KR102048495B1 - Etching solution for msap substrate - Google Patents

Abstract

The present invention relates to an etching solution for manufacturing an MSAP substrate, and more particularly, to an etching solution for manufacturing a modified semi additive process (MSAP) substrate capable of efficiently removing a seed layer used for forming a circuit. To this end, the etching solution for preparing the MSAP substrate is acid; Hydrogen peroxide; First etching inhibitor; And a second etching inhibitor, wherein the first etching inhibitor is an amino phosphonic compound, and the second etching inhibitor is at least one of a triazole compound and a tetrazole compound.

Description

Etching solution for manufacturing MSAP substrate {ETCHING SOLUTION FOR MSAP SUBSTRATE}

The present invention relates to an etching solution for manufacturing an MSAP substrate, and more particularly, to an etching solution for manufacturing a modified semi additive process (MSAP) substrate capable of efficiently removing a seed layer used for forming a circuit.

With the development of the electronics industry, electronic components have become highly functional and miniaturized. In particular, there is an increasing demand for reducing the thickness of components mounted in order to reduce the thickness of portable terminals.

Methods for forming a circuit during a printed circuit board manufacturing process used in a portable terminal or the like are divided according to the degree of miniaturization of the circuit, which can be classified as shown in FIG. 1.

Tenting-etching is a method of forming a circuit pattern by forming an etching resist pattern on a copper foil having a constant thickness on a copper clad laminate, and etching a portion other than a circuit by immersing the substrate in an etching solution. After forming a seed layer (seed layer) on the copper-free laminated plate is a method of forming a plating resist pattern, forming only the portion to be a circuit by plating, and then removing the plating resist and seed layer to implement a circuit pattern. As can be seen from Fig. 1 (right), the SAP method is applied to the manufacture of ultra-fine printed circuit boards of Line / Space 20/20 or less.

On the other hand, the modified semi-additive process (MSAP) method, which is an improvement of the SAP method, is applied to manufacturing a micro circuit board of Line / Space 20/20 or more, and uses a copper foil as a seed layer. Since the seed layer is thick (˜2 μm), the etching time is long, and the circuit line width is greatly reduced. In particular, sulfuric acid / hydrogen peroxide-based etching solution, hydrochloric acid / copper-based etching solution, and hydrochloric acid / ferrous iron-based etching solution used in the related art have a problem that the etching rate of copper foil is slower than that of the circuit (electrophoresis), resulting in a larger reduction in the circuit. It was not applicable to the manufacture of microcircuit boards.

Accordingly, there is a demand for the development of an etching solution capable of minimizing a reduction in circuit line width by selectively etching a seed layer quickly.

Republic of Korea Patent Publication No. 10-1618522

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide an etching solution for manufacturing a Modified Semi Additive Process (MSAP) substrate which can minimize the reduction of the circuit line width by efficiently removing the seed layer. have.

These and other objects and advantages of the present invention will become apparent from the following description of preferred embodiments.

The object is acid; Hydrogen peroxide; First etching inhibitor; And a second etching inhibitor, wherein the first etching inhibitor is an amino phosphonic compound, and the second etching inhibitor is at least one of a triazole compound and a tetrazole compound. Can be.

In this case, the acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, maleic acid, benzoic acid and glycolic acid.

In addition, the amino phosphonic series compounds include nitrilotri (methylphosphonic acid), diethylenetriaminepentakis (dimethylphosphonic acid), and hexamethylenediamine. -N, N, N ', N'-tetrakis (methylphosphonic acid) (Hexamethylenediamine-N, N, N', N'-tetrakis (methylphosphonic acid)), N, N-bis (phosphonomethyl) glycine ( N, N-Bis (phosphonomethyl) glycine), imindi (methylphosphonic acid), N- (phosphonomethyl) iminodiacetic acid (N- (Phosphonomethyl) iminodiacetic acid), 1-hydroxy 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxyethylidene diphosphonic acid (HEDP) and diethylenetriaminepenta ( Methylene phosphonic acid) (diethylenetriamine penta (methylene phosphonic acid), DTPMP) may be at least one selected from the group consisting of. .

In addition, the triazole-based compound is 1,2,4-triazole (1,2,4-Triazole), 1,2,3-triazole (1,2,3-Triazole), 4-amino-4H-1 , 2,4-triazole (4-Amino-4H-1,2,4-triazole), 3-amino-1,2,4-triazole, 3-H -1,2,4-triazole-3-amine (4H-1,2,4-Triazol-3-amine), 3-amino-5-methyl-4H-1,2,4-triazole (3- Amino-5-methyl-4H-1,2,4-triazole), 3,5-diamino-1,2,4-triazole and 3,5-diamino-1,2,4-triazole It may be at least one selected from the group consisting of 2,4-triazole-3-carboxylic acid (1,2,4-Triazole-3-carboxylic acid).

In addition, the tetrazole-based compound is 5-aminotetrazole (5-Aminotetrazole), 5-methyl-1H-tetrazole (5-Methyl-1H-tetrazole), 5- (aminomethyl) tetrazole (5- (aminomethyl) tetrazole) and 1H-tetrazole-5-acetic acid (1H-Tetrazole-5-acetic acid) may be at least one selected from the group consisting of.

Preferably, the concentration ratio of the first etching inhibitor and the second etching inhibitor may be 1: 1 to 10.

According to the present invention, it is possible to minimize the reduction in the circuit line width during the etching process by controlling the etching rate of the seed layer (seed layer) relative to the etching rate of the circuit.

In addition, when manufacturing a coreless substrate, there is an effect of minimizing a recession depth in a micro etching process of removing a carrier copper foil.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a view showing a manufacturing method of a printed circuit board.
2 is a view schematically showing an etching process of the MSAP method.
3 is a graph showing the etching rate test results of Examples and Comparative Examples.
4 is a view schematically showing the behavior of the first etching inhibitor and the second etching inhibitor.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings of the present invention. These examples are only presented by way of example only to more specifically describe the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

Also, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the case of conflict, the specification including definitions The description of will prevail.

In the drawings, parts irrelevant to the description are omitted to clearly describe the proposed invention, and like reference numerals designate like parts throughout the specification. In addition, when a part is said to "include" a certain component, this means that it may further include other components, without excluding other components unless otherwise stated. In addition, the "unit" described in the specification means one unit or block that performs a specific function.

In each step, an identification code (first, second, etc.) is used for convenience of description, and the identification code does not describe the order of each step, and each step does not explicitly describe a specific order in context. It may be carried out in a different order than described above. That is, each step may be performed in the same order as specified, may be performed substantially simultaneously, or may be performed in the reverse order.

Etching solution for producing MSAP substrate according to an embodiment of the present invention is an acid; Hydrogen peroxide; First etching inhibitor; And a second etching inhibitor, wherein the first etching inhibitor is an amino phosphonic compound, and the second etching inhibitor is at least one of a triazole compound and a tetrazole compound. The present invention includes a first etching inhibitor and a second etching inhibitor in an etching solution containing an acid and hydrogen peroxide (for example, sulfuric acid / peroxide type etching solution), thereby suppressing an undercut in manufacturing an MSAP substrate. By controlling the etch rate of the seed layer (seed layer) relative to the etch rate of to have a large effect to minimize the reduction in the circuit line width during the etching process (see Fig. 2).

The acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, maleic acid, benzoic acid and glycolic acid, with sulfuric acid being most preferred. Hydrogen peroxide may be included in an amount of 20 to 2000 parts by weight based on 100 parts by weight of acid.

The first etching inhibitor may be an amino phosphonic compound. The amino phosphonic series compound means a compound selected from phosphonic acid derivatives having an amino group and salts thereof, and may be nitrilotri (methylphosphonic acid) and / or derivatives thereof. . Preferably, nitrilotri (methylphosphonic acid), diethylenetriaminepentakis (methylphosphonic acid), hexamethylenediamine-N, N, N ′, N ′ Tetrakis (methylphosphonic acid) (Hexamethylenediamine-N, N, N ′, N′-tetrakis (methylphosphonic acid)), N, N-bis (phosphonomethyl) glycine (N, N-Bis (phosphonomethyl) glycine) , Iminedi (methylphosphonic acid), N- (phosphonomethyl) iminodiacetic acid, N- (Phosphonomethyl) iminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphone Acid (1-hydroxyethylidene-1,1-diphosphonic acid), 1-hydroxyethylidene diphosphonic acid (HEDP) and diethylenetriamine penta (methylene phosphonic acid) acid), DTPMP) may be at least one selected from the group consisting of: It is preferable that the density | concentration of a 1st etching inhibitor is 0.001-10 g / L. If it is less than 0.001 g / L, it may not function as an inhibitor, and if it exceeds 10 g / L, the effect of the second etching inhibitor may not be expressed.

The second etching inhibitor may be at least one of a triazole compound and a tetrazole compound. The triazole compound may be 1,2,4-triazole and / or derivatives thereof. Preferably, 1,2,4-triazole, 1,2,3-triazole, 4-amino-4H-1,2,4 -Triazole (4-Amino-4H-1,2,4-triazole), 3-amino-1,2,4-triazole, 4H-1,2 , 4-triazole-3-amine (4H-1,2,4-Triazol-3-amine), 3-amino-5-methyl-4H-1,2,4-triazole (3-Amino-5- methyl-4H-1,2,4-triazole), 3,5-diamino-1,2,4-triazole and 3,5-Diamino-1,2,4-triazole and 1,2,4- It may be at least one selected from the group consisting of triazole-3-carboxylic acid (1,2,4-Triazole-3-carboxylic acid). The tetrazole compound may be 5-aminotetrazole and / or derivatives thereof. Preferably, 5-aminotetrazole, 5-methyl-1H-tetrazole, 5- (aminomethyl) tetrazole and 1H It may be at least one selected from the group consisting of tetrazol-5-acetic acid (1H-Tetrazole-5-acetic acid). It is preferable that the density | concentration of a 2nd etching inhibitor is 0.001-20 g / L. If it is less than 0.001 g / L, it cannot function as an inhibitor, and if it exceeds 20 g / L, the etching selectivity of the seed layer relative to the circuit may be reduced.

Preferably, the concentration ratio of the first etching inhibitor and the second etching inhibitor may be 1: 1 to 10. Outside the concentration range, it may be difficult to control the etching rate of the seed layer relative to the etching rate of the circuit such that the performance of the second etching inhibitor is not exhibited.

Hereinafter, the configuration of the present invention and its effects through specific examples and comparative examples will be described in more detail. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

[Production example]

Etching solutions of Examples and Comparative Examples were prepared using the composition shown in Table 1 below.

TABLE 1

Experimental Example

The seed layer (copper foil) manufactured by Mitsui Co., Ltd. was used as a seed layer, and the circuit was used as a specimen prepared by electroplating, and a beaker test (rpm 1,400) was performed at a temperature of 30 ° C. The results are shown in Table 2 and FIG. 3.

TABLE 2

As can be seen from Table 2 and Figure 3, it can be seen that the embodiment can significantly increase the etching rate of the seed layer (seed layer) compared to the circuit etching rate compared to Comparative Examples 1 to 3. This is expected to be caused by the difference in the relative adsorptive force between the first and second etching inhibitors. That is, the first etching inhibitor (Nitrilotri (methylphosphonic acid)) having excellent suppression ability is more strongly adsorbed on the circuit surface than the second etching inhibitor (1,2,4-Triazole or 5-Aminotetrazole), and the second inhibiting ability is somewhat lower. It is expected that the etch inhibitor was strongly adsorbed on the surface of the seed layer (see FIG. 4) to increase the etching rate of the seed layer relative to the etching rate of the circuit.

In the present specification, only a few examples of various embodiments performed by the present inventors are described, but the technical idea of the present invention is not limited thereto, but may be variously modified and implemented by those skilled in the art.

Claims (6)

mountain; Hydrogen peroxide; First etching inhibitor; And a second etching inhibitor;
The first etching inhibitor is an amino phosphonic compound,
The second etching inhibitor is at least one of a triazole compound and a tetrazole compound,
The first etching inhibitor and the second etching inhibitor are included in the concentration range of 0.001 ~ 10 g / L and 0.001 ~ 20 g / L, respectively, the concentration ratio of the first etching inhibitor and the second etching inhibitor is 1: 1 ~ 10 ego,
The acid is at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, maleic acid, benzoic acid and glycolic acid,
Hydrogen peroxide is mixed in the range of 20 to 2000 parts by weight based on 100 parts by weight of acid,
In the manufacturing process of the MSAP board | substrate with which a circuit board was formed in the copper foil seed layer, the etching rate of a seed layer is larger than the etching rate of a circuit, The etching liquid for MSAP board | substrate manufacture. delete The method of claim 1, wherein the amino phosphonic compound,
Nitrilotri (methylphosphonic acid), diethylenetriaminepentakis (methylphosphonic acid), hexamethylenediamine-N, N, N ′, N′-tetrakis (Hexamethylenediamine-N, N, N ', N'-tetrakis (methylphosphonic acid)), N, N-bis (phosphonomethyl) glycine (N, N-Bis (phosphonomethyl) glycine), iminedi (Methylphosphonic acid) (Iminodi (methylphosphonic acid)), N- (phosphonomethyl) iminodiacetic acid (N- (Phosphonomethyl) iminodiacetic acid) and diethylenetriamine penta (methylene phosphonic acid) ), DTPMP), at least one selected from the group consisting of, MSAP substrate manufacturing etching liquid. The compound according to claim 1, wherein the triazole-based compound is
1,2,4-triazole, 1,2,3-triazole, 4-amino-4H-1,2,4-triazole (4-Amino-4H-1,2,4-triazole), 3-amino-1,2,4-triazole, 4H-1,2,4- Triazole-3-amine (4H-1,2,4-Triazol-3-amine), 3-amino-5-methyl-4H-1,2,4-triazole (3-Amino-5-methyl-4H -1,2,4-triazole), 3,5-diamino-1,2,4-triazole and 1,2,4-triazole- Etching solution for producing MSAP substrate, characterized in that at least any one selected from the group consisting of 3-carboxylic acid (1,2,4-Triazole-3-carboxylic acid). The method of claim 1, wherein the tetrazole-based compound,
5-Aminonotetrazole, 5-Methyl-1H-tetrazole, 5- (aminomethyl) tetrazole and 1H-tetrazole -5-acetic acid (1H-Tetrazole-5-acetic acid), at least any one selected from the group consisting of, MSAP substrate manufacturing etching solution.




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