CN115216771B - Printed circuit board copper surface roughening liquid and application thereof - Google Patents

Printed circuit board copper surface roughening liquid and application thereof Download PDF

Info

Publication number
CN115216771B
CN115216771B CN202211142619.7A CN202211142619A CN115216771B CN 115216771 B CN115216771 B CN 115216771B CN 202211142619 A CN202211142619 A CN 202211142619A CN 115216771 B CN115216771 B CN 115216771B
Authority
CN
China
Prior art keywords
copper surface
circuit board
copper
acid
surface roughening
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211142619.7A
Other languages
Chinese (zh)
Other versions
CN115216771A (en
Inventor
郝意
黄志齐
黄进
王银全
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Boardtech Co Ltd
Original Assignee
Shenzhen Boardtech Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Boardtech Co Ltd filed Critical Shenzhen Boardtech Co Ltd
Priority to CN202211142619.7A priority Critical patent/CN115216771B/en
Publication of CN115216771A publication Critical patent/CN115216771A/en
Application granted granted Critical
Publication of CN115216771B publication Critical patent/CN115216771B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067—Etchants

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention discloses a copper surface roughening liquid for a printed circuit board and application thereof, and relates to the field of circuit board manufacturing. The roughening liquid comprises: comprises the following components in mass concentration: 50-150g/L of sulfuric acid, 10-40g/L of hydrogen peroxide, 1-10g/L of stabilizer, 0.5-5g/L of promoter, 5-50g/L of divalent copper ions and the balance of deionized water; the stabilizer is a mixture of sodium silicate and an organic chelating agent, and the mass ratio of the sodium silicate to the organic chelating agent is 1: (0.2-6). The copper surface roughening solution for the printed circuit board provided by the invention can stabilize the roughening solution and prevent the phenomena of chromatic aberration and uneven roughening through the synergistic effect of the components of the stabilizer and the coordination of other components such as the accelerator. The surface of the printed circuit board after the super-roughening treatment has uniform color and ideal roughening effect, and the quality and yield of the printed circuit board can be effectively improved.

