CN114143978B - Solder mask preparation process for selective surface fine treatment of thick copper plate - Google Patents
Solder mask preparation process for selective surface fine treatment of thick copper plate Download PDFInfo
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- CN114143978B CN114143978B CN202111615383.XA CN202111615383A CN114143978B CN 114143978 B CN114143978 B CN 114143978B CN 202111615383 A CN202111615383 A CN 202111615383A CN 114143978 B CN114143978 B CN 114143978B
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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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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Abstract
The invention discloses a solder resist preparation process for selective surface fine treatment of a thick copper plate. The corrosion repairing agent prepared by the invention adopts the organosilicon modified vinylphenol epoxy resin with low viscosity, strong hydrophobicity and small molecular weight, and is mixed with the epoxy resin with high epoxy value, the wetting agent, the nano filler and the curing agent, so that the defects caused by lateral erosion can be effectively filled, and the printing of the solder resist ink is matched, and the printed circuit board with excellent performance is obtained.
Description
Technical Field
The invention relates to the field of solder resist, in particular to a solder resist preparation process for selective surface fine treatment of a thick copper plate.
Background
The application field and the demand of the thick copper plate are rapidly expanded in recent years, and the thick copper plate is a hot Printed Circuit Board (PCB) variety with good market development prospect; the thick copper plate is mostly a high-current substrate. The main application fields of the large-current substrate are two fields: power modules (power modules) and automotive electronics. The main terminal electronic product field is the same as the conventional PCB (such as portable electronic product, network product, base station device, etc.), and the main terminal electronic product field is different from the conventional PCB field, such as automobile, industrial control, power module, etc. The large-current substrate has different efficacy from the conventional PCB. The main function of a conventional PCB is to form a conductive line for transferring information. The large-current substrate is used for bearing a power device and has the main effects of protecting the bearing capacity of current and stabilizing a power supply. The development trend of the high-current substrate is to carry larger current, and heat emitted by larger devices needs to be dissipated, so that the passing high current is larger and larger, and the thickness of all copper foils of the substrate is thicker and thicker. The thickness of copper of the current manufactured high-current substrate is 210 μm.
In order to meet the requirement of insulation protection of a thick copper plate, the required thickness of solder resist ink is required to have more and more challenges on solder resist screen printing, and when the thickness of copper is more than or equal to 75 micrometers, the lateral erosion of a conductive copper path of the copper plate becomes obvious, so that the printing of the solder resist ink is seriously influenced. If the solder resist ink is printed normally, the ink at the circuit position (copper wire and copper surface covering position) of the circuit layer is thin and red, the base material position is thick, the development lateral erosion is too large, and the ink at the edge of the circuit is wrinkled and does not fall in place, so that gold plating or tin plating is caused in the surface treatment engineering, further, short circuit or false copper exposure is caused, and the printing difficulty is very high. And if the method of increasing the silk-screen pressure and slowing down the printing speed is adopted for printing, the solder resist ink is extremely easy to enter hole positions on the PCB, the technical requirements of operators by the printing process are correspondingly improved, the implementation is difficult, meanwhile, for thick copper plates, due to the side corrosion, in order to prevent the contact part of the side edge and the base material from being red, the ink needs to be printed for many times, the solder resist ink is filled in the circuit etching part, the consumption of the solder resist ink is huge, and the problem of solder resist ink entering holes cannot be solved. If solder mask oil is printed for many times, the problems of false copper exposure and the like can be solved, but because the thickness of the solder mask is far larger than the height of the bonding pad, dry film coverage cannot be realized, and the treatment of a selective surface process cannot be carried out, so that the prior art has defects and needs to be improved.
CN 103152992 a discloses a solder mask printing method for thick copper plate, which comprises: step 1, respectively manufacturing a copper layer area screen plate and a whole board area screen plate aiming at an area of a copper layer covered on the surface of a circuit board and the surface of the whole circuit board; step 2, covering the circuits and the copper surfaces on the surfaces of the circuit boards with printing ink by using the copper layer area screen printing plate; step 3, standing the circuit board; step 4, baking the circuit board; step 5, performing ink coating on the whole surface of the circuit board by using the whole-board screen plate; step 6, standing the circuit board again; and 7, baking the circuit board again. The method adopts a standard screen printing step, and adopts a method for improving the thickness of the printing ink to cover the problem of false copper exposure, waste the printing ink and easily cause printing ink holes.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a solder mask preparation process for selective surface fine treatment of a thick copper plate.
