TW201434366A - Copper foil surface modification method used in manufacturing process of printed circuit board - Google Patents

Abstract

A copper foil surface modification method used in a manufacturing process of a printed circuit board, comprising the following steps: preparing in advance a copper foil substrate and performing the surface cleaning and abrasion, then exerting the horizontal sprinkling or vertical immersion of the surface modifier, and lastly baking to prepare for the subsequent process. Because the present invention does not require the micro-etching technology, the problem of the hydrogen peroxide's eroding the machine or the contamination from the heavy metal will not occur, while the surface modifier even will not affect the roughness of the copper surface and can effectively enhance the bonding force of the super-fine copper process. Because the surface modifier can make the copper skin surface smooth, the problems of residue and foot on the dry film of the fine circuit can be completely overcome. Thus, the present invention is to enhance the traditional physical super-coarsening bonding ability into the occurrence of chemical bonding effect, thereby making the entire manufacturing process of the circuit board simplified and clean and being able to save the unnecessary cost.

Description

Copper foil surface modification method for printed circuit board process

The invention relates to a copper foil surface modification method for a printed circuit board process, in particular to a technology for modifying the surface of a copper foil to improve the surface bonding force and make the overall printed circuit board process simplified and clean. And can save unnecessary costs.

Generally, the manufacturing process of the printed circuit board is to first cut the base plate into working pieces and drill holes, and then perform through-hole plating, and the through-hole plating is to deposit copper ions by using chemical copper, and the thin layer is adsorbed on the hole wall. The copper layer starts to turn on both sides, and the whole process is a hole-filling agent→water washing→micro-etching→water washing→activation→water washing→speeding→water washing→chemical copper deposition→water washing→drying, after the through-hole plating, once After copper plating, the dry film is used to make the circuit, and then the copper printed circuit board is plated in the through hole, and the dry film is pressed on both sides of the working substrate by an automatic induction laminating machine, and finally exposed and developed. , circuit etching, stripping, anti-weld printing, nickel plating, gold plating, fishing molding, the completion of the printed circuit board process.

In the process of printed circuit board, most of the micro-etching agent is used to perform micro-etching treatment on the copper surface of the printed circuit board, which is mainly used to correspond to fine lines and effectively improve the adhesion. Most of them are used for dry film pre-treatment and printing. Pre-treatment of green paint, pre-treatment of copper-based copper treatment, pre-spray treatment or pre-compression treatment, since the micro-etching agent must be micro-etched on the copper surface of the printed circuit board, the micro-etching agent itself is corrosive, so it is very Prone to peroxide corrosion machine or heavy metal pollution The problem occurs, and the micro-etching agent will cause the copper surface to have a roughened surface to increase the adhesion of the copper surface, but this will roughen the copper surface. From Fig. 1A to Fig. 1D, it is known that the system is thick. Micro-etching agent, super-roughening micro-etching agent, micro-etching agent (sodium persulfate + sulfuric acid), micro-etching agent (sulfuric acid + ammonia + stabilizer), the surface roughness of the copper surface, and the average surface degree of the four It is 0.2~0.4 um, 0.4~0.8 um, 0.2~0.4 um, 0.2~0.4 um, respectively. It can be seen that the use of micro-etching technology will inevitably roughen the copper surface.

Therefore, if a copper foil surface modification method for a printed circuit board process can be established, the micro-etching technique is not required, so that the copper surface roughness is not changed, and the surface bonding force can be improved to make the overall printed circuit. The board process is simplified and clean, and saves unnecessary costs, so this should be the best solution.

The invention provides a copper foil surface modification method for a printed circuit board process, which refers to a technology for modifying the surface of a copper foil to improve the surface bonding force and make the overall printed circuit board process simplified and clean. And can save unnecessary costs.

The present invention is to provide a copper foil surface modification method for a printed circuit board process. Since the surface modification process does not require the use of a micro-etching technique, the copper surface is not roughened.

The method for modifying the surface of the copper foil for the printed circuit board process can be achieved by the steps of: preparing a copper foil substrate in advance and performing surface cleaning and brushing; after the brushing is completed, performing degreasing treatment and washing the copper foil substrate After that, the surface modification agent is sprayed horizontally or vertically; finally, after the copper foil substrate is washed again, the copper foil substrate is dried for use in subsequent processes.

More specifically, the subsequent process is a press process, a dry film press process or a solder resist process.

More specifically, the system is degreased using NaoH or KOH.

More specifically, the surface modifier has a temperature of 20 to 30 °C.

More specifically, the concentration of the surface modifier is from 1 to 5%.

More specifically, the horizontal spray or vertical immersion surface modifier is for 30 to 60 seconds.

More specifically, the spray pressure of the horizontal spray surface modifier is 0.8 to 1.2 kg/cm ² .