Description

Printed circuit board copper surface roughening liquid and application thereof
Technical Field
The invention relates to the field of circuit board manufacturing, in particular to a copper surface roughening solution for a printed circuit board and application thereof.
Background
In the production process of the printed circuit board, in order to ensure that the chemical copper plating layer is firmly combined with the matrix copper foil, the quality of the printed circuit board is improved, and the copper surface is generally subjected to pretreatment in order to avoid the attack of chemical agents in the subsequent developing and etching processes, the copper surface after super-roughening is cellular, so that the copper surface area can be obviously increased, the adhesive force between the film and the copper surface is improved, and the problem of the bonding force of the film in the process of manufacturing the fine circuit of the high-density circuit board is well solved. The hydrogen peroxide-sulfuric acid series inorganic acid super-roughening method is a super-roughening process which is widely applied at present, and the super-roughening method has the advantages of simple process operation, small environmental pollution and low treatment cost, but the phenomena of low roughening speed, unstable roughening and easy oxidation of a copper surface often exist, and if the super-roughening method is used for pretreatment of a circuit, the roughening effect, the roughening stability and the oxidation resistance of the copper surface need to be further improved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a copper surface roughening solution for a printed circuit board and application thereof. The method specifically comprises the following technical scheme:
in a first aspect, the roughening liquid for the copper surface of the printed circuit board comprises the following components in mass concentration:
50-150g/L of sulfuric acid,
10-40g/L of hydrogen peroxide,
1-10g/L of stabilizing agent,
0.5-5g/L of accelerator,
divalent copper ions 5-50g/L,
the balance of deionized water;
the stabilizer is a mixture of sodium silicate and an organic chelating agent, and the mass ratio of the sodium silicate to the organic chelating agent is 1: (0.2-6); the organic chelating agent is a mixture of diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid, and the mass ratio of the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1: (1-5); the accelerator is a mixture of formic acid and 3-amino-1, 2, 4-triazole, and the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1: (0.25-1); the divalent copper ions are selected from one of copper formate and copper sulfate.
Further, the copper surface roughening liquid for the printed circuit board comprises the following components in mass concentration:
60-140g/L of sulfuric acid,
15-35g/L of hydrogen peroxide,
2-8 g/L of stabilizing agent,
1.5-4.5g/L of accelerant,
divalent copper ions 10-45g/L,
the balance being deionized water.
Further, the copper surface roughening liquid for the printed circuit board comprises the following components in mass concentration:
65-130g/L of sulfuric acid,
20-30g/L of hydrogen peroxide,
3-7 g/L of stabilizing agent,
2-4g/L of an accelerant,
10-40g/L of divalent copper ions,
the balance being deionized water.
Further, the copper surface roughening liquid for the printed circuit board comprises the following components in mass concentration:
70-120g/L of sulfuric acid,
22-28g/L of hydrogen peroxide,
4-6 g/L of stabilizing agent,
2.5-4g/L of accelerant,
divalent copper ions 20-38g/L,
the balance being deionized water.
Further, the mass ratio of the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1: (2-4).
Further, the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1: (0.5-0.8).
Further, the copper surface roughening liquid for the printed circuit board comprises the following components in mass concentration:
100g/L of sulfuric acid is added,
25g/L of hydrogen peroxide solution,
5g/L of a stabilizing agent is added,
the content of the accelerator is 4g/L,
the concentration of the bivalent copper ions is 35g/L,
the balance of deionized water;
the stabilizer is a mixture of sodium silicate, diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid, and the mass ratio of the sodium silicate to the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1:1:3;
the accelerator is a mixture of formic acid and 3-amino-1, 2, 4-triazole, and the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1:0.6; the divalent copper ions are copper sulfate.
In a second aspect, a super-roughening method is provided, which is characterized in that the copper surface roughening solution of the printed circuit board in the first aspect is sprayed on a copper wire of the circuit board in a horizontal spraying mode, and the spraying pressure is 0.5-2.0kg/cm 2 。
Furthermore, the use temperature of the copper surface roughening liquid for the printed circuit board is 15-35 ℃.
Furthermore, the spraying time of the roughening liquid for the copper surface of the printed circuit board is 30-60s.
According to the invention, the composition compounded by adding the adsorption type stabilizer, namely the sodium silicate, the chelating type stabilizer and the organic chelating agent is used as the stabilizer, compared with a single type of stabilizer, the composite is more resistant to high temperature and high copper, and can more effectively stabilize the decomposition of hydrogen peroxide by matching; the organic chelating agents are reasonably compounded by two different types of organic chelating agents, namely organic phosphate type diethylenetriamine pentamethylene phosphonic acid and polycarboxylic polymethacrylic acid, so that the synergistic effect of the two chelating agents can be exerted, and the roughness and the micro-corrosion of the copper surface are controlled within an ideal range; the copper surface coarsening can be effectively promoted by the accelerant compounded by formic acid and 3-amino-1, 2, 4-triazole, so that the overall coarsening uniformity is ensured; by adding divalent copper ions, which mainly act as an oxidizing agent in the roughening solution, an effective roughening rate and uniformity of roughening can be provided. The components in the roughening solution are matched with each other, so that the roughening solution is stable, the binding force between the copper surface and the dry film is effectively enhanced, and the oxidation of the copper surface is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is an SEM photograph of test example 1 of the present invention;
