CN114554703B - Super-roughening process of printed circuit board - Google Patents
Super-roughening process of printed circuit board Download PDFInfo
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- CN114554703B CN114554703B CN202210271167.6A CN202210271167A CN114554703B CN 114554703 B CN114554703 B CN 114554703B CN 202210271167 A CN202210271167 A CN 202210271167A CN 114554703 B CN114554703 B CN 114554703B
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- 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
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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- 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
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- 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
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Abstract
The invention discloses a super-roughening process of a printed circuit board, and relates to the technical field of printed circuit board processing. The super-roughening process of the printed circuit board comprises the following steps: under the condition that the temperature is 25-32 ℃, spraying super-roughening liquid containing 0.3-0.5% of copper surface color difference color homogenizing agent by volume concentration onto a copper wire of a printed circuit board for 30-60 s; the copper surface color difference and color uniformity agent comprises the following components in percentage by mass: 3-15% of wetting dispersant, 0.02-0.5% of leveling agent, 0.05-1% of accelerator and the balance of water; the super-roughening liquid comprises: 20-80g/L of organic copper, 30-100g/L of formic acid, 15-45g/L of sodium formate, 15-45g/L of sodium chloride and the balance of deionized water. According to the invention, by adding the copper surface color difference color homogenizing agent and the super-roughening solution, the surface of the printed circuit board subjected to super-roughening treatment has uniform and mild color and ideal roughening effect, the problems of uneven roughening, large color difference and the like are avoided, and the quality and yield of the printed circuit board can be effectively improved.
Description
Technical Field
The invention relates to the technical field of printed circuit board processing, in particular to a super-roughening process of a printed circuit board.
Background
In recent years, with the rapid development of electronic devices, lines are more and more dense, and line widths and line distances are smaller and smaller. The printed circuit board circuit manufacture also adopts a photochemical pattern transfer process, and the basic process of the process comprises the following steps: copper surface pretreatment → hot pressing dry film → exposure and development → etching or electroplating → dry film removal. The designed circuit pattern is transferred to the printed circuit board through a photochemical transfer process, and the quality of the bonding force between a dry film as a plating resistance or an anti-corrosion layer and a copper surface directly influences the quality of the printed circuit board. Because the line width/line distance of the circuit pattern is smaller and smaller, the contact interface between the copper surface and the dry film is smaller and smaller, and the bonding force between the copper surface and the dry film is reduced. The traditional pretreatment processes of brushing, sand blasting, volcanic ash plate grinding, sodium persulfate microetching and medium coarsening reach the limit of the traditional pretreatment processes, and often cannot meet the requirement of a new technology.
The super-roughening process is characterized in that a special additive is added into super-roughening liquid to enable the copper surface to generate selective point-like different etching rates, so that a micro-honeycomb rough structure is obtained to enable the surface area of the copper surface to be remarkably increased, the bonding force between the copper surface and a dry film is improved, and the method is a copper surface pretreatment technology which is most used by high-density printed circuits in the industry at present. After the copper surface is super-roughened, the surface color is light red to dark red. According to optical principles, the darker the copper surface is, the greater the surface roughness, the greater the scattering of light. Because the lattice defect of the copper surface or the lattice distribution of the electroplated layer is not uniform, the color of the copper surface is not uniform or the color difference is large in the super-coarsening process. The occurrence of the above problems can cause the problem of detection error detection, such as multiple false points, multiple detection or missing detection, due to large light scattering during the outer layer AOI detection. The soft board covering film, the white oil process, the green oil process or other process flows with requirements on the color difference of the copper surface, which have high requirements on the appearance, can also be scrapped due to the problem of the heterochrosis of the copper surface, and the quality and the yield of the printed circuit board and the subsequent shipment are seriously influenced.
At present, the commonly used methods reduce the influence of the color difference of the copper surface by grinding and brushing or increasing a microetching flow, but the methods have the problems of easy occurrence of plate surface scratches and scratches, high cost, low production efficiency and the like.
Chemical polishing is also used in the prior art to reduce the chromatic aberration of the copper surface, such as:
1) benzotriazole used in chinese patent CN108085687A realizes the reduction of color difference, but benzotriazole remains on the copper surface, and the residue on the copper surface affects the next process, and has hidden trouble of production quality. In addition, the hydrogen peroxide in the Chinese patent CN108085687A is not added with a stabilizer, so that the decomposition of the hydrogen peroxide cannot be effectively inhibited, and the requirements of the stability and the reusability of the PCB liquid medicine are not met.