More specifically, the temperature of the dried copper foil substrate is 85 to 95 °C.

More specifically, the surface modifier has a chemical formula of (CH ₃ ) ₃ N ⁺ (M) ^- (R ₁ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; and (M) is F , Cl, Br, 1, OH or CH ₂ COO.

More specifically, the surface modifier has a chemical formula of (C ₆ H ₅ )(CH ₃ ) ₂ N ⁺ (M) ^- (R ₁ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; And (M) is F, Cl, Br, 1, OH or CH ₂ COO.

More specifically, the surface modifier has a chemical formula of (R ₁ )(CH ₃ ) ₂ N ⁺ (M) ^- (R ₂ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; ₂ ) is C ₁ ~ C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO.

More specifically, the surface modifier has a chemical formula of (R ₁ )(C=N(CH ₂ ) ₂ )N ⁺ (M) ^- (R ₂ )OH, wherein (R ₁ ) is C ₁ -C ₄₀ or benzene; (R ₂ ) is C ₁ to C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO.

More specifically, the surface modifier has a chemical formula of (R ₁ )(C ₅ H ₄ N)(M) ^- (R ₂ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; ₂ ) is C ₁ ~ C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO.

More specifically, the surface modifier has a chemical formula of (R ₁ )(CONH)(R ₂ )N ⁺ (CH ₃ ) ₂ (M) ^- , wherein (R ₁ ) is C ₁ to C ₄₀ or benzene (R ₂ ) is C ₁ to C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO.

More specifically, the surface modifier has a chemical formula of (R ₁ )(CONH)(R ₂ )N ⁺ (R ₃ )SO ₃ ^- , wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; R ₂ ) is C ₁ to C ₄₀ or benzene; and (R ₃ ) is C ₁ to C ₄₀ or benzene.

〔this invention〕

no

Fig. 1A is a schematic view showing the roughness of the copper surface of the roughened microetching agent in use of the conventional printed circuit board process.

Fig. 1B is a schematic view showing the roughness of the copper surface of the ultra-roughened micro-etching agent used in the conventional printed circuit board process.

Figure 1C is a schematic diagram showing the roughness of copper surface having a micro-etching agent of sodium persulfate and sulfuric acid used in the conventional printed circuit board process.

Fig. 1D is a schematic view showing the roughness of copper surface using a microetching agent of sulfuric acid, ammonia water and a stabilizer for the conventional printed circuit board process.

2 is a schematic flow chart of a copper foil surface modification method for a printed circuit board process according to the present invention.

3 is a copper surface display method for a copper foil surface modification method for a printed circuit board process of the present invention. intention.

Fig. 4 is a schematic view showing the comparison of a surface modifier and a conventional microetching agent for a copper foil surface modification method for a printed circuit board process.

Fig. 5 is a schematic view showing the results of the first embodiment of the copper foil surface modification method for the printed circuit board process of the present invention.

Fig. 6 is a schematic view showing the result of the second embodiment of the copper foil surface modification method for the printed circuit board process of the present invention.

Figure 7A is a schematic diagram of the pretreatment results of conventional anti-electroplating gold dry film.

FIG. 7B is a schematic diagram showing the result of the third embodiment of the copper foil surface modification method for the printed circuit board process of the present invention.

Fig. 8 is a schematic view showing the operation cost comparison of the syrup using the copper foil surface modification method for the printed circuit board process of the present invention.

The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.

2 is a schematic flow chart of a method for modifying a surface of a copper foil for a printed circuit board process according to the present invention. The steps are as follows: (1) preparing a copper foil substrate in advance and performing surface cleaning and brushing 201; After the brushing is completed, the degreasing treatment is performed, and after the copper foil substrate is washed with water, the surface modifying agent 202 is horizontally sprayed or vertically immersed; (3) Finally, after the copper foil substrate is washed again, the copper is dried. The foil substrate is prepared for subsequent processing 203.

In the above process, the degreasing treatment can be carried out using NaoH or KOH, and the surface modifier is at a temperature of 20 to 30 ° C, a concentration of 1 to 5%, a horizontal spray or a vertical soaking surface modifier. For 30~60 seconds, the spray pressure of the horizontal spray surface modifier is 0.8~1.2 kg/cm ² ; the temperature of the dried copper foil substrate is 85~95 °C.

Wherein the surface modifying agent is a cationic compound having the formula (CH ₃ ) ₃ N ⁺ (M) ^- (R ₁ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; and (M) is F , Cl, Br, 1, OH or CH ₂ COO.

Wherein the surface modifying agent is a cationic compound having a chemical formula of (C ₆ H ₅ )(CH ₃ ) ₂ N ⁺ (M) ^- (R ₁ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; And (M) is F, Cl, Br, 1, OH or CH ₂ COO.

