CN115181450B - Aluminum substrate hole plugging resin ink and ink hole plugging method - Google Patents
Aluminum substrate hole plugging resin ink and ink hole plugging method Download PDFInfo
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- CN115181450B CN115181450B CN202211095211.9A CN202211095211A CN115181450B CN 115181450 B CN115181450 B CN 115181450B CN 202211095211 A CN202211095211 A CN 202211095211A CN 115181450 B CN115181450 B CN 115181450B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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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
- H05K3/0094—Filling or covering plated through-holes or blind plated vias, e.g. for masking or for mechanical reinforcement
Abstract
The invention relates to an aluminum substrate hole plugging resin ink and an ink hole plugging method, and relates to the technical field of aluminum substrate processing. The aluminum substrate hole plugging resin ink is characterized by comprising the following components in parts by weight: 30-40 parts of epoxy resin, 0.1-2 parts of reactive diluent, 1-8 parts of latent curing agent, 0.1-1 part of imidazole curing accelerator and 50-60 parts of inorganic powder; the epoxy resin consists of polymer wax and an epoxy matrix, wherein the mass ratio of the polymer wax to the epoxy matrix is 1:1.5-4. The aluminum substrate hole plugging resin ink can be self-repaired, has high toughness and high secondary processability, and can pass a thermal stress test; meanwhile, the fly ash is recycled for the second time and is used as inorganic powder to interact with other components in the resin ink, so that the toughness of the resin ink is improved, and the environment protection is facilitated.
Description
Technical Field
The invention relates to the technical field of aluminum substrate processing, in particular to an aluminum substrate hole plugging resin ink and an ink hole plugging method.
Background
The aluminum substrate is a metal copper-clad circuit board with good heat dissipation performance, and in the field of printed circuit boards, the conventional hole filling resin is suitable for circuit boards with resin glass fibers as carriers. Because circuit board carrier panel material is different, conventional pore-filling resin is not suitable for aluminium base board pore-filling and has obvious downthehole resin fracture after the solidification, has obvious copper layer after the thermal stress test, and insulating layer and metal base layer peel off the phenomenon, and then lead to the finished product to scrap.
In addition, the hole of the aluminum substrate is large, so that the resin consumption is large, the aluminum substrate is low in thermal expansion coefficient, good in heat conduction and large in resin quantity, accumulated heat is generated after heating, and the aluminum substrate is easy to expand towards two ends, so that the resin for plugging the hole is required to have high heat resistance and low thermal expansion; meanwhile, after the resin is cured, secondary drilling and reprocessing are needed, and the resin needs to have certain toughness to ensure the reworkability and high resistivity. The via-filling resins for conventional substrates of FR-4 are difficult to meet.
Chinese patent application CN201310742198.6 discloses an epoxy resin composition which can improve the plump plugging, the reliability and the stability; however, it has low hardness after curing, and although it is easy to grind and drill, it is easy to have cracks and crazes during use, resulting in poor use effect of the wiring board and low reworkability.
The fly ash is the main solid waste discharged after the combustion of the pulverized coal in a thermal power plant and is the largest single source of industrial solid waste at present. The fly ash particles generally contain SiO 2 （52%-59%）、Al 2 O 3 （20%-25%）、FeO/Fe 2 O 3 MgO, and unburned carbon, and the like. Because the treatment of fly ash often occupies a large area and causes air and water pollution, the treatment of fly ash is always an important field concerned by the nation and the world. The fly ash has good thermal conductivity and mechanical property, so that the fly ash can be secondarily utilized in the hole plugging resin, the toughness of the hole plugging resin can be enhanced, the cost is reduced, and meanwhile, a secondary utilization way of the fly ash can be provided, and the environment protection is facilitated.
After reprocessing, the hole plugging resin still needs to keep certain toughness, so that the problem that the using effect of the circuit board is poor due to cracking and crazing in the using process is avoided; the yield of the aluminum substrate is possibly low in the secondary processing process, or the aluminum substrate is pressed, dropped, rubbed and the like, so that cracks and cracks are possibly generated, and defective products are generated; since it is too costly to scrap the defective products directly, the cost can be greatly saved by treating the defective products by self-repairing the resin.