FIG. 2 is an SEM photograph of test example 2 of the present invention;
FIG. 3 is an SEM photograph of comparative example 6 of the present invention;
FIG. 4 is an SEM photograph of comparative example 9 of the present invention;
FIG. 5 is an SEM photograph of comparative example 11 of the present invention;
FIG. 6 is an SEM photograph of comparative example 14 of the present invention.
Detailed Description
In the following, technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items and includes such combinations.
In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated with reference to specific embodiments.
Preparation method of copper surface roughening liquid for printed circuit board
S1, adding a proper amount of deionized water into sulfuric acid, stirring and dissolving, and uniformly mixing to obtain a phase A solution;
s2, adding a stabilizer and divalent copper ions into the phase A solution, stirring and dissolving, and uniformly mixing to obtain a phase B solution;
s3, adding hydrogen peroxide into the B phase solution, stirring and dissolving, and uniformly mixing to obtain a C phase solution;
and S4, adding an accelerator into the phase C solution, stirring and dissolving, and adding water to a standard volume to obtain the copper surface roughening solution for the printed circuit board.
Super-roughening method
Plate surface cleaning → water washing → copper surface roughening → water washing → acid washing → water washing → dry plate.
The copper surface roughening method comprises the following steps: spraying the copper surface roughening liquid of the printed circuit board to a copper wire path of the circuit board in a horizontal spraying mode under the condition that the temperature of the copper surface roughening liquid of the printed circuit board is 15-35 ℃, wherein the spraying pressure is 0.5-2.0kg/cm 2 The spraying time is 30-60s. And after the copper surface is coarsened, testing the test circuit board sample according to the following performance test method.
The performance test method comprises the following steps:
the test circuit board samples were tested according to the following performance test method:
1. surface appearance: visually, observing that the surface of the copper treated by the coarsening agent has uniform appearance and color, no darkness, flat surface, no pit and no scratch and is qualified;
2. and (3) detecting the microetching amount: the micro-etching amount is controlled between 0.5 and 1.0 micron by measuring the weight change detection of copper before and after coarsening;
3. roughness: detecting the roughness after coarsening by a white light interferometer, wherein the roughness Ra value is controlled between 0.25 and 0.35.
Test example 1
The copper surface roughening liquid for the printed circuit board comprises the following components in mass concentration: 100g/L of sulfuric acid, 25g/L of hydrogen peroxide, 5g/L of stabilizer, 4g/L of accelerator, 35g/L of divalent copper ions and the balance of deionized water; the stabilizer is a mixture of sodium silicate, diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid, and the mass ratio of the sodium silicate to the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1:1:3; the accelerator is a mixture of formic acid and 3-amino-1, 2, 4-triazole, and the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1:0.6; the divalent copper ions are copper sulfate.
The preparation method of the copper surface roughening liquid for the printed circuit board comprises the following steps: s1, adding a proper amount of deionized water into sulfuric acid, stirring and dissolving, and uniformly mixing to obtain a phase A solution; s2, adding a stabilizer and divalent copper ions into the phase A solution, stirring and dissolving, and uniformly mixing to obtain a phase B solution; s3, adding hydrogen peroxide into the B phase solution, stirring and dissolving, and uniformly mixing to obtain a C phase solution; and S4, adding an accelerator into the phase C solution, stirring and dissolving, and adding water to a standard volume to obtain the copper surface roughening solution for the printed circuit board.
And carrying out super-roughening treatment on the circuit board by adopting a copper surface roughening solution of the printed circuit board. The super-coarsening method comprises the following steps: plate surface cleaning → water washing → copper surface roughening → water washing → acid washing → water washing → dry plate. The copper surface roughening method comprises the following steps: spraying the copper surface roughening solution of the printed circuit board to a copper wire of the circuit board in a horizontal spraying mode under the condition that the temperature of the copper surface roughening solution of the printed circuit board is 25 ℃, wherein the spraying pressure is 1.5kg/cm 2 The spraying time was 45s. The wiring board of test example 1 was obtained after the copper surface was roughened. FIG. 1 is an SEM photograph of test example 1.
The methods for preparing the copper surface roughening solutions and the super-roughening methods for the printed wiring boards in test examples 2 to 5 were the same as in test example 1.
Test example 2
The copper surface roughening liquid for the printed circuit board comprises the following components in mass concentration: 65g/L of sulfuric acid, 20g/L of hydrogen peroxide, 3 g/L of stabilizer, 2g/L of accelerator, 10g/L of divalent copper ions and the balance of deionized water; the stabilizer is a mixture of sodium silicate, diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid, and the mass ratio of the sodium silicate to the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1:1:1; the accelerator is a mixture of formic acid and 3-amino-1, 2, 4-triazole, and the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1:0.25; the divalent copper ions are copper sulfate.
