A nano-graphite carbon pore process pore-regulating agent and preparation method thereof
By using a specific pore agent in the carbon pore process, the problem of excessive thickness of nanographite adsorption and separation of plating is solved, and the uniform conductive layer and strong binding force after the carbon pore are achieved, which improves the reliability of electroplating.
Patent Information
- Application Number
- CN202210909628.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-07-29
- Publication Date
- 2025-01-03
- Estimated Expiration
- 2042-07-29
AI Technical Summary
When traditional carbon pore whole agent adjusts the charge of the hole wall of the circuit board, it is easy to cause the nanographite to be adsorbed too thick, resulting in the separation of the plating layer and the hole wall, affecting the uniformity and binding force of the conductive layer.
A nanographite carbon pore process pore-integrating agent is adopted, including surfactant, charge regulator and adsorbent. Through specific component ratios and preparation methods, the membrane layer after the carbon pore is uniform, thin, and has good conductivity, and the bonding force is achieved. powerful.
The film layer after carbon pores is uniform and thin, with good conductivity, and strong bonding force between the plating and the hole wall, avoiding the problem of separation between the plating and the hole wall, and improving the reliability of electroplating.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of circuit board hole metallization, in particular to a nano-graphite carbon hole process pore-regulating agent and a preparation method thereof. Background Art
[0002] Carbon hole process is a process of hole metallization, which has the advantages of environmental friendliness, short process and low cost. It is a new process to replace traditional chemical copper deposition. Nanographite carbon hole uses nanographite as a conductive material to make a dispersion liquid, which is adsorbed on the glass fiber and substrate of the hole wall of the printed circuit board to form a uniform and fine conductive layer.
[0003] In order to ensure that the graphite particles in the carbon pore liquid can be firmly and evenly distributed on the pore wall substrate and the glass fiber surface, the carbon pore process includes two key processes, pore wholeing and carbon pore. Pore wholeing must be performed before entering the carbon pore to ensure that the negative charge of the pore wall substrate and the glass fiber surface of the circuit board is adjusted to a positive charge, so that the negatively charged graphite particles can be firmly adsorbed on the pore wall substrate and the glass fiber surface.
[0004] Traditional carbon pore-regulating agents are used to ensure the charge adjustment of the hole walls of the circuit board so that graphite particles are adsorbed on the hole walls. For example, patent CN00819273.1 discloses a composition and method for cleaning and conditioning the non-conductive surface of a printed circuit board having through holes. The composition uses a strong cationic surfactant to adjust the hole walls, which can easily cause excessive adsorption of nanographite on the hole walls. Since nanographite has a flaky structure, it can easily cause the adsorbed carbon layer to be too thick. Even after pickling, the carbon layer is still thick, which can easily cause the coating to have poor adsorption on the hole walls after electroplating, and easily separate from the hole walls. Summary of the invention
[0005] In view of the shortcomings of the prior art, the present invention provides a nano-graphite carbon pore process pore-regulating agent and a preparation method. The present invention can make the film layer behind the carbon pores uniformly thin, with good conductivity, strong bonding between the coating and the pore wall, and will not cause the problem of separation between the coating and the pore wall.
[0006] The technical solution of the present invention is: a nano-graphite carbon pore process pore-regulating agent, comprising the following components in weight percentage:
[0007] Surfactant 1-10%;
[0008] Charge regulator 1-10%;
[0009] Adsorbent 0.01-5%;
[0010] The balance is solvent.
[0011] Preferably, the pore-regulating agent comprises the following components in weight percentage:
[0012] Surfactant 2-7%;
[0013] Charge regulator 2-8%;
[0014] Adsorbent 0.01-4%;
[0015] Solvent Residue.
[0016] Preferably, the surfactant is a polyethylene glycol nonionic surfactant with a molecular weight of 2000-18000;
[0017] The adsorbent is polyacrylamide with a molecular weight of 2000-40000, the solvent is deionized water, and the charge regulator is polyquaternary ammonium salt.
[0018] Preferably, the polyquaternary ammonium salt is a charge regulator obtained by reacting a mixture of polyethyleneimine and polyamine compounds with an aryl / alkyl dihalide.