Wherein the surface modifier is a cationic compound having the formula (R ₁ )(CH ₃ ) ₂ N ⁺ (M) ^- (R ₂ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; ₂ ) is C ₁ ~ C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO.

Wherein the surface modifying agent is a cationic compound having the formula (R ₁ )(C=N(CH ₂ ) ₂ )N ⁺ (M) ^- (R ₂ )OH, wherein (R ₁ ) is C ₁ -C ₄₀ or benzene; (R ₂ ) is C ₁ to C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO.

Wherein the surface modifying agent is a cationic compound having the formula (R ₁ )(C ₅ H ₄ N)(M) ^- (R ₂ ), wherein (R ₁ ) is C ₁ -C ₄₀ or benzene; ₂ ) is C ₁ ~ C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO.

Wherein the surface modifying agent is a zwitterion having a chemical formula of (R ₁ )(CONH)(R ₂ )N ⁺ (CH ₃ ) ₂ (M) ⁻ , wherein (R ₁ ) is C ₁ to C ₄₀ or Benzene; (R ₂ ) is C ₁ to C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO.

Wherein the surface modifier is a zwitterion having the formula (R ₁ )(CONH)(R ₂ )N ⁺ (R ₃ )SO ₃ ^- , wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; (R ₂ ) is C ₁ to C ₄₀ or benzene; and (R ₃ ) is C ₁ to C ₄₀ or benzene.

The copper surface after the copper foil surface modification method (CSM-1000) is as shown in Fig. 3, and compared with the copper surface roughness map of the first 1 to 1D, it can be seen that the use of the surface modifier does not change the copper surface roughness. Therefore, the copper surface can be flattened, and the roughening micro-etching agent, ultra-roughening micro-etching agent, micro-etching agent (sodium persulfate + sulfuric acid), micro-etching agent (sulfuric acid + ammonia water + stabilizer) and the present are further compared. The difference of the invention, as can be seen from Fig. 4, since the invention does not use the microetching technique, the copper surface is not roughened (there is no data on the roughness of the copper surface and there is no data related to microetching); In contrast, the bathing method using the copper foil surface modification method (CSM-1000) is easy, free from chlorine pollution, and the operation mode can be continuous, the unit area is low, the waste liquid treatment cost is low, and the combination with the resist is used. High force, no need to pick up pickling and no need to use copper sulphate recovery machine, although medium coarsening micro-etching agent, super roughening micro-etching agent, micro-etching agent (sodium persulfate + sulfuric acid), micro-etching agent (sulfuric acid + Part of the advantages of ammonia water + stabilizers and the use of copper foil surface modification method (CSM-1000) However, some comparative items are inferior to the present invention. For example, the combination of the coarsening micro-etching agent and the super-roughening micro-etching agent and the resisting agent is high, but the medium coarsening micro-etching agent and the ultra-roughening micro-etching The agents all need to be mixed with pickling, so the comparison project is not as good as the present invention.

The first implementation process of the present invention is used to prove that the bonding capability between the copper surface and the interface is increased, and the first implementation process, as shown in FIG. 5, is a copper foil surface modification method after a copper treatment (CSM- 1000), after the dry film treatment, and then the secondary copper treatment, after entering the etching treatment, and finally performing the stripping treatment, the process flow is completed, and in addition to the above process, it can also be after one copper treatment , the copper foil surface modification method (CSM-1000), the final etching process and stripping process, complete the process flow; or a copper treatment and copper foil surface modification method (CSM-1000), and then dry film treatment, then second The copper treatment and finally the etching treatment show that the copper foil surface modification method of the present invention can be applied to any brand of dry film and solder resist green paint.

The second embodiment of the present invention proves that the present invention can be applied to the ultra-fine line dry film pretreatment. As can be seen from Fig. 6, after the vacuum sputtering, the copper foil surface modification method (CSM-1000) is used, and then used. Dry film treatment, followed by copper plating, nickel plating gold and etching treatment, in addition to dry film treatment, can also be used for ultra-fine line wet film pretreatment.

The third implementation process of the present invention is used for anti-electroplating gold dry film pretreatment, wherein the 7A figure is a schematic diagram of the pretreatment result of the conventional anti-electroplating gold film (100% permeation), as can be seen from the figure, After a single copper treatment, the transfer of the line image is performed in a printed circuit board process using a dry film photoresist (Hitachi dry-film 5040), and gold plating and etching are performed after completion; and in FIG. 7B, copper foil is used. The surface modification method (CSM-1000) is introduced into the anti-electroplating gold dry film pretreatment. As can be seen from the figure, after a copper treatment, the copper foil surface modification method (CSM-1000) is performed, followed by a dry film. After the photoresist (Changxing dry-film115) was transferred to the line image, gold plating and etching treatment were carried out. It can be seen from the comparison of Fig. 7A and Fig. 7B that the plating conditions after plating are significantly different.

