CN115975400A - Ball-milling modification method for silicate filler for PCB - Google Patents
Ball-milling modification method for silicate filler for PCB Download PDFInfo
- Publication number
- CN115975400A CN115975400A CN202211560102.XA CN202211560102A CN115975400A CN 115975400 A CN115975400 A CN 115975400A CN 202211560102 A CN202211560102 A CN 202211560102A CN 115975400 A CN115975400 A CN 115975400A
- Authority
- CN
- China
- Prior art keywords
- parts
- treatment
- ball
- silicate
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000498 ball milling Methods 0.000 title claims abstract description 59
- 239000000945 filler Substances 0.000 title claims abstract description 35
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002715 modification method Methods 0.000 title abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 65
- 239000007822 coupling agent Substances 0.000 claims abstract description 56
- 238000003756 stirring Methods 0.000 claims abstract description 38
- -1 compound silicate Chemical class 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 16
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000292 calcium oxide Substances 0.000 claims abstract description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229940039790 sodium oxalate Drugs 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 71
- 229910021389 graphene Inorganic materials 0.000 claims description 57
- 230000004048 modification Effects 0.000 claims description 44
- 238000012986 modification Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 21
- 230000000996 additive effect Effects 0.000 claims description 21
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 20
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229920001661 Chitosan Polymers 0.000 claims description 17
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 15
- 235000010413 sodium alginate Nutrition 0.000 claims description 15
- 239000000661 sodium alginate Substances 0.000 claims description 15
- 229940005550 sodium alginate Drugs 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- 150000002910 rare earth metals Chemical class 0.000 claims description 14
- RGDDVTHQUAQTIE-UHFFFAOYSA-N 2-pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC=C1O RGDDVTHQUAQTIE-UHFFFAOYSA-N 0.000 claims description 10
- 229960005489 paracetamol Drugs 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 11
- 239000012530 fluid Substances 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 6
- 239000007921 spray Substances 0.000 description 4
- UYUXSRADSPPKRZ-UHFFFAOYSA-N D-glucuronic acid gamma-lactone Natural products O=CC(O)C1OC(=O)C(O)C1O UYUXSRADSPPKRZ-UHFFFAOYSA-N 0.000 description 3
- UYUXSRADSPPKRZ-SKNVOMKLSA-N D-glucurono-6,3-lactone Chemical compound O=C[C@H](O)[C@H]1OC(=O)[C@@H](O)[C@H]1O UYUXSRADSPPKRZ-SKNVOMKLSA-N 0.000 description 3
- 229950002441 glucurolactone Drugs 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Abstract
The invention relates to the technical field of silicate fillers, and particularly discloses a ball-milling modification method for a silicate filler for a PCB (printed circuit board). A coupling agent compounding agent accounting for 10-20% of the total amount of the compound silicate is added into the modified compound silicate, and the compound silicate is subjected to thermalization treatment; then sending the mixture into a ball mill for ball milling treatment, and finishing ball milling, washing and drying; and performing heat treatment at 75-85 deg.C for 5-10min, and cooling at constant temperature. According to the invention, the silicate filler is compounded by silicon dioxide, calcium oxide and aluminum oxide, and is modified by stirring the modifying treatment agent, and the modifying treatment agent adopts lanthanum chloride solution, sodium oxalate and sodium alkyl sulfonate, so that the activity of the base fluid in the modifying treatment agent is improved, and the improvement of the activity performance of the filler is facilitated.
Description
Technical Field
The invention relates to the technical field of PCB silicate fillers, in particular to a ball-milling modification method of a silicate filler for PCB.
Background
The PCB is also called a printed circuit board, a printed circuit board and a printed circuit board, is an important electronic component, is a support body of an electronic component and is a provider for electrical connection of the electronic component; especially in electronic products such as computers, mobile phones and the like. Multilayer Printed Circuit (PCB) and integrated circuit substrates are typically constructed as follows: the intervening imaged conductive layers (e.g., copper-containing layers) and dielectric layers (e.g., partially cured semi-melt stage resins, i.e., prepregs, constitute a multi-layer sandwich that is then bonded together by the application of heat and pressure.