Test example 3
The copper surface roughening liquid for the printed circuit board comprises the following components in mass concentration: 70g/L of sulfuric acid, 22g/L of hydrogen peroxide, 4g/L of stabilizer, 2.5g/L of accelerator, 20g/L of divalent copper ions and the balance of deionized water; the stabilizer is a mixture of sodium silicate, diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid, and the mass ratio of the sodium silicate to the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1:1:2; the accelerator is a mixture of formic acid and 3-amino-1, 2, 4-triazole, and the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1:0.5; the divalent copper ions are copper sulfate.
Test example 4
The copper surface roughening liquid for the printed circuit board comprises the following components in mass concentration: 130g/L of sulfuric acid, 30g/L of hydrogen peroxide, 7 g/L of stabilizer, 4g/L of accelerator, 40g/L of divalent copper ions and the balance of deionized water; the stabilizer is a mixture of sodium silicate, diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid, and the mass ratio of the sodium silicate to the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1:1:1; the accelerator is a mixture of formic acid and 3-amino-1, 2, 4-triazole, and the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1:1; the divalent copper ions are copper sulfate.
Test example 5
The copper surface roughening liquid for the printed circuit board comprises the following components in mass concentration: 120g/L of sulfuric acid, 28g/L of hydrogen peroxide, 6 g/L of stabilizer, 4g/L of accelerator, 38g/L of divalent copper ions and the balance of deionized water; the stabilizer is a mixture of sodium silicate, diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid, and the mass ratio of the sodium silicate to the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1:1:4; the accelerator is a mixture of formic acid and 3-amino-1, 2, 4-triazole, and the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1:0.8; the divalent copper ions are copper formate.
The copper surface roughening solutions of the printed wiring boards of test examples 1 to 5 were subjected to performance tests, and the test results are shown in table 1:
table 1 test examples 1 to 5 results of performance test of copper surface roughening solutions for printed wiring boards
Figure 674496DEST_PATH_IMAGE001
FIG. 1 is an SEM photograph of test example 1 of the present invention; FIG. 2 is an SEM photograph of test example 2 of the present invention. As can be seen from the test results of FIG. 1, FIG. 2 and Table 1, the components of the copper surface roughening solution for the printed circuit board provided by the invention are matched with each other, and the roughening solution is stable and can control the roughness and the micro-etching amount of the copper surface within an ideal range.
The preparation method and super-roughening method of the copper surface roughening solution for the printed wiring boards of comparative examples 1 to 23 were the same as those of test example 1.
1. Based on the influence of different mass concentrations of sulfuric acid and hydrogen peroxide
The comparative examples 1-2 are different from the experimental example 1 in the mass concentration of sulfuric acid and hydrogen peroxide, and the rest conditions are the same. The copper surface roughening solutions of the printed wiring boards of the test example 1 and the comparative examples 1 to 2 were subjected to performance tests, and the test results are shown in table 2:
table 2 test example 1 and comparative examples 1 to 2 results of performance test of copper surface roughening solutions for printed wiring boards
Figure 326057DEST_PATH_IMAGE002
According to the test results shown in the table 2, when the mass concentration of sulfuric acid in the roughening solution for the copper surface of the printed circuit board is lower than 50g/L and the mass concentration of hydrogen peroxide is lower than 10g/L (comparative example 1), the phenomena of low micro-etching amount and low roughness value occur. When the mass concentration of sulfuric acid in the copper surface roughening solution of the printed circuit board exceeds 150g/L and the mass concentration of hydrogen peroxide is higher than 40g/L (comparative example 2), the phenomena of higher micro-etching amount and higher roughness can occur. Therefore, the mass concentration of the sulfuric acid in the roughening solution for the copper surface of the printed circuit board is preferably 50-150g/L, and the mass concentration of the hydrogen peroxide in the roughening solution for the copper surface of the printed circuit board is preferably 10-40 g/L.
2. Based on the influence of different mass concentrations of the stabilizer
Comparative examples 3 to 5 are different from test example 1 in the mass concentration of the stabilizer, and the other conditions were the same. The performance test was performed on the copper surface roughening solutions of the printed wiring boards of test example 1 and comparative examples 3 to 5, and the test results are shown in table 3:
table 3 test example 1, comparative examples 3 to 5, copper surface roughening solution performance test results for printed wiring boards
Figure 89483DEST_PATH_IMAGE003
As can be seen from the test results in Table 3, the copper surface roughening solution for the printed wiring board has the phenomenon that the surface appearance, the micro-etching amount and the roughness are unqualified when the copper surface roughening solution does not contain the stabilizer (comparative example 3), and the phenomenon that the surface appearance is unqualified and the roughness is low when the mass concentration of the stabilizer is lower than 1g/L (comparative example 4). When the mass concentration of the stabilizer exceeds 10g/L (comparative example 5), the surface appearance is unsatisfactory, the amount of microetching is low, and the roughness is high. Therefore, the mass concentration of the stabilizer in the roughening solution for the copper surface of the printed wiring board is preferably 1 to 10g/L.
3. Based on the influence of different kinds of stabilizers
Comparative examples 6 to 8 differ from test example 1 in the mass concentration of the stabilizer, and the other conditions were the same. The stabilizer of comparative example 6 was sodium silicate only, the stabilizer of comparative example 7 was a mixture of diethylenetriamine pentamethylenephosphonic acid and polymethacrylic acid, and the stabilizer of comparative example 8 was a mixture of sodium silicate and polymethacrylic acid. The copper surface roughening solutions of the printed wiring boards of test example 1 and comparative examples 6 to 8 were subjected to performance tests, and the test results are shown in table 4:
table 4 test results of performance test of copper surface roughening solutions for printed wiring boards of test example 1 and comparative examples 6 to 8
Figure 219113DEST_PATH_IMAGE004
FIG. 3 is an SEM photograph of comparative example 6 of the present invention. As can be seen from fig. 3 and table 4 showing the test results, the roughening of the copper surface of the printed wiring board occurred in a case where only sodium silicate was used as a stabilizer (comparative example 6), and the microetching occurred in a case where a mixture of diethylenetriamine pentamethylenephosphonic acid and polymethacrylic acid was used as a stabilizer (comparative example 7). When a mixture of sodium silicate and polymethacrylic acid was used as a stabilizer (comparative example 8), a phenomenon of high roughness occurred. Therefore, the stabilizer in the copper surface roughening solution for the printed circuit board is preferably a mixture of sodium silicate, diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid.
4. Based on the influence of different mass ratios of sodium silicate to organic chelating agent in the stabilizer
Comparative examples 9 to 10 are different from test example 1 in the mass ratio of sodium silicate to organic chelating agent in the stabilizer, and the other conditions are the same. The copper surface roughening solutions of the printed wiring boards of test example 1 and comparative examples 9 to 10 were subjected to performance tests, and the test results are shown in table 5:
TABLE 5 test results of copper surface roughening solution performance test results of test example 1 and comparative examples 9 to 10 for printed wiring boards
Figure 324789DEST_PATH_IMAGE006
FIG. 4 is an SEM photograph of comparative example 9 of the present invention. As can be seen from fig. 4 and table 5 showing the test results, the stabilizer for the roughening solution for copper surfaces of printed wiring boards has a phenomenon of a higher microetching amount and a lower roughness when the mass ratio of sodium silicate to the organic chelating agent in the stabilizer for the roughening solution for copper surfaces of printed wiring boards is lower than the mass ratio of the organic chelating agent in the stabilizer (comparative example 9), and has a phenomenon of a lower microetching amount and a higher roughness when the mass ratio of sodium silicate to the organic chelating agent in the stabilizer is higher than the mass ratio of the organic chelating agent in the stabilizer (comparative example 10). Therefore, the mass ratio of the sodium silicate to the organic chelating agent in the copper surface roughening solution stabilizer for the printed circuit board is preferably 1: (0.2-6).
5. Based on the influence of different mass ratios of diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid in the organic chelating agent
Comparative examples 11 to 12 are different from test example 1 in the mass ratio of diethylenetriamine pentamethylenephosphonic acid to polymethacrylic acid in the organic chelating agent, and the other conditions are the same. The performance test was performed on the copper surface roughening solutions of the printed wiring boards of test example 1 and comparative examples 11 to 12, and the test results are shown in table 6:
table 6 test results of performance test of copper surface roughening solutions for printed wiring boards of test example 1 and comparative examples 11 to 12
Figure 326243DEST_PATH_IMAGE007
FIG. 5 is an SEM photograph of comparative example 11 of the present invention. According to fig. 5 and the test result table 6, it can be seen that, in the organic chelating agent of the copper surface roughening solution for the printed wiring board, the phenomenon of lower roughness occurs when the mass ratio of diethylenetriamine pentamethylenephosphonic acid to polymethacrylic acid is lower (comparative example 11), and the phenomenon of lower microetching amount and higher roughness occurs when the mass ratio of diethylenetriamine pentamethylenephosphonic acid to polymethacrylic acid is higher (comparative example 12). Therefore, the mass ratio of the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid in the organic chelating agent of the printed circuit board copper surface roughening liquid stabilizer is preferably 1: (1-5).
6. Based on the influence of different mass concentrations of promoters
Comparative examples 13 to 16 are different from test example 1 in the mass concentration of the accelerator, and the other conditions were the same. The copper surface roughening solutions of the printed wiring boards of test example 1 and comparative examples 13 to 16 were subjected to performance tests, and the test results are shown in table 7:
table 7 test results of copper surface roughening solution performance of test example 1 and comparative examples 13 to 16
Figure 259564DEST_PATH_IMAGE008
FIG. 6 is an SEM photograph of comparative example 14 of the present invention. As can be seen from fig. 6 and table 7 of test results, the copper surface roughening solution for the printed wiring board does not contain the accelerator (comparative example 13) or only adopts 3-amino-1, 2, 4-triazole as the accelerator (comparative example 14), which causes the phenomena of unqualified surface appearance, micro-etching amount and roughness, and the accelerator with a mass concentration of less than 0.5g/L (comparative example 15), which causes the phenomena of unqualified surface appearance, high micro-etching amount and low roughness. When the mass concentration of the accelerator exceeds 5g/L (comparative example 16), the surface appearance becomes unsatisfactory, the amount of microetching becomes low, and the roughness becomes high. Therefore, the mass concentration of the accelerator in the copper surface roughening solution for the printed circuit board is preferably 0.5-5g/L.
7. Based on the influence of different mass ratios of formic acid and 3-amino-1, 2, 4-triazole in the accelerant
Comparative examples 17 to 18 are different from test example 1 in the mass ratio of formic acid to 3-amino-1, 2, 4-triazole in the accelerator, and the other conditions are the same. The copper surface roughening solutions of the printed wiring boards of test example 1 and comparative examples 17 to 18 were subjected to performance tests, and the test results are shown in table 8:
table 8 test results of performance test of copper surface roughening solutions for printed wiring boards of test example 1 and comparative examples 17 to 18
Figure 662863DEST_PATH_IMAGE009
According to the test results shown in table 8, the phenomena of large microetching amount and low roughness can occur when the mass ratio of formic acid to 3-amino-1, 2, 4-triazole in the accelerator for the copper surface roughening solution for the printed circuit board is lower than that of 3-amino-1, 2, 4-triazole (comparative example 17), and the phenomena of small microetching amount and large roughness can occur when the mass ratio of formic acid to 3-amino-1, 2, 4-triazole in the accelerator is higher than that of 3-amino-1, 2, 4-triazole (comparative example 18). Therefore, the mass ratio of formic acid to 3-amino-1, 2, 4-triazole in the accelerator of the copper surface roughening solution of the printed circuit board is preferably 1: (0.25-1).
8. Based on the influence of different mass concentrations of divalent copper ions
Comparative examples 19 to 21 are different from test example 1 in the mass concentration of cupric ions, and the other conditions were the same. The copper surface roughening solutions of the printed wiring boards of test example 1 and comparative examples 19 to 21 were subjected to performance tests, and the test results are shown in table 9:
table 9 test results of performance test of copper surface roughening solutions for printed wiring boards of test example 1 and comparative examples 19 to 21
Figure 390648DEST_PATH_IMAGE010
According to the test results shown in the table 9, the copper surface roughening solution for the printed wiring board does not contain divalent copper ions (comparative example 19), and the surface appearance, the microetching amount and the roughness are not qualified, and the mass concentration of the divalent copper ions is lower than 5g/L (comparative example 20), the surface appearance is not qualified, the microetching amount is high, and the roughness is low. When the mass concentration of the divalent copper ion exceeds 50g/L (comparative example 21), the surface appearance is unsatisfactory, the amount of microetching is low, and the roughness is high. Therefore, the mass concentration of the divalent copper ions in the roughening solution for the copper surface of the printed wiring board is preferably 5 to 50g/L.
9. Influence among different components of copper surface roughening liquid based on printed circuit board
Comparative example 3 is different from test example 1 in that it does not contain a stabilizer, and the other conditions are the same. Comparative example 13 differs from test example 1 in that no accelerator was included, and the other conditions were the same. Comparative example 22 is different from test example 1 in that stabilizers and accelerators are not contained and the other conditions are the same. Comparative example 23 is different from test example 1 in that it does not contain a stabilizer, a promoter and a divalent copper ion, and the remaining conditions are the same. The copper surface roughening solutions of the printed wiring boards of test example 1, comparative example 3, comparative example 13, and comparative examples 22 to 23 were subjected to performance tests, and the test results are shown in table 10:
TABLE 10 test results of performance test of copper surface roughening solutions for printed wiring boards of test example 1, comparative example 3, comparative example 13, and comparative examples 22 to 23
Figure 128666DEST_PATH_IMAGE011
From the test results table 10, it can be seen that the copper surface roughening solutions for printed wiring boards lacking multiple components (comparative example 22, comparative example 23) are less effective than those lacking a single component (comparative example 3, comparative example 13).
In conclusion, the printed circuit board copper surface roughening solution disclosed by the invention can be used for more effectively stabilizing the decomposition of hydrogen peroxide compared with a single type of stabilizer by adding a composition compounded by an adsorption type stabilizer, namely sodium silicate, a chelating type stabilizer and an organic chelating agent as the stabilizer. In addition, the organic chelating agent is reasonably compounded by organic phosphate type diethylenetriamine pentamethylene phosphonic acid and polycarboxylic polymethacrylic acid different types of organic chelating agents, so that the synergistic effect between the organic chelating agents and the polycarboxylic acid type polymethacrylic acid can be exerted, and the roughness and the micro-corrosion of the copper surface are controlled within an ideal range; the accelerator is compounded with 3-amino-1, 2, 4-triazole through formic acid, so that the copper surface roughening can be effectively promoted, and the integral roughening uniformity is ensured; by adding divalent copper ions, which mainly act as an oxidizing agent in the roughening solution, an effective roughening rate and uniformity of roughening can be provided. The components in the roughening solution are matched with each other, so that the roughening solution is stable, the binding force between the copper surface and the dry film is effectively enhanced, and the oxidation of the copper surface is reduced.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications and substitutions can be easily made by those skilled in the art within the technical scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (7)