A solder resist preparation process for selective surface fine treatment of a thick copper plate comprises the following steps:
(1) manufacturing a copper layer area screen printing plate aiming at the area of the surface of the circuit board covered with the copper layer;
(2) covering a copper layer area screen printing plate on a thick copper plate subjected to volcanic ash brushing treatment, horizontally immersing the thick copper plate into an etching compensating agent, soaking for 30-60s, slowly extracting the thick copper plate, placing the thick copper plate on a plane, performing ultrasonic treatment for 10-20min, wherein the ultrasonic power is 120-160W and the ultrasonic frequency is 10-20kHz, scraping excess etching compensating agent, standing for 10-20min, and drying at 70-80 ℃ for 20-30min to obtain an etching compensating thick copper plate;
(3) performing primary screen printing on the repaired thick copper plate obtained in the step (2) by using diluted solder resist ink, standing for 20-30min, and then drying at 70-80 ℃ for 40-60min to obtain a primary printed thick copper plate;
(4) uncovering the copper layer area screen printing plate on the primary printed thick copper plate prepared in the step (3), then carrying out secondary printing by adopting undiluted solder resist ink, standing for 20-30min, and finally, drying at 70-80 ℃ for 40-60min to obtain a secondary printed thick copper plate;
(5) and (4) carrying out exposure, development and high-temperature curing on the secondary printing thick copper plate obtained in the step (4) to obtain a solder mask thick copper plate, wherein the thickness of the solder mask ink is 30-36 μm.
The diluted solder resist ink is solder resist ink added with 1-3 wt% of a diluent; the diluent is acetone.
The preparation method of the corrosion inhibitor comprises the following steps:
s1, mixing 15-30 parts of 4-vinylphenol and 50-80 parts of epoxy chloropropane by mass, stirring at the rotation speed of 200-300r/min, adding 0.5-1 part of benzyltriethylammonium chloride, reacting at the temperature of 100-120 ℃ for 1-3h, dropwise adding 5-10 parts of 18-24 wt% NaOH aqueous solution at the speed of 15-40S/mL, transferring to the temperature of 70-90 ℃ and continuing to react for 4-6h, washing the obtained mixed solution with water, purifying by vacuum distillation to obtain a crude product, mixing the crude product with methanol according to the mass ratio of 1 (4-6), cooling to-8- (-4) DEG C, filtering to obtain a precipitate, and obtaining the vinylphenol epoxy resin;
s2, mixing 15-30 parts by mass of the vinylphenol epoxy resin obtained in the step S1 and 0.1-0.5 part by mass of karstedt catalyst solution, stirring at 35-45 ℃ for 1-3h, adding 15-30 parts by mass of triethoxysilane, transferring to 90-110 ℃ for refluxing for 20-30h, and purifying by vacuum distillation to obtain the organosilicon modified vinylphenol epoxy resin;
s3, mixing 50-60 parts of high epoxy value epoxy resin, 5-7 parts of wetting agent, 15-20 parts of nano filler, 0.5-1 part of curing agent and 10-20 parts of organosilicon modified vinylphenol epoxy resin prepared in the step S2 by mass, and stirring at the rotating speed of 100-200r/min for 1-2h to obtain the corrosion repairing agent.
The karstedt catalyst solution was a 2wt% solution of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane in xylene.
The wetting agent is one of ethylene glycol, absolute ethyl alcohol, propylene glycol and glycerol; preferably, the wetting agent is absolute ethyl alcohol.
The nano filler is one or a mixture of two of oily epoxy resin silane coupling agent modified nano silicon dioxide and silane coupling agent modified silicon dioxide; preferably, the nano filler is oil epoxy resin silane coupling agent modified nano silicon dioxide.
The curing agent is one of an amine curing agent or an anhydride curing agent.
The problem of the undercut always exists in the thick copper plate printing, and with the development of science and technology, the requirement for the current passing amount of the circuit board is higher and higher, and the required conductive copper path is thicker and thicker, so that the challenge of the undercut on the solder resist screen printing is greater and greater. At present, the method for solving the side etching influence is limited to filling the influence caused by the side etching as much as possible by means of multiple times of printing or increasing the printing pressure and the like. However, due to the limitation of the solder resist ink, the side etching part cannot be filled due to the difference of wettability and fluidity of the solder resist ink, the solder resist ink is too thick due to multiple times of printing, a large amount of solder resist ink is wasted, and the attractiveness is influenced; the printing pressure is increased, so that solder resist ink is easy to enter hole positions on the PCB, and the service performance of the printing plate is affected. On the other hand, the viscosity and the fluidity of the solder resist ink are adjusted, but the solder resist ink is too thin, a large amount of bubbles and even chaps are easily generated after dehydration, and due to the structure of the inward bending of the undercut part, the conventional solder resist ink is difficult to infiltrate and completely fill the undercut part, which is always the difficulty of thick copper plate printing, and the further increase of the thickness of the copper plate is limited.