The PCB is matched with the curing resin to form a coating, the bonding strength of the curing coating and the PCB base layer is poor, silicate filler is required to be added to optimize the bonding performance, the existing silicate filler adopts silicon dioxide compounded with other silicate and other raw materials, the surface interface property of the silicate filler is poor, meanwhile, the surface is rough, the bonding strength and the interface strength between the silicate filler and the raw materials are poor when the silicate filler is applied to a product, and the performance effect of the PCB product is reduced on the contrary.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a method for ball-milling modification of silicate filler for PCB, so as to solve the problems in the background art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a method for ball-milling modification of silicate filler for PCB, which comprises the following steps:
the method comprises the following steps: mixing silicon dioxide, calcium oxide and aluminum oxide according to the weight ratio of 6;
wherein: the specific method for stirring modification treatment of the modification treatment agent comprises the following steps:
s101: adding 5-10 parts of sodium oxalate into 20-30 parts of lanthanum chloride solution, and adding 2-5 parts of sodium alkyl sulfonate and 4-7 parts of modified graphene to obtain graphene composite rare earth modified solution;
s102: adding 2-6 parts of treatment additive into the graphene composite rare earth modified solution, and fully stirring to obtain a modified treatment agent;
s103: adding the compound silicate into the modification treatment agent according to the weight ratio of 1;
step two: preparing a coupling agent compound agent;
step three: adding a coupling agent compound agent accounting for 10-20% of the total amount of the compound silicate into the compound silicate subjected to modification treatment in the step one, and carrying out thermalization treatment;
step four: then sending the mixture into a ball mill for ball milling treatment, and finishing ball milling, washing and drying;
step five: and heat treating at 75-85 deg.C for 5-10min, and cooling at constant temperature.
Preferably, the mass fraction of the lanthanum chloride solution is 5-10%.
Preferably, the preparation method of the modified graphene comprises the following steps:
s11: placing graphene in 4-6 times of hydrochloric acid solution, uniformly stirring, washing with water, and drying;
s12: adding the graphene of S11 into a sodium alginate solution which is 5-10 times of the total amount of the graphene, adding a sulfuric acid aqueous solution which is 5-10% of the total amount of the graphene, fully stirring, washing with water, and drying;
s13: and finally, placing the graphene of S12 at 310-320 ℃ for heat treatment for 10-20min, then keeping the temperature at 65-70 ℃ at the speed of 2-5 ℃/min for 5-10min, finally uniformly dispersing in water at 1-4 ℃, finally washing and drying to obtain the modified graphene.
Preferably, the mass fraction of the hydrochloric acid solution is 2-6%; the mass fraction of the sodium alginate solution is 10-15%; the mass fraction of the sulfuric acid aqueous solution is 10-15%.
Preferably, the treatment additive comprises the following raw materials in parts by weight:
3-6 parts of tributyl citrate, 1-3 parts of propylene glycol, 6-10 parts of ethanol, 2-6 parts of chitosan aqueous solution and 1-2 parts of acetaminophen.
Preferably, the mass fraction of the chitosan aqueous solution is 10-20%.
Preferably, the preparation method of the coupling agent compound agent comprises the following steps:
s21: adding pentadecyl phenol into ethanol according to the weight ratio of 1;
s22: adding 2-4 parts of coupling agent KH560 and 1-4 parts of citric acid into 5-10 parts of deionized water, and fully stirring to obtain a coupling agent solution;
s23: and adding the coupling agent liquid into the S21 product according to the weight ratio of 2.
Preferably, the temperature of the thermalization treatment of the third step is 55-65 ℃, and the treatment time is 20-30min.
Preferably, the ball milling rotation speed of the ball milling treatment is 550-750r/min, and the ball milling time is 1-2h.
