CN115083660A - Easily-ground high-thermal-conductivity insulation hole plugging slurry, preparation method and application thereof - Google Patents
Easily-ground high-thermal-conductivity insulation hole plugging slurry, preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/025—Other inorganic material
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
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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
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0218—Composite particles, i.e. first metal coated with second metal
Abstract
The invention discloses an easily-ground high-thermal-conductivity insulation plug hole slurry, a preparation method and application thereof, wherein the insulation plug hole slurry comprises the following components in percentage by weight: 80-93 wt% of insulating heat-conducting powder, 6-15 wt% of resin, 0.2-2 wt% of curing agent and 0.8-3 wt% of auxiliary agent. The insulation plug hole slurry can be matched with a plate with high Tg and low CTE, has the characteristics of high heat conductivity coefficient, anti-sagging and easy abrasion after solidification, and is particularly suitable for plug hole on ceramic substrates and 5G high-frequency and high-power plates.
Description
Technical Field
The invention belongs to the technical field of hole plugging slurry, and particularly relates to easily-ground high-thermal-conductivity insulation hole plugging slurry, a preparation method and application thereof.
Background
With the rapid development of microelectronic technology, the integration density and assembly density of electronic products are continuously improved, and the PCB is used as a carrier of electronic components, so that the integration density and the power consumption of the components are more and more required, and especially under the 5G background, the heat conduction and heat dissipation requirements of high-frequency and high-power boards are more and more urgent, which all put higher requirements on various performances of PCB materials. The traditional hole plugging slurry has small heat conductivity coefficient, large thermal expansion coefficient and low glass transition temperature, and is difficult to meet the heat conduction and heat dissipation requirements of high-frequency and high-power plates under the condition of 5 g.
The hole plugging slurry is a material for filling and leveling through holes and buried holes of the PCB through a resin hole plugging process, and is favored in PCB products with high layer number and large thickness. The plug hole heat conduction slurry in the market mainly takes the conductive slurry as a main material and has a heat conduction function, although the heat conduction coefficient is higher, the conductive slurry has high cost and poor storage stability and is difficult to be used on a PCB in large quantity. And the filler used by the conductive slurry is generally metal powder, has a large thermal expansion coefficient and cannot be matched with a high-frequency and high-power plate.
The insulating heat-conducting plug hole slurry taking the ceramic powder as the filler has small thermal expansion coefficient and lower cost, and can be widely used on 5G plates. For example, the applicant's earlier patent CN109929220B discloses an insulating and heat-conducting paste, a preparation method and an application thereof, wherein the insulating and heat-conducting paste comprises the following components: the heat-conducting insulation material comprises insulating heat-conducting powder, resin, a monomer, a curing agent and an auxiliary agent; the insulating heat-conducting slurry disclosed by the patent has the characteristics of uniform dispersion of all components, stable slurry system, long storage time, high insulating heat conductivity and ultralow expansion coefficient under the synergistic action of the contained combination. The small-particle-size powder roller mill is adopted in the patent, but the thermal conductivity coefficient is difficult to improve due to the large interface thermal resistance of the small-particle-size powder, namely the thermal conductivity coefficient of the solidified insulating heat-conducting slurry in the prior art is still difficult to meet the heat conduction and heat dissipation requirements of a high-frequency and high-power plate, and the sagging phenomenon is easy to occur in the baking process, so that the subsequent easy-grinding performance is reduced, and the production requirement is difficult to meet. The easy-to-grind performance is a technical pain point of slurry taking ceramic powder as filling powder, and because a ceramic brush is needed for grinding, the ceramic brush is very high in price and is a consumable material, the easy-to-grind characteristic can obviously reduce grinding cost and improve grinding efficiency.
Therefore, there is still a need to develop an insulating paste with higher thermal conductivity, lower coefficient of thermal expansion at high temperature, and easy grinding.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the easily-ground high-thermal-conductivity insulation hole plugging slurry which is particularly suitable for plugging holes on ceramic substrates and 5G high-frequency and high-power plates.
The invention further aims to provide a preparation method of the easily-ground high-thermal-conductivity insulation plug hole slurry.
It is a further object of the present invention to provide the use of such an easily abradable high thermal conductivity insulating plug hole paste.