2) In the component leveling agent of the Chinese patent CN104342705A, surfactants such as LAS, LS, AOS, AES and the like are used for reducing color difference, but the surfactants cause excessive foam due to spraying in actual production and have the problem of difficult operation.
3) In the Chinese patent CN105624683A, a defoaming agent is used for eliminating the problem of excessive foam caused by a surfactant, and the defoaming agent causes silicon spots to remain on the walls of the tank due to the silicon-containing component, so that the problems of oil slick, oil floating and plate sticking are easily caused in the production, and potential quality hazards exist in the production of the subsequent process.
The three patents of the copper surface polishing agent all have respective technical defects, so most circuit board enterprises also adopt the most traditional grinding brush or other micro-etching for reducing chromatic aberration, thereby reducing the production efficiency, increasing the production cost and not bringing greater help to the improvement of the quality and yield of the printed circuit board.
Disclosure of Invention
In order to solve the technical problems, the invention provides a super-roughening process of a printed circuit board. According to the process, the problems of copper surface color difference (light red or dark red) and coarsening unevenness generated in the super-coarsening process are solved by adding the copper surface color difference color homogenizing agent and the super-coarsening liquid, and the production efficiency and the quality yield of the printed circuit board can be effectively improved. The method specifically comprises the following technical scheme:
the super-roughening process of the printed circuit board comprises the following steps:
under the condition that the temperature is 25-32 ℃, spraying super-roughening liquid containing 0.3-0.5% of copper surface color difference color homogenizing agent by volume concentration onto a copper wire of a printed circuit board for 30-60 s;
the copper surface color difference color homogenizing agent comprises the following components in percentage by mass: 3-15% of wetting dispersant, 0.02-0.5% of leveling agent, 0.05-1% of accelerator and the balance of water;
the super-roughening liquid comprises: 20-80g/L of organic copper, 30-100g/L of formic acid, 15-45g/L of sodium formate, 15-45g/L of sodium chloride and the balance of deionized water.
Further, the wetting dispersant is selected from one of polyethyleneimine, sulfated sodium ricinoleate, naphthenic sodium sulfate and fatty amide alkyl sodium sulfate; the leveling agent is selected from one of mannitol, galactitol, polyethylene glycol and azido polyethylene glycol carboxyl; the accelerant is selected from one of hexadecylamine, octadecylamine and ethylene diamine tetramethylene phosphonic acid sodium; the organic copper is selected from at least one of copper acetate, copper formate and copper propionate.
Further, the copper surface color difference color homogenizing agent comprises the following components in percentage by mass: 4 to 14 percent of wetting dispersant, 0.1 to 0.4 percent of leveling agent and 0.1 to 0.9 percent of accelerator.
Further, the copper surface color difference color homogenizing agent comprises the following components in percentage by mass: 8 to 13 percent of wetting dispersant, 0.15 to 0.3 percent of leveling agent and 0.4 to 0.8 percent of accelerator.
Further, the super-roughening liquid comprises: 30-60g/L of organic copper, 40-90g/L of formic acid, 20-40g/L of sodium formate, 20-40g/L of sodium chloride and the balance of deionized water.
Further, the super-roughening liquid comprises: 40-50g/L of organic copper, 50-80g/L of formic acid, 25-35g/L of sodium formate, 25-35g/L of sodium chloride and the balance of deionized water; the organic copper is copper acetate.
Further, the temperature is 26-30 ℃.
Further, the spraying time is 40-50 s.
Further, the temperature is 28-30 ℃; the spraying time is 45-50 s.
Further, the copper surface color difference color homogenizing agent comprises the following components in percentage by mass: 13% of polyethyleneimine, 0.15% of polyethylene glycol and 0.8% of octadecylamine.
According to the invention, by adding the copper surface color difference color homogenizing agent and the super-roughening solution, the surface of the printed circuit board subjected to super-roughening treatment has uniform and mild color and ideal roughening effect, the problems of uneven roughening, large color difference and the like are avoided, and the quality and yield of the printed circuit board can be effectively improved.
The copper surface color difference color homogenizing agent provided by the invention is prepared from wetting dispersants, leveling agents, accelerators and water with different contents. The copper surface color difference color homogenizing agent can be directly added into the super-roughening solution and is mainly used for repairing and improving the copper surface color difference after super-roughening.