[0019] Preferably, the molecular weight of the polyethyleneimine is 1000-70000, preferably 3000-30000, more preferably 5000-25000.
[0020] Preferably, the reaction temperature of the polyethyleneimine and the polyamino compound with the aryl / alkyl dihalide is 50°C-100°C, preferably 70-90°C.
[0021] Preferably, the polyamine compounds include but are not limited to diethylenetriamine, triethylenetetramine, arginine, ornithine, cetylamine, guanylthiourea, diguanylbenzene, propionylguanidine, and polyamine compounds containing more than 3 amino groups. The polyamine compounds can be selected as a mixture of one or more.
[0022] Preferably, the aryl / alkyl dihalide includes but is not limited to a mixture of one or more of 1,4-dihalobutane, 1,6-dihalohexane, 1,4-dihalobenzyl, dichlorodiethyl ether, 1,2-bis(2-chloroethoxy)ethane, and diethylene glycol dichloroethyl ester.
[0023] Preferably, the present invention also provides a method for preparing a nano-graphite carbon pore process pore-regulating agent, the method comprising: mixing and stirring a surfactant, a charge regulator, an adsorbent and deionized water, heating to 100°C, maintaining for 4 hours, and cooling to obtain the pore-regulating agent.
[0024] Preferably, the surfactant is a polyethylene glycol nonionic surfactant with a molecular weight of 2000-18000;
[0025] The adsorbent is polyacrylamide with a molecular weight of 2000-40000, the solvent is deionized water, and the charge regulator is polyquaternary ammonium salt.
[0026] The charge regulator is prepared by reacting a mixture of polyethyleneimine and polyamine compounds with an aryl / alkyl dihalide.
[0027] Preferably, the molecular weight of the polyethyleneimine is 1000-70000, preferably 3000-30000, more preferably 5000-25000.
[0028] Preferably, the polyamine compounds include but are not limited to diethylenetriamine, triethylenetetramine, arginine, ornithine, cetylamine, guanylthiourea, diguanylbenzene, propionylguanidine, and polyamine compounds containing more than 3 amino groups. The polyamine compounds can be selected as a mixture of one or more.
[0029] Preferably, the aryl / alkyl dihalide includes but is not limited to a mixture of one or more of 1,4-dihalobutane, 1,6-dihalohexane, 1,4-dihalobenzyl, dichlorodiethyl ether, 1,2-bis(2-chloroethoxy)ethane, and diethylene glycol dichloroethyl ester.
[0030] The beneficial effects of the present invention are:
[0031] 1. The hole-sizing agent of the present invention has a good charge adjustment effect on the hole wall substrate and glass fiber of the PCB board, and can make the film layer at the non-conductive position of the through hole of the circuit board after the carbon hole uniformly thin, with good conductivity, strong bonding between the coating and the hole wall, and no subsequent separation of the coating and the hole wall will occur;
[0032] 2. The pore-regulating agent of the present invention has a good charge adjustment effect on the fiber and substrate on the surface of the pore wall. The graphite adsorption layer is thin and uniform, which can improve the reliability of electroplating after the carbon pore. DETAILED DESCRIPTION
[0033] The specific embodiments of the present invention are further described below:
[0034] Example 1
[0035] This embodiment provides a method for preparing a charge regulator
[0036] 7 g of polyethyleneimine (molecular weight nw = 7000), 3.03 g of diethylenetriamine, and 1.7 g of arginine are added to a 150 ml three-necked flask, and 50 ml of deionized water is added. The mixture is stirred and heated to 80°C. Then 22.6 g of 1,4-dibromobutane is added and the mixture is reacted at 80°C for 4 hours to obtain a yellow transparent solution. The obtained product is included in the charge regulator at a content of 100%.
[0037] Example 2
[0038] This embodiment provides a method for preparing a charge regulator
[0039] 7 g of polyethyleneimine (molecular weight nw = 7000), 3.03 g of diethylenetriamine, and 1.7 g of arginine are added to a 150 ml three-necked flask, and 50 ml of deionized water is added. The mixture is stirred and heated to 80°C. Then 14.3 g of dichlorodiethyl ether is added and the mixture is reacted at 80°C for 4 hours to obtain a yellow transparent solution. The obtained product is included in the charge regulator at a content of 100%.
[0040] Example 3
[0041] This embodiment provides a method for preparing a pore-forming agent.
[0042] 2 g of polyethylene glycol nonionic surfactant (molecular weight 10000), 2 g of the charge regulator of Example 1, 0.05 g of polyacrylamide and 95.95 g of solvent were added to a 250 ml three-necked flask, then stirred and heated to 100°C for 4 hours, and then cooled to obtain a pore-forming agent.
[0043] The weight percentages of the components in this embodiment are: 2.0% surfactant, 2.0% charge regulator, 0.05% adsorbent, and 95.95% solvent.
[0044] Example 4
[0045] This embodiment provides a method for preparing a pore-forming agent.
[0046] 4 g of polyethylene glycol nonionic surfactant (molecular weight 10000), 4 g of the charge regulator of Example 1, 0.03 g of polyacrylamide and 91.97 g of solvent are added to a 250 ml three-necked flask, then stirred and heated to 100° C., maintained for 4 hours, and cooled to obtain a pore-forming agent. The weight fractions of the components are: 4.0% surfactant, 4.0% charge regulator, 0.03% adsorbent, and 91.97% solvent.
[0047] Example 5
[0048] This embodiment provides a method for preparing a pore-forming agent.
[0049] 4 g of polyethylene glycol nonionic surfactant (molecular weight 10000), 6 g of the charge regulator of Example 2, 0.02 g of polyacrylamide and 89.98 g of solvent are added to a 250 ml three-necked flask, then stirred and heated to 100° C., maintained for 4 hours, and cooled to obtain a pore-forming agent. The weight fractions of the components are: 4.0% surfactant, 6.0% charge regulator, 0.02% adsorbent, and 89.98% solvent.
[0050] Example 6
[0051] This embodiment provides a method for preparing a pore-forming agent.
[0052] 4 g of polyethylene glycol nonionic surfactant (molecular weight 10000), 8 g of the charge regulator of Example 2, 0.01 g of polyacrylamide and 87.99 g of solvent are added to a 250 ml three-necked flask, then stirred and heated to 100° C., maintained for 4 hours, and cooled to obtain a pore-forming agent. The weight fractions of the components are: 4.0% surfactant, 8.0% charge regulator, 0.03% adsorbent, and 87.99% solvent.
[0053] Example 7
[0054] Circuit board through hole metallization test
[0055] 1. Plate material: KB-150, pore diameter: 0.3mm, plate thickness: 1.5mm.
[0056] 2. Test process: degumming → neutralization → hole filling → graphite carbon hole → pickling → drying → hole filling → graphite carbon hole → pickling → drying → electroplating → thermal shock test.
[0057] 3. DTV hole climbing test: DTV test piece carbon hole after testing electroplating hole climbing effect
[0058] 4. Resistance measurement: Four-probe film layer square resistance measurement.
[0059] 5. Thermal shock test cracking percentage: 288°C, 10s, 6 times, measured according to the industry standard procedure IPC-TM-650-2.6.8. (Thermal Stress, Plated-Through Holes). The test results are shown in Table 1:
[0060] Table 1 Circuit board through hole metallization test results
[0061]
[0062]
[0063] Comparative Example 1
[0064] Take polyethyleneimine as a cationic charge regulator as a comparative example: add 4g polyethylene glycol nonionic surfactant (molecular weight 10000), 6g polyethyleneimine (cationic molecular weight 20000), 0.02g polyacrylamide and 89.98g solvent into a 250ml three-necked flask, then stir and add to 100°C, maintain for 4h, and cool to obtain a pore-forming agent (comparative example). The weight fractions of the components are: surfactant 4.0%, charge regulator 6.0%, adsorbent 0.02%, and solvent 89.98%.
[0065] Circuit board through hole metallization test
[0066] Plate KB-150, hole diameter 0.3mm, plate thickness 1.5mm
[0067] Test process: degumming → neutralization → hole filling (commercially available) → graphite carbon hole → pickling → drying → hole filling → graphite carbon hole → pickling → drying → electroplating → thermal shock test
[0068] DTV hole climbing test: DTV test piece carbon hole after testing electroplating hole climbing effect
[0069] Film thickness measurement: SEM was used to measure the film thickness after slicing
[0070] Resistance measurement: Four-probe film layer square resistance measurement
[0071] Thermal shock test cracking percentage: 288°C, 10s, 6 times, measured according to the industry standard procedure IPC-TM-650-2.6.8. (Thermal Stress, Plated-Through Holes). The test results are shown in Table 2:
[0072] Table 2 Test results
[0073]
[0074]
[0075] From the above, it can be seen that the pore-scaling agent prepared by the present invention has a good charge adjustment effect on the hole wall substrate and glass fiber of the PCB board. After passing through the nano-graphite carbon pores, a uniform nano-graphite film layer can be obtained with good conductivity and a thin film layer, so that a good electroplating effect and reliable quality can be obtained.
[0076] The above embodiments and descriptions are only for illustrating the principles and best embodiments of the present invention. Without departing from the spirit and scope of the present invention, the present invention may be subject to various changes and improvements, all of which fall within the scope of the present invention to be protected.
Claims
1. A nano-graphite carbon pore process pore-regulating agent, characterized in that: The composition includes the following weight percentages: Surfactant 2-7%; the surfactant is a polyethylene glycol nonionic surfactant with a molecular weight of 2000-18000; 2-8% of a charge regulator; the charge regulator is a polyquaternary ammonium salt obtained by reacting a mixture of polyethyleneimine and a polyamine compound with an aromatic / alkyl dihalide; Adsorbent 0.01-4%; the adsorbent is polyacrylamide with a molecular weight of 2000-40000; The balance is solvent, and the solvent is deionized water; The molecular weight of the polyethyleneimine is 1000-70000; The reaction temperature of the polyethyleneimine and the polyamino compound with the aryl / alkyl dihalide is 70°C-90°C; The polyamine compounds include diethylenetriamine, triethylenetetramine, arginine, ornithine, cetylamine, guanylthiourea, diguanylbenzene, propionylguanidine, and polyamine compounds containing more than three amine groups. The polyamine compounds can be selected from one or a mixture of more than one; The aryl / alkyl dihalide includes a mixture of one or more of 1,4-dihalobutane, 1,6-dihalohexane, 1,4-dihalobenzyl, dichlorodiethyl ether, 1,2-di(2-chloroethoxy)ethane, and diethylene glycol dichloroethyl ester.
2. A method for preparing the nano-graphite carbon pore process pore-regulating agent according to claim 1, characterized in that: The method described is: The surfactant, charge regulator, adsorbent and deionized water are mixed and stirred and heated to 100°C, maintained for 4 hours, and cooled to obtain a pore-forming agent; The charge regulator is a polyquaternary ammonium salt obtained by reacting a mixture of polyethyleneimine and polyamine compounds with an aryl / alkyl dihalide, and the reaction temperature of the polyethyleneimine and polyamine compounds with the aryl / alkyl dihalide is 70-90°C; The surfactant is a polyethylene glycol nonionic surfactant with a molecular weight of 2000-18000; the adsorbent is a polyacrylamide with a molecular weight of 2000-40000, and the solvent is deionized water; The molecular weight of the polyethyleneimine is 1000-70000; The polyamine compounds include diethylenetriamine, triethylenetetramine, arginine, ornithine, cetylamine, guanylthiourea, diguanylbenzene, propionylguanidine, and polyamine compounds containing more than three amine groups. The polyamine compounds can be selected from one or a mixture of more than one; The aryl / alkyl dihalide includes a mixture of one or more of 1,4-dihalobutane, 1,6-dihalohexane, 1,4-dihalobenzyl, dichlorodiethyl ether, 1,2-di(2-chloroethoxy)ethane, and diethylene glycol dichloroethyl ester.