Therefore, the invention develops a new way to try to firstly carry out the compensation etching on the lateral etching part before the printing is carried out, and the lateral etching part is filled by adopting a compensation agent, so that the printing of the solder resist ink is not influenced. The invention synthesizes the corrosion inhibitor, can effectively fill the defects caused by the side etching, is matched with the printing of the solder resist ink, and greatly reduces the problem of false copper exposure. The corrosion repairing agent adopted by the invention is prepared by mixing high epoxy value epoxy resin, a wetting agent, nano filler and a diluent. Considering that the concave part caused by chemical etching is not smooth and flat, the epoxy resin with high viscosity cannot penetrate into the concave part, and the concave part is also the main reason of causing false copper exposure. The invention adopts the epoxy resin with low epoxy value to reduce the viscosity of the corrosion repairing agent and increase the fluidity of the corrosion repairing agent; meanwhile, in order to further enhance the capability of the corrosion repairing agent for filling the side etching, a certain amount of wetting agent is added into the corrosion repairing agent, so that the infiltration capability of the corrosion repairing agent on the side etching is enhanced, and the corrosion repairing agent can be ensured to completely infiltrate into the side etching. Because the filling capacity of the epoxy resin is poor, modified silicon dioxide is further added into the corrosion repairing agent as a filler, so that the filling amount of a lateral etching part can be further increased, and the corrosion repairing effect is achieved; meanwhile, as the nano silicon dioxide is modified by oiliness, the hydrophobicity of the nano silicon dioxide is further enhanced, the wetting agent is not easy to attach to the surface of the nano silicon dioxide, the wetting agent in the corrosion repairing agent is further reduced after ultrasonic treatment, the gap formed by volatilization of the wetting agent in the drying process is reduced, and the filling density of the etched part is improved.
However, after the above-mentioned corrosion repairing agent is dried, as the wetting agent is volatilized, the copper plate is recessed at the side etching position and a large number of bubble-shaped defects are generated, which not only can not solve the problem of false copper exposure, but also can make the problem of false copper exposure more serious. Therefore, the invention further synthesizes the organic silicon modified vinyl phenol epoxy resin, which can effectively fill up the defects caused by the volatilization of the wetting agent, form a supporting structure and achieve excellent corrosion repairing effect. The organic silicon modified vinyl phenol epoxy resin prepared by the invention is obtained by reacting 4-vinyl phenol with epoxy chloropropane, reacting phenolic hydroxyl with halogenated hydrocarbon to obtain vinyl phenol epoxy propane, and then reacting silicon base with double bond to form grafting of triethoxysilane. The viscosity of the organosilicon modified vinylphenol epoxy resin is extremely low, namely 32.5 mPas, and the viscosity of the corrosion repairing agent can be greatly reduced, so that the fluidity of the corrosion repairing agent is increased; meanwhile, due to the small molecular weight, the epoxy resin can enter a cross-linked network formed by the epoxy resin and the curing agent to play a supporting role, so that the defects caused by volatilization and thermosetting of a wetting agent are reduced; in addition, due to the characteristic of low surface energy of the organosilicon material, the hydrophobicity of the prepared corrosion repairing agent is further increased, the wetting agent can be slowly transferred to the surface of the corrosion repairing agent in the ultrasonic oscillation process, and the epoxy resin with high fluidity and the nano filler supplement the position of the wetting agent, so that an excellent corrosion repairing effect is obtained. The wetting agent, the nano filler and the organic silicon modified vinyl phenol epoxy resin are synergistic, so that a good corrosion repairing effect is obtained, and the problem of false copper exposure is effectively solved.
Finally, because the corrosion repairing agent adopted by the invention takes the epoxy resin as the base material, the corrosion repairing agent is consistent with the main material of the solder resist ink, the caking property is good, and the printing effect of the solder resist ink can not be influenced.
The invention has the beneficial effects that:
1. the organosilicon modified vinylphenol epoxy resin with low viscosity, strong hydrophobicity and small molecular weight is prepared and mixed with the epoxy resin with high epoxy value, the wetting agent, the nano filler and the curing agent to prepare the corrosion repairing agent, so that the defects caused by side etching can be effectively filled, the printing of solder resist ink is matched, and the problem of false copper exposure is greatly reduced.
2. The invention uses the corrosion repairing agent to carry out surface treatment on a thick copper plate, and then carries out printing of solder resist ink, thus obtaining the printed circuit board with excellent performance.
Detailed Description
The screen of the copper layer area is made of nylon material, the aperture is 225 meshes, and a conductive copper circuit hardening layer is formed on the nylon screen by utilizing a photoreactive emulsion hardening method, so that the printing ink cannot penetrate through the conductive copper circuit hardening layer, and the rest parts are permeable meshes.
Solder resist ink, goods number: YX-90088G02, Yitide electro-technology, Inc., Hui Zhou.
4-vinylphenol, cat No.: h67990, Shanghai Ji to Biochemical technology, Inc.
Epichlorohydrin, cat number: e38700, Shanghai Ji to Biochemical technology, Inc.
Benzyltriethylammonium chloride, cat no: 18171083800, Hubei Jiahuixing Chengning Biotech, Inc.
Triethoxysilane, cat No.: r027300, shanghai yan chemical technology limited.
Platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane solution, cat #: r005382, shanghai yan chemical technology ltd.