1. The copper surface roughening liquid for the printed circuit board is characterized by comprising the following components in mass concentration:
70-120g/L of sulfuric acid,
22-28g/L of hydrogen peroxide,
4-6 g/L of stabilizing agent,
2.5-4g/L of accelerant,
divalent copper ions of 20-38g/L,
the balance of deionized water;
the stabilizer is a mixture of sodium silicate and an organic chelating agent, and the mass ratio of the sodium silicate to the organic chelating agent is 1: (0.2-6); the organic chelating agent is a mixture of diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid, and the mass ratio of the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1: (1-5); the accelerator is a mixture of formic acid and 3-amino-1, 2, 4-triazole, and the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1: (0.25-1); the divalent copper ions are selected from one of copper formate and copper sulfate.
2. The copper surface roughening solution for printed wiring boards according to claim 1, wherein the mass ratio of diethylenetriamine pentamethylenephosphonic acid to polymethacrylic acid is 1: (2-4).
3. The copper surface roughening solution for the printed wiring board as claimed in claim 2, wherein the mass ratio of formic acid to 3-amino-1, 2, 4-triazole is 1: (0.5-0.8).
4. The copper surface roughening liquid for the printed wiring board according to claim 1, which comprises the following components in concentration by mass:
100g/L of sulfuric acid is added,
25g/L of hydrogen peroxide solution,
5g/L of a stabilizing agent is added,
the content of the accelerator is 4g/L,
the divalent copper ions are 35g/L,
the balance of deionized water;
the stabilizer is a mixture of sodium silicate, diethylenetriamine pentamethylene phosphonic acid and polymethacrylic acid, and the mass ratio of the sodium silicate to the diethylenetriamine pentamethylene phosphonic acid to the polymethacrylic acid is 1:1:3;
the accelerator is a mixture of formic acid and 3-amino-1, 2, 4-triazole, and the mass ratio of the formic acid to the 3-amino-1, 2, 4-triazole is 1:0.6; the divalent copper ions are copper sulfate.
5. A super-roughening method, characterized in that the copper surface roughening liquid of the printed circuit board according to any one of claims 1 to 4 is sprayed onto copper wires of the circuit board in a horizontal spraying mode, and the spraying pressure is 0.5 to 2.0kg/cm 2 。
6. The super-roughening method as claimed in claim 5, wherein said copper surface roughening solution for printed wiring boards is used at a temperature of 15 to 35 ℃.
7. The super-roughening method as claimed in claim 5, wherein the spraying time of the copper surface roughening liquid for the printed wiring board is 30-60s.
CN202211142619.7A 2022-09-20 2022-09-20 Printed circuit board copper surface roughening liquid and application thereof Active CN115216771B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211142619.7A CN115216771B (en) 2022-09-20 2022-09-20 Printed circuit board copper surface roughening liquid and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211142619.7A CN115216771B (en) 2022-09-20 2022-09-20 Printed circuit board copper surface roughening liquid and application thereof

