a starting point, it is possible to deposit a substituted nickel film, which is not a tin film, Compound or a silane coupling agent are coexisted to form a film on the copper foil, the adhesion between the copper foil and the insulating resin remarkably improves, thereby completing the present invention.

In other words, the present invention 1 is a copper component in which a copper substrate is coated with an insulating resin material,

A plating bath for depositing a nickel film on the surface of the copper base facing the resin material to improve the adhesion between the copper base and the resin material,

(A) a soluble nickel salt,

(B) an acid or a salt thereof selected from an inorganic acid and an organic acid,

(C) Thiourea

, And contains no reducing agent,

and a pH of 7 or less.

A second aspect of the present invention is the second aspect of the present invention, wherein the copper base is a copper layer, the resin material is a resin layer,

Wherein the copper component is a copper laminated board in which a copper layer and a resin layer are laminated.

In the present invention 3, the plating bath may further comprise at least one functional group selected from the group consisting of an amino group, an epoxy group, a mercapto group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, And / or a silane coupling agent. The present invention relates to a substituted nickel plating bath for copper surface treatment, which comprises a hydrophilic polymer compound having a branch and / or a silane coupling agent.

A fourth aspect of the present invention is the fourth aspect of the present invention, wherein the hydrophilic polymer is at least one selected from the group consisting of poly (meth) acrylate, (meth) acrylate copolymer, polymaleic acid,

Wherein the silane coupling agent is at least one selected from the group consisting of a silane coupling agent having an amino group, a mercapto group, a vinyl group, a styryl group, a methacrylic group, an acryl group, an anionate group or an epoxy group, and a hydrophilic polymer compound modified with the silane coupling agent Wherein the nickel plating bath is a substituted nickel plating bath for copper surface treatment.

A fifth aspect of the present invention is a method of manufacturing a copper plating solution, comprising the steps of: forming a nickel coating on a copper base surface using a substitution plating bath according to any one of the first to fourth inventions; and coating the copper base with a resin material through the nickel coating Wherein the copper component is a copper component.

The present invention 6 is a copper part obtained by forming a nickel coating film on a copper base surface by using the displacement plating bath of any one of the above-mentioned inventions 1 to 4 and coating the copper base with a resin material through the nickel coating film .

According to the first aspect of the invention, since the resin layer is laminated on the nickel film deposited on the copper base surface by applying the substituted nickel plating bath to the copper base surface, the copper base of the copper part and the insulating layer The adhesion of the resin layer can be improved, and the reliability of the copper component can be enhanced.

In this case, if a nickel film is formed on the copper substrate by applying an electroless nickel plating bath containing a reducing agent, a firm adhesion between the copper substrate such as a substituted nickel film (not containing a reducing agent) and the insulating resin can not be obtained , It is important that the plating bath applied to the copper substrate is a substituted nickel plating bath rather than a reduced electroless nickel plating bath. However, the detailed mechanism of difference in adhesion between the reduced nickel bath and the substituted nickel bath is not clear.

Further, in the present invention 2, since the silane coupling agent and / or the specific hydrophilic polymer compound are used together with the liquid composition of the substituted nickel, the silane coupling agent or the like forms a crosslinked structure with the nickel film deposited on the copper base surface , And is brought into close contact with the nickel layer. The functional group of the silane coupling agent or the like is hydrogen bonded or covalently bonded to the resin layer to be in close contact with the resin layer. This further improves the adhesion between the copper layer and the resin layer.

In the substitutional plating baths of the present invention 1 and 2, the thioureas are complexed with copper to displace the electrode potential in the reduction (minus) direction, and the electrode potentials of nickel and copper (in particular, copper complexes) Nickel is precipitated on the surface of the copper layer even if there is no reducing agent in the plating bath (that is, no electron is donated to the nickel ion) because the electrode potential of the copper layer becomes positive with respect to copper.

In addition, in JP-A-6-101054 (hereinafter referred to as Prior Art 1), an electroless plating film (nickel, palladium, nickel-palladium, etc., see paragraphs 2, 52 and 54) is formed on the surface of a copper- A catalyst solution as a pretreatment agent for carrying out the present invention includes a soluble nickel salt and a thiourea.

Although the catalyst liquid component of this prior art document 1 overlaps with the replacement nickel plating bath of the present invention, in the prior art document 1, the presence or absence of formation of a nickel film by the catalytic treatment is unclear (since the catalytic action is exerted, And it is presumed to be the degree of particle adhesion), and it is different from the present invention in that it is an electroless metal plating layer (nickel, palladium, etc.) rather than a resin layer formed on the copper-

The present invention relates to a nickel plating bath for forming a nickel coating film which improves the adhesion between a copper base and a resin material by precipitating on a copper base surface, A substitution nickel plating bath for copper surface treatment which does not contain a reducing agent and secondly contains a specific hydrophilic polymer compound and a silane coupling agent in addition to the substituted nickel plating bath. Third, A nickel film is deposited on the copper foil, and then the copper foil is coated with an insulating resin material. Fourth, the copper part is the copper part.

The insulating resin is an epoxy resin, a polyimide resin, a phenol resin, a polyurethane resin, or the like.

The copper component refers to a multilayer wiring board in which a copper layer and a resin layer are laminated in multiple layers, a lead frame covered with an insulating resin, or a copper foil, a copper lead wire coated with a resin, or the like.

The essential component of the substituted nickel plating bath of the present invention 1 is,

(A) a soluble nickel salt,

(B) an acid selected from an inorganic acid and an organic acid or a salt thereof,

(C) thioureas.