In addition, as can be seen from Fig. 8, the cost of the syrup operation is ultra-roughened micro-etching syrup (1.00 NTD/sf)> medium coarsening micro-etching syrup (0.75 NTD/sf)> micro-etching syrup (sodium persulfate SPS) (0.70NTD/sf)>microetching syrup (sulfuric acid/hydrogen peroxide) (0.35NTD/sf)> surface modifier syrup (0.30NTD/sf) of the present invention, it can be seen that, compared with conventional microetching syrup, The present invention does indeed save unnecessary costs.

The copper foil surface modification method for the printed circuit board process provided by the invention has the advantages that when compared with other conventional techniques, the advantages are as follows:

(1) Since the micro-etching technique is not required in the process of the present invention, there is no problem of peroxide corrosion machine and chloride ion contamination, and since it does not corrode copper, it does not cause heavy metal pollution, and there is no waste. Trouble with handling.

(2) The surface modifier used in the invention does not change the roughness of the copper surface, and at the same time, the bonding force can be effectively improved for the ultra-thin copper process, and the surface of the copper skin can be flattened after the surface modification, and the fine lines are dried. Membrane residue and residual problems can be completely overcome.

(3) The present invention can enhance the traditional physical super-roughening bonding ability to the chemical bonding effect, so that the overall circuit board process is simplified and clean, and any brand dry film and anti-welding green paint can be applied, among other things. It can save unnecessary costs.

The features and spirit of the present invention will be more apparent from the detailed description of the preferred embodiments. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed.

Claims (15)

A copper foil surface modification method for a printed circuit board process, the steps of which are: preparing a copper foil substrate in advance, and performing surface cleaning brushing; after the brushing is completed, performing degreasing treatment, and after washing the copper foil substrate, applying The surface modifying agent is sprayed horizontally or vertically; and finally, after the copper foil substrate is washed again, the copper foil substrate is dried for use in subsequent processes. A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the subsequent process is a press process, a dry film press process or a solder resist process. A copper foil surface modification method for a printed circuit board process as described in claim 1 , wherein the degreasing treatment is carried out using NaoH or KOH. A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the surface modifier has a temperature of 20 to 30 ° C. A method for modifying a surface of a copper foil for a printed circuit board process according to the invention of claim 1 , wherein the concentration of the surface modifier is from 1 to 5%. A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the time for horizontally spraying or vertically immersing the surface modifier is 30 to 60 seconds. A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the horizontal spray surface modifier has a spray pressure of 0.8 to 1.2 kg/cm ² . A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the temperature of the dried copper foil substrate is 85 to 95 °C. A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the surface modifier has a chemical formula of (CH ₃ ) ₃ N ⁺ (M) ^- (R ₁ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO. A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the chemical modifier of the surface modifier is (C ₆ H ₅ )(CH ₃ ) ₂ N ⁺ (M) ^- (R ₁ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO. A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the surface modifier has a chemical formula of (R ₁ )(CH ₃ ) ₂ N ⁺ (M) ^- (R ₂ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; (R ₂ ) is C ₁ to C ₄₀ or benzene: and (M) is F, Cl, Br, 1, OH or CH ₂ COO. A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the surface modifier has a chemical formula of (R ₁ )(C=N(CH ₂ ) ₂ )N ⁺ ( M) ^- (R ₂ )OH, wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; (R ₂ ) is C ₁ to C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH Or CH ₂ COO. A copper foil surface modification method for a printed circuit board process according to claim 1 , wherein the surface modifier has a chemical formula of (R ₁ )(C ₅ H ₄ N)(M) ^- (R) ₂ ), wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; (R ₂ ) is C ₁ to C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO. A method for modifying a copper foil surface for a printed circuit board process according to claim 1 , wherein the surface modifier has a chemical formula of (R ₁ )(CONH)(R ₂ )N ⁺ (CH ₃ ) ₂ (M) ^- , wherein (R ₁ ) is C ₁ -C ₄₀ or benzene; (R ₂ ) is C ₁ -C ₄₀ or benzene; and (M) is F, Cl, Br, 1, OH or CH ₂ COO. A method for modifying a copper foil surface for a printed circuit board process according to claim 1 , wherein the surface modifier has a chemical formula of (R ₁ )(CONH)(R ₂ )N ⁺ (R ₃ ) SO ₃ ^- , wherein (R ₁ ) is C ₁ to C ₄₀ or benzene; (R ₂ ) is C ₁ to C ₄₀ or benzene; and (R ₃ ) is C ₁ to C ₄₀ or benzene.