Preferably, the rate of the constant temperature cooling treatment is 2-5 ℃/min.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the silicate filler is compounded by silicon dioxide, calcium oxide and aluminum oxide, the modified treatment agent is stirred and modified by the modified treatment agent, the modified treatment agent adopts a lanthanum chloride solution, sodium oxalate and sodium alkylsulfonate, so that the activity degree of a matrix fluid in the modified treatment agent is improved, the improvement on the activity performance of the filler is facilitated, the graphene has a sheet structure, after modification, the activity performance of the graphene is enhanced by sequentially dispersing a hydrochloric acid solution, a sodium alginate solution and a sulfuric acid solution composite material, and finally, through high-temperature heat treatment, constant-temperature cooling and low-temperature dispersion are performed, so that the flexibility of the graphene is improved, the graphene is conveniently matched with a treatment additive in the modified treatment agent to play a role, the treatment additive adopts ethanol solvents such as chitosan solution, tributyl citrate and acetaminophen, on the one hand, the activity performance of the compounded silicate is optimized, the acetaminophen provides an active functional group, the coupling agent compounding agent is conveniently matched in ball milling, synergy is realized, the interface performance of a silicate filler product system is enhanced, meanwhile, the chitosan solution is matched with tributyl citrate and the like, so that the permeability of the filler is enhanced, the raw material is conveniently stirred and modified by the modified treatment agent, and the performance of the PCB is enhanced; in the coupling agent compound agent, in order to improve the dispersion effect of the compound silicate, the compound silicate is treated by the coupling agent in a ball mill, the coupling agent adopts a system of KH560+ citric acid, pentadecylphenol and glucuronolactone, and the interfacial activity of the filler is further optimized through the combined system of the pentadecylphenol, the glucuronolactone and the like, so that the performance of the compound silicate for preparing the adhesive is optimized and improved when the compound silicate is used for a PCB.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The method for ball-milling modification of the silicate filler for the PCB comprises the following steps:
the method comprises the following steps: mixing silicon dioxide, calcium oxide and aluminum oxide according to the weight ratio of 6;
wherein: the concrete method for stirring and modifying the modifying treating agent comprises the following steps:
s101: adding 5-10 parts of sodium oxalate into 20-30 parts of lanthanum chloride solution, and adding 2-5 parts of sodium alkyl sulfonate and 4-7 parts of modified graphene to obtain graphene composite rare earth modified solution;
s102: adding 2-6 parts of treatment additive into the graphene composite rare earth modified solution, and fully stirring to obtain a modified treatment agent;
s103: adding the compound silicate into the modification treatment agent according to the weight ratio of 1;
step two: preparing a coupling agent compound agent;
step three: adding a coupling agent compound agent accounting for 10-20% of the total amount of the compound silicate into the compound silicate subjected to modification treatment in the step one, and carrying out thermalization treatment;
step four: then sending the mixture into a ball mill for ball milling treatment, and finishing ball milling, washing and drying;
step five: and performing heat treatment at 75-85 deg.C for 5-10min, and cooling at constant temperature.
The mass fraction of the lanthanum chloride solution in this example is 5-10%.
The preparation method of the modified graphene of the embodiment comprises the following steps:
s11: placing graphene in 4-6 times of hydrochloric acid solution, uniformly stirring, washing with water, and drying;
s12: then adding graphene into a sodium alginate solution which is 5-10 times of the total amount of the graphene, adding a sulfuric acid aqueous solution which is 5-10% of the total amount of the graphene, fully stirring, washing with water, and drying;
s13: and finally, placing the graphene at 310-320 ℃ for heat treatment for 10-20min, then keeping the temperature at 65-70 ℃ at the speed of 2-5 ℃/min for 5-10min, finally uniformly dispersing in water at 1-4 ℃, and finally washing and drying to obtain the modified graphene.
The mass fraction of the hydrochloric acid solution in the embodiment is 2-6%; the mass fraction of the sodium alginate solution is 10-15%; the mass fraction of the sulfuric acid aqueous solution is 10-15%.
The treatment additive of the embodiment comprises the following raw materials in parts by weight:
3-6 parts of tributyl citrate, 1-3 parts of propylene glycol, 6-10 parts of ethanol, 2-6 parts of chitosan aqueous solution and 1-2 parts of acetaminophen.
The mass fraction of the chitosan aqueous solution in this example was 10-20%.
The preparation method of the coupling agent compound agent of the embodiment comprises the following steps:
s21: adding pentadecyl phenol into ethanol according to the weight ratio of 1;
s22: adding 2-4 parts of coupling agent KH560 and 1-4 parts of citric acid into 5-10 parts of deionized water, and fully stirring to obtain a coupling agent solution;
s23: and (3) adding the coupling agent liquid into the S21 product according to the weight ratio of 2.
In the third step of this embodiment, the thermal treatment temperature is 55-65 deg.C, and the treatment time is 20-30min.
The ball milling rotation speed of the ball milling treatment of the embodiment is 550-750r/min, and the ball milling time is 1-2h.
The rate of the constant temperature cooling treatment of this example was 2-5 deg.C/min.
Example 1.
The method for ball-milling modification of the silicate filler for the PCB comprises the following steps:
the method comprises the following steps: mixing silicon dioxide, calcium oxide and aluminum oxide according to the weight ratio of 6;
wherein: the concrete method for stirring and modifying the modifying treating agent comprises the following steps:
s101: adding 5 parts of sodium oxalate into 20 parts of lanthanum chloride solution, and adding 2 parts of sodium alkylsulfonate and 4 parts of modified graphene to obtain graphene composite rare earth modified solution;
s102: adding 2 parts of treatment additive into the graphene composite rare earth modified solution, and fully stirring to obtain a modified treatment agent;
s103: adding the compound silicate into the modification treatment agent according to the weight ratio of 1;
step two: preparing a coupling agent compound agent;
step three: adding a coupling agent compound agent accounting for 10 percent of the total amount of the compound silicate into the compound silicate subjected to modification treatment in the step one, and carrying out thermalization treatment;
step four: then sending the mixture into a ball mill for ball milling treatment, and finishing ball milling, washing and drying;
step five: and then heat-treating at 75 deg.C for 5min, and finally cooling at constant temperature.