Therefore, in order to solve the problems of low toughness and secondary processability and high fraction defective of the conventional hole plugging resin suitable for the aluminum substrate, it is necessary to research a hole plugging resin ink which can be self-repaired, has high toughness and high secondary processability and can pass a thermal stress test.
Disclosure of Invention
In order to solve the technical problems, the invention provides the aluminum substrate hole plugging resin ink which has high toughness and secondary processability, can pass a thermal stress test, has self-repairing capability, and can perform self-repairing when crazing is caused by using for a period of time or external force action, so that the yield is improved; meanwhile, the fly ash is used as inorganic powder, so that the mechanical properties such as toughness, strength and the like of the resin ink are improved under the condition of not influencing the thermal stability of the resin ink, the cost is reduced, and the environment protection is facilitated. The invention also provides an ink hole plugging method, which is used for plugging the hole of the aluminum substrate by using the aluminum substrate hole plugging resin ink and has the advantages of simple method, easy operation and low cost.
On one hand, the invention provides an aluminum substrate hole plugging resin ink which comprises the following components in parts by weight: 30-40 parts of epoxy resin, 0.1-2 parts of reactive diluent, 1-8 parts of latent curing agent, 0.1-1 part of imidazole curing accelerator and 50-60 parts of inorganic powder;
the epoxy resin consists of polymer wax and an epoxy matrix, wherein the mass ratio of the polymer wax to the epoxy matrix is 1:1.5-4; the molecular weight of the high-molecular wax is more than 5000, the high-molecular wax is selected from at least one of polyethylene wax and polypropylene wax, and the epoxy matrix is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin;
the inorganic powder consists of micron-sized fly ash and modified fly ash, wherein the mass percent of the modified fly ash is 2-8%; the preparation method of the modified fly ash comprises the step of carrying out coupling reaction on the micron-sized fly ash and a coupling agent, wherein the coupling agent accounts for 0.8-1.2% of the mass of the micron-sized fly ash.
Preferably, the coupling agent is one or more of aminosilane, epoxy silane, sulfenyl silane, vinyl silane, phenyl silane and alkyl silane.
Preferably, the reactive diluent is at least one of bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, butyl glycidyl ether, alkyl glycidyl ether, and phenyl glycidyl ether.
Preferably, the latent curing agent is one or a mixture of more of an organic hydrazide curing agent, an organic anhydride curing agent, a lewis acid-amine complex curing agent and a microcapsule curing agent.
Preferably, the imidazole-based curing accelerator is imidazole and derivatives and salts thereof, and is selected from one or more of 2-methylimidazole and derivatives thereof, imidazole metal salt complex, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and melt-mixed derivatives of diaminodiphenylmethane and imidazole.
The invention also provides a preparation method of the aluminum substrate hole plugging resin ink, which comprises the following steps:
s1, heating an epoxy matrix and high-molecular wax to 60-100 ℃, mixing and stirring, adding an active diluent, mixing and stirring to obtain a resin mixture;
s2, adding a latent curing agent and an imidazole curing accelerator into the resin mixture, and mixing and stirring;
s3, continuously adding the modified fly ash and stirring;
s4, continuously adding the micro-fly ash, stirring, mixing and stirring to obtain an ink mixture;
and S5, grinding and stirring the ink mixture in vacuum to obtain the resin ink for plugging the hole of the aluminum substrate.
Preferably, in each of the steps S2-S4, the stirring temperature is lower than 50 ℃.
Preferably, in the step S5, the grinding temperature is lower than 50 ℃, and the grinding is carried out until the viscosity is 200-300dpa.s/25-30 ℃.
Preferably, in the step S5, the vacuum stirring time is 1-5h.
On the other hand, the invention provides an ink hole plugging method for an aluminum substrate, which adopts the above-mentioned resin ink for hole plugging of the aluminum substrate to plug holes and comprises the following steps:
pre-curing the aluminum substrate hole plugging resin ink at the temperature of 90-100 ℃ for 30-35min, and then carrying out secondary curing at the temperature of 140-160 ℃ for 50-90 min.