The invention adopts a multi-component matching method to inhibit excessive corrosion, so that the coarsening appearance of the copper surface is uniform, and the color difference of the copper surface is reduced. According to the super-coarsening principle: the better the copper density, the more difficult the roughening, the worse the copper density, the easier the roughening, and the problem that the copper lattice defect may cause the etching depth to be too large.
The leveling agent, the wetting dispersant and the accelerator are combined to take part of copper crystals with better compactness of the copper surface as an important coarsening object, and the copper with poorer compactness only needs to keep normal coarsening. The leveling agent in the copper surface color difference color homogenizing agent has good leveling capability, and under the synergistic action of the wetting dispersant and the accelerator, the copper surface can obtain a uniform micro-honeycomb copper coarse structure after being subjected to super coarsening. Therefore, pits with uneven coarsening and microcellular depths are not formed on the copper surface, and the problem of large chromatic aberration of the copper surface of the printed circuit board is solved.
The copper surface color difference color homogenizing agent is directly added into the super-roughening solution, so that the permeability and the dispersibility of the super-roughening solution are stronger, the leveling agent and the accelerating agent are matched to effectively and uniformly roughen the copper surface with lattice defects or non-uniform distribution, and the problem of color difference caused by non-uniform roughening of the copper surface is solved. The abnormal problems of more detection false points and uneven copper surface color of the coating solder resist ink caused by large copper surface color difference of AOI in the subsequent process are well improved, and the production efficiency and the quality yield of the printed circuit board can be well improved finally.
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 a diagram of a printed wiring board measurement location according to the present invention;
FIG. 2 is a SEM image of a copper surface treated by the super-roughening process in example 1 of the present invention;
FIG. 3 is an SEM image of a copper surface after being processed by the super-roughening process in example 28;
FIG. 4 is a SEM image of a copper surface after being processed by the super-roughening process in example 29 of the present invention;
FIG. 5 is a SEM image of a copper surface after being processed by the super-roughening process in example 30 of the present invention;
FIG. 6 is a SEM image of a copper surface after being processed by the super-roughening process in example 31 of the present invention;
FIG. 7 is a SEM image of a copper surface after being processed by the super-roughening process in example 32;
FIG. 8 is a SEM image of a copper surface after being processed by the super-roughening process in example 33 of the present invention;
FIG. 9 is a SEM image of a copper surface after being subjected to a super-roughening process in example 34;
FIG. 10 is an SEM image of a copper surface after being processed by the super-roughening process in example 35 of the present invention;
fig. 11 is an SEM image of a copper surface after being processed by the super-roughening process in example 36 of the present invention;
FIG. 12 is an SEM image of a copper surface after being treated by the super-roughening process of comparative example 14 according to the present invention;
FIG. 13 is a SEM image of a copper surface treated by the super-roughening process of comparative example 15 according to the invention;
FIG. 14 is an SEM image of a copper surface after being treated by the super-roughening process of comparative example 16 according to the present invention;
FIG. 15 is a SEM image of a copper surface treated by the super-roughening process of comparative example 17 according to the invention;
FIG. 16 is an SEM image of a copper surface after being treated by the super-roughening process of comparative example 18 according to the invention;
FIG. 17 is an SEM image of a copper surface treated by the super-roughening process of comparative example 19 according to the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within 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. As used in this specification 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 and includes any and all possible combinations of one or more of the associated listed items.
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.
The preparation method of the copper surface color difference color homogenizing agent comprises the following steps:
mixing the wetting dispersant, the leveling agent, the accelerant and a proper amount of water together according to the mass percentage, stirring for 30-60 minutes at normal temperature, standing for 10-20 minutes to obtain the copper surface color difference leveling agent, and then directly packaging by a barrel.
The super-roughening process flow comprises the following steps:
s1: plate surface cleaning (degreasing or scrubbing); s2: washing with water; the method comprises the following steps of S3, super-coarsening, S4, water washing, S5, hydrochloric acid washing, S6, water washing, S7, drying and S8, preparing a lower plate.
The super-roughening step of S3 includes: spraying super-coarsening liquid containing copper surface color difference color homogenizing agent with volume concentration of 0.3-0.5% onto a copper wire of a printed circuit board at the temperature of 25-32 ℃, wherein the spraying pressure is 1.5-2.5 kg.f/cm 2 And the spraying time is 30-60s, and after the super-roughening step is finished, the production is carried out according to the normal flow of the super-roughening process.