The mass fraction of the lanthanum chloride solution in this example is 5-10%.
The preparation method of the modified graphene of the embodiment comprises the following steps:
s11: placing graphene in 4 times of hydrochloric acid solution, uniformly stirring, washing with water, and drying;
s12: then adding graphene into a sodium alginate solution which is 5 times of the total amount of the graphene, adding a sulfuric acid aqueous solution which is 5% of the total amount of the graphene, fully stirring, washing with water, and drying;
s13: and finally, carrying out heat treatment on the graphene at 310 ℃ for 10min, then, heating to 65 ℃ at the speed of 2 ℃/min, keeping the temperature for 5min, finally, uniformly dispersing in water at 1 ℃, and finally, washing and drying to obtain the modified graphene.
The mass fraction of the hydrochloric acid solution in the embodiment is 2%; the mass fraction of the sodium alginate solution is 10 percent; the mass fraction of the sulfuric acid aqueous solution is 10%.
The treatment additive comprises the following raw materials in parts by weight:
3 parts of tributyl citrate, 1 part of propylene glycol, 6 parts of ethanol, 2 parts of chitosan aqueous solution and 1 part of acetaminophen.
The mass fraction of the chitosan aqueous solution in this example was 10%.
The preparation method of the coupling agent compounding agent of the embodiment comprises the following steps:
s21: adding pentadecyl phenol into ethanol according to the weight ratio of 1;
s22: adding 2 parts of a coupling agent KH560 and 1 part of citric acid into 5 parts of deionized water, and fully stirring to obtain a coupling agent solution;
s23: and adding the coupling agent liquid into the S21 product according to the weight ratio of 2.
The temperature of the thermalization treatment in the third step of this example was 55 ℃ and the treatment time was 20min.
The ball milling speed of the ball milling treatment in this example was 550r/min, and the ball milling time was 1h.
The rate of the constant temperature cooling treatment of this example was 2 deg.C/min.
Example 2.
The method for ball-milling modification of the silicate filler for the PCB comprises the following steps:
the method comprises the following steps: mixing silicon dioxide, calcium oxide and aluminum oxide according to the weight ratio of 6;
wherein: the concrete method for stirring and modifying the modifying treating agent comprises the following steps:
s101: adding 10 parts of sodium oxalate into 30 parts of lanthanum chloride solution, and adding 5 parts of sodium alkyl sulfonate and 7 parts of modified graphene to obtain graphene composite rare earth modified solution;
s102: adding 6 parts of treatment additive into the graphene composite rare earth modified solution, and fully stirring to obtain a modified treatment agent;
s103: adding the compound silicate into the modification treatment agent according to the weight ratio of 1;
step two: preparing a coupling agent compound agent;
step three: adding a coupling agent compounding agent accounting for 20 percent of the total amount of the compound silicate into the compound silicate subjected to modification treatment in the step one, and carrying out thermalization treatment;
step four: then sending the mixture into a ball mill for ball milling treatment, and finishing ball milling, washing and drying;
step five: and then heat-treating at 85 deg.C for 10min, and finally cooling at constant temperature.
The lanthanum chloride solution of this example was 10% by mass.
The preparation method of the modified graphene of the embodiment comprises the following steps:
s11: placing graphene in 6 times of hydrochloric acid solution, uniformly stirring, washing with water, and drying;
s12: adding graphene into a sodium alginate solution which is 10 times of the total amount of the graphene, adding a sulfuric acid aqueous solution which is 10% of the total amount of the graphene, fully stirring, washing with water, and drying;
s13: and finally, carrying out heat treatment on the graphene at 320 ℃ for 20min, then, keeping the temperature at 70 ℃ at the speed of 5 ℃/min for 10min, finally, uniformly dispersing the graphene in water at 4 ℃, and finally, washing and drying the graphene to obtain the modified graphene.
The mass fraction of the hydrochloric acid solution in the embodiment is 6%; the mass fraction of the sodium alginate solution is 15 percent; the mass fraction of the sulfuric acid aqueous solution is 15%.
The treatment additive comprises the following raw materials in parts by weight:
6 parts of tributyl citrate, 3 parts of propylene glycol, 10 parts of ethanol, 6 parts of chitosan aqueous solution and 1-2 parts of acetaminophen.