The oily epoxy resin silane coupling agent modified nano silicon dioxide has the following types: HN-SP30S, particle size: 30nm, Hengnan New materials, Inc. in Hangzhou.
Isophorone diamine, product No.: m12857, CAS: 2855-13-2, Merrel chemical technologies, Inc. of Shanghai.
High epoxy value epoxy resin, good No.: 2021-HYSZ-1, viscosity: 11000 + 14000mPas, Hebeilin Jing anticorrosive materials Co.
Example 1
A solder mask preparation process for selective surface fine treatment of a thick copper plate comprises the following steps:
(1) manufacturing a copper layer area screen printing plate aiming at the area of the surface of the circuit board covered with the copper layer;
(2) covering a copper layer area screen printing plate on a thick copper plate subjected to volcanic ash brushing treatment, performing primary screen printing by using diluted solder resist ink, standing for 28min, and then drying at 75 ℃ for 50min to obtain a primary printed thick copper plate;
(3) uncovering the copper layer area screen printing plate on the primary printing thick copper plate prepared in the step (2), then carrying out secondary printing by adopting undiluted solder resist ink, standing for 28min, and finally, drying at 75 ℃ for 50min to obtain a secondary printing thick copper plate;
(4) and (4) carrying out exposure, development and high-temperature curing on the secondary printing thick copper plate obtained in the step (3) to obtain a solder mask thick copper plate, wherein the thickness of the solder mask ink is 32 μm.
The diluted solder resist ink is solder resist ink added with 2wt% of diluent; the diluent is acetone.
Example 2
A solder mask preparation process for selective surface fine treatment of a thick copper plate comprises the following steps:
(1) manufacturing a copper layer area screen printing plate aiming at the area of the surface of the circuit board covered with the copper layer;
(2) covering a copper layer area screen printing plate on a thick copper plate subjected to volcanic ash brushing treatment, horizontally immersing the thick copper plate into a corrosion repairing agent, soaking for 40s, slowly extracting, placing on a plane, performing ultrasonic treatment for 15min, wherein the ultrasonic power is 140W and the ultrasonic frequency is 15kHz, scraping off excessive corrosion repairing agent, standing for 15min, and placing at 75 ℃ for drying for 28min to obtain a corrosion repairing thick copper plate;
(3) carrying out primary screen printing on the repaired thick copper plate obtained in the step (2) by using diluted solder resist ink, standing for 28min, and then drying at 75 ℃ for 50min to obtain a primary printed thick copper plate;
(4) uncovering the copper layer area screen printing plate on the primary printing thick copper plate prepared in the step (3), then carrying out secondary printing by adopting undiluted solder resist ink, standing for 28min, and finally, drying at 75 ℃ for 50min to obtain a secondary printing thick copper plate;
(5) and (4) carrying out exposure, development and high-temperature curing on the secondary printing thick copper plate obtained in the step (4) to obtain a solder mask thick copper plate, wherein the thickness of the solder mask ink is 32 μm.
The diluted solder resist ink is solder resist ink added with 2wt% of diluent; the diluent is acetone.
The preparation method of the corrosion inhibitor comprises the following steps: and mixing 55 parts of high-epoxy-value epoxy resin and 0.6 part of curing agent by mass, and stirring at the rotating speed of 150r/min for 1.5 hours to obtain the corrosion repairing agent.
The curing agent is isophorone diamine.
Example 3
A solder mask preparation process for selective surface fine treatment of a thick copper plate comprises the following steps:
(1) manufacturing a copper layer area screen printing plate aiming at the area of the surface of the circuit board covered with the copper layer;
(2) covering a copper layer area screen printing plate on a thick copper plate subjected to volcanic ash brushing treatment, horizontally immersing the thick copper plate into a corrosion repairing agent, soaking for 40s, slowly extracting, placing on a plane, performing ultrasonic treatment for 15min, wherein the ultrasonic power is 140W and the ultrasonic frequency is 15kHz, scraping off excessive corrosion repairing agent, standing for 15min, and placing at 75 ℃ for drying for 28min to obtain a corrosion repairing thick copper plate;
(3) carrying out primary screen printing on the repaired thick copper plate obtained in the step (2) by using diluted solder resist ink, standing for 28min, and then drying at 75 ℃ for 50min to obtain a primary printed thick copper plate;
(4) uncovering the copper layer area screen printing plate on the primary printing thick copper plate prepared in the step (3), then carrying out secondary printing by adopting undiluted solder resist ink, standing for 28min, and finally, drying at 75 ℃ for 50min to obtain a secondary printing thick copper plate;
(5) and (4) carrying out exposure, development and high-temperature curing on the secondary printing thick copper plate obtained in the step (4) to obtain a solder mask thick copper plate, wherein the thickness of the solder mask ink is 32 μm.
The diluted solder resist ink is solder resist ink added with 2wt% of diluent; the diluent is acetone.