As the soluble nickel salt (A), any soluble salt capable of generating nickel ion in an aqueous solution can be used, and there is no particular limitation, and insoluble salts are not excluded. Specific examples thereof include nickel sulfate, nickel oxide, nickel chloride, nickel ammonium sulfate, nickel acetate, nickel nitrate, nickel carbonate, nickel sulfamate or nickel salts of organic sulfonic acid and carboxylic acid. Nickel Nickel and the like are preferable.

The acid or its salt (B) is a bath based on an organic acid bath, an inorganic acid bath, an alkali metal salt thereof, an alkaline earth metal salt, an ammonium salt, an amine salt or the like.

Examples of the organic acid include an organic sulfonic acid and an aliphatic carboxylic acid. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, acetic acid, sulfamic acid, hydrofluoric acid, and hydrous silicic acid.

The organic sulfonic acid may be an alkanesulfonic acid, an alkanesulfonic acid, a sulfosuccinic acid, an aromatic sulfonic acid or the like, and the alkanesulfonic acid may be represented by the formula C _n H _{2n + 1} SO ₃ H (for example, n = 1 to 11) Specific examples thereof include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid and pentanesulfonic acid.

As the alkanol sulfonic acid,

C _m H _{2m + 1} -CH (OH) -C _p H _2p -SO ₃ H (for example, m = 0 to 6, p = 1 to 5) Hydroxypropane-1-sulfonic acid (2-propanol sulfonic acid), 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentane-1-sulfonic acid, etc. Hydroxypropane-1-sulfonic acid, 4-hydroxybutane-1-sulfonic acid, 2-hydroxyhexane-1-sulfonic acid, and the like.

The aromatic sulfonic acid is basically selected from the group consisting of benzenesulfonic acid, alkylbenzenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid and naphthosulfonic acid. Specific examples of the aromatic sulfonic acid include 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, toluenesulfonic acid, Phenolsulfonic acid, cresol sulfonic acid, sulfosalicylic acid, nitrobenzenesulfonic acid, sulfobenzoic acid, diphenylamine-4-sulfonic acid and the like.

Among the above organic sulfonic acids, methanesulfonic acid, ethanesulfonic acid, 2-propanol sulfonic acid, 2-hydroxyethanesulfonic acid and the like are preferable.

Specific examples of the aliphatic carboxylic acid include oxycarboxylic acid, polycarboxylic acid, and monocarboxylic acid. Specific examples thereof include gluconic acid, citric acid, glucoheptanoic acid, gluconolactone, glucoheptolactone, formic acid, acetic acid, , Oxalic acid, malonic acid, succinic acid, glycolic acid, lactic acid, malic acid, tartaric acid, diglycolic acid and the like.

As the acid, organic sulfonic acid, lactic acid, malic acid, glycolic acid, sulfamic acid and the like are suitable, and lactic acid, malic acid and the like are preferable from the viewpoint of smooth plating progress and precipitation after the bathing.

The acid or its salt may be used singly or in combination, and the content of substituted nickel bath is 1 to 500 g / L, preferably 3 to 300 g / L.

The thioureas (C) are thiourea and thiourea derivatives.

Examples of thiourea derivatives include 1,3-dimethylthiourea, trimethylthiourea, diethylthiourea, N, N'-diisopropylthiourea, allylthiourea, acetylthiourea, Diphenylthiourea, thiourea dioxide, thiosemicarbazide, and the like.

The thioureas may be used singly or in combination. The content of the thioureas relative to the substituted nickel bath is 5 to 300 g / L, preferably 10 to 250 g / L.

The substituted nickel plating bath may contain various additives such as nonionic, amphoteric, cationic and anionic surfactants and pH adjusters in addition to the above essential components.

Examples of the nonionic surfactant include C1-C20 alkanol, phenol, naphthol, bisphenols, (poly) C1-C25 alkylphenol, (poly) arylalkylphenol, C1-C25 alkylnaphthol, (EO) and / or propylene oxide (PO) are condensed with 2 to 300 moles of the compound (salt), sorbitan ester, polyalkylene glycol, C1-C22 aliphatic amine and C1- C25 alkoxylated phosphoric acid (salt), and the like.

Examples of the cationic surfactant include quaternary ammonium salts and pyridium salts. Specific examples thereof include lauryltrimethylammonium salt, stearyltrimethylammonium salt, lauryldimethylethylammonium salt, octadecyldimethylethylammonium salt, dimethylbenzylamine, There may be mentioned ammonium salts such as ammonium, cetyldimethylbenzylammonium salts, octadecyldimethylbenzylammonium salts, trimethylbenzylammonium salts, triethylbenzylammonium salts, dimethyldiphenylammonium salts, benzyldimethylphenylammonium salts, hexadecylpyridinium salts, laurylpyridinium salts, dodecylpyridinium salts , Stearylamine acetate, laurylamine acetate, octadecylamine acetate, and the like.

Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkylbenzenesulfonates, and {(mono, di (tri) alkyl} naphthalenesulfonates.

Examples of the amphoteric surfactant include carboxybetaine, imidazo betaine, sulfobetaine, aminocarboxylic acid, and the like. Sulfation or sulfonation products of condensation products of ethylene oxide and / or propylene oxide with alkyl amines or diamines can also be used.

The surfactant is preferably a nonionic surfactant, and the content of the surfactant in the substituted nickel bath is 0.3 to 50 g / L, preferably 0.5 to 20 g / L.

Examples of the pH adjuster include bases such as various acids such as hydrochloric acid, sulfuric acid, acetic acid, oxalic acid and formic acid, ammonia water, sodium hydroxide, potassium hydroxide, ammonium hydroxide and amines.