The mass fraction of the chitosan aqueous solution in this example was 20%.
The preparation method of the coupling agent compound agent of the embodiment comprises the following steps:
s21: adding pentadecyl phenol into ethanol according to the weight ratio of 1;
s22: adding 4 parts of coupling agent KH560 and 4 parts of citric acid into 10 parts of deionized water, and fully stirring to obtain a coupling agent solution;
s23: and adding the coupling agent liquid into the S21 product according to the weight ratio of 2.
The temperature of the thermalization treatment in the third step of this example was 65 ℃ and the treatment time was 30min.
The ball milling speed of the ball milling treatment in the embodiment is 750r/min, and the ball milling time is 2h.
The rate of the constant temperature cooling treatment of this example was 5 deg.C/min.
Example 3.
The method for ball-milling modification of the silicate filler for the PCB comprises the following steps:
the method comprises the following steps: mixing silicon dioxide, calcium oxide and aluminum oxide according to the weight ratio of 6;
wherein: the specific method for stirring modification treatment of the modification treatment agent comprises the following steps:
s101: adding 7.5 parts of sodium oxalate into 25 parts of lanthanum chloride solution, and adding 3.5 parts of sodium alkyl sulfonate and 5 parts of modified graphene to obtain graphene composite rare earth modified solution;
s102: adding 4 parts of treatment additive into the graphene composite rare earth modified solution, and fully stirring to obtain a modified treatment agent;
s103: adding the compound silicate into the modification treatment agent according to the weight ratio of 1;
step two: preparing a coupling agent compound agent;
step three: adding a coupling agent compound agent accounting for 15 percent of the total amount of the compound silicate into the compound silicate subjected to modification treatment in the step one, and carrying out thermalization treatment;
step four: then sending the mixture into a ball mill for ball milling treatment, and finishing ball milling, washing and drying;
step five: and then heat-treating at 80 deg.C for 7.5min, and finally cooling at constant temperature.
The lanthanum chloride solution of this example was 7.5% by mass.
The preparation method of the modified graphene of the embodiment comprises the following steps:
s11: placing graphene in 5 times of hydrochloric acid solution, uniformly stirring, washing with water, and drying;
s12: then adding graphene into a sodium alginate solution 7.5 times of the total amount of the graphene, adding a sulfuric acid aqueous solution 7.5% of the total amount of the graphene, fully stirring, washing with water, and drying;
s13: and finally, carrying out heat treatment on the graphene at 315 ℃ for 15min, then heating to 67 ℃ at the speed of 3.5 ℃/min, keeping the temperature for 7.5min, finally uniformly dispersing in water at 2.5 ℃, and finally washing and drying to obtain the modified graphene.
The mass fraction of the hydrochloric acid solution in this example was 4%; the mass fraction of the sodium alginate solution is 12.5 percent; the mass fraction of the sulfuric acid aqueous solution was 12.5%.
The treatment additive comprises the following raw materials in parts by weight:
4.5 parts of tributyl citrate, 2 parts of propylene glycol, 8 parts of ethanol, 4 parts of chitosan aqueous solution and 1.5 parts of acetaminophen.
The mass fraction of the chitosan aqueous solution in this example was 15%.
The preparation method of the coupling agent compounding agent of the embodiment comprises the following steps:
s21: adding pentadecyl phenol into ethanol according to the weight ratio of 1;
s22: adding 3 parts of coupling agent KH560 and 2.5 parts of citric acid into 7.5 parts of deionized water, and fully stirring to obtain a coupling agent solution;
s23: and adding the coupling agent liquid into the S21 product according to the weight ratio of 2.
In the third step of this example, the temperature of the thermalization treatment was 60 ℃ and the treatment time was 25min.
The ball milling speed of the ball milling treatment in this example was 600r/min, and the ball milling time was 1.5h.
The rate of the constant temperature cooling treatment of this example was 3.5 deg.C/min.
Example 4.
The method for ball-milling modification of the silicate filler for the PCB comprises the following steps:
the method comprises the following steps: mixing silicon dioxide, calcium oxide and aluminum oxide according to the weight ratio of 6;
wherein: the specific method for stirring modification treatment of the modification treatment agent comprises the following steps:
s101: adding 6 parts of sodium oxalate into 22 parts of lanthanum chloride solution, and adding 3 parts of sodium alkylsulfonate and 5 parts of modified graphene to obtain graphene composite rare earth modified solution;
s102: adding 3 parts of treatment additive into the graphene composite rare earth modified solution, and fully stirring to obtain a modified treatment agent;
s103: adding the compound silicate into the modifying treatment agent according to the weight ratio of 1;
step two: preparing a coupling agent compound agent;
step three: adding a coupling agent compound agent accounting for 12 percent of the total amount of the compound silicate into the compound silicate subjected to modification treatment in the step one, and carrying out thermalization treatment;
step four: then sending the mixture into a ball mill for ball milling treatment, and finishing ball milling, washing and drying;
step five: and then heat-treating at 78 deg.C for 6min, and finally cooling at constant temperature.
