CN116144143B - Low-temperature-resistant high-heat-conductivity hole plugging resin and resin hole plugging method - Google Patents
Low-temperature-resistant high-heat-conductivity hole plugging resin and resin hole plugging method Download PDFInfo
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Abstract
The invention discloses low-temperature-resistant high-heat-conductivity hole plugging resin and a resin hole plugging method, and relates to the technical field of circuit board production. The low-temperature-resistant high-heat-conductivity plug hole resin comprises the following components in parts by weight: 23-35 parts of epoxy resin, 15-30 parts of reactive diluent, 2-6 parts of latent curing agent, 0.1-1 part of imidazole curing accelerator, 0.01-0.1 part of defoamer and 40-60 parts of filler; the epoxy resin is a mixture of bisphenol a epoxy resin and bisphenol f epoxy resin; the filler is a mixture of boron nitride nanotubes, graphene and modified micron-sized silica. The invention combines a plurality of active ingredients, so that the low-temperature-resistant high-heat-conductivity hole plugging resin has the characteristics of good low-temperature mechanical property and better insulativity and heat conductivity, and is applied to the hole plugging of the circuit board, so that the circuit board after hole plugging can be suitable for special working environments such as low temperature, humidity and the like.
Description
Technical Field
The invention relates to the technical field of circuit board production, in particular to low-temperature-resistant high-heat-conductivity hole plugging resin and a resin hole plugging method.
Background
In recent years, the development of high-end technical fields such as superconducting technology and 5G communication has been rapid. The high-temperature superconducting technology has the characteristics of zero resistance, complete diamagnetism, low loss and the like, so that the high-density energy storage, high-capacity high-voltage power transmission and transformation, rapid and effective current limiting and the like can be realized, and the high-temperature superconducting technology has become a main direction of the development of the electric power technology in the future.
The superconducting device is mainly composed of a conductor and an insulating system, and has high requirements on electrical insulation, thermal conductivity and the like of materials, and meanwhile, the superconducting device needs to be operated at a liquid nitrogen temperature for a long time, so that excellent low temperature resistance is required.
However, because the traditional epoxy resin has brittleness at low temperature and hot spots with lower heat conductivity at room temperature, the requirements of the superconducting device on the low-temperature mechanical property and the insulating heat conduction property of the epoxy resin are difficult to meet; there is less research in China about low temperature conduction, and less research about circuit boards in superconducting devices of low temperature conduction. In addition, with the development of technology, the requirements of the fields of deep sea, deep space, polar exploration and the like on high-performance low-temperature-resistant resin and composite materials thereof are also becoming urgent.
Therefore, it is necessary to develop an epoxy resin with good low-temperature mechanical properties and good insulativity and thermal conductivity, which is applied to the circuit board plug holes, so that the circuit board after plug holes can be suitable for special working environments such as low temperature, humidity and the like, and provides references for the subsequent study of the resin suitable for the low-temperature superconducting device.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the low-temperature-resistant high-heat-conductivity hole plugging resin, which combines a plurality of active ingredients such as an active diluent, a latent curing agent, a curing accelerator, a filler and the like, so that the hole plugging resin has the characteristics of good low-temperature mechanical property, good insulativity and high heat conductivity, is applied to hole plugging of a circuit board, and can be suitable for special working environments such as low temperature, humidity and the like.
Specifically, the low-temperature-resistant high-heat-conduction plug hole resin comprises the following components in parts by weight:
23-35 parts of epoxy resin, 15-30 parts of reactive diluent, 2-6 parts of latent curing agent, 0.1-1 part of imidazole curing accelerator, 0.01-0.1 part of defoamer and 40-60 parts of filler;
the epoxy resin is a mixture of bisphenol a epoxy resin and bisphenol f epoxy resin, and the mass ratio of the bisphenol a epoxy resin to the bisphenol f epoxy resin is 2-4:1;
the reactive diluent is a mixture of dipropylene glycol diglycidyl ether and 1, 2-cyclohexanediol diglycidyl ether, and the mass ratio of the dipropylene glycol diglycidyl ether to the 1:1-3;
the latent curing agent is a mixture of methyl nadic anhydride and aliphatic polyanhydride, and the mass ratio of the methyl nadic anhydride to the aliphatic polyanhydride is 3-5:1, a step of;
the imidazole type curing accelerator 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, 2-undecylimidazole and 2-heptadecylimidazole;
the filler is a mixture of boron nitride nanotubes, graphene and modified micron-sized silicon dioxide; the sum of the graphene and the boron nitride nanotube accounts for 1-5% of the mass of the low-temperature-resistant high-heat-conductivity plug hole resin.
Preferably, the modification method of the modified micron-sized silicon dioxide comprises the steps of carrying out coupling reaction on the micron-sized silicon dioxide and a silane coupling agent; the silane coupling agent accounts for 0.5-1.2% of the mass of the micron-sized silicon dioxide.
Preferably, the silane coupling agent is selected from at least one of KH550, KH560, KH570 and KH 108.
Preferably, the micron-sized silica has a particle size of 1 to 20 μm.
Preferably, the aliphatic polyanhydride is selected from one or more of polyazelaic anhydride, polysebacic anhydride and polyadipic anhydride.
Preferably, the molecular weight of the aliphatic polyanhydride is 2000-5000.
Preferably, the defoaming agent is an organosilicon type defoaming agent.
The invention also discloses a preparation method of the low-temperature-resistant high-heat-conductivity plug hole resin, which comprises the following steps:
s1, heating epoxy resin and a reactive diluent to 60-90 ℃, and stirring and mixing;
s2: continuously adding an antifoaming agent, a latent curing agent and an imidazole type curing accelerator, and uniformly mixing;
s3: continuously adding the filler, stirring and mixing to obtain a resin mixture;
s4: grinding, vacuum stirring and degassing the resin mixture of the step S3 to obtain the low-temperature-resistant high-heat-conductivity plug hole resin.
Preferably, in the step S3, the stirring temperature is 40-50 ℃.
The invention also discloses a resin hole plugging method, which comprises the steps of plugging the circuit board by adopting the low-temperature-resistant high-heat-conduction hole plugging resin, pre-curing at the temperature of 100-130 ℃ for 20-60min, and then performing secondary curing at the temperature of 150-180 ℃ for 60-120 min.
Compared with the prior hole plugging resin and method, the invention has the beneficial effects that:
(1) The low-temperature-resistant high-heat-conductivity hole plugging resin disclosed by the invention is prepared by compounding bisphenol F type epoxy resin and bisphenol A type epoxy resin, wherein the bisphenol F type epoxy resin is better than the bisphenol A type epoxy resin in flexibility, shearing performance and cold-hot cycle impact at low temperature, but is weaker in other mechanical properties, and after the bisphenol F type epoxy resin and the bisphenol A type epoxy resin are compounded, the specific reactive diluent, the latent curing agent, the curing accelerator, the inorganic filler and the like are added, so that the hole plugging resin has the advantages of good flexibility, shearing performance, cold-hot cycle impact at low temperature, high strength and other mechanical properties.
Specifically, the mixture of dipropylene glycol diglycidyl ether and 1, 2-cyclohexanediol diglycidyl ether compounded in a specific ratio is selected as a diluent, so that a molecular structure containing a flexible long chain of fat which participates in the curing reaction of the epoxy resin can be provided, the viscosity of the epoxy resin can be effectively reduced, the tensile strength and the like can be improved, and the water absorption and the thermal stability of the epoxy resin are not influenced. The methyl nadic anhydride and the aliphatic polyanhydride which are compounded in a specific proportion are selected as the curing agent, so that not only can the electric insulation performance be enhanced, but also the cold and hot shock resistance performance can be improved, and meanwhile, the water absorption of the resin is prevented from being basically unchanged or slightly improved; because the activity of the anhydride is low and the curing temperature is high, a proper amount of imidazole curing accelerator is needed to be matched, and the curing temperature is reduced; meanwhile, the amount of the imidazole type curing accelerator is strictly limited, so that the influence on the curing process of the epoxy resin is prevented, the mechanical property of the epoxy resin is prevented from being reduced, the pot life is shortened, and the like.
In the filler, the silane coupling agent is used for modifying the micron-sized silicon dioxide, so that a siloxane structure is effectively introduced into a resin matrix, and meanwhile, the boron nitride nanotube and the graphene can cooperate to form a good heat conduction channel in the epoxy resin, so that the mechanical property, the thermal property and the electrical insulation property toughness of the epoxy resin are improved; due to the effects of the boron nitride nanotubes and the graphene, the micrometer silicon oxide can be uniformly dispersed in the resin, so that the mechanical property, the thermal property and the toughness of the resin are further improved; and the network structure formed by the boron nitride nanotubes, the graphene and the modified micron-sized silicon dioxide can improve the water resistance to a certain extent.
(2) In the low-temperature-resistant high-heat-conductivity hole plugging resin, various active components such as the reactive diluent, the latent curing agent, the curing accelerator and the filler are combined, so that the hole plugging resin has the characteristics of good low-temperature mechanical property, good insulativity and high heat conductivity, is applied to hole plugging of a circuit board, enables the circuit board after hole plugging to be suitable for special working environments such as low temperature, humidity and the like, and provides references for the resin suitable for subsequent research of a low-temperature superconducting device.
(3) The resin hole plugging method utilizes the low-temperature-resistant high-heat-conductivity hole plugging resin to plug holes of the circuit board, is simple and convenient to operate, and can be suitable for large-scale production and processing; meanwhile, the circuit board has excellent low temperature resistance, good electrical insulation, high toughness and high thermal conductivity.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a circuit board slice diagram of a plugging operation according to embodiment 1 of the present invention;
FIG. 2 is a circuit board slice diagram of the plugging operation of embodiment 2 of the present invention;
fig. 3 is an enlarged view of a portion of a circuit board cut-out for comparative example 5 plugging operation.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the terms "comprises" and "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in the present specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
It should be further understood that, as used in the present specification and appended claims, the term "concentration" refers to mass concentration, and "%" refers to mass percent; unless otherwise indicated.
The low-temperature-resistant high-heat-conductivity plug hole resin comprises the following components in parts by weight:
23-35 parts of epoxy resin, 15-30 parts of reactive diluent, 2-6 parts of latent curing agent, 0.1-1 part of imidazole curing accelerator, 0.01-0.1 part of defoamer and 40-60 parts of filler;
the epoxy resin is a mixture of bisphenol a epoxy resin and bisphenol f epoxy resin, and the mass ratio of the bisphenol a epoxy resin to the bisphenol f epoxy resin is 2-4:1; bisphenol f epoxy resin has flexibility, shearing performance, cold and hot cycle impact and lower viscosity at low temperature; bisphenol a epoxy resin has better mechanical properties, can be compounded with the bisphenol a epoxy resin, can be mutually coordinated, has good flexibility and shearing property, can bear cold and hot cycle impact, and has higher mechanical properties such as tensile strength and the like. Meanwhile, too large or too small proportion of bisphenol f epoxy resin can lead to the decrease of mechanical properties, so that the proportion relation between the bisphenol f epoxy resin and the bisphenol f epoxy resin should be strictly controlled.
The reactive diluent is a mixture of dipropylene glycol diglycidyl ether and 1, 2-cyclohexanediol diglycidyl ether, and the mass ratio of the dipropylene glycol diglycidyl ether to the 1:1-3; the two can reduce the viscosity of the epoxy resin, effectively gram the brittleness of the epoxy cured product, improve the tensile property, impact property and the like of the epoxy cured product, and basically have no influence on the water absorption and thermal stability of the epoxy cured product.
The latent curing agent is a mixture of methyl nadic anhydride and aliphatic polyanhydride, and the mass ratio of the methyl nadic anhydride to the aliphatic polyanhydride is 3-5:1, a step of; both have good electrical insulation, wherein, the cold and hot cycle impact resistance of aliphatic polyanhydride is better, but the water absorption is high, and the two can interact, the problem in the aspect of water absorption is balanced to the compound formula, has cold and hot cycle impact resistance and good electrical insulation simultaneously. The aliphatic polyanhydride is selected from one or a mixture of more of polyazelaic anhydride (b 1), polysebacic anhydride (b 2) and polyadipic anhydride (b 3). Preferably, the molecular mass is 2000-5000.
Imidazole-type curing accelerator the imidazole-type curing accelerator is selected from one or more of 2-methylimidazole and its derivatives (a 1), imidazole metal salt complex (a 2), 2-ethyl-4-methylimidazole (a 3), 2-ethylimidazole (a 4), 2-phenylimidazole (a 5), 1-cyanoethyl-2-undecylimidazole (a 6), 1-cyanoethyl-2-ethyl-4-methylimidazole (a 7), 2-undecylimidazole (a 8), 2-heptadecylimidazole (a 9);
the filler is a mixture of boron nitride nanotubes, graphene and modified micron-sized silica. Preferably, the sum of the graphene and the boron nitride nanotube accounts for 1-5% of the mass of the low-temperature-resistant high-heat-conductivity plug hole resin.
In the filler, the silane coupling agent is used for modifying the micron-sized silicon dioxide, so that a siloxane structure is effectively introduced into a resin matrix, and meanwhile, the boron nitride nanotube and the graphene can cooperate to form a good heat conduction channel in the epoxy resin, so that the mechanical property, the thermal property and the electrical insulation property toughness of the epoxy resin are improved; due to the effects of the boron nitride nanotubes and the graphene, the micrometer silicon oxide can be uniformly dispersed in the resin, so that the mechanical property, the thermal property and the toughness of the resin are further improved; and also to improve the water resistance to some extent.
The modification method of the modified micron-sized silicon dioxide comprises the steps of carrying out coupling reaction on the micron-sized silicon dioxide and a silane coupling agent; the silane coupling agent accounts for 0.5-1.2% of the mass of the micron-sized silicon dioxide. The silane coupling agent is at least one selected from KH550, KH560, KH570, KH108, and KH560 is particularly preferable.
The coupling reaction is selected from one of a dry method, a wet method and a dry-wet combination method, and is preferably a self-drying method; specifically, the dry modification is as follows: heating the micron-sized silicon dioxide to 100-120 ℃, adding a silane coupling agent (specifically KH560 with the mass of 1.0% of that of the micron-sized silicon dioxide), stirring and mixing at a high speed for 30-60min, and cooling in a dry environment to obtain the modified micron-sized silicon dioxide. Among them, the particle diameter of the micron-sized silica is preferably 1 to 20 μm (here, specifically 10 μm); thereby preparing the modified micron-sized silica.
The defoaming agent is an organosilicon defoaming agent.
The preparation method of the low-temperature-resistant high-heat-conductivity plug hole resin comprises the following steps:
s1, heating epoxy resin and a reactive diluent to 60-90 ℃, and stirring and mixing;
s2: continuously adding an antifoaming agent, a latent curing agent and an imidazole type curing accelerator, and uniformly mixing;
s3: continuously adding the filler, stirring and mixing to obtain a resin mixture;
s4: grinding, vacuum stirring and degassing the resin mixture of the step S3 to obtain the low-temperature-resistant high-heat-conductivity plug hole resin.
In the step S3, the stirring temperature is 40-50 ℃.
Before preparation, the epoxy resin, the reactive diluent, the latent curing agent, the imidazole type curing accelerator and the filler are required to be baked at the baking temperature of 60-100 ℃ for 60-90min; after the treatment, the preparation is carried out.
Specifically, heating the epoxy resin and the reactive diluent to 60-90 ℃, mixing and stirring for 30-60min; then adding a latent curing agent, an imidazole curing accelerator and a defoaming agent, mixing and stirring for 20-40min; continuously adding the uniformly mixed boron nitride nanotubes, graphene and modified micron-sized silicon dioxide, mixing and stirring, placing the materials in a dispersing machine, introducing circulating cooling water at 10-30 ℃, keeping the temperature of the materials below 50 ℃ (specifically 40-50 ℃), and stirring for 1-4 hours; transferring the mixed material to a three-roller grinder, introducing circulating cooling water in the grinding process, ensuring the temperature to be lower than 50 ℃, and grinding for 4 times until the viscosity of the mixed material is 400-1000dPa.s/25 ℃; and transferring the mixed material into a vacuum stirrer, and vacuumizing and stirring for 1-4 hours to obtain the low-temperature-resistant high-heat-conductivity plug hole resin.
With reference to the ratios in Table 1, the hole plugging resins of examples and comparative examples were prepared as shown in tables 1-2.
Table 1 proportion Table of the hole plugging resin of the examples
Table 2 comparative examples of the ratio Table of the hole plugging resins
Wherein, the molecular weight of b1 is 3000, and the molecular weight of b2 is 5000; b3 has a molecular weight of 2000.
The plug hole resins prepared in examples and comparative examples were tested for viscosity with a viscometer and for pot life at 25 ℃; meanwhile, the resin is plugged into the circuit board through a silk screen vacuum plug hole, and is put into a baking oven to be baked for 20-60min at 120 ℃, and then is heated to 160 ℃ to be baked for 60-120min; taking the time that the viscosity of the hole plugging resin increases by 10% at room temperature as the pot life, preparing the prepared hole plugging resin into 60 mm multiplied by 60 multiplied by mm multiplied by 1.55 mm blocks for curing, drying at 105 ℃ for 1H, cooling to room temperature in a dryer, taking out for weighing, putting into distilled water at 23 ℃ for soaking for 24H, taking out, drying with dry cloth, weighing immediately, and obtaining the water absorption rate of the sample according to the mass increase percentage; testing Tg and CTE testing was performed using a thermo-mechanical analyzer TMA; the thermal conductivity is tested by using a laser thermal conductivity meter; and determining the dielectric loss thereof according to the relevant regulations; the circuit board after hole plugging and curing is continuously tested for 2 hours at a high temperature of 85 ℃ and then continuously tested for two hours at a place of-40 ℃, and the test procedure is continuously completed for 20 rounds to determine the high and low temperature stability.
The performance tables of the examples and comparative examples obtained are shown in tables 3 to 5 below.
Table 3 performance table of examples
Table 4 Performance tables for comparative examples 1-8
Table 5 Performance Table comparing examples 9-15
As can be seen from tables 3-5, the hole plugging resin of examples 1-3 has the characteristics of good low temperature mechanical properties, good insulativity and good high thermal conductivity, and is applied to circuit board hole plugging, so that the circuit board after hole plugging can be suitable for special working environments such as low temperature, humidity and the like, the water absorption rate of the low temperature resistant high thermal conductivity hole plugging resin prepared by the embodiment of the application is not higher than 0.15%, the CET is lower than 64 ppm/DEG C, the dielectric loss is lower than 0.012, the pot life is not lower than 72h, the hole plugging effect is good, and the excellent high-low temperature stability is achieved. The low temperature resistance means that the high temperature stability and the low temperature stability can be tested, and the hole plugging resin is not peeled off from the copper covered by the hole plugging resin after being cured, is not cracked in a cavity, and is not obviously contracted or expanded; high thermal conductivity means that the thermal conductivity is more than or equal to 4.15W/mK.
As can be seen from Table 4, in comparative examples 1 to 4, too much or too little bisphenol f epoxy resin affects the mechanical properties and toughness, and fails the high and low temperature stability test, while too much bisphenol a epoxy resin increases the water absorption and fails the high and low temperature stability test. Comparative examples 5 to 8 show that excessive dipropylene glycol diglycidyl ether in the reactive diluent causes an increase in water absorption, failing to pass the high-low temperature stability test; and the dipropylene glycol diglycidyl ether is too small, so that the best mechanical property cannot be achieved, the thermal expansion coefficient is high, and the high-low temperature stability test cannot be passed.
As is clear from Table 5, in comparative examples 9 to 12, too much aliphatic polyanhydride leads to an increase in water absorption and thermal expansion coefficient, while too little aliphatic polyanhydride decreases water absorption, but the low-temperature performance is poor, and the high-temperature and low-temperature stability test cannot be passed. In comparative examples 13-15, the boron nitride nanotubes and graphene can synergistically act to form good heat conduction channels in the epoxy resin; therefore, the boron nitride nanotubes and the graphene lack any one, cannot play a synergistic effect, and the contents of the boron nitride nanotubes and the graphene are too low to form an effective amount of heat conduction channels in the epoxy resin, so that the thermodynamic performance is reduced, and the electric conductivity is influenced; and when the content of the boron nitride nanotube and the graphene is low, the dispersibility is poor, and the hole plugging effect is also influenced, so that the water absorption rate is influenced.
The circuit board slice diagram for plugging operation in embodiment 1 of the present invention is shown in fig. 1; the circuit board slicing diagram for plugging operation in embodiment 2 of the present invention is shown in fig. 2; comparative example 5 an enlarged schematic view of a portion of a circuit board slice of a plugging operation is shown in fig. 3.
In the foregoing embodiments, the descriptions of the embodiments are focused on, and for those portions of one embodiment that are not described in detail, reference may be made to the related descriptions of other embodiments.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The low-temperature-resistant high-heat-conductivity plug hole resin is characterized by comprising the following components in parts by weight:
23-35 parts of epoxy resin, 15-30 parts of reactive diluent, 2-6 parts of latent curing agent, 0.1-1 part of imidazole curing accelerator, 0.01-0.1 part of defoamer and 40-60 parts of filler;
the epoxy resin is a mixture of bisphenol a epoxy resin and bisphenol f epoxy resin, and the mass ratio of the bisphenol a epoxy resin to the bisphenol f epoxy resin is 2-4:1;
the reactive diluent is a mixture of dipropylene glycol diglycidyl ether and 1, 2-cyclohexanediol diglycidyl ether, and the mass ratio of the dipropylene glycol diglycidyl ether to the 1:1-3;
the latent curing agent is a mixture of methyl nadic anhydride and aliphatic polyanhydride, and the mass ratio of the methyl nadic anhydride to the aliphatic polyanhydride is 3-5:1, a step of;
the imidazole type curing accelerator 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, 2-undecylimidazole and 2-heptadecylimidazole;
the filler is a mixture of boron nitride nanotubes, graphene and modified micron-sized silicon dioxide; the sum of the graphene and the boron nitride nanotube accounts for 1-5% of the mass of the low-temperature-resistant high-heat-conductivity plug hole resin.
2. The low-temperature-resistant high-heat-conductivity plug hole resin according to claim 1, wherein the modification method of the modified micron-sized silica is that the micron-sized silica is subjected to a coupling reaction with a silane coupling agent; the silane coupling agent accounts for 0.5-1.2% of the mass of the micron-sized silicon dioxide.
3. The low temperature resistant high thermal conductivity jack resin according to claim 2, wherein said micron-sized silica has a particle size of 1 to 20 μm.
4. The low temperature resistant and high thermal conductivity jack resin according to claim 3, wherein said silane coupling agent is selected from at least one of KH550, KH560, KH570, KH 108.
5. The low temperature resistant, high thermal conductivity jack resin of claim 1, wherein said aliphatic polyanhydride is selected from the group consisting of polyazelaic anhydride, polysebacic anhydride, polyadipic anhydride, and mixtures of one or more thereof.
6. The low temperature resistant, high thermal conductivity via fill resin according to claim 5, wherein said aliphatic polyanhydride has a molecular weight of 2000 to 5000.
7. The low temperature resistant, high thermal conductivity via fill resin of claim 1, wherein said defoamer is a silicone type defoamer.
8. The method for preparing the low-temperature-resistant high-heat-conductivity plug hole resin according to any one of claims 1 to 7, comprising the steps of:
s1, heating epoxy resin and a reactive diluent to 60-90 ℃, and stirring and mixing;
s2: continuously adding an antifoaming agent, a latent curing agent and an imidazole type curing accelerator, and uniformly mixing;
s3: continuously adding the filler, stirring and mixing to obtain a resin mixture;
s4: grinding, vacuum stirring and degassing the resin mixture of the step S3 to obtain the low-temperature-resistant high-heat-conductivity plug hole resin.
9. The method according to claim 8, wherein in the step S3, the stirring temperature is 40 to 50 ℃.
10. A resin plugging method, characterized in that the circuit board is plugged by adopting the low-temperature-resistant high-heat-conduction plugging resin as claimed in any one of claims 1 to 7, and the circuit board is pre-cured under the conditions of 100 to 130 ℃ and 20 to 60min of curing time, and then is secondarily cured under the conditions of 150 to 180 ℃ and 60 to 120min of curing time.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5883160A (en) * | 1996-12-06 | 1999-03-16 | Somar Corporation | Flame-retardant epoxy resin composition for case potting of film capacitors |
| CN101240066A (en) * | 2007-02-07 | 2008-08-13 | 天津大学 | Polyoctadecane dibasic acid anhydride and its preparation method and application |
| CN102827566A (en) * | 2012-09-19 | 2012-12-19 | 三友（天津）高分子技术有限公司 | Single-component high/low-temperature-resistant epoxy resin composition |
| CN103254406A (en) * | 2013-04-18 | 2013-08-21 | 艾达索高新材料无锡有限公司 | Degradable organic amines and organic aromatic ammonium salts latent epoxy resin curing agent and application |
| JP2014118576A (en) * | 2012-12-18 | 2014-06-30 | Air Products And Chemicals Inc | Epoxy resin composition including solvated solid |
| CN105331187A (en) * | 2015-12-03 | 2016-02-17 | 深圳市板明科技有限公司 | Silicon-dioxide-type hole plugging ink and preparing method thereof |
| CN109536140A (en) * | 2017-08-07 | 2019-03-29 | 罗杰斯公司 | Heat-conductive composite material, preparation method and the product comprising the composite material |
| CN112778948A (en) * | 2020-12-23 | 2021-05-11 | 北京康美特科技股份有限公司 | Conductive silver adhesive and preparation method and application thereof |
| CN114710886A (en) * | 2022-06-02 | 2022-07-05 | 深圳市板明科技股份有限公司 | Ink hole plugging method for high-heat-conductivity PCB |
-
2023
- 2023-04-17 CN CN202310407338.8A patent/CN116144143B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5883160A (en) * | 1996-12-06 | 1999-03-16 | Somar Corporation | Flame-retardant epoxy resin composition for case potting of film capacitors |
| CN101240066A (en) * | 2007-02-07 | 2008-08-13 | 天津大学 | Polyoctadecane dibasic acid anhydride and its preparation method and application |
| CN102827566A (en) * | 2012-09-19 | 2012-12-19 | 三友（天津）高分子技术有限公司 | Single-component high/low-temperature-resistant epoxy resin composition |
| JP2014118576A (en) * | 2012-12-18 | 2014-06-30 | Air Products And Chemicals Inc | Epoxy resin composition including solvated solid |
| CN103254406A (en) * | 2013-04-18 | 2013-08-21 | 艾达索高新材料无锡有限公司 | Degradable organic amines and organic aromatic ammonium salts latent epoxy resin curing agent and application |
| CN105331187A (en) * | 2015-12-03 | 2016-02-17 | 深圳市板明科技有限公司 | Silicon-dioxide-type hole plugging ink and preparing method thereof |
| CN109536140A (en) * | 2017-08-07 | 2019-03-29 | 罗杰斯公司 | Heat-conductive composite material, preparation method and the product comprising the composite material |
| CN112778948A (en) * | 2020-12-23 | 2021-05-11 | 北京康美特科技股份有限公司 | Conductive silver adhesive and preparation method and application thereof |
| CN114710886A (en) * | 2022-06-02 | 2022-07-05 | 深圳市板明科技股份有限公司 | Ink hole plugging method for high-heat-conductivity PCB |
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