The preparation method of the corrosion inhibitor comprises the following steps: according to the mass parts, 55 parts of high epoxy value epoxy resin, 18 parts of nano filler and 0.6 part of curing agent are mixed and stirred for 1.5 hours at the rotating speed of 150r/min to obtain the corrosion repairing agent.
The nano filler is oily epoxy resin silane coupling agent modified nano silicon dioxide.
The curing agent is isophorone diamine.
Example 4
A solder mask preparation process for selective surface fine treatment of a thick copper plate comprises the following steps:
(1) manufacturing a copper layer area screen printing plate aiming at the area of the surface of the circuit board covered with the copper layer;
(2) covering a copper layer area screen printing plate on a thick copper plate subjected to volcanic ash brushing treatment, horizontally immersing the thick copper plate into a corrosion repairing agent, soaking for 40s, slowly extracting, placing on a plane, performing ultrasonic treatment for 15min, wherein the ultrasonic power is 140W and the ultrasonic frequency is 15kHz, scraping off excessive corrosion repairing agent, standing for 15min, and placing at 75 ℃ for drying for 28min to obtain a corrosion repairing thick copper plate;
(3) carrying out primary screen printing on the repaired thick copper plate obtained in the step (2) by using diluted solder resist ink, standing for 28min, and then drying at 75 ℃ for 50min to obtain a primary printed thick copper plate;
(4) uncovering the copper layer area screen printing plate on the primary printing thick copper plate prepared in the step (3), then carrying out secondary printing by adopting undiluted solder resist ink, standing for 28min, and finally, drying at 75 ℃ for 50min to obtain a secondary printing thick copper plate;
(5) and (4) carrying out exposure, development and high-temperature curing on the secondary printing thick copper plate obtained in the step (4) to obtain a solder mask thick copper plate, wherein the thickness of the solder mask ink is 32 μm.
The diluted solder resist ink is solder resist ink added with 2wt% of diluent; the diluent is acetone.
The preparation method of the corrosion inhibitor comprises the following steps: according to the mass parts, 55 parts of high epoxy value epoxy resin, 6 parts of wetting agent, 18 parts of nano filler and 0.6 part of curing agent are mixed and stirred at the rotating speed of 150r/min for 1.5 hours to obtain the corrosion repairing agent.
The wetting agent is absolute ethyl alcohol.
The nano filler is oily epoxy resin silane coupling agent modified nano silicon dioxide.
The curing agent is isophorone diamine.
Example 5
A solder mask preparation process for selective surface fine treatment of a thick copper plate comprises the following steps:
(1) manufacturing a copper layer area screen printing plate aiming at the area of the surface of the circuit board covered with the copper layer;
(2) covering a copper layer area screen printing plate on a thick copper plate subjected to volcanic ash brushing treatment, horizontally immersing the thick copper plate into a corrosion repairing agent, soaking for 40s, slowly extracting, placing on a plane for ultrasonic treatment for 15min, wherein the ultrasonic power is 140W and the ultrasonic frequency is 15kHz, scraping off excess corrosion repairing agent, standing for 15min, and placing at 75 ℃ for drying for 28min to obtain a thick corrosion repairing copper plate;
(3) carrying out primary screen printing on the repaired thick copper plate obtained in the step (2) by using diluted solder resist ink, standing for 28min, and then drying at 75 ℃ for 50min to obtain a primary printed thick copper plate;
(4) uncovering the copper layer area screen printing plate on the primary printing thick copper plate prepared in the step (3), then carrying out secondary printing by adopting undiluted solder resist ink, standing for 28min, and finally, drying at 75 ℃ for 50min to obtain a secondary printing thick copper plate;
(5) and (4) carrying out exposure, development and high-temperature curing on the secondary printing thick copper plate obtained in the step (4) to obtain a solder mask thick copper plate, wherein the thickness of the solder mask ink is 32 μm.
The diluted solder resist ink is solder resist ink added with 2wt% of diluent; the diluent is acetone.
The preparation method of the corrosion inhibitor comprises the following steps:
s1, mixing 20 parts of 4-vinylphenol and 70 parts of epoxy chloropropane by mass, stirring at the rotating speed of 280r/min, then adding 0.7 part of benzyltriethylammonium chloride, reacting at 110 ℃ for 2h, then dropwise adding 8 parts of 20 wt% NaOH aqueous solution at the speed of 30S/mL, transferring to 80 ℃ for continuous reaction for 5h, washing the obtained mixed solution with water, purifying by vacuum distillation to obtain a crude product, finally mixing the crude product with methanol according to the mass ratio of 1:5, cooling to-5 ℃, filtering the mixture, and taking a precipitate to obtain the vinylphenol epoxy resin;
s2, mixing 20 parts by mass of the vinylphenol epoxy resin obtained in the step S1 and 0.2 part by mass of karstedt catalyst solution, stirring at 40 ℃ for 2 hours, adding 19 parts by mass of triethoxysilane, transferring to 100 ℃ for refluxing for 24 hours, and purifying by vacuum distillation to obtain the organosilicon modified vinylphenol epoxy resin;
s3, mixing 55 parts of high epoxy value epoxy resin, 6 parts of wetting agent, 18 parts of nano filler, 0.6 part of curing agent and 15 parts of organosilicon modified vinylphenol epoxy resin prepared in the step S2 by mass, and stirring at the rotating speed of 150r/min for 1.5 hours to obtain the corrosion repairing agent.