The lanthanum chloride solution of this example was found to have a mass fraction of 6%.
The preparation method of the modified graphene of the embodiment comprises the following steps:
s11: placing graphene in 5 times of hydrochloric acid solution, uniformly stirring, washing with water, and drying;
s12: adding graphene into a sodium alginate solution 6 times of the total amount of graphene, adding a sulfuric acid aqueous solution 6% of the total amount of graphene, stirring fully, washing with water, and drying;
s13: and finally, carrying out heat treatment on the graphene at 312 ℃ for 12min, then heating to 67 ℃ at the speed of 3 ℃/min, keeping the temperature for 6min, finally uniformly dispersing in water at 2 ℃, and finally washing and drying to obtain the modified graphene.
The mass fraction of the hydrochloric acid solution in the embodiment is 3%; the mass fraction of the sodium alginate solution is 12 percent; the mass fraction of the sulfuric acid aqueous solution is 12%.
The treatment additive of the embodiment comprises the following raw materials in parts by weight:
4 parts of tributyl citrate, 2 parts of propylene glycol, 7 parts of ethanol, 3 parts of chitosan aqueous solution and 1.2 parts of acetaminophen.
The mass fraction of the chitosan aqueous solution in this example was 12%.
The preparation method of the coupling agent compound agent of the embodiment comprises the following steps:
s21: adding pentadecyl phenol into ethanol according to the weight ratio of 1;
s22: adding 3 parts of coupling agent KH560 and 2 parts of citric acid into 6 parts of deionized water, and fully stirring to obtain a coupling agent solution;
s23: and adding the coupling agent liquid into the S21 product according to the weight ratio of 2.
In the third step of this example, the temperature of the thermalization treatment was 56 ℃ and the treatment time was 22min.
The ball milling speed of the ball milling treatment of the embodiment is 600r/min, and the ball milling time is 1.2h.
The rate of the constant temperature cooling treatment of this example was 3 deg.C/min.
Comparative example 1.
The difference from example 3 is that the modification treatment was not carried out by stirring with the modification treatment agent.
Comparative example 2.
The difference from the example 3 is that the modified graphene is not added in the preparation of the modified treating agent.
Comparative example 3.
The difference from example 3 is that no treatment additive was added in the preparation of the modified treatment agent.
Comparative example 4.
The difference from example 3 is that the modified graphene is replaced by graphene.
Comparative example 5.
The difference from example 3 is that no acetaminophen or chitosan aqueous solution was added to the treatment additive preparation.
Comparative example 6.
Unlike example 3, no coupling agent combination was used.
Comparative example 7.
The difference from example 3 is that no coupling agent solution was added in the preparation of the coupling agent compounded agent.
Comparative example 8.
The difference from the example 3 is that pentadecyl phenol and glucuronolactone are not added in the preparation of the coupling agent compounded agent.
Mixing the products of the examples 1-4 and the comparative examples 1-8 with an epoxy resin curing agent according to a weight ratio of 1; meanwhile, placing the substrate under the condition of 5% salt mist for 24h, and testing the salt mist resistance;
as can be seen from comparative examples 1 to 8 and examples 1 to 4;
the product obtained in the embodiment 3 of the invention has excellent peel strength, excellent peel strength under the salt spray condition and excellent salt spray resistance;
the salt spray resistance and the peeling strength of the product are obviously poor due to the fact that the modification treatment agent is not adopted for stirring and modifying treatment, meanwhile, the modified graphene and the treatment additive are not added in the preparation of the treatment additive, the peeling strength and the salt spray resistance of the product tend to be poor, the graphene replaces the modified graphene, the effect change is small, and only the modification treatment agent prepared by the modified graphene matched treatment additive has an obvious optimized modification effect on the product;
the method does not adopt a coupling agent compounding agent for treatment, coupling agent liquid is not added in the preparation of the coupling agent compounding agent, and the coupling agent liquid is not added in the preparation of the coupling agent compounding agent, so that the performance of the product is deteriorated.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A method for ball-milling modification of silicate filler for PCB is characterized by comprising the following steps:
the method comprises the following steps: mixing silicon dioxide, calcium oxide and aluminum oxide according to the weight ratio of 6;
wherein: the specific method for stirring modification treatment of the modification treatment agent comprises the following steps:
s101: adding 5-10 parts of sodium oxalate into 20-30 parts of lanthanum chloride solution, and adding 2-5 parts of sodium alkyl sulfonate and 4-7 parts of modified graphene to obtain graphene composite rare earth modified solution;
s102: adding 2-6 parts of treatment additive into the graphene composite rare earth modified solution, and fully stirring to obtain a modified treatment agent;
s103: adding the compound silicate into the modification treatment agent according to the weight ratio of 1;
step two: preparing a coupling agent compound agent;
step three: adding a coupling agent compound agent accounting for 10-20% of the total amount of the compound silicate into the compound silicate subjected to modification treatment in the step one, and carrying out thermalization treatment;
step four: then sending the mixture into a ball mill for ball milling treatment, and finishing ball milling, washing and drying;
step five: and performing heat treatment at 75-85 deg.C for 5-10min, and cooling at constant temperature.