The pH of the substituted nickel bath of the present invention is 7 or less, and does not include the strongly alkaline region.

Further, since the nickel plating bath of the present invention is a substituted nickel bath, it does not contain a reducing agent.

The reducing agent is a hypophosphorous acid, a phosphorous acid, an amine borane, a hydrogenated boron compound, a hydrazine or the like.

Examples of the hypophosphorous acids and hypophosphoric acids include hypophosphorous acid, phosphorous acid, and salts thereof.

Examples of the amine borane include dimethylamine borane, diethylamine borane, trimethylamine borane, phosphorus propylamine borane, and morpholine borane.

Examples of the borohydride compound include sodium borohydride and potassium borohydride.

Examples of the hydrazine derivatives include hydrazine hydrate, hydrazine hydrochloride, and phenylhydrazine.

Therefore, the nickel bath of the present invention is characterized by a substituted nickel bath which does not contain the reducing agent.

Meanwhile, the substituted nickel plating bath of the present invention 2 contains at least one of a specific hydrophilic polymer compound and a silane coupling agent in addition to the substitution nickel bath of the present invention 1.

The hydrophilic polymer compound may be a water-soluble polymer compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, a mercapto group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group and an imino group, , And 0.1% by weight of water at 25 占 폚 water for 24 hours or more, and a hydrophilic polymer compound having a carboxyl group is preferable.

The hydrophilic polymer compound having a carboxyl group may be selected from poly (meth) acrylate, (meth) acrylate copolymer, polymaleic acid, polytetarboxylic acid and the like. Here, (meth) acrylate means acrylate and methacrylic acid.

The (meth) acrylate copolymer is obtained by copolymerizing (meth) acrylate with a hydrophilic monomer such as maleic acid, itaconic acid, fumaric acid, 2-acrylamide-2-methylpropanesulfonic acid and the like, 2-hydroxyethyl methacrylate, (Meth) acrylamides such as acrylamide, N-methylol acrylamide and methacrylamide, and the like; hydrophobic monomers such as hydroxypropyl acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate, And at least one of acrylonitrile, acrylonitrile, diallyl, glycidyl methacrylate, and acrylonitrile is reacted.

When the hydrophilic polymer having a carboxyl group has a functional group other than a carboxyl group, the decrease in adhesion after being exposed for a long time under high temperature and high humidity is further suppressed.

The silane coupling agent may be selected from the following (1) to (2).

(1) A silane coupling agent having an amino group, a mercapto group, a vinyl group, a styryl group, a methacryl group, an acryl group, an isocyanate group or an epoxy group

(2) a hydrophilic polymer compound modified with the silane coupling agent

Examples of the silane coupling agent having an epoxy group in the silane coupling agent (1) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltri Lt; / RTI >

Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl- -Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and the like.

Examples of the silane coupling agent having an acryl group include 3-acryloxypropyltrimethoxysilane and the like.

Examples of the methacrylic group-containing silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane.

Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

Examples of the silane coupling agent having an isocyanate group include 3-isocyanatepropyltriethoxysilane and the like.

The hydrophilic polymer compound (2) modified with a silane coupling agent is a compound obtained by reacting the silane coupling agent with the hydrophilic polymer compound. For example, the hydrophilic polymer compound (2) modified by an epoxy silane coupling reaction with a silane coupling agent having an epoxy group and a polyacrylate Polyacrylate, and the like.

For example, in the reaction of a silane coupling agent having an epoxy group with a hydrophilic polymer having a carboxyl group, the reaction is carried out in the presence of a catalyst such as tetrabutylammonium bromide at a heating temperature of 80 to 95 ° C and a reaction time of 10 to 180 hours do. By conducting the reaction in water, the alkoxy group of the silane coupling agent is hydrolyzed with a silanol group.

The weight average molecular weight of the hydrophilic polymer compound or the silane coupling agent is generally 2,000 to 10,000,000, preferably 10,000 to 1,000,000.

If the weight average molecular weight is smaller than the proper range, there is a fear that the smooth coating film formation on the copper foil will be hindered. If the weight average molecular weight is larger than the proper range, the viscosity of the substituted nickel liquid mixed with the hydrophilic polymer compound or the silane coupling agent increases, There is a possibility of causing it.

The content of the hydrophilic polymer compound or the silane coupling agent to the substituted nickel liquid of the present invention is 0.5 to 300 g / L, preferably 2 to 200 g / L, more preferably 3 to 100 g / L.

If the content of the hydrophilic polymer compound or the silane coupling agent is less than the proper range, there is a fear that the adhesion strengthening action between the nickel film and the insulating resin material becomes insufficient. If the content is larger than the proper range, the adhesion between the copper foil and the nickel film is reduced .

A fifth aspect of the present invention is a method for manufacturing a copper part comprising a step of forming a nickel coating on a copper base surface using the above displacement plating bath and a step of covering the copper base with a resin material through the nickel coating, 6 is the copper part obtained by the method.

As described above, the copper component of the present invention is typically a multilayer wiring board (build-up wiring board) in which a copper layer and a resin layer are laminated in multilayers. The copper wiring board includes a flexible substrate formed of copper foil, A resin-coated copper lead wire, a copper foil with a resin, and the like.

As described above, the insulating resin may be an epoxy resin, a polyimide resin, a phenol resin, a polyurethane resin, a bismaleimide triazine resin, a modified polyphenylene ether resin, a cyanate ester resin, a benzocyclobutene resin, Fluorinated resins, modified products of these resins with various functional groups, glass fibers, aramid fibers, reinforcing materials by other fibers, and the like.

When the copper substrate is replaced with a substituted nickel plating bath of the present invention, the plating temperature is 10 to 70 캜, preferably 20 to 50 캜, and the plating time is 30 to 15 minutes, preferably 1 to 5 minutes.

This plating condition is the case of only the substituted nickel bath and the case of adding the hydrophilic polymer or the silane coupling agent to the substituted nickel bath, and there is no particular change.

The pH of the substituted nickel bath is 7 or less, preferably 6 or less, and more preferably 5 or less.

The plating temperature for substituting the copper substrate with the substituted nickel plating bath of the present invention is 10 to 70 캜, preferably 20 to 50 캜, and the plating time is 30 to 15 minutes, preferably 1 to 5 minutes.

This plating condition is not particularly changed when the hydrophilic polymer or the silane coupling agent is added to the substituted nickel bath alone or the substituted nickel bath.

The pH of the substituted nickel bath is 7 or less, preferably 6 or less, and more preferably 5 or less.

For example, the basic principle of manufacturing a copper-clad laminate, which is a simplified model of a multilayer wiring board, will be described. The copper foil, which is the object to be plated, is acid-cleaned beforehand to clean the surface- Subsequently, a substituted nickel plating treatment is performed to form a substituted nickel coating on the surface of the copper foil, followed by washing with water and drying, coating a substrate (for example, a glass epoxy resin substrate) with an insulating resin layer, The multilayer wiring board is manufactured by laminating the above-mentioned substrate on which the copper foil and the resin are adhered, with the nickel film interposed therebetween, with the stratum in contact with the nickel film.

The multilayer wiring board is manufactured by laminating and pressing an inner layer board having a conductive layer made of copper on its surface portion with another resin layer interposed therebetween with an insulating resin. In the present invention, a laminate type build- up board of a sequential build-up type.

In this case, the multilayer wiring board includes an outer layer substrate and a single layer substrate having a copper material on the outermost layer. The outer layer substrate may include one or both of the outer layer substrates provided on one or both surfaces of the outermost layer of the copper material.

The thickness of the substituted nickel film formed on the copper substrate is 0.001 to 3.0 탆, preferably 0.002 to 2.0 탆, more preferably 0.005 to 1.0 탆.

If the film thickness is thinner than the proper range, there is a possibility that the adhesion with the copper substrate is lowered. Conversely, even if the film thickness is thicker than the proper range, the adhesion strength does not change so much, which is a waste of cost. However, if it is within an appropriate range, it is possible to sufficiently secure the adhesion while being thin.

[Example]

Production examples in which a copper-clad laminate was produced by using each of the substituted nickel baths of Examples and Examples of the replacement nickel plating bath for copper surface treatment of the present invention, Evaluation Tests (Comparative Examples 1 and 2) for evaluating the peeling strength Respectively.

Here, the present invention is not limited to the following examples, production examples and test examples, and it goes without saying that certain modifications may be made within the scope of the technical idea of the present invention.

<Examples of Substituted Nickel Plating Bath for Copper Surface Treatment>

Of the following Examples 1 to 28, Examples 1 to 15 are examples of only substituted nickel plating baths, Examples 16 to 28 are examples of hydrophilic polymer compounds and / or silane coupling agents in a substituted nickel plating bath of any one of Examples 1 to 15 Ring agent is added in combination.

Of the above Examples 1 to 15, Examples 5 and 12 are examples in which a substituted nickel bath contains a nonionic surfactant, and the other examples are those containing no surfactant. Example 10 is an example in which two kinds of acids (glycolic acid and lactic acid) are used in combination.

Of the above Examples 16 to 28, Example 16 is an example in which polyacrylate (hydrophilic polymer) is contained in the substituted nickel plating bath of Example 3, Example 17 is a case of containing a silane coupling agent having an epoxy group in Example 3 As an example, Example 18 contains an epoxy silane modified polyacrylate in Example 3, Example 19 contains polyacrylate in Example 6, Example 20 contains an amino group-containing silane in Example 6 Example 21 is an example containing a mixture of a silane coupling agent having a mercapto group and a silane coupling agent having an incinerate group in Example 6, Example 22 is an example containing a mixture of an epoxy silane modified acrylic Example 23 contains an acrylate copolymer in Example 10, Example 24 contains an amino-modified epoxy resin in Example 10, Example 25 contains an acrylate copolymer in Example 10, Silane coupling agent having a mercapto group And a silane coupling agent having an epoxy group, Example 26 is an example containing a mixture of a silane coupling agent having a mercapto group and a silane coupling agent having an amino group in Example 15, Example 27 is an example containing a mixture of a silane coupling agent having a mercapto group and an amino group, Containing polyacrylate and a silane coupling agent having an epoxy group, Example 28 is an example of containing polyethyleneimine in Example 10.

On the other hand, of the following Comparative Examples 1 to 4, Comparative Example 1 is an example based on Patent Documents 2 to 4 described above as a substituted tin plating bath. Comparative Example 2 is an example of a reduced electroless nickel plating bath and is common to a substituted nickel bath in that it belongs to a broad electroless nickel plating bath, but is different from a substituted nickel bath in that it contains a reducing agent. Comparative Example 3 is an example in which a polyacrylate (hydrophilic polymer) was added to the reduced electroless nickel bath of Comparative Example 2 in combination. Comparative Example 4 is a blank example in which no plating film is formed between the copper base and the insulating resin layer.

(1) Example 1

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

10 g / L of nickel methanesulfonate (as Ni ²⁺ )

Methanesulfonic acid 35 g / L

Thiourea 100 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.03 m]

(2) Example 2

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Nickel sulfate (as Ni ²⁺ ) 20 g / L

Sulfuric acid 25 g / L

Thiourea 100 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.04 m]

(3) Example 3

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Sulphamic acid nickel (as Ni ^{2 +} ) 30 g / L

Sulfamic acid 50 g / L

Thiourea 100 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.06 m]

(4) Example 4

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Nickel sulfate (as Ni ²⁺ ) 20 g / L

Glycolic acid 50 g / L

Thiourea 100 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.04 m]

(5) Example 5

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Nickel sulfate (as Ni ²⁺ ) 20 g / L

Malic acid 100 g / L

Thiourea 100 g / L

Tristylated phenol polyethoxylate (EO 20 moles) 1 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.05 m]

(6) Example 6

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Nickel sulfate (as Ni ²⁺ ) 20 g / L

Lactic acid 200 g / L

Thiourea 100 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.05 m]

(7) Example 7

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Sulphamic acid nickel (as Ni ^{2 +} ) 20 g / L

Malic acid 50 g / L

1,3-dimethylthiourea 100 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.06 m]

(8) Example 8

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Sulphamic acid nickel (as Ni ^{2 +} ) 20 g / L

Glycolic acid 35 g / L

1,3-diethylthiourea 100 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.04 m]

(9) Example 9

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Sulphamic acid nickel (as Ni ^{2 +} ) 20 g / L

Lactic acid 100 g / L

Trimethylthiourea 100 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.05 m]

(10) Example 10

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Sulphamic acid nickel (as Ni ^{2 +} ) 20 g / L

Glycolic acid 20 g / L

Lactic acid 80 g / L

Thiourea 100 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.03 m]

(11) Example 11

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Nickel sulfate (as Ni ^{2 +} ) 20 g / L

Lactic acid 150 g / L

Thiourea 50 g / L

1,3-diethylthiourea 30 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.05 m]

(12) Example 12

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Sulphamic acid nickel (as Ni ^{2 +} ) 50 g / L

Lactic acid 200 g / L

Thiourea 200 g / L

Laurylamine polyethoxylate (EO 15 moles) 1 g / L

pH (20 ℃) 2 or less

[Film thickness: 0.04 m]

(13) Example 13

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Sulphamic acid nickel (as Ni ^{2 +} ) 30 g / L

Glycolic acid 100 g / L

Thiourea 75 g / L

pH (20 캜, adjusted with ammonia) 4.0

[Film thickness: 0.05 m]

(14) Example 14

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Sulphamic acid nickel (as Ni ^{2 +} ) 30 g / L

Lactic acid 150 g / L

Thiourea 75 g / L

pH (adjusted at 20 캜 with sodium hydroxide) 5.0

[Film thickness: 0.05 m]

(15) Example 15

The substituted nickel plating bath was subjected to a bath bath under the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Sulphamic acid nickel (as Ni ^{2 +} ) 30 g / L

Methanesulfonic acid 50 g / L

Thiourea 75 g / L

pH (20 캜, adjusted with sodium hydroxide) 7.0

[Film thickness: 0.05 m]

(16) Example 16

The hydrophilic polymer was contained in the following nickel plating bath of Example 3 in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Polyacrylate (molecular weight 2000000) 25 g / L

[Film thickness: 0.06 m]

 (17) Example 17

A silane coupling agent having an epoxy group was contained in the substituted nickel plating bath of Example 3 in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

3-glycidoxypropyltriethoxysilane

(KBM403, manufactured by SHINETSU CHEMICAL INDUSTRIES CO., LTD.) 13 g / L

[Film thickness: 0.06 m]

(18) Example 18

First, an epoxy silane modified polyacrylate was prepared by the following method.

[Production of epoxysilane-modified polyacrylate]

89 parts by weight of deionized water was placed in a four-necked flask, and the mixture was heated to 80 占 폚. Next, 10 parts by weight of acrylate and 1 part by weight of 10% aqueous solution of sodium persulfate were added dropwise to the dropping funnel in deionized water in a four-necked flask over 60 minutes. Thereafter, aging was carried out for 60 minutes to obtain a polyacrylate having a solid content of 10% and a molecular weight of 20,000.

To 82.2 parts by weight of deionized water, 12.5 parts by weight of the polyacrylate as a hydrophilic polymer having a carboxyl group and 0.2 part by weight of tetrabutylammonium bromide as a catalyst were added and the temperature was raised to 80 占 폚. Subsequently, 5 parts by weight of 3-glycidoxypropyltriethoxysilane (KBM403, manufactured by SHINETSU KAGAKU KOGYO CO., LTD., Active ingredient 100%) as a coupling agent was uniformly added dropwise over 15 minutes and then reacted for 2 hours to give an epoxy silane- Polyacrylate was obtained.

[Solubilization of Substituted Nickel Plating Bath]

Subsequently, the above-mentioned epoxy silane-modified polyacrylate was contained in the replacement nickel plating bath of Example 3 in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Epoxy silane modified polyacrylate 15 g / L

[Thickness: 0.06 m]

(19) Example 19

The hydrophilic polymer was contained in the following nickel plating bath of Example 6 in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Polyacrylate (molecular weight 200000) 20 g / L

[Film thickness: 0.05 m]

(20) Example 20

A silane coupling agent having an amino group in the following ratio was contained in the substituted nickel plating bath of Example 6 above.

The film thickness of the nickel film formed by using the plating bath is as follows.

3-aminopropyltrimethoxysilane

(KBM903, manufactured by SHINETSU CHEMICAL INDUSTRIES CO., LTD.) 15 g / L

[Film thickness: 0.05 m]

(21) Example 21

First, a silane coupling agent mixture was prepared in the following manner.

[Preparation of silane coupling agent mixture]

3-mercaptopropyltrimethoxysilane (KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and an insocyanate silane (KBE9007, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a weight ratio of 1: 1 and diluted to 5% to obtain a mixture.

[Solubilization of Substituted Nickel Plating Bath]

Subsequently, the above-mentioned substituted nickel plating bath of Example 6 contained the silane coupling agent mixture in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Silane coupling agent mixture 20 g / L

[Film thickness: 0.05 m]

(22) Example 22

First, an epoxy silane modified acrylate copolymer was prepared by the following method.

[Preparation of epoxy silane modified acrylate copolymer]

89 parts by weight of deionized water was placed in a four-necked flask, and the mixture was heated to 80 占 폚. Next, a mixture of 7 parts by weight of acrylate and 3 parts by weight of acrylate-2-hydroxyethyl and 1 part by weight of a 10% aqueous solution of sodium persulfate was placed in a dropping funnel and uniformly added to deionized water in a four-necked flask over 60 minutes . Further, by aging for 60 minutes, a polyacrylate copolymer having a solid content of 10% and a molecular weight of 20,000 was obtained.

To 82.2 parts by weight of deionized water, 12.5 parts by weight of the above polyacrylate copolymer as a hydrophilic polymer having a carboxyl group and 0.2 part by weight of tetrabutylammonium bromide as a catalyst were added and the temperature was raised to 80 占 폚. Subsequently, 5 parts by weight of 3-glycidoxypropyltriethoxysilane (KBM403, Shin-Etsu Chemical Co., Ltd., effective component: 100%) as a coupling agent was uniformly added dropwise over 15 minutes and reacted for another 2 hours to obtain an epoxy silane- Acrylate copolymer.

[Solubilization of Substituted Nickel Plating Bath]

Subsequently, the above-mentioned substituted nickel plating bath of Example 6 contained the epoxy silane modified acrylate copolymer in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Epoxy silane modified acrylate copolymer 13 g / L

[Film thickness: 0.05 m]

(23) Example 23

First, an acrylate copolymer was prepared by the following method.

[Preparation of acrylate copolymer]

Was reacted with an acrylate: acrylate-2-hydroxyethyl = 7: 3 (molar ratio) according to a conventional method to obtain a copolymer of acrylate and acrylate-2-hydroxyethyl (molecular weight: 200,000).

[Solubilization of Substituted Nickel Plating Bath]

Subsequently, the above-mentioned acrylate copolymer was contained in the substituted nickel plating bath of Example 10 in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Acrylate copolymer 18 g / L

[Film thickness: 0.03 m]

(24) Example 24

In the substituted nickel plating bath of Example 10, a hydrophilic polymer compound was contained in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Amino-modified epoxy resin (Adeka Resin EP4100, manufactured by Adeka Co., Ltd.) 16 g / L

[Film thickness: 0.03 m]

(25) Example 25

First, a silane coupling agent mixture was prepared by the following method.

[Preparation of silane coupling agent mixture]

3-mercaptopropyltrimethoxysilane (KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-glycidoxypropyltriethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a weight ratio of 1: To obtain a mixture.

[Solubilization of Substituted Nickel Plating Bath]

Subsequently, the above-mentioned nickel plating bath of Example 10 contained the silane coupling agent mixture in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Silane coupling agent mixture 15 g / L

[Film thickness: 0.03 m]

(26) Example 26

First, a silane coupling agent mixture was prepared by the following method.

[Preparation of silane coupling agent mixture]

3-mercaptopropyltrimethoxysilane (KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Kagaku Kogyo) were mixed at a weight ratio of 1: 1 and diluted to 5% To obtain a mixture.

[Solubilization of Substituted Nickel Plating Bath]

Subsequently, the above-mentioned nickel plating bath of Example 15 contained the silane coupling agent mixture in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Silane coupling agent mixture 18 g / L

[Film thickness: 0.05 m]

(27) Example 27

First, a mixture of a polyacrylate and a silane coupling agent having an epoxy group was prepared by the following method.

[Preparation of silane coupling agent mixture having polyacrylate and epoxy group]

1% by weight of 3-glycidoxypropyltriethoxysilane (KBM403, Shin-Etsu Chemical Co., Ltd.) was added to 5% by weight of polyacrylate and stirred at room temperature for 30 minutes to obtain a silane coupling agent mixture having polyacrylate and epoxy group &Lt; / RTI &gt;

[Solubilization of Substituted Nickel Plating Bath]

Subsequently, the substituted nickel plating bath of Example 15 contained a silane coupling agent mixture having the polyacrylate and epoxy groups in the following ratios.

The film thickness of the nickel film formed by using the plating bath is as follows.

Silane coupling agent mixture 15 g / L

[Film thickness: 0.05 m]

(28) Example 28

The hydrophilic polymer compound was contained in the replacement nickel plating bath of Example 10 in the following ratio.

The thickness of the nickel film formed by using the plating bath is as follows.

Polyethyleneimine 15 g / L

[Film thickness: 0.03 m]

(29) Comparative Example 1

The substituted tin plating bath was conditioned with the following composition.

The film thickness of the tin film formed by using the plating bath is as follows.

30 g / L stannous methane sulfonate (as Sn ^{2 +} )

Methanesulfonic acid 100 g / L

Thiourea 100 g / L

[Film thickness: 0.08 m]

[Plating condition: 35 DEG C, 30 seconds]

(30) Comparative Example 2

A reducing electroless nickel plating bath (a plating bath containing a reducing agent) was subjected to a bath bath in the following composition.

The film thickness of the nickel film formed by using the plating bath is as follows.

Nickel sulfate · hexahydrate (as Ni ^{2 +} ) 5.6 g / L

Sodium hypophosphite monohydrate 30.0 g / L

Succinic acid 25.0 g / L

pH (adjusted at 20 캜 with sodium hydroxide) 4.6

[Film thickness: 0.2 m]

[Plating condition: 85 캜, 60 seconds]

(31) Comparative Example 3

A hydrophilic polymer compound was contained in the reduced electroless nickel plating bath of Comparative Example 2 in the following ratio.

The film thickness of the nickel film formed by using the plating bath is as follows.

Polyacrylate (molecular weight 2000000) 15 g / L

[Film thickness: 0.1 m]

[Plating condition: 85 캜, 60 seconds]

(32) Comparative Example 4

This is an example of a blank in which no plating film is formed between the copper foil and the insulating resin layer. Therefore, the plating bath was not conditioned.

&Lt; Production Example of Preparing Copper Laminates >

Here, using the substituted nickel baths of Examples 1 to 28 and the substituted tin plating baths or the reduced electroless nickel plating baths of Comparative Examples 1 to 3, a copper-clad laminate, which is a simplified model of a multilayer laminated board, was prepared.

That is, on the surface of electrolytic copper foil having a thickness of 50 탆, which had been washed with acid, washed with water and dried, each plating bath of the example or the comparative example was used and subjected to plating at 30 캜 for 3 minutes (in Comparative Examples 1 to 3, (According to the plating conditions shown at the end of each comparative example), a nickel coating film (tin coating film of Comparative Example 1) was deposited at the film thicknesses shown in the respective Examples and Comparative Examples, and an epoxy-based insulating material (FR-4 made by Panasonic Co., Ltd., plate thickness: 1.0 mm) having a double-sided copper-clad glass epoxy resin substrate on which a roughness treatment was carried out was superimposed on the surface of a copper foil / m ² in 0.5 hours -> 150 ℃, 30kg / m ² in 0.5 hours -> 180 ℃, and then heated at 30kg / m ² under the conditions of 1.5 hours laminating press, 80 ℃, and cooled under the conditions of 1.5 hours After completion of the press, the plate was cooled at 20 캜 for 20 minutes to produce a copper-clad laminate.

&Lt; Evaluation test example of peeling strength of copper-clad laminate &

Each copper-clad laminate produced by using the plating baths of Examples 1 to 28 and Comparative Examples 1 to 3 was evaluated as a sample, and the adhesion between the nickel coating (tin coating of Comparative Example 1) and insulating resin was evaluated.

Under the conditions of a load cell of 100 kg / m ² , a range of 2%, and a crosshead speed of 50 mm / min at a chart speed of 20 mm / min, in accordance with JIS-C-6481 with a universal testing machine (Tensilon manufactured by Japan A & (Peeling strength: kN / m) between the resin for insulation and the insulating resin was measured.

With respect to this adhesion, two types of adhesion were tested: initial adhesion and adhesiveness when the sample was subjected to HAST (Highly Accelerated Temperature and humidity Stress Test) treatment.

The HAST treatment conditions are: temperature: 130 DEG C, humidity: 85%, exposure time: 100 hours.

Hereinafter, the test results are shown. Note that &quot; HAST &quot; in the following table indicates adhesion after HAST treatment.

<Evaluation of Peeling Strength of Copper Clad Laminate>

(A) Initial adhesion

First, in Comparative Example 4, which is a blank example in which an insulating resin layer is directly laminated on a copper substrate without interposing a plated film, the strength is "0.00" in the sense that adhesion can not be obtained on the basis of setting standards of the tester, It is the standard value.

Next, Comparative Example 1 in which an insulating resin is laminated on a copper substrate through a tin coating film formed using a substitution tin plating bath is an example based on the above-described Patent Documents 2 to 4. In this case, the peeling strength is 0.35 (Unit is omitted; the same is applied hereinafter), and the adhesion of Comparative Example 1 is apparently increased in comparison with the standard of Comparative Example 4.

However, with respect to the strength (0.35) of Comparative Example 1, the strengths of Examples 1 to 28 in which the substituted nickel film was interposed between the copper base and the insulating resin layer were 0.53 to 1.25. Particularly, the hydrophilic polymer and / In Examples 16 to 28 in which a silane coupling agent was added in combination, 0.95 to 1.25, and the strengths of Examples 1 to 28 were significantly higher than those of Comparative Example 1. [

Therefore, it can be concluded that the adhesion between the copper substrate and the insulating resin layer is remarkably improved in Examples 1 to 28 in which the substituted nickel film was deposited, as compared with Comparative Example 1 in which the substituted tin coating was deposited on the copper substrate.

On the other hand, the strength of Comparative Example 2 in which a reduced nickel film formed of a reduced electroless nickel bath was interposed was 0.40, which was slightly higher than Comparative Example 1 (substituted tin coating), and the adhesion strengths of Examples 1 to 28 (0.53 to 1.25) is remarkably high. In Examples 1 to 28 and Comparative Example 2, they are common in that they belong to a broad electroless nickel plating bath. However, unexpectedly, each of the substituted nickel films of Examples 1 to 28 is clearly different in adhesiveness from the reduced nickel film of Comparative Example 2 Show superiority. As a result, the importance of selecting a substituted nickel bath using a complexing agent without using a reducing agent instead of a reducing nickel bath has been supported as a nickel bath to deposit on a copper substrate.