The karstedt catalyst solution is a xylene solution of 2wt% platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane.
The wetting agent is absolute ethyl alcohol.
The nano filler is oily epoxy resin silane coupling agent modified nano silicon dioxide.
The curing agent is isophorone diamine.
Test example 1
Adopting the solder resist preparation process of the selective surface fine treatment of the thick copper plate of each embodiment to prepare the printed circuit board, wherein the copper thickness is 200 mu m, and the exposure: exposing under ultraviolet lamp for 4min, with ultraviolet lamp power of 80W, developing time of 85s, and high temperature curing time of 150 deg.C for 45 min. 1000 printed circuit boards were prepared for each example and tested for false copper exposure.
False copper exposure rate is false copper exposure printed circuit board number/1000 × 100%
Table 1: test results of false copper-exposure rate of printed circuit boards prepared in each example
| False copper exposure rate | |
| Example 1 | 8.2％ |
| Example 2 | 8.4％ |
| Example 3 | 5.2％ |
| Example 4 | 3.1％ |
| Example 5 | 0％ |
As can be seen from Table 1, the false copper exposure rate of the printed circuit board obtained by silk-screen printing after the treatment of the corrosion inhibitor prepared by the invention is low. In particular, in example 5, the pseudo copper-exposure rate was 0% for 1000 printed circuit boards. This is because the corrosion inhibitor used in example 5 was made by mixing a high epoxy number epoxy resin, a wetting agent, a nanofiller and a diluent. Considering that the concave part caused by chemical etching is not smooth and flat, the epoxy resin with high viscosity cannot penetrate into the concave part, and the concave part is also the main reason of causing false copper exposure. Example 5 a low epoxy resin was used to reduce the viscosity and increase the flow of the corrosion inhibitor; meanwhile, in order to further enhance the capability of the corrosion repairing agent for filling the side etching, a certain amount of wetting agent is added into the corrosion repairing agent, so that the infiltration capability of the corrosion repairing agent on the side etching is enhanced, and the corrosion repairing agent can be ensured to completely infiltrate into the side etching. Because the filling capacity of the epoxy resin is poor, modified silicon dioxide is further added into the corrosion repairing agent as a filler, so that the filling amount of a lateral etching part can be further increased, and the corrosion repairing effect is achieved; meanwhile, as the nano silicon dioxide is modified by oiliness, the hydrophobicity of the nano silicon dioxide is further enhanced, the wetting agent is not easy to attach to the surface of the nano silicon dioxide, the wetting agent in the corrosion repairing agent is further reduced after ultrasonic treatment, the gap formed by volatilization of the wetting agent in the drying process is reduced, and the filling density of the etched part is improved. Furthermore, the organosilicon modified vinylphenol epoxy resin is synthesized, so that the defects caused by volatilization of the wetting agent can be effectively filled, a supporting structure is formed, and an excellent corrosion repairing effect is achieved. The organic silicon modified vinyl phenol epoxy resin prepared by the invention is obtained by reacting 4-vinyl phenol with epoxy chloropropane, reacting phenolic hydroxyl with halogenated hydrocarbon to obtain vinyl phenol epoxy propane, and then reacting silicon base with double bond to form grafting of triethoxysilane. The viscosity of the organosilicon modified vinylphenol epoxy resin is extremely low, is only 32.5 mPa.s, and can greatly reduce the viscosity of a corrosion repairing agent and increase the fluidity of the corrosion repairing agent; meanwhile, due to the small molecular weight, the epoxy resin can enter a cross-linked network formed by the epoxy resin and the curing agent to play a supporting role, so that the defects caused by volatilization and thermosetting of a wetting agent are reduced; in addition, due to the characteristic of low surface energy of the organosilicon material, the hydrophobicity of the prepared corrosion repairing agent is further increased, the wetting agent can be slowly transferred to the surface of the corrosion repairing agent in the ultrasonic oscillation process, and the epoxy resin with high fluidity and the nano filler supplement the position of the wetting agent, so that the excellent corrosion repairing effect is obtained, and the problem of false copper exposure is perfectly solved.