The effect test method of the super-roughening process, namely the white light interferometer test:
the roughness of the copper surface of the printed wiring board was measured by using a white light interferometer, and 5 points were taken for each printed wiring board (front or back surface), and the Δ Ra value (Ra: arithmetic mean difference in profile) and the Δ Rz value (Rz: ten-point mean height of microscopic unevenness) were measured, respectively, and the Δ value = (maximum value-minimum value)/mean value. The larger the value of Δ, the more uneven the roughening of the copper surface, and the more uneven the roughening of the copper surface, indicating that the color difference of the copper surface is larger. The test site map of the printed wiring board is shown in fig. 1.
The effect test method of the super-roughening process, AOI test:
AOI: and (3) automatic optical detection, which detects common defects encountered in welding production by using an optical principle. The defects on the PCB are detected through automatic detection, and the defects are displayed/marked through a display or an automatic mark.
Example 1: the printed circuit board treated by the super-roughening process of the printed circuit board
And cleaning the plate surface (removing oil or brushing), washing with water, mixing 13% by mass of polyethyleneimine, 0.15% by mass of polyethylene glycol, 0.8% by mass of octadecylamine and a proper amount of water together after washing, stirring for 45 minutes at normal temperature, and standing for 15 minutes to obtain the copper surface color difference homogenizing agent. Mixing 45g/L of copper acetate, 65g/L of formic acid, 30g/L of sodium formate, 30g/L of sodium chloride and a proper amount of deionized water together to obtain super-coarsening liquid.
Spraying the super-coarsening liquid containing the copper surface color difference color homogenizing agent with the volume concentration of 0.3-0.5% onto a copper wire path of a printed circuit board under the condition that the temperature is 29 ℃, wherein the spraying pressure is 1.5-2.5 kg.f/cm 2 And the spraying time is 45s, and the super-roughening treatment is completed. And after the super-roughening, performing overflow washing, hydrochloric acid washing, overflow washing and drying to obtain the printed circuit board embodiment 1.
Firstly, based on the influence of different contents of polyethyleneimine in wetting dispersant on super-roughening process
Examples 2 to 6 and comparative examples 1 to 3 differ from example 1 in the mass percent of polyethyleneimine as the wetting dispersant, and the other conditions are the same. White light interferometer tests were performed on examples 1 to 6 and comparative examples 1 to 3, and the results were as follows:
TABLE 1 test results of white light interferometers for examples 1-6 and comparative examples 1-3
As can be seen from the test results shown in Table 1, the copper surface color difference homogenizing agent does not contain the wetting dispersant polyethyleneimine (comparative example 1), so that the coarsening of the copper surface is not uniform, and the color difference of the copper surface is large. When the addition amount of the wetting dispersant polyethyleneimine is small (comparative example 2), the coarsening of the copper surface is not uniform; when the mass percent of the wetting dispersant polyethyleneimine exceeds 15% (comparative example 3), the influence of the addition amount of the wetting dispersant polyethyleneimine on the copper surface coarsening effect is small, so that the mass percent of the wetting dispersant in the copper surface color difference leveling agent is preferably 3-15%.
Secondly, based on the influence of different types of wetting dispersants on the super-roughening process
Examples 7 to 10 were different from example 1 in the kind of the wetting dispersant, and the other conditions were the same. White light interferometer tests were performed on example 1 and examples 7 to 10, and the test results were as follows:
TABLE 2 test results of white light interferometer in example 1 and examples 7-10
As can be seen from the test results in table 2, the wetting dispersant in the copper shading color homogenizing agent is selected from polyethyleneimine (example 1), sulfated sodium ricinoleate (example 2), sodium naphthenate sulfate (example 3), fatty amidoalkyl sodium sulfate (example 4) or a combination of polyethyleneimine and sulfated sodium ricinoleate (example 5), which has little effect on the coarsening effect of the copper surface, and thus, the wetting dispersant in the copper shading color homogenizing agent may be selected from one of polyethyleneimine, sulfated sodium ricinoleate, sodium naphthenate sulfate, fatty amidoalkyl sodium sulfate or a combination of polyethyleneimine and sulfated sodium ricinoleate.
Thirdly, based on the influence of different contents of polyethylene glycol in the leveling agent on the super-roughening process
Examples 11 to 15 and comparative examples 4 to 6 were different from example 1 in the mass percentage of the leveling agent polyethylene glycol, and the other conditions were the same. White light interferometer tests were performed on example 1, examples 11 to 15, and comparative examples 4 to 6, respectively, and the results were as follows:
TABLE 3 test results of white light interferometer for examples 1, 11-15 and 4-6
According to the test results shown in table 3, it can be seen that the leveling agent polyethylene glycol (comparative example 4) is not added in the copper surface color difference leveling agent, the coarsening of the copper surface is not uniform, and the color difference of the copper surface is large. When the addition amount of polyethylene glycol serving as a leveling agent is small (comparative example 5), the coarsening of the copper surface is uneven; when the mass percentage of the leveling agent polyethylene glycol exceeds 0.5% (comparative example 6), the addition amount of the leveling agent polyethylene glycol has little influence on the coarsening effect of the copper surface, and therefore, the mass percentage of the leveling agent in the copper surface color difference color homogenizing agent is preferably 0.02-0.5%.
Fourthly, based on the influence of different leveling agents on the super-roughening process
Examples 16 to 19 differ from example 1 in the kind of leveling agent and the rest of the conditions were the same. White light interferometer tests were performed on example 1 and examples 16 to 19, and the test results were as follows:
TABLE 4 test results of white light interferometer in examples 1 and 16-19
As can be seen from the test results table 4, the kind of the leveling agent in the copper surface color difference leveling agent is selected from polyethylene glycol (example 1), mannitol (example 16), galactitol (example 17), azido polyethylene glycol carboxyl (example 18) or a combination of polyethylene glycol and mannitol (example 19), which has little effect on the roughening effect of the copper surface, and therefore, the leveling agent in the copper surface color difference leveling agent may be selected from one of polyethylene glycol, mannitol, galactitol and azido polyethylene glycol carboxyl or a combination of polyethylene glycol and mannitol.
Fifthly, based on the influence of different contents of accelerator octadecylamine on the super-roughening process
Examples 20 to 24 and comparative examples 7 to 9 differ from example 1 in the mass percent of the accelerator octadecylamine and the other conditions are the same. White light interferometer tests were performed on example 1, examples 20 to 24, and comparative examples 7 to 9, respectively, and the results were as follows:
TABLE 5 test results of white light interferometer for example 1, examples 20-24, and comparative examples 7-9
According to the test results shown in Table 5, it can be seen that the copper surface color difference color homogenizing agent does not contain octadecylamine (comparative example 7) as an accelerator, so that the coarsening of the copper surface is not uniform, and the color difference of the copper surface is large. When the addition amount of the accelerator octadecylamine is small (comparative example 8), the coarsening of the copper surface is not uniform; when the mass percent of the accelerator octadecylamine exceeds 1 percent (comparative example 9), the addition amount of the leveling agent polyethylene glycol has little influence on the coarsening effect of the copper surface, so the mass percent of the accelerator in the copper surface color difference color homogenizing agent is preferably 0.05 to 1 percent.
Sixthly, influence of different types of accelerators on the super-roughening process
Examples 25 to 27 differ from example 1 in the kind of accelerator and the other conditions are the same. The white light interferometer test was performed on example 1 and examples 25 to 27, and the test results were as follows:
TABLE 6 test results of white light interferometer for examples 1 and 25-27
As can be seen from the test results in Table 6, the kind of accelerator selected from octadecylamine (example 1), hexadecylamine (example 25), sodium ethylene diamine tetramethylene phosphonate (example 26) or the combination of octadecylamine and hexadecylamine (example 27) in the copper surface color difference leveling agent has less influence on the roughening effect of the copper surface, and thus, the accelerator selected from octadecylamine, hexadecylamine and sodium ethylene diamine tetramethylene phosphonate in the copper surface color difference leveling agent
Or a combination of octadecylamine and hexadecylamine.
Seventh, based on the influence of the combination of wetting dispersant, leveling agent and accelerator on the super-roughening process
Comparative example 1 is different from example 1 in that the wetting dispersant is not contained, and the other conditions are the same. Comparative example 4 is different from example 1 in that it does not contain a leveling agent, and the rest of the conditions are the same. Comparative example 7 differs from example 1 in that no accelerator is included and the conditions are the same. Comparative example 10 is different from example 1 in that it does not contain a wetting dispersant and a leveling agent, and the rest of the conditions are the same. Comparative example 11 differs from example 1 in that the wetting dispersant and accelerator are not included and the remaining conditions are the same. Comparative example 12 differs from example 1 in that it does not contain leveling agents and accelerators, and the remaining conditions are the same. Comparative example 13 is different from the examples in that the copper-based color difference homogenizer is not included. White light interferometer tests were performed on example 1, comparative example 4, comparative example 7, and comparative examples 10 to 13, and the test results were as follows:
TABLE 7 test results of white light interferometer for example 1, comparative example 4, comparative example 7, and comparative examples 10 to 13
According to the test results shown in table 7, the lack of the single component of the wetting dispersant (comparative example 1), the leveling agent (comparative example 4) or the accelerator (comparative example 7) in the copper surface color difference leveling agent has a large influence on the super-roughening process, which causes uneven roughening of the copper surface and large color difference of the copper surface. Two or more components in the copper surface color difference homogenizing agent lack have larger influence on super coarsening than the single component lack.