Has the advantages that:
(1) According to the invention, through compounding the polymer wax and the epoxy matrix, the viscosity of the epoxy matrix can be reduced, and the thixotropy is improved; meanwhile, the aluminum substrate can be used as a dispersion phase to form a sea-island structure, so that the wear resistance and the impact resistance are improved, and a certain self-repairing effect is achieved when cracks and crazes are generated in the aluminum substrate reprocessing process or the aluminum substrate using process.
(2) The inorganic powder is fly ash, so that the fly ash can be secondarily utilized, the dispersibility, the thermal stability and the like of the modified fly ash are improved, and the dispersibility, the viscosity, the thixotropy, the thermal stability and the mechanical property of the modified fly ash can be balanced by combining the modified fly ash with micron-sized fly ash; and the inorganic powder is combined with the epoxy resin, so that the mechanical property of the epoxy resin can be enhanced and the self-repairing effect of the epoxy resin can be enhanced under the condition of not changing the thermal stability by matching with the sea-island structure of the epoxy resin.
(3) The hole plugging resin ink disclosed by the invention has the advantages that through the interaction of various effective components such as epoxy resin, inorganic powder, a diluent, a curing agent and the like, the hole plugging resin ink is low in viscosity and stable in thixotropy, and has good mechanical properties such as toughness and strength after being cured; specifically, the components such as the polymer wax and the inorganic powder have stable chemical properties, acid and alkali corrosion resistance, high insulativity, low dielectric constant, low thermal expansion coefficient and high toughness, so that the hole plugging resin ink has excellent heat resistance, good electrical property, low water absorption rate, excellent mechanical property and self-repairing effect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a photograph of a gold image cut after the heat resistance test of sample 1 according to the present invention;
FIG. 2 is a cross-sectional view of a golden image of sample 4 of the present invention after heat resistance testing;
FIG. 3 is a photograph of a gold image cut after the heat resistance test of comparative sample 1;
FIG. 4 is a photograph of a gold image cut after the heat resistance test of comparative sample 2;
FIG. 5 is a schematic of sample 2 of the present invention after curing for rework;
FIG. 6 is a schematic representation of sample 3 of the present invention being cured and then reworked;
FIG. 7 is a schematic illustration of comparative sample 5 being cured and then reworked;
FIG. 8 is a schematic representation of comparative sample 6 being cured and then reworked.
Detailed Description
In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated with reference to the following specific embodiments.
All percentages, parts and ratios are by weight of the total composition of the invention, unless otherwise specified. All qualities relating to the listed ingredients are given to the content of active substance, unless otherwise specified, and therefore they do not include solvents or by-products that may be contained in commercially available materials. The term "mass percent content" herein may be represented by the symbol "%".
All molecular weights herein are weight average molecular weights expressed in daltons, unless otherwise indicated.
All formulations and tests herein occur at 25 ℃ environment, unless otherwise indicated.
The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass the non-exclusive inclusion, as such terms are not to be construed. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of and" consisting essentially of 82303030A ". The compositions and methods/processes of the present invention comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein. The terms "potency", "performance", "effect" and "efficacy" are not distinguished from one another herein.
The hole plugging resin ink for the aluminum substrate comprises the following components in parts by weight: 30-40 parts of epoxy resin, 0.1-2 parts of active diluent, 1-8 parts of latent curing agent, 0.1-1 part of imidazole curing accelerator and 50-60 parts of inorganic powder;
the epoxy resin is composed of polymer wax and an epoxy matrix, and the mass ratio of the polymer wax to the epoxy matrix is 1:1.5-4; the molecular weight of the high-molecular wax is more than 5000, the high-molecular wax is selected from at least one of polyethylene wax and polypropylene wax, and the epoxy matrix is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and phenol novolac epoxy resin;
the reactive diluent is at least one of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, butyl glycidyl ether, alkyl glycidyl ether and phenyl glycidyl ether;
the latent curing agent is one or a mixture of more of an organic hydrazide curing agent, an organic anhydride curing agent, a Lewis acid-amine complex curing agent and a microcapsule curing agent;
the imidazole curing accelerator is imidazole and derivatives and salts thereof, and is selected from one or a mixture of more of 2-methylimidazole and derivatives thereof, imidazole metal salt complex, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and melt mixed derivatives of diaminodiphenylmethane and imidazole;
the inorganic powder consists of micron-sized fly ash and modified fly ash, wherein the mass percent of the modified fly ash is 2-8%. The preparation method of the modified fly ash comprises the step of carrying out coupling reaction on the micron-sized fly ash and a coupling agent, wherein the coupling agent accounts for 0.8-1.2% of the mass of the micron-sized fly ash, and the coupling agent is one or a mixture of aminosilane, epoxy silane, sulfenyl silane, vinyl silane, phenyl silane and alkyl silane. Wherein, the coupling reaction is selected from one of a dry method, a wet method and a dry-wet combination method, and is preferably selected from a dry method.