The false copper-exposure rate of the printed circuit board prepared in example 4 is higher than that of example 5, because the organosilicon modified vinyl phenol epoxy resin is not added, the epoxy resin with low epoxy degree has poor supporting capability, and the corrosion repairing effect is influenced by the volatilization of the wetting agent, so that the false copper-exposure rate is increased. The false copper exposure rate of the printed circuit board prepared in example 3 is higher than that of example 4, because no wetting agent is added, the viscosity of the epoxy resin and the nano filler is high, the fluidity is poor, and the side etching part cannot be completely filled, so that the false copper exposure rate is further increased. The false copper exposure rate of the printed circuit board prepared in example 2 is higher than that of example 3, because the epoxy resin and the curing agent are directly adopted to fill the undercut, the epoxy resin cannot enter the undercut part, and the filling effect is difficult to achieve. On the contrary, the curing effect is poor due to the low epoxy degree, and the effect of directly carrying out screen printing twice in the embodiment 1 is better than that of the embodiment 2.
Test example 2
Adopting the solder resist preparation process of the selective surface fine treatment of the thick copper plate of each embodiment to prepare the printed circuit board, wherein the thickness of copper is 200 μm, and the exposure is as follows: exposing under ultraviolet lamp for 4min, with ultraviolet lamp power of 80W, developing time of 85s, and high temperature curing time of 150 deg.C for 45 min. 1000 printed circuit boards were prepared for each example and tested for ink lather.
Ink foaming ratio ═ ink foaming printed circuit board number/1000 × 100%
Table 2: results of testing foaming ratio of ink for printed circuit board prepared in each example
| Foaming on the whole surface | Non-fixed foaming | No foaming phenomenon | |
| Example 1 | 7.2％ | 12.3％ | 80.5％ |
| Example 2 | 16.4％ | 83.6％ | 0％ |
| Example 3 | 8.9％ | 91.1％ | 0％ |
| Practice ofExample 4 | 2.1％ | 97.8％ | 0.1％ |
| Example 5 | 0.2％ | 1.6％ | 98.2％ |
As can be seen from Table 2, the printed circuit board obtained in example 5 has the lowest bubbling rate, because the corrosion inhibitor used in the present invention is based on epoxy resin, is consistent with the main material of solder resist ink, has good adhesion, and does not affect the printing effect of solder resist ink. In addition, the side etching not only can cause false copper exposure, but also can easily generate static electricity when the solder mask printing is carried out due to the fact that the roughness between the corners of the circuit is larger due to the rough side line, light gas impurities are adsorbed at the positions with the charges, and the solder mask foaming is directly formed without the discharged gas impurities remaining in the ink skin layer. In example 5, epoxy resin with low epoxy value is used to reduce the viscosity of the corrosion repairing agent and increase the fluidity thereof; meanwhile, in order to further enhance the capability of the corrosion repairing agent for filling the side etching, a certain amount of wetting agent is added into the corrosion repairing agent, so that the infiltration capability of the corrosion repairing agent on the side etching is enhanced, and the corrosion repairing agent can be ensured to completely infiltrate into the side etching; according to the invention, modified silicon dioxide is further added into the corrosion repairing agent as a filler, so that the filling amount of a lateral etching part can be further increased, and the corrosion repairing effect is achieved; meanwhile, as the nano silicon dioxide is modified by oiliness, the hydrophobicity of the nano silicon dioxide is further enhanced, the wetting agent is not easy to attach to the surface of the nano silicon dioxide, the wetting agent in the corrosion repairing agent is further reduced after ultrasonic treatment, gaps formed by volatilization of the wetting agent in the drying process are reduced, and the filling density of the side etching part is improved; and furthermore, the organosilicon modified vinylphenol epoxy resin is synthesized, so that the defects caused by volatilization of the wetting agent can be effectively filled, a supporting structure is formed, and an excellent corrosion repairing effect is achieved. Thereby obtaining excellent repairing corrosion effect, perfectly solving the problem of false copper exposure and reducing the foaming rate of the printing ink of the printed circuit board. The foaming ratio of the printed circuit board obtained in example 4 is higher than that of example 5, and the foaming ratio of the printed circuit board obtained in example 3 is higher than that of example 4, and it is presumed that the effect of the corrosion inhibitor used in example 4 on solving the pseudo copper exposure is worse than that of example 5, and the effect of the corrosion inhibitor used in example 3 on solving the pseudo copper exposure is worse than that of example 4. Example 2 showed the highest foaming rate because the corrosion inhibitor used in example 2 only contains low epoxy level epoxy resin and curing agent, which easily absorbs moisture in the air and hardly releases gas completely, and at the final high temperature curing, the low epoxy level epoxy resin increased in fluidity due to the higher temperature, releasing gas and moisture, and causing a large amount of bubbles.