2. The method for ball-milling modification of a silicate filler for a PCB as claimed in claim 1, wherein the lanthanum chloride solution is 5-10% by mass.
3. The method for ball-milling modification of silicate filler for PCB according to claim 1, wherein the preparation method of the modified graphene comprises the following steps:
s11: placing graphene in 4-6 times of hydrochloric acid solution, uniformly stirring, washing with water, and drying;
s12: then adding graphene into a sodium alginate solution which is 5-10 times of the total amount of the graphene, adding a sulfuric acid aqueous solution which is 5-10% of the total amount of the graphene, fully stirring, washing with water, and drying;
s13: and finally, placing the graphene at 310-320 ℃ for heat treatment for 10-20min, then keeping the temperature at 65-70 ℃ at the speed of 2-5 ℃/min for 5-10min, finally uniformly dispersing in water at 1-4 ℃, and finally washing and drying to obtain the modified graphene.
4. The method for ball-milling modification of silicate filler for PCB as claimed in claim 3, wherein the mass fraction of the hydrochloric acid solution is 2-6%; the mass fraction of the sodium alginate solution is 10-15%; the mass fraction of the sulfuric acid aqueous solution is 10-15%.
5. The method for ball-milling modification of silicate fillers for PCBs as claimed in claim 1, wherein the treatment additive comprises the following raw materials in parts by weight:
3-6 parts of tributyl citrate, 1-3 parts of propylene glycol, 6-10 parts of ethanol, 2-6 parts of chitosan aqueous solution and 1-2 parts of acetaminophen.
6. The method for ball-milling modification of silicate fillers for PCBs as claimed in claim 5, wherein the mass fraction of the aqueous solution of chitosan is 10-20%.
7. The method for ball-milling modification of silicate filler for PCB as claimed in claim 1, wherein the preparation method of the coupling agent compounding agent comprises:
s21: adding pentadecyl phenol into ethanol according to the weight ratio of 1;
s22: adding 2-4 parts of coupling agent KH560 and 1-4 parts of citric acid into 5-10 parts of deionized water, and fully stirring to obtain a coupling agent solution;
s23: and adding the coupling agent liquid into the S21 product according to the weight ratio of 2.
8. The method for ball-milling modification of silicate filler for PCB of claim 1, wherein the temperature of the third thermal treatment is 55-65 ℃ and the treatment time is 20-30min.
9. The method for ball-milling modification of silicate filler for PCB according to claim 1, wherein the ball-milling rotation speed of the ball-milling process is 550-750r/min, and the ball-milling time is 1-2h.
10. The method for ball-milling modification of silicate filler for PCB as claimed in claim 1, wherein the constant temperature cooling treatment rate is 2-5 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211560102.XA CN115975400A (en) | 2022-12-07 | 2022-12-07 | Ball-milling modification method for silicate filler for PCB |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211560102.XA CN115975400A (en) | 2022-12-07 | 2022-12-07 | Ball-milling modification method for silicate filler for PCB |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115975400A true CN115975400A (en) | 2023-04-18 |
Family
ID=85957140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211560102.XA Pending CN115975400A (en) | 2022-12-07 | 2022-12-07 | Ball-milling modification method for silicate filler for PCB |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115975400A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008122427A2 (en) * | 2007-04-04 | 2008-10-16 | Atotech Deutschland Gmbh | Use of silane compositions for the production of mutilayer laminates |
| CN102415226A (en) * | 2009-04-24 | 2012-04-11 | 安美特德国有限公司 | Multilayer printed circuit board manufacture |
| CN103788410A (en) * | 2014-01-04 | 2014-05-14 | 安徽雪城超细碳酸钙有限公司 | Rare earth compound/titanate coupling agent modified ultrafine calcium carbonate filler |
| CN114574787A (en) * | 2022-02-28 | 2022-06-03 | 江苏万奇电器集团有限公司 | Lightweight carbon fiber steel plate composite material for bridge frame |
| CN115180923A (en) * | 2022-08-19 | 2022-10-14 | 广东欧文莱陶瓷有限公司 | Method for preparing ceramic tile with fine surface by taking recycled waste as raw material |
| CN115386749A (en) * | 2022-08-30 | 2022-11-25 | 福建华能电气有限公司 | Gravity casting process of aluminum-magnesium alloy explosion-proof box |
-
2022
- 2022-12-07 CN CN202211560102.XA patent/CN115975400A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008122427A2 (en) * | 2007-04-04 | 2008-10-16 | Atotech Deutschland Gmbh | Use of silane compositions for the production of mutilayer laminates |
| CN101627668A (en) * | 2007-04-04 | 2010-01-13 | 安美特德国有限公司 | The application of silane in making the multilayer pressing plate |
| CN102415226A (en) * | 2009-04-24 | 2012-04-11 | 安美特德国有限公司 | Multilayer printed circuit board manufacture |
| CN103788410A (en) * | 2014-01-04 | 2014-05-14 | 安徽雪城超细碳酸钙有限公司 | Rare earth compound/titanate coupling agent modified ultrafine calcium carbonate filler |
| CN114574787A (en) * | 2022-02-28 | 2022-06-03 | 江苏万奇电器集团有限公司 | Lightweight carbon fiber steel plate composite material for bridge frame |
| CN115180923A (en) * | 2022-08-19 | 2022-10-14 | 广东欧文莱陶瓷有限公司 | Method for preparing ceramic tile with fine surface by taking recycled waste as raw material |
| CN115386749A (en) * | 2022-08-30 | 2022-11-25 | 福建华能电气有限公司 | Gravity casting process of aluminum-magnesium alloy explosion-proof box |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103087665B (en) | High-heat-conductivity insulation low-viscosity epoxy resin pouring sealant and preparation method thereof | |
| WO2017080040A1 (en) | Damp-heat-resistant and highly reliable conductive silver epoxy adhesive, method for preparing same, and application thereof | |
| CN116535940B (en) | Wear-resistant and conductive coordinated metal substrate coating and method thereof | |
| CN110093087A (en) | A kind of double-component aqueous graphene heavy antisepsis heat radiation coating and preparation method | |
| CN114410046A (en) | Preparation method of hydrocarbon resin base plate material for high-frequency copper-clad plate | |
| CN111004598B (en) | Conductive silver adhesive applied to electronic resonator and preparation method | |
| CN104629643B (en) | Conducting resinl, its preparation method and wiring board | |
| CN115975400A (en) | Ball-milling modification method for silicate filler for PCB | |
| CN108419367A (en) | A kind of method for plugging of printed wiring board | |
| CN111849296A (en) | Low-carbon environment-friendly anticorrosive paint and preparation method thereof | |
| CN114149685B (en) | High-frequency high-speed copper-clad plate containing nano inorganic mullite alumina hollow microbeads | |
| CN114987005A (en) | Epoxy resin-based copper-clad plate filled with aluminum oxide and preparation method thereof | |
| JPH0529667B2 (en) | ||
| JPH03249274A (en) | Glass fiber substrate and glass-fiber reinforced resin laminated board using the same glass fiber substrate as reinforcing material | |
| CN101823151B (en) | Waterborne through-hole silver paste and preparation method and application thereof | |
| Inada et al. | Fundamental study on adhesive strength of electrical conductive adhesives (ECAs) | |
| CN104099061A (en) | Preparation method of electrolytic copper foil surface treating agent | |
| CN115181524B (en) | Preparation method of inorganic-organic hybrid silica/epoxy resin adhesive | |
| CN114603133B (en) | Conductive silver paste containing nano filler with multilevel structure and preparation method thereof | |
| CN112961626B (en) | Long-acting anti-oxidation high-conductivity conductive adhesive and preparation method thereof | |
| CN115216116B (en) | Environment-friendly hole plugging resin and resin hole plugging method | |
| CN114806476B (en) | Epoxy resin conductive adhesive containing composite conductive filler and preparation method thereof | |
| CN117896899A (en) | Preparation method of surface film of HDI circuit board | |
| CN116925645B (en) | Organosilicon high-temperature-resistant paint formula and preparation method thereof | |
| JPS6270476A (en) | Adhesive for printed circuit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |