KR101184558B1 - Pre-treating agent for electroless metal plating and manufacturing method of circuit board using the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pretreatment agent for electroless metal plating and a method for manufacturing a circuit board using the same, and discloses a pretreatment agent for electroless metal plating containing a nitrogen compound, a surfactant, a sulfur compound, and a cocatalyst.

Description

Pretreatment agent for electroless metal plating and manufacturing method of circuit board using the same

The present invention relates to a pretreatment for electroless metal plating and a method of manufacturing a circuit board using the same.

In addition to increasing the density of electronic components, surface treatment of circuit boards is being performed at various angles. In particular, conventionally used electroless nickel / gold (Ni / Au) (hereinafter referred to as ENIG) and electroless nickel / palladium / gold (Ni / Pd / Au) (hereinafter referred to as ENEPIG), which are recently attracting attention, have good solder connection reliability, Wire bonding It is used in various fields as well as package board because of its reliability.

However, as the densification progresses, such surface treatment problems are erupted due to the miniaturization of wiring. One of them is the problem of precipitation of electroless metal, for example, electroless nickel, which occurs between patterns. This cause occurs due to the presence of, for example, palladium remaining between the patterns among the catalytic treatment chemicals that are indispensable for film formation of the electroless metal.

Conventionally, mineral acids, such as hydrochloric acid and sulfuric acid, have been used for catalyst residue removal. However, in mines, there is a problem that the affinity with the catalyst is low, the removal ability is low, and the equipment is corroded.

Alternatively, removal agents using cyanide compounds exist. However, cyanide compounds, as known, are very toxic, creating a large burden on the working environment and drainage.

The present invention is to solve the above-mentioned problems of the prior art, an aspect of the present invention is excellent in the removal performance for the catalyst residue to prevent the bridge (bride) caused by the electroless plating precipitation between the patterns The present invention provides a pretreatment for sea metal plating and a method of manufacturing a circuit board using the same.

Another aspect of the present invention is to provide an electroless metal plating pretreatment agent capable of implementing a fine circuit with excellent selective removal of catalyst residues and a method of manufacturing a circuit board using the same.

Another aspect of the present invention is to provide an environmentally friendly electroless metal plating pretreatment agent and a method of manufacturing a circuit board using the same.

According to a first preferred aspect of the invention,

Nitrogen compound represented by the following formula (1):

Wherein X and Y are the same as or different from each other, H, CH ₂ Cl, CH ₂ Br, CH ₂ I, CH ₂ OH, CH ₂ COOH, C ₂ H ₄ Cl, C ₂ H ₄ Br, C ₂ H ₄ I, C ₂ H ₄ OH or C ₂ H ₄ COOH, n is an integer from 1 to 3 and m is an integer from 1 to 6;

Surfactants;

Sulfur compounds represented by the following formula (2) or (3):

Wherein R, R ₁ and R ₂ are the same as or different from each other, or an alkyl or aryl group having 1 to 6 carbon atoms, and X ₁ , X ₂ and Y ₂ are the same as or different from each other or H, OH or COOH; And

Cocatalysts;

There is provided a pretreatment agent for electroless metal plating comprising a.

In the pretreatment agent,

The nitrogen compound may be selected from the group consisting of diamine compounds, triamine compounds, pentamine compounds, hexamine compounds, halogenated alkylamine compounds, amino alcohol compounds, amino acid compounds and mixtures thereof.

The nitrogen compound is also ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, tripropylenetetraamine, tributylenetetraamine, tetraethylenepenta Min, tetrapropylenepentamine, tetrabutylenepentamine, pentaethylenehexamine, pentapropylenehexamine, pentabutylenehexamine, 1-chloroethylene-N-ethylene diamine, di (1-bromoethylene) -N, N'-propylene diamine, 1-hydroxymethylene-N-ethylene diamine, 1-hydroxyethylene-N-butylene diamine, 1-aminoethylene-N-glycine, ethylenediamine-N, N'-diacetic acid (EDDA ) And mixtures thereof.

The surfactant is a polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene alkyl ether, alkyl sulfonic acid of 12 to 18 carbon atoms, alkylsulfosuccinic acid of 12 to 18 carbon atoms, dialkylsulfosuccinic acid of 12 to 18 carbon atoms and their It may be selected from the group consisting of a mixture.

The sulfur compound may be selected from the group consisting of mercaptan compounds, disulfide compounds and mixtures thereof.

The sulfur compound may also be selected from the group consisting of methylmercaptan, ethylmercaptan, thiophenol, thioglycol, thioglycolic acid, dithioglycol, dithioglycolic acid and mixtures thereof.

The subcatalyst may be an ion of a metal selected from the group consisting of Pb, Bi, Sb, and combinations thereof.

The content of the nitrogen compound in the pretreatment may be 0.001 to 10 mol / L.

The amount of the surfactant in the pretreatment may be 1 × 10 ⁻⁸ to 0.1 mol / L.

The content of the sulfur compound in the pretreatment may be 1 × 10 ^-8 to 0.1 mol / L.

The content of the subcatalyst in the pretreatment may be 1 × 10 ⁻⁸ to 0.1 mol / L.

According to a second preferred aspect of the invention,

Applying a catalyst for electroless metal plating to the base substrate;

The base substrate is treated with a nitrogen compound represented by the following formula (1), a surfactant, a sulfur compound represented by the following formula (2) or (3), and a pretreatment agent for electroless metal plating containing a subcatalyst to form an insulating layer of the base substrate. To remove the catalyst from the surface:

(Formula 1)

Wherein X and Y are the same as or different from each other, H, CH ₂ Cl, CH ₂ Br, CH ₂ I, CH ₂ OH, CH ₂ COOH, C ₂ H ₄ Cl, C ₂ H ₄ Br, C ₂ H ₄ I, C ₂ H ₄ OH or C ₂ H ₄ COOH, n is an integer from 1 to 3, m is an integer from 1 to 6;

(Formula 2)

X ₁ -R-SH

In which R is an alkyl or aryl group having 1 to 6 carbon atoms, X ₁ is H, OH or COOH;

(Formula 3)

X ₂ -R ₁ -SS-R ₂ -Y ₂

Wherein R ₁ and R ₂ are the same as or different from each other, or an alkyl or aryl group having 1 to 6 carbon atoms, and X ₂ and Y ₂ are the same as or different from each other to H, OH or COOH; And

Forming a metal plating layer on the base substrate treated with the pretreatment agent through electroless metal plating;

There is provided a method of manufacturing a circuit board comprising a.

In the above production method,

The treating with the pretreatment may be performed by immersing the base substrate in a bath containing the pretreatment.

Treatment with the pretreatment may also be performed by spraying the pretreatment on the base substrate.

The step of applying a catalyst for electroless metal plating to the base substrate:

Preparing a base substrate having a connection pad exposed by a solder resist open portion; And

Applying a catalyst for electroless metal plating to a connection pad of the base substrate;

. ≪ / RTI >

The metal may be nickel.

The features and advantages of the present invention will become more apparent from the following detailed description based on the accompanying drawings.

Prior to that, terms and words used in the present specification and claims should not be construed in a conventional and dictionary sense, and the inventor may properly define the concept of the term in order to best explain its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

According to one preferred aspect of the present invention, a bridging phenomenon due to deposition of electroless plating between patterns on a circuit board by providing a pretreatment agent of an electroless metal plating having excellent removal performance of catalyst residues through a combination of specific components. Can be prevented.

In addition, high performance selective catalyst residue removal performance can be exhibited to improve inter-pattern plating deposition of a densified substrate.

According to another preferred aspect of the present invention, the catalyst residue removal process may be environmentally friendly by not blending a toxic compound such as a conventional mine or cyan compound in the pretreatment agent for electroless metal plating.

Therefore, the previous equipment corrosion can be reduced and the work environment and drainage burden can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram schematically illustrating components of a pretreatment agent for electroless metal plating according to a preferred embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The objectives, specific advantages and novel features of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. It should be noted that, in the present specification, the reference numerals are added to the constituent elements of the drawings, and the same constituent elements are assigned the same number as much as possible even if they are displayed on different drawings. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail. In this specification, the terms first, second, etc. are used to distinguish one element from another, and the element is not limited by the terms.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Pretreatment Agent for Electroless Metal Plating

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram schematically illustrating components of a pretreatment agent for electroless metal plating according to a preferred embodiment of the present invention.

Referring to FIG. 1, the electroless metal plating pretreatment, that is, the catalyst remover 100 is represented by the nitrogen compound 101 represented by the following Chemical Formula 1, the surfactant 102, and the following Chemical Formula 2 or Chemical Formula 3 Sulfur compound (103) and subcatalyst (104) comprising:

(Formula 1)

Wherein X and Y are the same as or different from each other, H, CH 2 Cl, CH 2 Br, CH 2 I, CH 2 OH, CH 2 COOH, C 2 H 4 Cl, C 2 H 4 Br, C 2 H 4 I, C 2 H 4 OH or C 2 H 4 COOH, n is an integer from 1 to 3, m is from 1 to 6 Is an integer.

(Formula 2)

X1-R-SH

(Formula 3)

X2-R1-SS-R2-Y2

Wherein R, R1 and R2 are the same as or different from each other, or an alkyl or aryl group having 1 to 6 carbon atoms (for example, a phenyl group and / or a naphthyl group), and X1, X2 and Y2 are the same as or different from each other, H, OH Or COOH.

The nitrogen compound 101 forms a stable compound with a catalyst, for example, Pd ion, which is a catalyst of an electroless nickel plating process. However, it does not react with the metallized catalyst on the metal pattern, for example copper pattern. The nitrogen compound is water soluble and easily dissolved in the treatment agent. Further, when the nitrogen compound is treated to the metal pattern, the catalyst metal is deposited on the metal pattern by the reaction scheme shown below.

(Scheme 1)

Cu + [PdA] ²⁺ → Cu ²⁺ + Pd + A

In the above scheme, A is a nitrogen compound.

The concentration of the nitrogen compound in the pretreatment may be 0.001 to 10 mol / L, more preferably 0.1 to 5.0 mol / L.

When the concentration of the nitrogen compound is lower than 0.001 mol / L, the concentration of the nitrogen compound reacting with the catalyst ions may be too low to exert its capacity as a catalyst remover. In addition, when the concentration of the compound exceeds 10 mol / L, there is a fear that the nitrogen compound is in a supersaturated state, the viscosity is too high and may adversely affect the permeability of the catalyst remover in the microcircuit. In addition, drug costs may rise, which may be disadvantageous in terms of cost versus efficiency.

Representative materials include, but are not limited to, diamine compounds such as ethylenediamine, propylenediamine, and butylenediamine, diethylenetriamine, dipropylenetriamine, and dibutylenetriamine ( Triamine compounds such as dibuthylenetriamine, tetraamine compounds such as triethylenetetramine, tripropylnentetramine, tributylenetetramine, tetraethylenepentamine ), Pentamine compounds such as tetrapropylnenpentamine, tetrabutylenepentamine, pentaethylenehexamine, pentapropylenehexamine, pentabutylenehexamine Hexamine compounds such as), 1-chloroethylene-N-ethylenediamine (1-ch Halogenated alkyl amine compounds such as loroethylene-N-ethylen dimaine and di (1-bromoethylene) -N, N'-propylene diamine (Di (1-bromoethylene) -N, N'-propylene diamine) Amino alcohols such as 1-hydroxymethylene-N-ethylene diamine and 1-hydroxyethylene-N-butylene diamine ) Compounds, 1-aminoethylene-N-glycine, and amino acid compounds such as ethylenediamine-N, N'-diacetic acid (Ethylenediamine-N, N'-diacetic acid (EDDA)). It may be mentioned, but is not particularly limited thereto.

The surfactant 102 serves as an organic compound to assist the permeability of the catalyst remover penetrating into the microcircuit, and at the same time, lowers the surface energy of the metal pattern to smoothly replace the catalyst with the metal.

The concentration of the surfactant in the pretreatment may be 1 × 10 ⁻⁸ to 0.1 mol / L, preferably 1 × 10 ⁻⁶ to 0.01 mol / L. When the concentration of the surfactant is lower than 1 × 10 ⁻⁸ mol / L, the permeability in the fine circuit of the catalyst remover is hardly improved and the catalyst remover capability may be reduced. When the concentration of the surfactant exceeds 0.1 mol / L, the water solubility of the organic compound is lowered, and when adsorbed in a large amount on the surface of the metal pattern due to precipitation or suspension, poor adhesion during the next step of electroless metal plating or It may cause the appearance defect.

Preferably, as the surfactant, an organic material having a hydrophile-lipophile balance (HLB) value of 10 to 16 may be used. When the HLB value is small, the water solubility is lowered and is likely to be precipitated or suspended, and may be disadvantageous in terms of cost.

The surfactant includes, for example, a polyoxyethylene-polyoxypropylene block copolymer having a molecular weight of 2,000 to 200,000, a polyoxyethylene alkylether having an HLB value of 10 to 16. ), Alkyl sulfonic acid of 12 to 18 carbon atoms, alkyl sulfosuccinic acid of 12 to 18 carbon atoms, and / or dialkyl sulfosuccinic acid of 12 to 18 carbon atoms, and the like, but is not particularly limited thereto.

The sulfur compound is a substance that binds to the catalyst ions and interferes with the catalytic activity when the removal of the catalyst is prevented from proceeding smoothly due to some reason.

The concentration of the sulfur compound in the pretreatment may be 1 × 10 ^-8 to 0.1 mol / L, preferably 1 × 10 ^-6 to 0.01 mol / L. When the concentration of the sulfur compound is lower than 1 × 10 ⁻⁸ mol / L, the permeability of the catalyst remover in the fine circuit of the catalyst is hardly improved, and the catalyst remover capability may be reduced. When the concentration of the sulfur compound exceeds 0.1 mol / L, the water solubility of the organic compound may decrease, and may be precipitated or suspended, and when adsorbed in a large amount on the surface of the metal, the next step is electroless metal plating. It can be the cause of poor adhesion or poor appearance.

Examples of the sulfur compound include mercaptan compounds such as methylmercaptan, ethylmercaptan, thiophenol, thioglycol, thioglycolic acid, and dithio. Disulfide compounds, such as glycol (Dithiodiglycol), Dithiodiglycolic acid, etc. may be mentioned, but it is not specifically limited.

Here, if the plating precipitation prevention liquid between the pattern containing the sulfur compound as a base and the catalyst removal liquid based on the nitric acid are constituted by separate lines, the chemicals containing the sulfur compound have less removal effect, The chemicals based on the base are likely to dissolve the metal constituting the pattern, for example, copper, and also need to be expanded in two steps. On the contrary, in the present invention, by combining the specific nitrogen compound and the specific sulfur compound with the surfactant and the cocatalyst, the catalyst removal process can be performed in an environmentally friendly and economical process while achieving high catalyst residue removal performance.

The subcatalyst 104 is added to prevent precipitation of plating abnormalities, thereby improving the patternability of the electroless metal plating, and is suitable for high density circuit implementation. Hydrogen gas is generated during the plating precipitation reaction of the electroless plating process, and this hydrogen gas promotes the plating precipitation property, and thus, plating is deposited in the insulating layer between the fine patterns without the catalyst, so that such plating abnormal deposition prevention is required. .

Examples of the subcatalyst may include Pb ions, Bi ions, Sb ions, and the like, but are not particularly limited to those known in the art.

The concentration of the subcatalyst in the pretreatment may be 1 × 10 ⁻⁸ to 0.1 mol / L, preferably 1 × 10 ⁻⁶ to 0.01 mol / L. When the concentration of the subcatalyst is lower than 1 × 10 ⁻⁸ mol / L, the concentration may be too low, so that the effect as the subcatalyst may not be sufficient. When the concentration of the subcatalyst exceeds 0.1 mol / L, the water solubility of the organic compound may decrease, and may be precipitated or suspended, and when adsorbed in a large amount on the surface of the metal pattern, the next step is electroless metal plating. It may be the cause of poor adhesion, poor appearance, or poor deposition.

Optionally, the pretreatment may include other additives known in the art within a range that does not interfere with the desired effect. The additive may include, for example, a pH adjusting agent such as NaOH or sulfuric acid, an indicator for analysis, and the like, but is not particularly limited thereto.

On the other hand, the pH of the pretreatment is not particularly limited, but considering the effect on the substrate it is preferable to use the pH in the range of 4 to 12. If the pH is too low, the blended sulfur-based compound may lose water solubility, give off a characteristic odor and worsen the working environment. Too high a pH can lead to solder resist or substrate dissolution, which can have serious effects.

The pretreatment agent is not particularly limited in its use temperature when the aqueous solution is maintained. For example, the temperature which can be used is 0-100 degreeC, but it is preferable to use between 20-80 degreeC in reality.

Manufacturing Method of Circuit Board

Hereinafter, one preferable embodiment of the method of manufacturing a circuit board using the pretreatment agent of electroless metal plating mentioned above is demonstrated. However, since the pretreatment agent of the electroless metal plating is as described above, overlapping detailed description is omitted.

According to the method according to one embodiment of the present invention, first, a base substrate to be subjected to electroless metal plating is prepared.

The base substrate may be a semiconductor substrate or a printed circuit board as a circuit board on which one or more circuits including connection pads are formed in an insulating layer. In addition, a general multilayer circuit board having one or more circuits formed on an insulating layer may be applied to the base substrate.

In general, the connection pad is a connection portion on which an electronic component or an external connection terminal is mounted, and is exposed to the outside by an opening of a protective layer, for example, a solder resist, and the exposed connection pad is subjected to a subsequent process to be described later. Through the electroless metal plating, a surface treatment layer such as an electroless nickel / gold plating layer is formed.

The circuit including the connection pad may be applied without limitation as long as it is used as a conductive metal for circuit in the circuit board field, and copper is typically used in a printed circuit board.

For example, a resin insulating layer in the case of a printed circuit board or a ceramic insulating layer in the case of a semiconductor substrate may be used as the insulating layer. As the resin insulating layer, a thermosetting resin such as an epoxy resin, a thermoplastic resin such as polyimide, or a resin impregnated with a reinforcing material such as a glass fiber or an inorganic filler, for example, a prepreg can be used, And / or a photo-curable resin may be used, but the present invention is not limited thereto.

The solder resist functions as a protective layer to protect the outermost layer circuit in the printed circuit board and is formed for electrical insulation, and an open portion is formed to expose the outermost connection pads. The solder resist may be composed of, for example, a solder resist ink, a solder resist film or an encapsulant, as is known in the art, but is not particularly limited thereto.

Next, a catalyst for electroless metal plating is applied to the base substrate.

Preferably, the catalyst for electroless metal plating may be applied to a pattern on which the electroless metal plating is to be performed, that is, a connection pad.

In this case, the metal of the electroless metal plating may be nickel.

Next, the base substrate is treated with a pretreatment agent for electroless metal plating as described above to remove the catalyst formed on the surface of the insulating layer of the base substrate.

After providing the catalyst for electroless metal plating, by treating with a pretreatment agent as described above, the catalyst remaining on the surface of the insulating layer, for example, can be removed to prevent the bridge phenomenon due to plating precipitation between the patterns. That is, the treatment using the pretreatment agent is typically applied between the catalyst providing process for electroless metal plating and the electroless metal plating process.

The treatment method is sufficient to immerse the substrate in a chemical, that is, a bath containing a pretreatment agent, which is conventionally carried out. However, in some cases, a spraying method such as a spray may be applied.

Next, an electroless metal plating layer is formed on a base substrate treated with a pretreatment agent as described above, for example, a connection pad, through a conventional electroless metal plating process known in the art, for example, an electroless nickel plating process. .

Subsequently, solder bumps may be formed through a conventional subsequent process known in the art, and the solder bumps may electrically connect the semiconductor device or an external component with an inner layer circuit of the circuit board.

According to the method of the present invention, by treating the base substrate using the above-described pretreatment agent between the catalyst providing step for electroless metal plating and the electroless metal plating step, the remaining catalyst residues between patterns can be removed with excellent performance without bridging phenomenon. Fine circuit implementation is possible.

In addition, by using a pretreatment agent that does not use the existing mine or cyan compound, it is possible to perform the catalyst removal process in an environmentally friendly and economical process.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited thereto.

[Examples 1-5 and Comparative Examples 1-4]

A substrate on which Bond-finger was assumed was manufactured and used by the MSAP method. Pattern space is set to 15, 18, 20, 25, 30, 35㎛ and after catalyst addition, the catalyst is removed by treatment with a pretreatment agent, and the space after the plating process is observed by 50 times optical microscope. Precipitation was compared.

Here, degreasing, soft-etching, catalyzing, catalyst removal (pretreatment) and electroless metal plating before catalyst application were carried out under the conditions shown in Table 1 below, and the pretreatment composition was shown in Tables 2 and 3 below. It was combined and performed together.

The results obtained therefrom are shown in Table 4 below.

fair Maker Temperature (℃) Processing time (minutes) Degreasing ACL-007 (Uyemura) 45 5 Soft-etching Na ₂ S ₂ O ₃ 25 One Catalyzing MSR-28 (Uyemura) 40 3 Catalyst removal See Examples / Comparative Examples 25-70 One Electroless nickel plating ICP-GIB (Okuno) 80 20

Material name Example 1 Example 2 Example 3 Example 4 Example 5 1 ^* 2.0mol / L 2 ^* 0.5mol / L 3.0mol / L 3 ^* 0.1mol / L 0.2mol / L 4 ^* 10 ^-3 mol / L 10 ^-2 mol / L 10 ^-2 mol / L 5 ^* 10 ^-3 mol / L 10 ^-3 mol / L 6 ^* 10 ^-4 mol / L 10 ^-3 mol / L 7 ^* 10 ^-3 mol / L 10 ^-2 mol / L 10 ^-2 mol / L 8 ^* 10 ^-5 mol / L 10 ^-5 mol / L 10 ^-5 mol / L 9 ^* 10 ^-5 mol / L 10 ^-4 mol / L pH 6.0 9.0 9.0 5.0 8.0 Temperature (℃) 60 45 25 30 70

1 ^* : triethylenetetraamine

2 ^* : ethylenediamine

3 ^* : EDDA

4 ^* : alkyl sulfonate (C = 14)

5 ^* : dialkyl sulfo succinate (C = 12)

6 ^* : ethyl mercaptan

7 ^* : dithiodiglycolic acid

8 ^* : SbCl ₃

9 ^* : Bi (NO ₃ ) ₃

Material name Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 1 ^* 8.4 × 10 ^-3 mol / L No removal process 2 ^* 0.1mol / L 3 ^* 0.13 mol / L pH 8.0 8.0 8.0 Temperature (℃) 30 30 30

1 ^* : mercaptothiazoline

2 ^* : KSCN

3 ^* : Na ₂ S ₂ O ₃

Pattern interval
(Μm) 15 18 20 25 30 35 Example 1 ○ ◎ ◎ ◎ ◎ ◎ Example 2 ○ ◎ ◎ ◎ ◎ ◎ Example 3 ○ ◎ ◎ ◎ ◎ ◎ Example 4 ○ ◎ ◎ ◎ ◎ ◎ Example 5 ○ ◎ ◎ ◎ ◎ ◎ Comparative Example 1 × ○ ○ ○ ◎ ◎ Comparative Example 2 × ○ ○ ○ ◎ ◎ Comparative Example 3 × ○ ○ ○ ◎ ◎ Comparative Example 4 × × × × × ○

◎ ： There is no precipitation phenomenon between patterns

○: Precipitation but no problem in use

× ： Not a lot of precipitation occurs and cannot be used.

From the above result, when the pretreatment for catalyst removal is not performed like Comparative Example 4, it cannot be used for the substrate which has a space of 30 micrometers or less. Moreover, in Comparative Examples 1-3, precipitation between patterns of 30 micrometers or less is seen. On the other hand, in Examples 1 to 5 in which the substrates were prepared using the pretreatment agent according to the present invention, no precipitation was observed up to 18 µm in all, and even in 15 µm, there was no problem in use.

Although the present invention has been described in detail through specific examples, it is intended to specifically describe the present invention, and the electroless metal plating pretreatment agent according to the present invention and a method of manufacturing a circuit board using the same are not limited thereto. It is apparent that modifications and improvements are possible by those skilled in the art within the technical idea of the present invention.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

100: catalyst remover
101: nitrogen compound
102: surfactant
103: sulfur compound
104: subcatalyst

Claims (20)

Nitrogen compound represented by the following formula (1):
(Formula 1)

Wherein X and Y are the same as or different from each other, H, CH ₂ Cl, CH ₂ Br, CH ₂ I, CH ₂ OH, CH ₂ COOH, C ₂ H ₄ Cl, C ₂ H ₄ Br, C ₂ H ₄ I, C ₂ H ₄ OH or C ₂ H ₄ COOH, n is an integer from 1 to 3 and m is an integer from 1 to 6;
Surfactants;
Sulfur compounds represented by the following formula (2) or (3):
(2)
X ₁ -R-SH
(Formula 3)
X ₂ -R ₁ -SS-R ₂ -Y ₂
Wherein R, R ₁ and R ₂ are the same as or different from each other, or an alkyl or aryl group having 1 to 6 carbon atoms, and X ₁ , X ₂ and Y ₂ are the same as or different from each other or H, OH or COOH; And
Cocatalysts;
Pretreatment agent for electroless metal plating comprising a.
The method according to claim 1,
The nitrogen compound is a pretreatment for electroless metal plating selected from the group consisting of diamine compounds, triamine compounds, pentamine compounds, hexamine compounds, halogenated alkylamine compounds, amino alcohol compounds, amino acid compounds and mixtures thereof.
The method according to claim 1,
The nitrogen compound is ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetraamine, tripropylenetetraamine, tributylenetetraamine, tetraethylenepentamine , Tetrapropylenepentamine, tetrabutylenepentamine, pentaethylenehexamine, pentapropylenehexamine, pentabutylenehexamine, 1-chloroethylene-N-ethylene diamine, di (1-bromoethylene) -N, N '-Propylene diamine, 1-hydroxymethylene-N-ethylene diamine, 1-hydroxyethylene-N-butylene diamine, 1-aminoethylene-N-glycine, ethylenediamine-N, N'-diacetic acid (EDDA) And a mixture of electroless metal plating selected from the group consisting of these.
The method according to claim 1,
The surfactant is a polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene alkyl ether, alkyl sulfonic acid of 12 to 18 carbon atoms, alkylsulfosuccinic acid of 12 to 18 carbon atoms, dialkylsulfosuccinic acid of 12 to 18 carbon atoms and their A pretreatment agent for electroless metal plating selected from the group consisting of mixtures.
The method according to claim 1,
The sulfur compound is a pretreatment for electroless metal plating selected from the group consisting of mercaptan compounds, disulfide compounds and mixtures thereof.
The method according to claim 1,
The sulfur compound is a pretreatment for electroless metal plating selected from the group consisting of methyl mercaptan, ethyl mercaptan, thiophenol, thioglycol, thioglycolic acid, dithioglycol, dithioglycolic acid and mixtures thereof.
The method according to claim 1,
The subcatalyst is an electrolytic metal plating pretreatment agent which is an ion of a metal selected from the group consisting of Pb, Bi, Sb, and combinations thereof.
The method according to claim 1,
The pretreatment agent of the electroless metal plating is the content of the nitrogen compound in the pretreatment agent is 0.001 to 10 mol / L.
The method according to claim 1,
The amount of the surfactant in the pretreatment agent is 1 × 10 ^-8 to 0.1 mol / L pre-treatment of the electroless metal plating.
The method according to claim 1,
The content of the sulfur compound in the pretreatment agent is a pretreatment of electroless metal plating is 1 × 10 ^-8 to 0.1 mol / L.
The method according to claim 1,
The precatalyst content of the pretreatment agent is 1 × 10 ^-8 to 0.1 mol / L.
Applying a catalyst for electroless metal plating to the base substrate;
The base substrate is treated with a nitrogen compound represented by the following formula (1), a surfactant, a sulfur compound represented by the following formula (2) or (3), and a pretreatment agent of an electroless metal plating containing a subcatalyst to form an insulating layer of the base substrate. To remove the catalyst from the surface:
(Formula 1)

Wherein X and Y are the same as or different from each other, H, CH ₂ Cl, CH ₂ Br, CH ₂ I, CH ₂ OH, CH ₂ COOH, C ₂ H ₄ Cl, C ₂ H ₄ Br, C ₂ H ₄ I, C ₂ H ₄ OH or C ₂ H ₄ COOH, n is an integer from 1 to 3, m is an integer from 1 to 6;
(2)
X ₁ -R-SH
In which R is an alkyl or aryl group having 1 to 6 carbon atoms, X ₁ is H, OH or COOH;
(Formula 3)
X ₂ -R ₁ -SS-R ₂ -Y ₂
Wherein R ₁ and R ₂ are the same as or different from each other, or an alkyl or aryl group having 1 to 6 carbon atoms, and X ₂ and Y ₂ are the same as or different from each other to H, OH or COOH; And
Forming a metal plating layer on the base substrate treated with the pretreatment agent through electroless metal plating;
Method of manufacturing a circuit board comprising a.
The method of claim 12,
The step of treating with the pretreatment agent is performed by immersing the base substrate in a bath containing the pretreatment agent.
The method of claim 12,
And treating the pretreatment agent with spraying the pretreatment agent on the base substrate.
The method of claim 12,
The step of applying a catalyst for electroless metal plating to the base substrate:
Preparing a base substrate having a connection pad exposed by a solder resist open portion; And
Applying a catalyst for electroless metal plating to a connection pad of the base substrate;
Method of manufacturing a circuit board comprising a.
The method of claim 12,
And said metal is nickel.
The method of claim 12,
Wherein said nitrogen compound is selected from the group consisting of diamine compounds, triamine compounds, pentamine compounds, hexamine compounds, halogenated alkylamine compounds, amino alcohol compounds, amino acid compounds and mixtures thereof.
The method of claim 12,
The surfactants are polyoxyethylene-polyoxypropylene block copolymers, polyoxyethylene alkyl ethers, alkyl sulfonic acids having 12 to 18 carbon atoms, alkylsulfosuccinic acids having 12 to 18 carbon atoms, dialkylsulfosuccinic acids having 12 to 18 carbon atoms, and their A method for producing a circuit board selected from the group consisting of mixtures.
The method of claim 12,
Wherein said sulfur compound is selected from the group consisting of mercaptan compounds, disulfide compounds and mixtures thereof.
The method of claim 12,
And the subcatalyst is an ion of a metal selected from the group consisting of Pb, Bi, Sb, and combinations thereof.

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