In order to realize the purpose, the invention adopts the following technical scheme:
an easily-ground high-thermal-conductivity insulation hole plugging slurry comprises the following components in percentage by weight:
80-93 wt% of insulating heat-conducting powder;
6-15 wt% resin;
0.2-2 wt% of a curing agent;
0.8-3 wt% of auxiliary agent.
In a specific embodiment, the insulating and heat conducting powder is selected from at least any two of boron nitride, aluminum oxide and aluminum nitride, and is preferably aluminum oxide and aluminum nitride or aluminum oxide and boron nitride.
In a specific embodiment, the shape of the insulating and heat conducting powder is a combination of at least any two of a sheet shape, a sphere shape or an angle shape; preferably, the insulating heat-conducting powder is spherical, spheroidal or angular alumina powder and flaky boron nitride powder; more preferably, the alumina powder is modified for a resin system, and the mass ratio of the alumina powder to the boron nitride powder is 80: 1-10: 1.
In a specific embodiment, the insulating and heat conducting powder comprises small-particle insulating and heat conducting powder with the average particle size of 0.5-1 μm and large-particle insulating and heat conducting powder with the average particle size of 10-15 μm, and the maximum particle size of the insulating and heat conducting powder is not more than 40 μm; preferably, the mass ratio of the small-particle insulating heat-conducting powder to the large-particle insulating heat-conducting powder is 5:1-50: 1.
In a specific embodiment, the resin is a liquid epoxy resin without organic solvent, preferably at least one selected from bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin, silicone modified epoxy resin, and special multifunctional epoxy resin; more preferably one or a combination of more of liquid bisphenol A epoxy resin, bisphenol F epoxy resin or special polyfunctional epoxy resin.
In a specific embodiment, the curing agent is selected from at least any one of amino resins, imidazoles, organic acid anhydrides and dicyandiamide; imidazoles and dicyandiamide are preferred.
In a specific embodiment, the auxiliary agent comprises wetting dispersant, diluent; preferably, the wetting and dispersing agent is selected from one or two combinations of modified polysiloxane or polyurethane compounds; the diluent is epoxy reactive diluent, preferably one or a combination of more of monofunctional glycidyl ether or multifunctional glycidyl ether.
On the other hand, the preparation method of the easily-ground high-thermal-conductivity insulation plug hole paste comprises the following steps:
1) uniformly mixing resin, a curing agent and insulating heat-conducting powder with the granularity not more than 15 mu m in a certain proportion by a high-speed mixer to obtain a primary base material;
2) grinding the base material preliminarily dispersed in the step 1) by using a three-roller mill to obtain a heat-conducting base material;
3) and sequentially adding an auxiliary agent and insulating heat-conducting powder with the granularity of more than 15 mu m into the heat-conducting base material, and uniformly stirring in a planetary stirring device to form the final easy-grinding high-heat-conducting insulating hole plugging slurry.
In a specific embodiment, the rotating speed of the roller mill in the step 2) is 200r/min-300r/min, and the roller mill is carried out until the fineness is below 15 micrometers; preferably, the rotation speed of stirring in the step 3) is 1500r/min-2000r/min, and the time duration is 2-5 hours.
On the other hand, the easy-grinding high-thermal-conductivity insulation plug hole slurry or the easy-grinding high-thermal-conductivity insulation plug hole slurry prepared by the method is applied to plug holes on ceramic substrates and 5G high-frequency or high-power plates.
Compared with the prior art, the invention has the following beneficial effects:
the high-frequency and high-power printed circuit board used in the 5g field needs the plugging slurry with higher heat conductivity coefficient and lower thermal expansion coefficient to be matched with the printed circuit board, and in order to improve the grinding efficiency after plugging and reduce the material cost of the grinding process, the cured slurry needs to have the characteristic of easy grinding. At present, the whole slurry of the heat-conducting hole-plugging slurry needs to be ground by a three-roller machine, so that the powder with the particle size larger than 15 micrometers cannot be used in the selection of heat-conducting powder. The heat-conducting powder with small particle size has large oil absorption, which easily causes the rapid increase of system viscosity, and the heat-conducting performance is difficult to be improved because the powder with small particle size is fully wrapped by resin and the interface thermal resistance is large.
The easily-grinded high-thermal-conductivity insulation plug hole slurry provided by the invention can realize a high thermal conductivity effect by matching different shapes and different particle sizes of insulation powder, and can improve the storage stability of a system and the easily-grinded performance of the cured slurry. The preparation method provided by the invention can ensure that the small-particle-size powder is uniformly dispersed and the whole slurry system is more stable. The small-particle-size powder, the resin, the auxiliary agent and the curing agent are uniformly ground by a three-roll mill, so that the agglomeration phenomenon of the small-particle-size powder can be avoided, and the thixotropic property of the system can be improved due to better compatibility with the resin; the powder with large particle size has small specific surface area, so that the filling amount of the powder can be obviously improved, the powder with large particle size has lower interface thermal resistance, and the powder with large particle size have synergistic effect to improve the heat conductivity coefficient and realize high heat conduction effect.
The invention can further improve the storage stability of the system and improve the easy grinding performance of the solidified slurry by grading the insulating powder with different shapes and particle sizes and selecting proper resin and auxiliary agent.
After the insulation plug hole slurry is cured under proper curing conditions, the thermal expansion coefficient is ultralow, the insulation plug hole slurry can be matched with a ceramic substrate, and the glass transition temperature is high. In addition, due to the use of the graded powder with specific shape and granularity, the filling amount can be obviously increased, the sagging phenomenon of slurry in the baking process can be improved, and the high-selectivity hole plugging condition can be met.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting.
As shown in fig. 1, the easily-grinded high-thermal-conductivity insulation plug hole paste is prepared by the following steps:
1) weighing resin, curing agent and insulating heat-conducting powder with the granularity of less than or equal to 15 micrometers according to a proportion, and uniformly mixing the materials by a high-speed mixer to obtain a primary dispersed base material;
2) performing roller milling on the primarily dispersed base material by using a three-roller mill, controlling the fineness to be less than 15 micrometers, and further improving the dispersion performance of the powder in the resin to obtain a heat-conducting base material;
3) sequentially adding an auxiliary agent and insulating heat-conducting powder with the particle size larger than 15 micrometers into the heat-conducting base material, and stirring for 0.5h in a planetary stirring device in vacuum to form the final heat-conducting slurry.
Wherein, the weight percentage of the resin, the curing agent, the insulating heat-conducting powder and the auxiliary agent is 80 to 93 weight percent of the insulating heat-conducting powder, 6 to 15 weight percent of the resin, 0.2 to 2 weight percent of the curing agent and 0.8 to 3 weight percent of the auxiliary agent.
The weight percentages of the insulating and heat-conducting powder include but are not limited to 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92% and 93%; weight percentages of resin include, but are not limited to, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%; the weight percentage of the curing agent includes but is not limited to 0.3%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2%; the weight percentage of the auxiliary agent includes, but is not limited to, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%.
The insulating heat-conducting powder comprises insulating heat-conducting powder with the average grain diameter of 0.5-1 mu m and insulating heat-conducting powder with the average grain diameter of 10-15 mu m, and the maximum grain diameter of the insulating powder is less than or equal to 40 mu m. In the preparation process, the insulating heat-conducting powder is screened according to the particle size, and the insulating heat-conducting powder with different particle sizes is added in different steps. The powder with small particle size can prevent slurry from sagging in the baking process so as to improve the grindability, and the powder with large particle size can obviously improve the addition of the filler so as to improve the heat conductivity.
The insulating heat-conducting powder is at least two of boron nitride, aluminum oxide and aluminum nitride; the shape of the insulating heat-conducting powder is at least two combinations of sheet, sphere-like, spherical and angular; in a preferred scheme, the insulating heat-conducting powder is mixed powder of aluminum oxide and aluminum nitride or mixed powder of aluminum oxide and boron nitride, and the aluminum nitride and the boron nitride have low density, so that the slurry can be prevented from flowing vertically, the high-selectivity hole plugging condition can be met, and the solidified slurry has the characteristic of easy grinding. In a more preferable scheme, the alumina powder and the boron nitride mixed powder are spherical, spheroidal or angular, and the alumina powder is modified aiming at a resin system, so that the modified alumina powder can improve the compatibility with the resin, obviously reduce the viscosity of the system, and improve the addition of a filler, thereby improving the heat conductivity of the product. The boron nitride powder is flaky, and the mass ratio of the aluminum oxide powder to the boron nitride powder is 80: 1-10: 1. The spherical/spheroidal and angular powder is filled in the gaps of the flaky powder to form more compact accumulation, and the heat conductivity is improved.