Claims (7)
1. A solder mask preparation process for selective surface fine treatment of a thick copper plate is characterized by comprising the following steps:
(1) manufacturing a copper layer area screen printing plate aiming at the area of the surface of the circuit board covered with the copper layer;
(2) covering a copper layer area screen printing plate on a thick copper plate subjected to volcanic ash brushing treatment, horizontally immersing the thick copper plate into an etching compensating agent, soaking for 30-60s, slowly extracting the thick copper plate, placing the thick copper plate on a plane, performing ultrasonic treatment for 10-20min, wherein the ultrasonic power is 120-160W and the ultrasonic frequency is 10-20kHz, scraping excess etching compensating agent, standing for 10-20min, and drying at 70-80 ℃ for 20-30min to obtain an etching compensating thick copper plate;
(3) performing primary screen printing on the repaired thick copper plate obtained in the step (2) by using diluted solder resist ink, standing for 20-30min, and then drying at 70-80 ℃ for 40-60min to obtain a primary printed thick copper plate;
(4) uncovering the copper layer area screen printing plate on the primary printed thick copper plate prepared in the step (3), then carrying out secondary printing by adopting undiluted solder resist ink, standing for 20-30min, and finally, drying at 70-80 ℃ for 40-60min to obtain a secondary printed thick copper plate;
(5) and (4) carrying out exposure, development and high-temperature curing on the secondary printing thick copper plate obtained in the step (4) to obtain the solder resist thick copper plate.
2. The solder mask preparation process for the selective surface fine treatment of the thick copper plate as claimed in claim 1, wherein the diluted solder mask ink is solder mask ink added with 1wt% -3wt% of a diluent; the diluent is acetone.
3. The solder mask manufacturing process for selective surface fine processing of a thick copper plate according to claim 1, wherein the preparation method of the etching-compensating agent comprises the following steps:
s1, mixing 15-30 parts of 4-vinylphenol and 50-80 parts of epoxy chloropropane by mass, stirring at the rotation speed of 200-300r/min, adding 0.5-1 part of benzyltriethylammonium chloride, reacting at the temperature of 100-120 ℃ for 1-3h, dropwise adding 5-10 parts of 18-24 wt% NaOH aqueous solution at the speed of 15-40S/mL, transferring to the temperature of 70-90 ℃ and continuing to react for 4-6h, washing the obtained mixed solution with water, purifying by vacuum distillation to obtain a crude product, mixing the crude product with methanol according to the mass ratio of 1 (4-6), cooling to-8- (-4) DEG C, filtering to obtain a precipitate, and obtaining the vinylphenol epoxy resin;
s2, mixing 15-30 parts by mass of the vinylphenol epoxy resin obtained in the step S1 and 0.1-0.5 part by mass of karstedt catalyst solution, stirring at 35-45 ℃ for 1-3h, adding 15-30 parts by mass of triethoxysilane, transferring to 90-110 ℃ for refluxing for 20-30h, and purifying by vacuum distillation to obtain the organosilicon modified vinylphenol epoxy resin;
s3, mixing 50-60 parts of high epoxy value epoxy resin, 5-7 parts of wetting agent, 15-20 parts of nano filler, 0.5-1 part of curing agent and 10-20 parts of organosilicon modified vinylphenol epoxy resin prepared in the step S2 by mass, and stirring at the rotating speed of 100-200r/min for 1-2h to obtain the corrosion repairing agent.
4. The process for preparing a solder resist for selective surface fine treatment of a thick copper plate according to claim 3, wherein the karstedt catalyst solution is a 2wt% xylene solution of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane.
5. The process for preparing solder masks for selective surface fine treatment of thick copper plates according to claim 3, wherein the wetting agent is one of ethylene glycol, absolute ethyl alcohol, propylene glycol and glycerin.
6. The process for preparing a solder mask for selective surface fine treatment of a thick copper plate according to claim 3, wherein the nano filler is one or a mixture of two of oil epoxy resin, silane coupling agent modified nano silica and silane coupling agent modified silica.
7. The process for preparing a solder resist for selective surface fine processing of a thick copper plate according to claim 3, wherein the curing agent is one of an amine curing agent or an acid anhydride curing agent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4978423A (en) * | 1988-09-26 | 1990-12-18 | At&T Bell Laboratories | Selective solder formation on printed circuit boards |
| CN109496082A (en) * | 2018-10-13 | 2019-03-19 | 奥士康科技股份有限公司 | A kind of super thick copper sheet anti-welding printing method |
| CN111586989A (en) * | 2020-04-28 | 2020-08-25 | 珠海杰赛科技有限公司 | Solder mask manufacturing method of thick copper circuit board |
| CN111698839A (en) * | 2020-06-29 | 2020-09-22 | 百强电子（深圳）有限公司 | Solder resist printing method for selective surface treatment of thick copper plate |
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2021
- 2021-12-27 CN CN202111615383.XA patent/CN114143978B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4978423A (en) * | 1988-09-26 | 1990-12-18 | At&T Bell Laboratories | Selective solder formation on printed circuit boards |
| CN109496082A (en) * | 2018-10-13 | 2019-03-19 | 奥士康科技股份有限公司 | A kind of super thick copper sheet anti-welding printing method |
| CN111586989A (en) * | 2020-04-28 | 2020-08-25 | 珠海杰赛科技有限公司 | Solder mask manufacturing method of thick copper circuit board |
| CN111698839A (en) * | 2020-06-29 | 2020-09-22 | 百强电子（深圳）有限公司 | Solder resist printing method for selective surface treatment of thick copper plate |
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