Publications (2)

Publication Number Publication Date
CN115216771A CN115216771A (en) 2022-10-21
CN115216771B true CN115216771B (en) 2022-12-16

Family

ID=83617285

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211142619.7A Active CN115216771B (en) 2022-09-20 2022-09-20 Printed circuit board copper surface roughening liquid and application thereof

Country Status (1)

Country Link
CN (1) CN115216771B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6494254B2 (en) * 2014-11-18 2019-04-03 関東化學株式会社 Copper / molybdenum metal laminated film etching solution composition, etching method using the composition, and method for extending the life of the composition
CN109778190A (en) * 2017-11-10 2019-05-21 深圳市华星光电技术有限公司 A kind of Cu-MoTi etching solution
CN112323068A (en) * 2020-11-06 2021-02-05 深圳市煜杰兴电子材料有限公司 Copper surface roughening agent capable of being recycled through electrolytic regeneration and preparation method thereof
CN112899685A (en) * 2021-01-22 2021-06-04 中山市金普利电子科技有限公司 Metal micro-treating agent for sulfuric acid and hydrogen peroxide
CN114672807A (en) * 2022-05-26 2022-06-28 深圳市板明科技股份有限公司 Organic acid super-roughening micro-etching solution with high copper content and application thereof

Also Published As

Publication number Publication date
CN115216771A (en) 2022-10-21

Similar Documents

Publication Publication Date Title
JP2002047583A (en) Microetching agent for copper or copper alloy and microetching method using the same
CN102286745B (en) Microetching agent for coarsing copper surface
CN114686885B (en) Copper surface super-roughening solution for circuit board, preparation method and application thereof
CN111020585A (en) Coarsening micro-etching solution of hydrogen sulfate peroxide system and application thereof
CN113789553B (en) Nickel plating solution applied to printed circuit board and nickel electroplating method thereof
CN115216772B (en) Environment-friendly roughening treatment fluid suitable for copper surface and application thereof
CN115074734B (en) Copper-reducing additive for aluminum substrate circuit board and preparation method and use method thereof
KR19990062987A (en) Composition for manufacturing circuit board
CN114025489B (en) Microetching solution for copper surface treatment, application of microetching solution in PCB (printed circuit board) manufacturing process and PCB production flow
CN115216771B (en) Printed circuit board copper surface roughening liquid and application thereof
CN116607149B (en) Copper surface microetching roughening solution for IC carrier plate and preparation method and application thereof
JP2000297387A (en) Surface treating agent for copper and copper alloy
CN104694909B (en) Copper surface coarsening agent
CN115094421B (en) Copper surface roughening solution for high-frequency printed circuit board and preparation method thereof
JPH06252530A (en) Pattern etching method
CN110093606A (en) A kind of etching solution and preparation method thereof for pcb board
US20050098538A1 (en) Methods of cleaning copper surfaces in the manufacture of printed circuit boards
CN114980531B (en) Microetching solution, copper surface regeneration microetching method, copper plate and circuit board
CN117488302B (en) Circuit etching solution
CN110016701A (en) Aluminum foil substrate film plating process
CN115261859B (en) Copper etching liquid composition and preparation method thereof
CN115110072B (en) Environment-friendly chemical copper deposition solution for circuit board and copper deposition method
CN115433928B (en) Chemical silver plating liquid medicine and chemical silver plating method for 5G high-frequency circuit board
CN115058715B (en) Microetching solution for rolled copper foil surface and preparation method and application thereof
JPH0697627A (en) Peeling method of water-soluble dry film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant