KR-102962793-B1 - Surface modifier, laminate, method for forming a metal wiring pattern, and method for manufacturing a printed circuit board

KR102962793B1KR 102962793 B1KR102962793 B1KR 102962793B1KR-102962793-B1

Abstract

The objective of the present invention is to provide a surface modifier that achieves compatibility between etchability and peelability of a resist material, a laminate using said surface modifier, a method for forming a metal wiring pattern, and a method for manufacturing a printed circuit board. The surface modifier of the present invention is characterized by containing a nitrogen-containing complex aromatic ring compound having a structure represented by the following general formula (1), wherein the ClogP of said nitrogen-containing complex aromatic ring compound is within the range of 2 to 5. [In general formula (1), X1 to X5 each independently represent a nitrogen atom or CR1 . R1 each independently represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a thiol group, a carbonyl group, a halogen group, a trifluoromethyl group, or a hydroxyl group, and may additionally have substituents.]

Inventors

아리타 히로아키
하라 준
야마다 데츠야

Assignees

코니카 미놀타 가부시키가이샤

Dates

Publication Date: 20260508
Application Date: 20220623
Priority Date: 20210715

Claims (12)

As a surface modifier used between a metal layer and a resist layer in forming a metal wiring pattern, A nitrogen-containing complex cyclic compound having a structure represented by the following general formula (1), and A surface modifier characterized by the ClogP of the nitrogen-containing complex cyclic compound being within the range of 2 to 5. [In general formula (1), X1 to X5 each independently represent a nitrogen atom or CR1 . R1 each independently represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a thiol group, a carbonyl group, a halogen group, a trifluoromethyl group, or a hydroxyl group, and may additionally have substituents.]
In Article 1, A surface modifier characterized in that, in the above general formula (1), X1 , X2 and X4 represent CR1 , and X3 and X5 represent nitrogen atoms.
In Article 1, A surface modifier characterized by the concentration of the above-mentioned nitrogen-containing complex aromatic ring compound being within the range of 0.1 to 500 mass ppm.
In Article 1, A surface modifier characterized by containing at least water or alcohols as a solvent.
A laminate having a metal layer, a surface modification layer, and a resist layer, The above surface modification layer contains a nitrogen-containing complex cyclic compound having a structure represented by the following general formula (1), and A laminate characterized in that the ClogP of the nitrogen-containing complex cyclic compound is within the range of 2 to 5. [In general formula (1), X1 to X5 each independently represent a nitrogen atom or CR1 . R1 each independently represents a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a cyano group, a thiol group, a carbonyl group, a halogen group, a trifluoromethyl group, or a hydroxyl group, and may additionally have substituents.]
In Article 5, A laminate characterized in that, in the above general formula (1), X1 , X2 and X4 represent CR1 , and X3 and X5 represent nitrogen atoms.
In Article 5, A laminate characterized in that the above metal layer is a layer having copper or a copper alloy as its main component.
A method for forming a metal wiring pattern by photolithography, A method for forming a metal wiring pattern characterized by having a process of forming a surface modification layer between a metal layer and a resist layer using a surface modification agent described in claim 1.
In Article 8, A method for forming a metal wiring pattern characterized by having the following processes (A) to (F). Process (A): A process for acid cleaning a metal-clad laminate having a metal layer formed on an insulating layer. Process (B): A process of forming a surface modification layer on the metal layer of the metal-clad laminate using the surface modification agent described in claim 1. Process (C): A process of forming a resist layer containing a photosensitive resin on the surface modification layer. Process (D): A process for patterning the above resist layer by exposure and development. Process (E): A process of etching the surface modification layer and the metal layer through the resist layer. Process (F): A process of peeling off the resist layer from the metal-clad laminate.
In Article 9, A method for forming a metal wiring pattern, characterized by having a process of washing the metal-clad laminate on which the surface modification layer is formed between the above process (B) and the above process (C).
In Article 8, A method for forming a metal wiring pattern characterized in that the metal layer is a layer having copper or a copper alloy as its main component.
A method for manufacturing a printed circuit board by photolithography, A method for manufacturing a printed circuit board characterized by including a method for forming a metal wiring pattern as described in claim 8.

Description

Surface modifier, laminate, method for forming a metal wiring pattern, and method for manufacturing a printed circuit board The present invention relates to a surface modifier, a laminate, a method for forming a metal wiring pattern, and a method for manufacturing a printed circuit board. More specifically, the invention relates to a surface modifier that achieves both etchability and peelability of a resist material. Recently, with the advancement of data society, there is a demand for printed circuit boards with high-density and high-precision wiring. When manufacturing such printed circuit boards by photolithography, it is necessary to etch the metal layer by interposing a resist layer in which lines (areas where metal wiring is formed) and spaces (areas between metal wiring where metal wiring is not formed) are narrowly patterned. In the case of a narrow line, the contact area between the resist layer and the metal layer is small, which lowers the adhesion between the two layers and may lead to etching defects, such as the etching solution dissolving and removing the necessary parts. As a means to improve the adhesion between the resist layer and the metal layer, Patent Document 1 discloses a technique for forming a molecular bonding layer between the resist layer and the metal layer. In addition, Patent Document 2 discloses a surface treatment agent capable of strongly adhering to a dry film resist, etc. However, it was found that these prior art technologies had a problem with the peelability of the resist layer. Since the resist layer needs to be peeled off without residue after the etching process, it is necessary to achieve both adhesion and peelability, rather than simply increasing the adhesion between the resist layer and the metal layer. In addition, when the line is narrow, the effect of side etching of the metal layer becomes more pronounced, making it difficult to achieve both adhesion and peelability, and the aforementioned prior art was not able to sufficiently solve such problems. FIG. 1 is a diagram showing the process of forming a metal wiring pattern (metal-clad laminate). FIG. 2 is a diagram showing the process of forming a metal wiring pattern (formation of a surface modification layer). FIG. 3 is a diagram showing the process of forming a metal wiring pattern (formation of a resist layer). FIG. 4 is a diagram showing the process of forming a metal wiring pattern (patterning of the resist layer). FIG. 5 is a diagram showing the process of forming a metal wiring pattern (etching of the surface modification layer and the metal layer). FIG. 6 is a diagram showing the process of forming a metal wiring pattern (peeling of the resist layer). The surface modifier of the present invention is a surface modifier used between a metal layer and a resist layer in forming a metal wiring pattern, and is characterized by containing a nitrogen-containing complex aromatic ring compound having a structure represented by the general formula (1), wherein the ClogP of the nitrogen-containing complex aromatic ring compound is within the range of 2 to 5. This feature is a technical feature common to or corresponding to the following embodiments. In an embodiment of the surface modifier of the present invention, in order to improve adhesion and peelability in a good balance, it is preferable that X1 , X2 and X4 in general formula (1) represent CR1 , and X3 and X5 represent nitrogen atoms. In an embodiment of the surface modifier of the present invention, from the perspective of solubility, it is preferable that the concentration of the nitrogen-containing complex aromatic ring compound be within the range of 0.1 to 500 mass ppm. In an embodiment of the surface modifier of the present invention, it is preferable to contain at least water or alcohols as a solvent from the perspective of solubility. The laminate of the present invention is a laminate comprising a metal layer, a surface modification layer, and a resist layer, wherein the surface modification layer contains a nitrogen-containing complex aromatic ring compound having a structure represented by the general formula (1), and the ClogP of the nitrogen-containing complex aromatic ring compound is within the range of 2 to 5. In an embodiment of the laminate of the present invention, in order to improve adhesion and peelability in a good balance, it is preferable that X1 , X2 , and X4 in the general formula (1) represent CR1 , and X3 and X5 represent nitrogen atoms. In an embodiment of the laminate of the present invention, from the perspective of processability or conductivity, it is preferable that the metal layer is a layer having copper or a copper alloy as the main component. The method for forming a metal wiring pattern according to the present invention is a method for forming a metal wiring pattern by photolithography, characterized by having a process of forming a surface modification layer between a metal layer and a resist layer using a surfac