The strength of Comparative Example 3 in which the hydrophilic polymer compound was added to the reduced nickel plating bath of Comparative Example 2 was not different from that of Comparative Example 2. In the case of the reduced nickel bath, the addition of the hydrophilic polymer compound contributed greatly to the improvement of the adhesion .

Next, Examples 1 to 28 will be examined in detail.

As for the film thickness of the nickel film, for example, the film of Example 10 having a film thickness of 0.03 mu m is higher than that of Example 3 having a film thickness of 0.06 mu m, so that the peeling strength is not high. It can be seen that the adhesion can be improved even with a thin film thickness as in Example 10.

On the other hand, in Examples 1 to 15 in which only the substituted nickel bath was used, the baths of Examples 16 to 28 (combined baths) in which the hydrophilic polymer and / or the silane coupling agent were added to these single baths were used, The peeling strengths of Examples 16 to 28 were improved.

For example, in Examples 16 to 18, a polyacrylate (hydrophilic polymer), a conventional silane coupling agent (silane coupling agent having an epoxy group), an epoxy silane modified polyacrylate (silane coupling agent (1.10), Example 17 (1.15) and Example 18 (1.20) were significantly improved (Example 1) than Example 3 (0.55) .

Then, Examples 19 to 22 were prepared by mixing polyacrylate, a mixture of a silane coupling agent having an amino group (a silane coupling agent having an amino group) and a silane coupling agent (a silane coupling agent having a mercapto group And a silane coupling agent having an isocyanate group) and an epoxy silane modified acrylate copolymer (hydrophilic high molecular compound modified with a silane coupling agent), respectively. When the strength was compared, Example 19 (1.10), Example 20 (1.08), Example 21 (1.12) and Example 22 (1.25) were clearly improved than Example 6 (0.63).

In Examples 23 to 25, a mixture of an acrylate copolymer (hydrophilic polymer), an amino-modified epoxy resin (hydrophilic polymer) and a silane coupling agent (a silane coupling agent having a mercapto group) (1.06), Example 24 (1.00) and Example 25 (1.10) were the same as those of Example 10 (0.72) in that the strength was inferior to that of Example 10 Clearly improved.

On the other hand, in contrast to Example 18 in which an epoxy silane modified polyacrylate was added to a substituted nickel bath and Example 27 in which a mixture of a polyacrylate and a silane coupling agent having an epoxy group was added to a substituted nickel bath, Since the difference between Example 18 (1.20) and Example 27 (1.22) is not much different, in this case, it is preferable that the counterpart to the single bath for replacement nickel has adhesiveness more than the substitution nickel single bath It can be judged that it can be improved to the same level.

(B) Adhesion after HAST treatment

The sample was subjected to HAST treatment to examine the adhesiveness when exposed to a harsh atmosphere of high temperature and high humidity for a long time.

When the adhesion after the HAST treatment was compared with the initial adhesion, in Examples 1 to 28, about 90% of the adhesion after HAST treatment was secured at about 70% of the initial value.

On the other hand, in Comparative Example 2-3, the adhesion after HAST treatment was remarkably lowered to 13 to 25% of the initial value, and in Comparative Example 1 (tin coating), it was 43% of the initial value.

That is, the superiority of Examples 1 to 28 for Comparative Examples 1 to 3 was more clearly demonstrated by exposing the sample to a harsh atmosphere for a long time.

Claims (10)

1. A copper component coated with an insulating resin material on a copper base,
A plating bath for forming a nickel coating film which improves adhesion between a copper base deposited on a surface of a copper base facing a resin material and a resin material,
(A) a soluble nickel salt,
(B) an acid selected from an inorganic acid and an organic acid or a salt thereof,
(C) Thiourea
But contains no reducing agent,
and a pH of 7 or less. The method of claim 1, wherein
Wherein the copper base is a copper layer, the resin material is a resin layer,
Wherein the copper component is a copper laminated board in which a copper layer and a resin layer are laminated. 3. The method according to claim 1 or 2,
The plating bath may further contain a hydrophilic polymer compound and / or a silane coupling agent having at least one functional group selected from the group consisting of an amino group, an epoxy group, a mercapto group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, Wherein said nickel plating bath is a nickel plating bath for copper surface treatment. The method of claim 3,
Wherein the hydrophilic polymer is at least one selected from the group consisting of poly (meth) acrylate, (meth) acrylate copolymer, polymaleic acid,
Wherein the silane coupling agent is at least one selected from the group consisting of a silane coupling agent having an amino group, a mercapto group, a vinyl group, a styryl group, a methacrylic group, an acryl group, an anionate group or an epoxy group and a hydrophilic polymer compound modified with the silane coupling agent Type nickel plating bath for copper surface treatment. A process for producing a copper foil comprising the steps of forming a nickel film on a copper base surface using the substitution plating bath according to claim 1 or 2 and coating the resin material on the copper base with the nickel film interposed therebetween A method of manufacturing a component. A process for producing a copper part, comprising the steps of: forming a nickel coating on a copper base surface using the displacement plating bath according to claim 3; and coating the copper base with a resin material through the nickel coating . A process for producing a copper part, comprising the steps of: forming a nickel coating on a copper base surface using the displacement plating bath according to claim 4; and coating the copper base with a resin material through the nickel coating . A copper part having a nickel plating film formed on a copper base surface by using the substitution plating bath according to claim 1 or 2 and a copper base coated with a resin material through the nickel plating film. A copper part having a nickel plating film formed on a copper base surface by using the substitution plating bath according to claim 3 and a copper base coated with a resin material through the nickel plating film. A copper part having a nickel plating film formed on a copper base surface by using the substitution plating bath according to claim 4, and a copper base coated with a resin material through the nickel plating film.