Eighthly, influence of printed circuit board based on copper surface color difference color homogenizing agent on super-roughening process
Examples 28 to 36 are different from example 1 in the composition and content of the color homogenizing agent for copper surface color difference, and the other conditions are the same. The white light interferometer test was performed on example 1 and examples 28 to 36, and the test results were as follows:
TABLE 8 test results of white light interferometers for examples 1 and 28-36
Comparative example 14 is different from example 1 in that the copper-based color difference equalizer is not included, and the other conditions are the same. Comparative examples 15 to 23 are the same as examples 28 to 36 except that the copper-based color difference homogenizer was not included. AOI tests were performed on example 1, examples 28 to 36, and comparative examples 14 to 23, respectively, and the results were as follows:
TABLE 9 AOI test results for example 1, examples 28-36, and comparative examples 14-23
Fig. 2 is an SEM image of a copper surface after being processed by the super-roughening process in example 1 of the present invention, and fig. 3 to 11 are SEM images of a copper surface after being processed by the super-roughening process in examples 28 to 36 of the present invention; FIGS. 12-17 are SEM images of copper surfaces treated by the super-roughening process of comparative examples 14-19 according to the present invention.
According to the test result table 9 and fig. 2 to 17, it can be seen that the printed circuit boards (example 1 and examples 28 to 36) added with the copper-based color difference homogenizing agent have significantly reduced AOI scanning report and significantly improved defect yield compared with the printed circuit boards (comparative examples 14 to 23) not added with the copper-based color difference homogenizing agent, thereby greatly improving the production efficiency and the shipment speed.
Based on the influence of different temperatures on the super-roughening process
Examples 37 to 41 and comparative examples 24 to 25 were different from example 1 in temperature, and the other conditions were the same. White light interferometer tests were performed on example 1, examples 37 to 41, and comparative examples 24 to 25, respectively, and the results were as follows:
TABLE 10 test results of white light interferometer for example 1, examples 37 to 41, and comparative examples 24 to 25
As can be seen from the test result table 10, the influence of the temperature on the super-roughening process is large. When the temperature is less than 25 deg.c (comparative example 24) or more than 32 deg.c (comparative example 25), the coarsening of the copper surface is less uniform, and thus the temperature is preferably 25 to 32 deg.c.
Influence on the super-roughening process based on different spraying time
Examples 42 to 45 and comparative examples 26 to 27 differ from example 1 in respect of the spraying time, and the other conditions were the same. White light interferometer tests were performed on example 1, examples 42 to 45, and comparative examples 26 to 27, respectively, and the results were as follows:
TABLE 11 test results of white light interferometers for examples 1, 42-45 and 26-27
As can be seen from the test results table 11, the influence of the spraying time on the super-roughening process is large. The spraying time is less than 30s (comparative example 26) or longer than 60s (comparative example 27), the coarsening of the copper surface is less uniform, and thus the spraying time is preferably in the range of 30s to 60 s.
Eleven, based on the influence of different contents of organic copper and copper acetate on the super-roughening process
Examples 46 to 51 and comparative examples 28 to 30 were different from example 1 in the content of copper organocopper acetate and the other conditions were the same. White light interferometer tests were performed on examples 1, 46 to 51 and comparative examples 28 to 30, and the results were as follows:
TABLE 12 white light interferometer test results for examples 1, 46-51 and comparative examples 28-30
As can be seen from the test results in Table 12, the super-roughening solution, in which no organic copper acetate was added (comparative example 28), had non-uniform roughening of the copper surface and large color difference of the copper surface. When the addition amount of the organic copper acetate is small (comparative example 29), the coarsening of the copper surface is not uniform; when the content of the organocopper acetate exceeds 80g/L (comparative example 30), the amount of the organocopper acetate added has a small influence on the copper surface roughening effect, and therefore, the content of the organocopper acetate in the super-roughening solution is preferably 20 to 80 g/L.
Twelve, based on the influence of different kinds of organic copper on the super-roughening process
Examples 52 to 55 were different from example 1 in the kind of organic copper, and the other conditions were the same. White light interferometer tests were performed on example 1 and examples 52 to 55, and the test results were as follows:
TABLE 13 test results of white light interferometer for examples 1 and 52-55
As can be seen from the test results table 13, the organic copper species in the super-roughening solution were selected from copper acetate (example 1), copper formate (example 52), copper propionate (example 53), or a combination of copper acetate and copper formate (example 54), and a combination of copper formate and copper propionate (example 55), which had a small effect on the roughening effect on the copper surface. Wherein, the organic copper in the super-roughening solution is selected as copper acetate, and the super-roughening effect is optimal. Therefore, the organic copper in the super-roughening solution can be selected from copper acetate, copper formate, copper propionate or a combination of copper acetate and copper formate, a combination of copper formate and copper propionate, and preferably copper acetate.
Thirteen, based on the influence of different contents of formic acid on the super-roughening process
Examples 56 to 61 and comparative examples 31 to 33 were different from example 1 in the formic acid content, and the other conditions were the same. White light interferometer tests were performed on example 1, examples 56 to 61, and comparative examples 31 to 33, and the results were as follows:
TABLE 14 test results of white light interferometer for example 1, examples 56 to 61 and comparative examples 31 to 33
As is clear from the test results Table 14, it was found that formic acid was not added to the super-roughening solution (comparative example 31), the roughening of the copper surface was not uniform, and the color difference of the copper surface was large. When the addition amount of formic acid is less (comparative example 32), the coarsening of the copper surface is less uniform; when the formic acid content exceeds 100g/L (comparative example 33), the effect of roughening the copper surface is less affected by the amount of copper organocopper acetate added, and therefore, the formic acid content in the super-roughening solution is preferably 30 to 100 g/L.
Fourteen, based on the influence of different sodium formate contents on the super-roughening process
Examples 62 to 67 and comparative examples 34 to 36 were different from example 1 in the content of sodium formate, and the other conditions were the same. White light interferometer tests were performed on examples 1, 62 to 67, and comparative examples 34 to 36, and the results were as follows:
TABLE 15 white light interferometer test results for examples 1, 62-67, and comparative examples 34-36
As can be seen from the test results Table 15, the super-roughening solution, in which no sodium formate was added (comparative example 34), had non-uniform roughening of the copper surface and large color difference of the copper surface. When the addition amount of sodium formate is small (comparative example 35), the coarsening of the copper surface is not uniform; when the content of sodium formate exceeds 45g/L (comparative example 36), the addition amount of sodium formate has less influence on the copper surface roughening effect, and therefore, the content of sodium formate in the super-roughening liquid is preferably 15 to 45 g/L.
Fifteen, based on the influence of different contents of sodium chloride on the super-roughening process
Examples 68 to 73 and comparative examples 37 to 39 were the same as in example 1 except for the sodium chloride content. White light interferometer tests were performed on examples 1, 68 to 73 and comparative examples 37 to 39, and the results were as follows:
TABLE 16 test results of white light interferometers for examples 1, 68-73 and comparative examples 37-39
As is clear from the test results Table 16, it can be seen that the super-roughening solution, in which sodium chloride was not added (comparative example 37), had non-uniform roughening of the copper surface and large color difference of the copper surface. When the addition amount of sodium chloride is small (comparative example 38), the coarsening of the copper surface is not uniform; when the content of sodium chloride exceeds 45g/L (comparative example 39), the effect of roughening the copper surface is less affected by the amount of sodium chloride added, and therefore, the content of sodium chloride in the super-roughening liquid is preferably 15 to 45 g/L.
Sixthly, the influence of the combination based on organic copper, formic acid, sodium formate and sodium chloride on the super-roughening process
Comparative example 28 differs from example 1 in that no organocopper is present and the conditions are the same. Comparative example 31 differs from example 1 in that formic acid is not included and the conditions are the same. Comparative example 34 is identical to example 1 except that it does not contain sodium formate, and comparative example 37 is identical to example 1 except that it does not contain sodium chloride. Comparative example 40 differs from example 1 in that it does not contain organocopper and formic acid and the conditions are the same. Comparative example 41 differs from example 1 in that it does not contain organocopper and sodium formate and the conditions are the same. Comparative example 42 differs from example 1 in that no organocopper and no sodium chloride are present, and the conditions are otherwise the same. Comparative example 43 differs from example 1 in that it does not contain a super-roughening solution. White light interferometer tests were performed on example 1, comparative example 28, comparative example 31, comparative example 34, comparative example 37, and comparative examples 40 to 43, and the results were as follows:
TABLE 17 test results of white light interferometer of example 1, comparative example 28, comparative example 31, comparative example 34, comparative example 37, and comparative examples 40 to 43
As can be seen from the test results in Table 17, the lack of the single component in the organic copper (comparative example 28), formic acid (comparative example 31), sodium formate (comparative example 34) or sodium chloride (comparative example 37) in the super-roughening solution has a large effect on the super-roughening process, which results in uneven roughening of the copper surface and large color difference of the copper surface. The lack of more than two components in the super-roughening solution has a greater effect on super-roughening than the lack of a single component.
In conclusion, in the process of transferring the photochemical pattern of the printed circuit board, after the copper surface is subjected to the super-roughening treatment by adding the copper surface color difference color homogenizing agent and the super-roughening solution, the roughening uniformity of the copper surface is effectively improved, a uniform micro-honeycomb-shaped roughening appearance is formed, the roughness of the copper surface can completely meet the production requirement, and the color difference of the copper surface is obviously reduced.
The super-roughening process of the printed circuit board can effectively solve the problem of large color difference of the copper surface treated by the super-roughening solution, and is simple to operate. Because the problem that the color difference of the roughened copper surface is large is solved, the phenomenon that the AOI false detection rate and the color of the surface of the plate after solder resist ink is coated are uneven can be greatly reduced, and the production efficiency and the quality yield are greatly improved.
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. A super-roughening process of a printed circuit board is characterized by comprising the following steps:
under the condition that the temperature is 25-32 ℃, spraying super-roughening liquid containing 0.3-0.5% of copper surface color difference color homogenizing agent by volume concentration onto a copper wire of a printed circuit board for 30-60 s;
the copper surface color difference and color uniformity agent comprises the following components in percentage by mass: 3-15% of wetting dispersant, 0.02-0.5% of leveling agent, 0.05-1% of accelerator and the balance of water;
the super-roughening liquid comprises: 40-50g/L of organic copper, 50-80g/L of formic acid, 25-35g/L of sodium formate, 25-35g/L of sodium chloride and the balance of deionized water; the organic copper is copper acetate; the wetting dispersant is selected from one of polyethyleneimine, sulfated sodium ricinoleate, naphthenic sodium sulfate and fatty amide alkyl sodium sulfate; the leveling agent is selected from one of mannitol, galactitol, polyethylene glycol and azido polyethylene glycol carboxyl; the accelerant is one selected from hexadecylamine, octadecylamine and ethylene diamine tetramethylene phosphonic acid sodium.
2. The super-roughening process for the printed wiring board according to claim 1, wherein the copper surface color difference color homogenizing agent comprises the following components in percentage by mass: 4 to 14 percent of wetting dispersant, 0.1 to 0.4 percent of leveling agent and 0.1 to 0.9 percent of accelerator.
3. The super-roughening process of the printed wiring board as claimed in claim 2, wherein the copper surface color difference color-homogenizing agent comprises the following components in percentage by mass: 8 to 13 percent of wetting dispersant, 0.15 to 0.3 percent of leveling agent and 0.4 to 0.8 percent of accelerator.
4. The process for super-roughening a printed wiring board according to claim 1, wherein said temperature is 26 to 30 ℃.
5. The process for super-roughening a printed wiring board according to claim 4, wherein said spraying time is 40 to 50 seconds.
6. The super-roughening process for the printed wiring board according to claim 5, wherein the temperature is 28-30 ℃; the spraying time is 45-50 s.
7. The super-roughening process for the printed wiring board according to claim 1, wherein the copper surface color difference color homogenizing agent comprises the following components in percentage by mass: 13% of polyethyleneimine, 0.15% of polyethylene glycol and 0.8% of octadecylamine.
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| CN114875409B (en) * | 2022-06-07 | 2023-09-01 | 深圳市板明科技股份有限公司 | Circuit board microetching roughening liquid circulation regeneration additive and application thereof |
| CN115094421B (en) * | 2022-08-24 | 2022-11-08 | 深圳市板明科技股份有限公司 | Copper surface roughening solution for high-frequency printed circuit board and preparation method thereof |
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