The preparation method of the aluminum substrate hole plugging resin ink comprises the following steps:
s1, heating an epoxy matrix and high-molecular wax to 60-100 ℃, mixing and stirring, adding an active diluent, and mixing and stirring to obtain a resin mixture;
s2, adding a latent curing agent and an imidazole curing accelerator into the resin mixture, and mixing and stirring;
s3, continuously adding the modified fly ash and stirring;
s4, continuously adding the micro-rice fly ash, stirring, mixing and stirring to obtain an ink mixture;
s5, grinding and vacuum stirring the ink mixture to obtain the hole plugging resin ink;
in the step S5, the grinding temperature is lower than 50 ℃, the grinding is carried out until the viscosity is 200-300dpa.s/25-30 ℃, and the vacuum stirring time is 1-5h.
Specifically, the epoxy matrix and the polymer wax are heated to 60-100 ℃, mixed and stirred for 20-40min; adding an active diluent, mixing and stirring, then adding a latent curing agent and an imidazole curing accelerator, mixing and stirring, then adding the modified fly ash, mixing and stirring for 30-60min, putting the mixture into a dispersing machine during stirring, introducing 15-30 ℃ circulating cooling water, and keeping the temperature of the materials below 50 ℃; adding micron-sized fly ash, and stirring for 1-5h; transferring the mixed material to a three-roll grinder, grinding the mixed material until the viscosity is 200-300dpa.s/25-30 ℃, and introducing circulating cooling water in the grinding process to ensure that the temperature is lower than 50 ℃; and transferring the mixed material into a vacuum stirrer, vacuumizing and stirring for 1-5 hours to obtain the aluminum substrate hole plugging resin ink.
Physical property test of aluminum substrate hole plugging resin ink
And (3) viscosity testing: testing the viscosity of the prepared hole plugging resin sample at room temperature by using a viscometer VT-06;
and (3) testing the storage property: placing in a refrigerator for cold storage at a temperature lower than 10 ℃, taking out for testing, and taking the storage period as the day when the viscosity reaches + 10%; testing at 25 deg.C, and determining the using period when the day of viscosity reaches + 10%;
halogen test: testing the content of halogen by an element analyzer IC;
RoHS test: roHS is a mandatory standard established by European legislation and is called ' directive about Restriction of use of certain harmful components in electronic and electrical equipment ' (Restriction of Hazardous substations) ', namely, whether 10 harmful Substances meet requirements or not is detected;
glass transition temperature and thermal performance testing: tg means glass transition temperature; CTE α refers to the coefficient of thermal expansion at temperatures less than Tg; CTE β refers to the coefficient of thermal expansion at temperatures greater than Tg;
and (4) testing thermal stress: and (3) filling holes in the uniformly mixed hole filling resin into an aluminum substrate, baking, grinding, laminating and covering an outer copper foil insulating layer, and then sampling a 10CM/10CM aluminum substrate copper-clad plate. And putting the lead-free tin into a tin furnace to be melted into liquid high-temperature tin liquid at 320 ℃, immersing the sampled aluminum substrate copper-clad plate into the tin liquid for 10min, and performing golden image slicing to analyze whether the resin cracking and laminated layer stripping phenomenon exists.
Chemical performance test of aluminum substrate hole plugging resin ink
The plugging resins were cured to make cubes having a volume of 10cm x 0.5cm x 10cm and then each plugging resin was tested for chemical resistance by soaking the cubes in a chemical reagent. The specific test conditions are as follows: soaking the cube in 10wt% sulfuric acid solution and 10wt% sodium hydroxide solution at normal temperature for 60min, and measuring acid resistance and alkali resistance; soaking the cube in 100 deg.C water for 60min, and measuring its boiling water resistance; the cube was immersed in 25 ℃ isopropanol, dichloromethane, acetone for 60min, respectively, and the isopropanol, dichloromethane, acetone resistance was measured.
Resin hole plugging method for aluminum substrate
Proportioning, mixing, dispersing, aluminum substrate hole filling, solidifying, grinding and pressing
The curing comprises the following steps: pre-curing the aluminum substrate hole plugging resin ink at the temperature of 90-100 ℃ for 30-35min, and then carrying out secondary curing at the temperature of 140-160 ℃ for 50-90 min.
Example 1
The aluminum substrate hole plugging resin ink comprises the following components in parts by weight:
8 parts of polyethylene wax, 24 parts of bisphenol A epoxy resin, 0.4 part of bisphenol A diglycidyl ether, 0.6 part of phenyl glycidyl ether, 1.2 parts of Lewis acid-amine complex curing agent, 0.8 part of organic acid anhydride curing agent, 0.2 part of imidazole metal salt complex, 0.4 part of 2-ethylimidazole, 50 parts of micron-sized fly ash and 4 parts of modified fly ash.
Specifically, the aluminum substrate hole plugging resin ink comprises the following components: 80g of polyethylene wax, 240g of bisphenol A epoxy resin, 4g of bisphenol A diglycidyl ether, 6g of phenyl glycidyl ether, 12g of Lewis acid-amine complex curing agent, 8g of organic anhydride curing agent, 2g of imidazole metal salt complex, 4g of 2-ethylimidazole, 500g of micron-sized fly ash and 40g of modified fly ash.
Example 2
The aluminum substrate hole plugging resin ink comprises the following components in parts by weight:
8 parts of polypropylene wax, 32 parts of bisphenol F epoxy resin, 1.0 part of bisphenol F diglycidyl ether, 1.0 part of butyl glycidyl ether, 2.5 parts of organic hydrazide curing agent, 5.5 parts of microcapsule curing agent, 0.4 part of 2-methylimidazole and derivatives thereof, 0.6 part of 2-ethyl-4-methylimidazole, 58.5 parts of micron-sized fly ash and 1.5 parts of modified fly ash.
Specifically, the aluminum substrate hole plugging resin ink comprises the following components: 80g of polypropylene wax, 320g of bisphenol F epoxy resin, 10g of bisphenol F diglycidyl ether, 10g of butyl glycidyl ether, 25g of organic hydrazide curing agent, 55g of microcapsule curing agent, 4g of 2-methylimidazole and derivatives thereof, 6g of 2-ethyl-4-methylimidazole, 585g of micron-sized fly ash and 15g of modified fly ash.
Example 3
The aluminum substrate hole plugging resin ink comprises the following components in parts by weight:
14 parts of polypropylene wax, 21 parts of bisphenol A epoxy resin, 0.1 part of alkyl glycidyl ether, 0.1 part of phenyl glycidyl ether, 0.2 part of organic hydrazide curing agent, 0.8 part of organic acid anhydride curing agent, 0.1 part of 2-phenylimidazole, 0.1 part of 1-cyanoethyl-2-undecylimidazole, 49 parts of micron-sized fly ash and 1 part of modified fly ash.
Specifically, the aluminum substrate hole plugging resin ink comprises the following components: 140g of polypropylene wax, 210g of bisphenol A epoxy resin, 1g of alkyl glycidyl ether, 1g of phenyl glycidyl ether, 2g of organic hydrazide curing agent, 8g of organic acid anhydride curing agent, 1g of 2-phenylimidazole, 1g of 1-cyanoethyl-2-undecylimidazole, 490g of micron-sized fly ash and 10g of modified fly ash.
Example 4
The aluminum substrate hole plugging resin ink comprises the following components in parts by weight:
8 parts of polyethylene wax, 24 parts of bisphenol S epoxy resin, 0.4 part of bisphenol A diglycidyl ether, 0.6 part of phenyl glycidyl ether, 1.2 parts of Lewis acid-amine complex curing agent, 0.8 part of organic acid anhydride curing agent, 0.2 part of fused and mixed derivative of aminodiphenylmethane and imidazole, 0.4 part of 1-cyanoethyl-2-ethyl-4-methylimidazole, 46 parts of micron-sized fly ash and 4 parts of modified fly ash.
Specifically, the aluminum substrate hole plugging resin ink comprises the following components: 80g of polyethylene wax, 240g of bisphenol S epoxy resin, 4g of bisphenol A diglycidyl ether, 6g of phenyl glycidyl ether, 12g of Lewis acid-amine complex curing agent, 8g of organic acid anhydride curing agent, 2g of fused and mixed derivative of aminodiphenylmethane and imidazole, 4g of 1-cyanoethyl-2-ethyl-4-methylimidazole, 460g of micron-sized fly ash and 40g of modified fly ash.
Samples 1 to 4 of the hole plugging resin ink for aluminum substrates were prepared according to the following preparation methods in all of the above examples 1 to 4.
Preparing the aluminum substrate hole plugging resin ink, specifically, heating an epoxy matrix and high polymer wax to 60-100 ℃, and mixing and stirring for 20-40min; adding an active diluent, mixing and stirring, then adding a latent curing agent and an imidazole curing accelerator, mixing and stirring, then adding the modified fly ash, mixing and stirring for 30-60min, putting the mixture into a dispersing machine in the stirring process, introducing 15-30 ℃ circulating cooling water, and keeping the temperature of the materials below 50 ℃; then adding micron-sized fly ash, and stirring for 1-5h; transferring the mixed material to a three-roll grinder, grinding the mixed material until the viscosity is 200-300dpa.s/25-30 ℃, and introducing circulating cooling water in the grinding process to ensure that the temperature is lower than 50 ℃; and transferring the mixed material into a vacuum stirrer, vacuumizing and stirring for 1-5 hours to obtain the resin ink for plugging the hole on the aluminum substrate.
Comparative samples 1 to 9 were prepared in the same manner as in example 1, except that comparative examples 1 to 9 in Table 1 were different from example 1.
TABLE 1 differences between comparative examples 1 to 9 and example 1
Physical property tests were performed on samples 1 to 4, and the test results are shown in tables 2 to 3.
TABLE 2 results of physical Properties measurements of samples 1-4
TABLE 3 results of physical Properties measurements of samples 1-4
Physical tests were performed on a portion of the control samples and the results are shown in table 4.
TABLE 4 results of physical Property measurements of comparative samples 1-6
As can be seen from tables 2 to 3, the physical properties of samples 1 to 4 were excellent. As can be seen from table 4, the viscosity of the comparative samples 1, 5, and 6 is increased due to no polyethylene wax, no reactive diluent, and no modified fly ash, so that the dispersibility of the resin ink is insufficient, and the storage property is poor; the comparative sample 5 does not contain a reactive diluent, and a sample can still be prepared because the polyethylene wax can reduce the viscosity of the resin and has a lubricating effect, namely a certain diluting effect. The polyethylene wax content in comparative sample 3 was higher, resulting in a lower viscosity.
Samples 1-4 were tested for chemical properties and the results are shown in table 5.
TABLE 5 results of chemical Properties measurements of samples 1-4
The aluminum substrates were subjected to plugging operation using sample 1 and comparative samples 1 to 9, baked, ground, and then laminated with an outer copper foil insulation layer, followed by sampling of a 10cm-10cm aluminum substrate copper-clad plate, and then subjected to typical heat resistance test (reflow test, thermal stress test, tin-sprayed heat resistance) and slicing analysis. The results of the heat resistance test of the sample and a part of the comparative sample are shown in table 6.
Table 6 test results of heat resistance of the sample and the comparative sample
As can be seen from table 6, comparative samples 1 to 7 have poor heat resistance, specifically, comparative sample 1 does not contain polyethylene wax, and thus fails to form a sea-island structure, resulting in poor impact resistance; the molecular weight of the polyethylene wax in the comparative sample 2 is too low, and the sea-island structure can not be formed; the polyethylene wax in the comparative sample 3 has higher components, lower melting point and easy cracking and expansion at high temperature; the comparative sample 5 does not contain an active diluent, so that the viscosity of the components is too high, the toughness is insufficient, and the components are easy to crack and expand; the comparative sample 6 does not contain modified fly ash, the micron-sized fly ash has poor dispersibility and is easy to be bonded into a mass, so that the viscocity is too high, the toughness is insufficient, and the resin is easy to crack and expand; the comparative sample 7 has a large content of added modified fly ash, which causes the toughness to be reduced and the thermal stress test to be difficult to pass; in the comparative sample 8, the modified fly ash is replaced by the micron glass fiber powder, the micron glass fiber powder can also improve the toughness of the resin, but the content of the micron glass fiber powder is too low to pass a thermal stress test; the toughness of the epoxy resin selected in comparative sample 9 is not good, and even though polyethylene wax and modified fly ash are added, the epoxy resin still has difficulty in passing the thermal stress test.
Meanwhile, a gold image slice image of the sample 1 subjected to a heat resistance test is shown as 1, the aperture is about 1500um, and the orifice resin is flat and has no protrusion; the golden image slice after the heat resistance test of sample 4 is shown in fig. 2, the aperture is 1500um, the copper surface of the aperture resin and the laminated layer is flat without any bulge, and the resin is uniform. The image of the golden image cut after the heat resistance test of the comparative sample 1 is shown in fig. 3, and the cut is obviously separated from the pressing layer and cracked; the golden image after the heat resistance test of comparative sample 2 is shown in fig. 4, and the cut piece is separated from the laminated layer and cracked.
Moreover, the schematic diagram of the sample 2 which is processed after being cured is shown in FIG. 5, and the resin has no cracking and other problems; the schematic diagram of the sample 3 which is processed after being cured is shown in FIG. 6, and the resin has no cracking and other problems; the comparative sample 5 was cured and then processed as shown in FIG. 7, and a significant cracking problem was observed; the comparative sample 6 was cured and then processed as shown in fig. 8, and the copper surface was raised by the bulge of the sample, and the slice was clearly separated from the copper layer.
Carrying out self-repairing tests on the sample 1 and the comparative samples 1-9, specifically, carrying out quantitative mechanical failure tests on the samples by using a QHZ type coating scratch instrument, wherein the minimum weight increment is 200g, the fastest speed of needle point scratching is 10cm/s, and observing and recording failure conditions under different loads by using an XSP-8CA type image microscope; then the temperature is raised to 120 ℃, and the repairing situation is observed within 10 min.
The self-repairing properties of the resulting sample 1 and comparative samples 1-9 are shown in Table 7 below.
TABLE 7 self-healing Performance results for sample 1 and comparative samples 1-9
As can be seen from table 7, sample 1 has a good self-repairing effect, and comparative sample 3, comparative sample 7, and comparative sample 9 can also realize self-repairing, but comparative sample 3 has excessive polyethylene wax, which results in a resin portion being depressed due to melting of the polyethylene wax, and thus has no practical applicability. The comparative sample 1, the comparative sample 2, the comparative samples 4 to 6 and the comparative sample 8 can not achieve the same repairing effect, and the polyethylene wax is not uniformly dispersed due to insufficient dispersed phase, so that the self-repairing effect is poor.
The technical contents of the present invention are further illustrated by the examples, so as to facilitate the understanding of the reader, but the embodiments of the present invention are not limited thereto, and any technical extension or re-creation based on the present invention is protected by the present invention.
Claims (10)
1. The aluminum substrate hole plugging resin ink is characterized by comprising the following components in parts by weight: 30-40 parts of epoxy resin, 0.1-2 parts of reactive diluent, 1-8 parts of latent curing agent, 0.1-1 part of imidazole curing accelerator and 50-60 parts of inorganic powder;
the epoxy resin is composed of polymer wax and an epoxy matrix, and the mass ratio of the polymer wax to the epoxy matrix is 1:1.5-4; the weight average molecular weight of the high polymer wax is more than 5000, the high polymer wax is selected from at least one of polyethylene wax and polypropylene wax, and the epoxy matrix is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin;
the inorganic powder consists of micron-sized fly ash and modified fly ash, wherein the mass percent of the modified fly ash is 2-8%; the preparation method of the modified fly ash comprises the step of carrying out coupling reaction on micron-sized fly ash and a coupling agent, wherein the coupling agent accounts for 0.8-1.2% of the mass of the micron-sized fly ash.
2. The aluminum substrate via hole resin ink as claimed in claim 1, wherein the coupling agent is one or more mixture of aminosilane, epoxysilane, sulfenyl silane, vinyl silane, phenyl silane, alkyl silane.
3. The aluminum substrate via hole resin ink according to claim 2, wherein the reactive diluent is at least one of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, butyl glycidyl ether, alkyl glycidyl ether, and phenyl glycidyl ether.
4. The aluminum substrate hole plugging resin ink according to claim 3, wherein said latent curing agent is one or more of organic hydrazide curing agent, organic anhydride curing agent, lewis acid-amine complex curing agent and microcapsule curing agent.
5. The aluminum substrate via hole resin ink as claimed in claim 4, wherein the imidazole-based curing accelerator is imidazole and its derivatives and salts selected from one or more of 2-methylimidazole and its derivatives, imidazole metal salt complex, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, diaminodiphenylmethane and melt-mixed derivatives of imidazole.
6. The method for preparing the aluminum substrate hole plugging resin ink as claimed in claim 5, comprising the following steps:
s1, heating an epoxy matrix and high-molecular wax to 60-100 ℃, mixing and stirring, adding an active diluent, mixing and stirring to obtain a resin mixture;
s2, adding a latent curing agent and an imidazole curing accelerator into the resin mixture, and mixing and stirring;
s3, continuously adding the modified fly ash and stirring;
s4, continuously adding the micro-fly ash, stirring, mixing and stirring to obtain an ink mixture;
and S5, grinding and stirring the ink mixture in vacuum to obtain the resin ink for plugging the hole of the aluminum substrate.
7. The method according to claim 6, wherein the stirring temperature in each of the steps S2 to S4 is less than 50 ℃.
8. The method according to claim 7, wherein the grinding temperature in step S5 is lower than 50 ℃ and the grinding is carried out until the viscosity is 200-300dpa.s/25-30 ℃.
9. The method according to claim 8, wherein the vacuum stirring time in step S5 is 1-5 hours.
10. An ink hole plugging method for an aluminum substrate, which is characterized in that the hole plugging is performed by using the aluminum substrate hole plugging resin ink according to any one of claims 1 to 5, and comprises the following steps:
pre-curing the aluminum substrate hole plugging resin ink at the temperature of 90-100 ℃ for 30-35min, and then carrying out secondary curing at the temperature of 140-160 ℃ for 50-90 min.
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| CN202211095211.9A CN115181450B (en) | 2022-09-08 | 2022-09-08 | Aluminum substrate hole plugging resin ink and ink hole plugging method |
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| CN202211095211.9A CN115181450B (en) | 2022-09-08 | 2022-09-08 | Aluminum substrate hole plugging resin ink and ink hole plugging method |
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| CN115181450B true CN115181450B (en) | 2022-11-25 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101336052A (en) * | 2008-07-30 | 2008-12-31 | 惠州中京电子科技有限公司 | Jack process of printed circuit board |
| CN110746150A (en) * | 2019-12-05 | 2020-02-04 | 盈创新材料(苏州)有限公司 | High-performance ground ink for 3D printing |
| CN114885507A (en) * | 2022-07-06 | 2022-08-09 | 深圳市板明科技股份有限公司 | Disposable full continuous hole plugging device and method |
-
2022
- 2022-09-08 CN CN202211095211.9A patent/CN115181450B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101336052A (en) * | 2008-07-30 | 2008-12-31 | 惠州中京电子科技有限公司 | Jack process of printed circuit board |
| CN110746150A (en) * | 2019-12-05 | 2020-02-04 | 盈创新材料(苏州)有限公司 | High-performance ground ink for 3D printing |
| CN114885507A (en) * | 2022-07-06 | 2022-08-09 | 深圳市板明科技股份有限公司 | Disposable full continuous hole plugging device and method |
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| CN115181450A (en) | 2022-10-14 |
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