JP2012102392A - Pretreatment agent of electroless metal plating, and method for manufacturing circuit substrate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pretreatment agent of electroless metal plating, which has excellent removing performance relative to catalyst residue and prevents a bridge phenomena caused by the electroless plating deposition from occurring between patterns, and to provide a method for manufacturing a circuit substrate using the same.SOLUTION: The pretreatment agent of electroless metal plating contains: a nitrogenous compound; a surface acting agent; a sulfuric compound; and an auxiliary catalyst.

Description

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

With the increase in the density of electronic components, the surface treatment of circuit boards is also performed at multiple angles. In particular, electroless nickel / gold (Ni / Au) (hereinafter referred to as “ENIG”) that has been used conventionally, or electroless nickel / palladium / gold (Ni / Pd / Au) (hereinafter referred to as “ENIG”) that has been attracting attention in recent years. ENEPIG ”is used not only for package substrates but also for many fields because it has good soldering reliability and wire bonding reliability.

However, as the density increases, surface treatment problems are spouted due to miniaturization of wiring. One of them is a deposition problem of an electroless metal such as electroless nickel generated between patterns. The cause is that a catalyst treatment chemical, for example, palladium, which is indispensable for forming an electroless metal film, remains between the patterns.
Conventionally, mineral acids such as hydrochloric acid and sulfuric acid have been used to remove catalyst residues. However, the mineral acid has a low affinity for the catalyst, a low removal capability, and the facilities are corroded.

  As another method, there is a use of a removal chemical using a cyanide compound. However, as is well known, cyanide is very toxic and causes a heavy burden on the working environment and wastewater treatment.

The present invention is to solve the above-mentioned problems of the prior art, and its purpose is excellent in removal performance against catalyst residues, and thus prevents a bridge phenomenon due to deposition of electroless plating between patterns. An object of the present invention is to provide a pretreatment agent for electroless metal plating and a method for producing a circuit board using the same.

Another object of the present invention is to provide a pretreatment agent for electroless metal plating and a method for producing a circuit board using the same, which can realize a fine circuit because of excellent selective removal performance with respect to catalyst residues. It is in.

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

式中、ＸおよびＹは、互いに同じでも異なってもよく、それぞれＨ、ＣＨ_２Ｃｌ、ＣＨ_２Ｂｒ、ＣＨ_２Ｉ、ＣＨ_２ＯＨ、ＣＨ_２ＣＯＯＨ、Ｃ_２Ｈ_４Ｃｌ、Ｃ_２Ｈ_４Ｂｒ、Ｃ_２Ｈ_４Ｉ、Ｃ_２Ｈ_４ＯＨまたはＣ_２Ｈ_４ＣＯＯＨを示し、ｎは１〜３の整数を示し、ｍは１〜６の整数を示す；
界面活性剤；
下記化学式２または化学式３で表される硫黄化合物：

式中、Ｒ、Ｒ_１およびＲ_２は、互いに同じでも異なってもよく、それぞれ炭素数１〜６のアルキル基またはアリール基を示し、Ｘ_１、Ｘ_２およびＹ_２は、互いに同じでも異なってもよく、それぞれＨ、ＯＨまたはＣＯＯＨを示す；および
副触媒；を含む、無電解金属メッキの前処理剤が提供される。 According to a preferred first aspect of the present invention,
Nitrogen compounds represented by the following chemical formula 1:

In the formula, X and Y may be the same as or different from each other, and 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 represents an integer of 1 to 3, and m represents an integer of 1 to 6;
Surfactants;
Sulfur compounds represented by the following chemical formula 2 or chemical formula 3:

In the formula, R, R ₁ and R ₂ may be the same or different from each other, and each represents an alkyl group or aryl group having 1 to 6 carbon atoms, and X ₁ , X ₂ and Y ₂ are the same or different from each other. There is also provided a pretreatment agent for electroless metal plating, comprising: H, OH or COOH, respectively; and a secondary catalyst.

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 ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tripropylenetetramine, tributylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, tetrabutylenepentamine, Pentaethylenehexamine, pentapropylenehexamine, pentabylenehexamine, 1-chloroethylene-N-ethylenediamine, di (1-bromoethylene) -N, N′-propylenediamine, 1-hydroxymethylene-N-ethylenediamine, 1-hydroxyethylene -N-butylenediamine, 1-aminoethylene-N-glycine, ethylenediamine-N, N'-diacetic acid (EDDA), and mixtures thereof It may be selected from Li Cheng group.
The surfactant includes polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene alkyl ether, alkyl sulfonic acid having 12 to 18 carbon atoms, alkyl sulfosuccinic acid having 12 to 18 carbon atoms, and dialkyl sulfosuccinic acid having 12 to 18 carbon atoms. It may be selected from the group consisting of acids and mixtures thereof.

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 methyl mercaptan, ethyl mercaptan, thiophenol, thioglycol, thioglycolic acid, dithioglycol, dithioglycolic acid, and mixtures thereof.
The secondary catalyst may be a metal ion selected from the group consisting of Pb, Bi, Sb, and combinations thereof.
The nitrogen compound content in the pretreatment agent may be 0.001 to 10 mol / L.
The content of the surfactant in the pretreatment agent may be 1 × 10 ^{−8 to} 0.1 mol / L.
The content of the sulfur compound in the pretreatment agent may be 1 × 10 ^{−8 to} 0.1 mol / L.
The content of the secondary catalyst in the pretreatment agent may be 1 × 10 ^{−8 to} 0.1 mol / L.

式中、ＸおよびＹは、互いに同じでも異なってもよく、それぞれＨ、ＣＨ_２Ｃｌ、ＣＨ_２Ｂｒ、ＣＨ_２Ｉ、ＣＨ_２ＯＨ、ＣＨ_２ＣＯＯＨ、Ｃ_２Ｈ_４Ｃｌ、Ｃ_２Ｈ_４Ｂｒ、Ｃ_２Ｈ_４Ｉ、Ｃ_２Ｈ_４ＯＨまたはＣ_２Ｈ_４ＣＯＯＨを示し、ｎは１〜３の整数を示し、ｍは１〜６の整数を示し；

式中、Ｒは炭素数１〜６のアルキル基またはアリール基を示し、Ｘ_１はＨ、ＯＨまたはＣＯＯＨを示し；

式中、Ｒ、Ｒ_１およびＲ_２は、互いに同じでも異なってもよく、それぞれ炭素数１〜６のアルキル基またはアリール基を示し、Ｘ_１、Ｘ_２およびＹ_２は、互いに同じでも異なってもよく、それぞれＨ、ＯＨまたはＣＯＯＨを示す；および
前記前処理剤で処理されたベース基板に無電解金属メッキによって金属メッキ層を形成する段階；を含む、回路基板の製造方法が提供される。 According to a preferred second aspect of the present invention,
Applying a catalyst for electroless metal plating to a base substrate;
By treating the base substrate with a pretreatment agent for electroless metal plating containing a nitrogen compound represented by the following chemical formula 1, a surfactant, a sulfur compound represented by the following chemical formula 2 or 3 and a secondary catalyst. Removing the catalyst on the surface of the insulating layer of the base substrate:

In the formula, X and Y may be the same as or different from each other, and 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 represents an integer of 1 to 3, and m represents an integer of 1 to 6;

In the formula, R represents an alkyl group having 1 to 6 carbon atoms or an aryl group, and X ₁ represents H, OH or COOH;

In the formula, R, R ₁ and R ₂ may be the same or different from each other, and each represents an alkyl group or aryl group having 1 to 6 carbon atoms, and X ₁ , X ₂ and Y ₂ are the same or different from each other. There is also provided a method of manufacturing a circuit board, comprising: each showing H, OH or COOH; and forming a metal plating layer on the base substrate treated with the pretreatment agent by electroless metal plating.

In the manufacturing method, the step of treating with the pretreatment agent may be performed by immersing the base substrate in a bath containing the pretreatment agent.
The step of treating with the pretreatment agent may be performed by spraying the pretreatment agent onto the base substrate.
The step of applying an electroless metal plating catalyst to the base substrate includes preparing a base substrate having a connection pad exposed by a solder resist oven, and applying an electroless metal plating catalyst to the connection pad of the base substrate. A step of granting.
The metal may be nickel.

According to a preferred aspect of the present invention, by providing a pretreatment agent for electroless metal plating that is excellent in removal performance for catalyst residues by a combination of specific components, electroless plating between patterns on a circuit board can be achieved. Bridging phenomenon due to precipitation can be prevented.
Moreover, the high performance selective catalyst residue removal performance can be shown, and the plating deposition between the patterns of the densified substrate can be improved.

According to another preferred aspect of the present invention, the catalyst residue removing step can be performed in an environmentally friendly manner by not adding an existing mineral acid or a toxic compound such as a cyanide compound to the pretreatment agent for electroless metal plating. .
Therefore, the corrosion of facilities can be reduced, and the work environment can be deteriorated and the burden of wastewater treatment can be reduced.

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

Objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and preferred embodiments when taken in conjunction with the accompanying drawings.
Prior to this, terms or words used in the specification and claims should not be construed in a normal and lexical sense, so that the inventor best describes the invention. Based on the principle that the concept of terms can be appropriately defined, it should be interpreted with a meaning and concept consistent with the technical idea of the present invention.
In the present invention, it is to be noted that when reference numerals are added to components in each drawing, the same components are given the same numbers as much as possible even if they are displayed on other drawings. . In the description of the present invention, when it is determined that there is a possibility that a specific description of a related known technique may unnecessarily disturb the gist of the present invention, a detailed description thereof will be omitted. In the present specification, terms such as “first” and “second” are used to distinguish one component from another component, and do not limit the component.

式中、ＸおよびＹは、互いに同じでも異なってもよく、それぞれＨ、ＣＨ_２Ｃｌ、ＣＨ_２Ｂｒ、ＣＨ_２Ｉ、ＣＨ_２ＯＨ、ＣＨ_２ＣＯＯＨ、Ｃ_２Ｈ_４Ｃｌ、Ｃ_２Ｈ_４Ｂｒ、Ｃ_２Ｈ_４Ｉ、Ｃ_２Ｈ_４ＯＨまたはＣ_２Ｈ_４ＣＯＯＨを示し、ｎは１〜３の整数を示し、ｍは１〜６の整数を示す。

式中、Ｒ、Ｒ_１およびＲ_２は、互いに同じでも異なってもよく、それぞれ炭素数１〜６のアルキル基またはアリール基を示し、Ｘ_１、Ｘ_２およびＹ_２は、互いに同じでも異なってもよく、それぞれＨ、ＯＨまたはＣＯＯＨを示す。
前記窒素化合物１０１は、触媒、例えば無電解ニッケルメッキ工程の触媒であるＰｄイオンと安定な化合物を形成する。ところが、金属パターン、例えば銅パターン上の金属化触媒と反応しない。前記窒素化合物は、水溶性であって、処理剤内で容易に溶解される。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Electroless Metal Plating Pretreatment Agent FIG. 1 is a diagram schematically showing components of the electroless metal plating pretreatment agent according to a preferred embodiment of the present invention.
Referring to FIG. 1, a pretreatment agent for electroless metal plating, that is, a catalyst removing agent 100, is represented by a nitrogen compound 101 represented by the following chemical formula 1, a surfactant 102, and a chemical formula 2 or 3 below. Comprising a sulfur compound 103 and a secondary catalyst 104:

In the formula, X and Y may be the same as or different from each other, and 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 represents an integer of 1 to 3, and m represents an integer of 1 to 6.

In the formula, R, R ₁ and R ₂ may be the same or different from each other, and each represents an alkyl group or aryl group having 1 to 6 carbon atoms, and X ₁ , X ₂ and Y ₂ are the same or different from each other. Or H, OH or COOH, respectively.
The nitrogen compound 101 forms a stable compound with a catalyst, for example, Pd ion which is a catalyst in an electroless nickel plating process. However, it does not react with a metallization catalyst on a metal pattern, such as a copper pattern. The nitrogen compound is water-soluble and is easily dissolved in the treatment agent.

Further, when the nitrogen compound is processed into a metal pattern, a catalytic metal is deposited on the metal pattern according to the following reaction formula.
[Reaction Formula 1]
Cu + [PdA] ²⁺ → Cu ²⁺ + Pd + A
In the above reaction formula, A represents a nitrogen compound.
The concentration of the nitrogen compound in the pretreatment agent may be 0.001 to 10 mol / L, more preferably 0.1 to 5.0 mol / L.
If the concentration of the nitrogen compound is less than 0.001 mol / L, the concentration of the nitrogen compound that reacts with the catalyst ions is so low that the ability as a catalyst removing agent cannot be exhibited. In addition, if the concentration of the nitrogen compound exceeds 10 mol / L, the nitrogen compound may be supersaturated, the viscosity is too high, and the permeability of the catalyst remover into the fine circuit may be adversely affected. . In addition, the cost of medicine may increase, which may be disadvantageous in terms of efficiency versus cost.

Representative examples of the nitrogen compound include diamine compounds such as ethylenediamine (Ethylenediamine), propylenediamine (Propylenediamine), and butylenediamine (Diethylenetriamine), dipropylenetriamine (Dipropylenetriamine), and dibutylenetriamine (Dibuthylenetriamine). Triamine compounds such as Triethylenetetramine, Tripropylenetetramine, Tributhylenetetramine, and other tetramine compounds, Tetraethylenepentamine, Tetrapropylenepentamine ), Pentamine compounds such as tetrabutylenepentamine (Tetrabuthylenepentamine), pentaethylenehexamine, pentapropylenehexamine (Pentapropylenehexami) ne), hexamine compounds such as Pentabuthylenehexamine, 1-chloroethylene-N-ethyleneediamine, di (1-bromoethylene) -N, N′-propylene Halogenated alkylamine compounds such as diamine (Di- (1-bromoethylene) -N, N'-propylene diamine), 1-hydroxymethylene-N-ethylenediamine, 1-hydroxyethylene- Amino alcohol compounds such as 1-hydroxyethylene-N-buthylene diamine, 1-aminoethylene-N-glycine, ethylenediamine-N, N′-diacetic acid (Ethylenediamine) An amino acid compound such as -N, N'-diacetic acid (EDDA) can be mentioned, but is not particularly limited thereto.

The surfactant 102 is an organic compound, and assists the permeability of the catalyst removing agent that penetrates into the fine circuit. At the same time, the surface energy of the metal pattern is lowered to cause a smooth substitution reaction between the catalyst and the metal. Acts.
The concentration of the surfactant in the pretreatment agent may be 1 × 10 ^{−8 to} 0.1 mol / L, preferably 1 × 10 ^{−6 to} 0.01 mol / L. If the concentration of the surfactant is less than 1 × 10 ⁻⁸ mol / L, the permeability of the catalyst remover into the fine circuit is hardly improved, and the ability of the catalyst remover may be reduced. If the concentration of the surfactant is more than 0.1 mol / L, the water solubility of the organic compound is reduced, and the resulting solution is in the form of a precipitation solution or suspension. This may cause poor adhesion or poor appearance during electroless metal plating, which is a step of the above.

Preferably, as the surfactant, an organic substance having a hydrophilic / lipophilic balance (HLB) value of 10 to 16 can be used. When the HLB value is small, the water solubility is lowered and the precipitate tends to be in the form of a precipitate or suspension, which may be disadvantageous in terms of cost.
Examples of the surfactant include a polyoxyethylene-polyoxypropylene block copolymer having a molecular weight of 2,000 to 200,000, a polyoxyethylene alkyl ether having an HLB value of 10 to 16, and a carbon number of 12 to 18 alkyl sulfonic acids, C12-18 alkylsulfosuccinic acids, and / or C12-18 dialkylsulfosuccinic acids may be included, but are not particularly limited thereto.

The sulfur compound is a substance that binds to a catalyst ion and hinders its catalytic activity when smooth progress is hindered by the reason why the catalyst is removed.
The concentration of the sulfur compound in the pretreatment agent may be 1 × 10 ^{−8 to} 0.1 mol / L, preferably 1 × 10 ^{−6 to} 0.01 mol / L. If the concentration of the sulfur compound is less than 1 × 10 ⁻⁸ mol / L, the permeability of the catalyst remover into the fine circuit of the catalyst is hardly improved, and the ability of the catalyst remover may be reduced. If the concentration of the sulfur compound is more than 0.1 mol / L, the water solubility of the organic compound may be reduced, resulting in a precipitate or suspension state. In the next step, electroless metal plating, it may cause poor adhesion or poor appearance.

Examples of the sulfur compounds include mercaptan compounds such as methyl mercaptan, ethyl mercaptan, thiophenol, thioglycol, and thioglycolic acid, dithiodiglycol, Examples thereof include, but are not limited to, disulfide compounds such as dithioglycolic acid.
Here, if the anti-plating solution between the patterns formulated based on the sulfur compound and the catalyst removal solution based on nitric acid are configured in separate lines, the chemical compounded with the sulfur compound has little removal effect, Nitric acid-based chemicals can dissolve the metals that make up the pattern, such as copper, and require a two-step process, which is economically disadvantageous. . In contrast, in the present invention, a specific nitrogen compound and a specific sulfur compound are blended with a surfactant and a non-catalyst to achieve high catalyst residue removal performance, and at the same time, an environmentally friendly and economical catalyst removal step. It can be performed.
The sub-catalyst 104 is added to prevent abnormal deposition of plating, and is suitable for realizing a high-density circuit by improving the pattern property of electroless metal plating. Hydrogen gas is generated during the plating deposition reaction process in the electroless plating process, but such hydrogen gas promotes plating deposition, and even if there is no catalyst, plating is deposited from the insulating layer between the fine patterns. Prevention of such abnormal deposition of plating is required.

Examples of the secondary catalyst include Pb ions, Bi ions, Sb ions and the like, but are not particularly limited as long as they are known in the art.
The concentration of the secondary catalyst in the pretreatment agent may be 1 × 10 ^{−8 to} 0.1 mol / L, and preferably 1 × 10 ^{−6 to} 0.01 mol / L. If the concentration of the sub-catalyst is less than 1 × 10 ⁻⁸ mol / L, the concentration is so low that the effect as a sub-catalyst may be insufficient. If the concentration of the secondary catalyst is more than 0.1 mol / L, the water solubility of the organic compound may be reduced, resulting in a precipitate or suspension state. In the next step, electroless metal plating, it may cause poor adhesion, poor appearance or poor deposition.

Optionally, the pretreatment agent may contain other additives known in the art within a range that does not interfere with the intended effect. Examples of the additive may include, but are not limited to, a pH adjuster such as NaOH or sulfuric acid, an indicator material for analysis, and the like.
On the other hand, the pH of the pretreatment agent is not particularly limited, but in consideration of the influence on the substrate, the pH is preferably in the range of 4 to 12. If the pH is too low, the compounded sulfur-based compound loses water solubility, and there is a possibility that the working environment is deteriorated by producing a peculiar odor. If the pH is too high, dissolution of the solder resist or the substrate may occur and may have a serious effect.
When the aqueous solution state is maintained, the use temperature of the pretreatment agent is not particularly limited. For example, the usable temperature is 0 to 100 ° C., but it is practically preferable to use at a temperature of 20 to 80 ° C.

Method of manufacturing circuit board Hereinafter, a preferred embodiment of a method of manufacturing a circuit board using the above-described pretreatment agent for electroless metal plating will be described. However, since the pretreatment agent for electroless metal plating is as described above, a detailed description thereof is omitted.

According to a method according to an embodiment of the present invention, first, a base substrate for electroless metal plating is prepared.
The base substrate is a circuit substrate in which one or more layers including connection pads are formed in an insulating layer, and is a semiconductor substrate or a printed substrate. The base substrate may be a normal multilayer circuit board in which at least one circuit is formed on an insulating layer.
Usually, the connection pad is a connection part where an electronic component or an external connection terminal is mounted, and is exposed to the outside by a protective layer, for example, an open portion of a solder resist. The exposed connection pad will be described later. A surface treatment layer such as an electroless nickel / gold plating layer is formed by electroless metal plating through a subsequent process.

The circuit including the connection pads can be applied without limitation as long as it is used as a conductive metal for circuits in the circuit board field, and copper is typically used for printed boards.
As the insulating layer, for example, a resin insulating layer can be used in the case of a printed board, and a ceramic insulating layer can be used in the case of a semiconductor substrate. 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 glass fiber or inorganic filler, for example, a prepreg can be used. In addition, as the resin insulating layer, a thermosetting resin and / or a photocurable resin may be used, but is not particularly limited thereto.

The solder resist functions as a protective layer that protects the outermost layer circuit on the printed circuit board and is formed for electrical insulation, and an open portion is formed to expose the outermost connection pad. The The solder resist can be composed of, for example, a solder resist ink, a solder resist film, or an encapsulating agent as is well 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 electroless metal plating catalyst can be applied to a pattern in which electroless metal plating is performed, that is, a connection pad.

At this time, the metal of the electroless metal plating may be nickel.
Thereafter, 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 applying the electroless metal plating catalyst, it is treated with a pretreatment agent as described above. Between the patterns, for example, the catalyst remaining on the surface of the insulating layer is removed, and a bridge is formed by plating deposition between the patterns. The phenomenon can be prevented. That is, the treatment using the pretreatment agent is typically applied between the electroless metal plating catalyst applying step and the electroless metal plating step.

As the treatment method, a method such as immersing a substrate in a chemical, that is, a bath containing a pretreatment agent, which has been practiced in the past is sufficient, but in some cases, a spraying method such as spraying may be applied. Absent.
Then, as described above, an electroless metal plating layer is formed on a base substrate treated with a pretreatment agent, for example, a connection pad by a conventional electroless metal plating process known in the art, for example, an electroless nickel plating process. .
Subsequently, solder bumps can be formed through a normal subsequent process known in the art, and the semiconductor element or external component can be electrically connected to the inner layer circuit of the circuit board via the solder bumps.

According to the method of the present invention, by treating the base substrate with the above pretreatment agent between the electroless metal plating catalyst application step and the electroless metal plating step, the catalyst residue remaining between the patterns It is possible to realize a fine circuit without bridging phenomenon by removing with excellent performance.
Further, by using a pretreatment agent that does not use an existing mineral acid or cyanide compound, an environmentally friendly and economical catalyst removal step can be performed.

１^＊：トリエチレンテトラミン
２^＊：エチレンジアミン
３^＊：ＥＤＤＡ
４^＊：アルキルスルホン酸（Ｃ＝１４）
５^＊：ジアルキルスルホコハク酸（Ｃ＝１２）
６^＊：エチルメルカプタン
７^＊：ジチオジグリコール酸
８^＊：ＳｂＣｌ_３
９^＊：Ｂｉ（ＮＯ_３）_３

１^＊：メルカプトチアゾリン
２^＊：ＫＳＣＮ
３^＊：Ｎａ_２Ｓ_２Ｏ_３

◎：パターン間の析出現象なし
○：析出があるが、使用においては問題がない
×：少なくない析出が発生して使用不可 Hereinafter, the present invention will be described more specifically with reference to the following examples and comparative examples, but these do not limit the scope of the present invention.
[Examples 1 to 5 and Comparative Examples 1 to 4]
A substrate assuming a bond-finger was manufactured by the MSAP method and used. The pattern space is set to 15, 18, 20, 25, 30, 35 μm, and after applying the catalyst, the catalyst is removed by treatment with a pretreatment agent, and the space after performing the plating process is a 50 × optical microscope. And the presence or absence of precipitation between the patterns was compared.
Here, degreasing before catalyst application, soft etching, catalyst application, catalyst removal (pretreatment) and electroless metal plating were performed under the conditions shown in Table 1 below. The composition of the pretreatment agent was blended as shown in Tables 2 and 3 below.
The results obtained are shown in Table 4 below.

1 ^* : Triethylenetetramine 2 ^* : Ethylenediamine 3 ^* : EDDA
4 ^* : alkylsulfonic acid (C = 14)
5 ^* : Dialkylsulfosuccinic acid (C = 12)
6 ^* : Ethyl mercaptan 7 ^* : Dithiodiglycolic acid 8 ^* : SbCl ₃
9 ^* : Bi (NO ₃ ) ₃

1 ^* : Mercaptothiazoline 2 ^* : KSCN
3 ^* : Na ₂ S ₂ O ₃

◎: No precipitation phenomenon between patterns ○: There is precipitation, but there is no problem in use ×: Not a few precipitations occur and cannot be used

As can be seen from the above results, when the pretreatment for removing the catalyst is not performed as in Comparative Example 4, it cannot be used for a substrate having a space of 30 μm or less. Moreover, in Comparative Examples 1-3, precipitation between patterns of 30 micrometers or less is visible. On the other hand, in Examples 1 to 5 in which the substrate was manufactured using the pretreatment agent according to the present invention, no precipitation was seen up to 18 μm, and even 15 μm was in a state where there was no problem in use.

  As described above, the present invention has been described in detail on the basis of specific examples. However, this is for the purpose of specifically explaining the present invention, and a pretreatment agent for electroless metal plating according to the present invention and the same are used. The method of manufacturing the circuit board is not limited to this, and various modifications and improvements can be made by those having ordinary knowledge in the art within the technical idea of the present invention. All simple variations and modifications of the present invention shall fall within the scope of the present invention, and the specific scope of protection of the present invention will be clearly determined by the claims.

100 Catalyst Remover 101 Nitrogen Compound 102 Surfactant 103 Sulfur Compound 104 Secondary Catalyst

Claims (20)

Nitrogen compounds represented by the following chemical formula 1:

In the formula, X and Y may be the same as or different from each other, and 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 represents an integer of 1 to 3, and m represents an integer of 1 to 6;
Surfactants;
Sulfur compounds represented by the following chemical formula 2 or chemical formula 3:

In the formula, R, R ₁ and R ₂ may be the same or different from each other, and each represents an alkyl group or aryl group having 1 to 6 carbon atoms, and X ₁ , X ₂ and Y ₂ are the same or different from each other. A pretreatment agent for electroless metal plating, characterized by comprising: H, OH or COOH, respectively; and a secondary catalyst.   The nitrogen compound is selected from the group consisting of a diamine compound, a triamine compound, a pentamine compound, a hexamine compound, a halogenated alkylamine compound, an amino alcohol compound, an amino acid compound, and a mixture thereof. The pretreatment agent for electroless metal plating as described.   The nitrogen compound is ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tripropylenetetramine, tributylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, tetrabutylenepentamine, Pentaethylenehexamine, pentapropylenehexamine, pentabylenehexamine, 1-chloroethylene-N-ethylenediamine, di (1-bromoethylene) -N, N′-propylenediamine, 1-hydroxymethylene-N-ethylenediamine, 1-hydroxyethylene -N-butylenediamine, 1-aminoethylene-N-glycine, ethylenediamine-N, N'-diacetic acid (EDDA), and mixtures thereof Characterized in that it is selected from the group consisting of pre-processing agent for electroless metal plating of claim 1.   The surfactant includes polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene alkyl ether, alkyl sulfonic acid having 12 to 18 carbon atoms, alkyl sulfosuccinic acid having 12 to 18 carbon atoms, and dialkyl sulfosuccinic acid having 12 to 18 carbon atoms. The pretreatment agent for electroless metal plating according to claim 1, wherein the pretreatment agent is selected from the group consisting of an acid and a mixture thereof.   The pretreatment agent for electroless metal plating according to claim 1, wherein the sulfur compound is selected from the group consisting of a mercaptan compound, a disulfide compound, and a mixture thereof.   2. The sulfur compound according to claim 1, wherein the sulfur compound is selected from the group consisting of methyl mercaptan, ethyl mercaptan, thiophenol, thioglycol, thioglycolic acid, dithioglycol, dithioglycolic acid, and mixtures thereof. Pretreatment agent for electroless metal plating.   The pretreatment agent for electroless metal plating according to claim 1, wherein the secondary catalyst is a metal ion selected from the group consisting of Pb, Bi, Sb, and combinations thereof.   The pretreatment agent for electroless metal plating according to claim 1, wherein the content of the nitrogen compound in the pretreatment agent is 0.001 to 10 mol / L. 2. The pretreatment agent for electroless metal plating according to claim 1, wherein the content of the surfactant in the pretreatment agent is 1 × 10 ^{−8 to} 0.1 mol / L. 2. The pretreatment agent for electroless metal plating according to claim 1, wherein the content of the sulfur compound in the pretreatment agent is 1 × 10 ^{−8 to} 0.1 mol / L. 2. The pretreatment agent for electroless metal plating according to claim 1, wherein the content of the secondary catalyst in the pretreatment agent is 1 × 10 ^{−8 to} 0.1 mol / L. Applying a catalyst for electroless metal plating to a base substrate;
By treating the base substrate with a pretreatment agent for electroless metal plating containing a nitrogen compound represented by the following chemical formula 1, a surfactant, a sulfur compound represented by the following chemical formula 2 or 3 and a secondary catalyst. Removing the catalyst on the surface of the insulating layer of the base substrate:

In the formula, X and Y may be the same as or different from each other, and 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 represents an integer of 1 to 3, and m represents an integer of 1 to 6;

In the formula, R represents an alkyl group having 1 to 6 carbon atoms or an aryl group, and X ₁ represents H, OH or COOH;

In the formula, R, R ₁ and R ₂ may be the same or different from each other, and each represents an alkyl group or aryl group having 1 to 6 carbon atoms, and X ₁ , X ₂ and Y ₂ are the same or different from each other. And a step of forming a metal plating layer by electroless metal plating on the base substrate treated with the pretreatment agent, each of which represents H, OH, or COOH. .   The method of manufacturing a circuit board according to claim 12, wherein 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 manufacturing a circuit board according to claim 12, wherein the step of treating with the pretreatment agent is performed by spraying a pretreatment agent on the base substrate. The step of applying a catalyst for electroless metal plating to the base substrate includes:
Preparing a base substrate having connection pads exposed by a solder resist oven section;
The method for manufacturing a circuit board according to claim 12, further comprising: applying a catalyst for electroless metal plating to the connection pad of the base substrate.   The method for manufacturing a circuit board according to claim 12, wherein the metal is nickel.   The nitrogen compound is selected from the group consisting of a diamine compound, a triamine compound, a pentamine compound, a hexamine compound, a halogenated alkylamine compound, an amino alcohol compound, an amino acid compound, and a mixture thereof. The manufacturing method of the circuit board of description.   The surfactant includes polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene alkyl ether, alkyl sulfonic acid having 12 to 18 carbon atoms, alkyl sulfosuccinic acid having 12 to 18 carbon atoms, and dialkyl sulfosuccinic acid having 12 to 18 carbon atoms. The method for producing a circuit board according to claim 12, wherein the circuit board is selected from the group consisting of an acid and a mixture thereof.   The method for manufacturing a circuit board according to claim 12, wherein the sulfur compound is selected from the group consisting of a mercaptan compound, a disulfide compound, and a mixture thereof.   The method of manufacturing a circuit board according to claim 12, wherein the secondary catalyst is a metal ion selected from the group consisting of Pb, Bi, Sb, and combinations thereof.

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