Specifically, the modified alumina powder is mainly used for modifying an epoxy system, a silicon-oxygen bond in a silane coupling agent and a hydroxyl group on the surface of the alumina powder are utilized to generate a chemical bond, and an organic molecule is tightly coated on the surface of the powder through the acting force of the chemical bond, so that the surface of the powder is organized, and the compatibility with an organic system is improved. The specific modification method is, for example, chemical coupling modification, wherein dipropylene glycol methyl ether is used as a solvent, and the weight ratio of alumina powder: stirring the silane coupling agent for 2 to 5 hours at the ratio of 1000:1.4, and baking the mixture for 1.5 to 3 hours at the temperature of 130 ℃ to obtain the modified powder. The silane coupling agent may be at least one of vinyltris- (beta-methoxyethoxysilane), gamma-mercaptopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and beta- (3, 4-epoxyhexyl) ethyltrimethoxysilane.
The resin is liquid epoxy resin, does not contain organic solvent, and comprises one or a combination of more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin, organic silicon modified epoxy resin, special polyfunctional epoxy resin and the like, but is not limited to the above. The liquid epoxy resin is used as the polymer matrix resin of the insulating heat-conducting slurry, and has excellent physical property, electric insulating property and bonding property. In a preferred scheme, the liquid epoxy resin is one or a combination of liquid bisphenol A epoxy resin, bisphenol F epoxy resin and special multifunctional epoxy resin, and the resin has the characteristics of low viscosity, excellent chemical resistance, high temperature resistance, high crosslinking density and the like.
The curing agent is at least one of amino resins, imidazoles, organic acid anhydrides and dicyandiamide. The curing agent and the main resin have long storage period and have good physical and mechanical properties after being cured at a proper baking temperature.
The auxiliary agent comprises wetting dispersant, diluent and the like; the wetting dispersant is one or the combination of two of modified polysiloxane or polyurethane compounds; the diluent is epoxy active diluent which is one or a combination of more of monofunctional glycidyl ether or polyfunctional glycidyl ether; the wetting dispersant can uniformly disperse all components, and the epoxy diluent contains an active epoxy functional group, participates in reaction, is used for adjusting viscosity, and improves the storage stability of the heat-conducting slurry. The auxiliary agent can improve the excellent stability of the insulating and heat-conducting slurry dispersion system and improve the stability according to the type of the auxiliary agent.
The invention is further illustrated, but not limited, by the following more specific examples.
The modified alumina powder used in the examples was prepared by the following method:
dipropylene glycol methyl ether is used as a solvent, and the weight ratio of alumina powder: the amount of the silane coupling agent (gamma-mercaptopropyltrimethoxysilane) is 1000:1.4, the mixture is stirred for 3 hours and is baked for 2 hours at the temperature of 130 ℃, and the modified powder is obtained.
Example 1
The embodiment provides an insulating and heat-conducting slurry, which comprises the following components in percentage by mass: 3% of liquid bisphenol A epoxy resin, 5% of liquid bisphenol F epoxy resin, 0.6% of curing agent (Japanese monosodium glutamate PN-40, imidazoles), 79.5% of modified spherical alumina (D50 is 14 μm), 10% of modified flaky alumina (D50 is 7 μm or less), 2% of flaky boron nitride (average particle size is 1 μm or less), and 1.9% of p-tert-butylphenyl glycidyl ether.
The preparation method comprises the following steps:
1. weighing bisphenol A type epoxy resin, bisphenol F type epoxy resin, imidazole curing agent, modified spherical alumina with the granularity not more than 15 mu m, modified flaky alumina and flaky boron nitride according to the content in the formula, uniformly mixing, then performing roll milling on a three-roll mill, and controlling the gap between the rolls to roll the mixture for three times to obtain the base material, wherein the fineness of the roll milling is less than 15 mu m;
2. sequentially adding p-tert-butylphenyl glycidyl ether and large-particle-size heat-conducting powder with the particle size of more than 15 mu m into the base material while stirring, stirring at a high speed, transferring the stirred slurry into a vacuum stirrer, and stirring for 2 hours in vacuum;
3. and (3) setting a defoaming program for the vacuum defoamed slurry in a revolution and rotation defoaming machine to obtain the heat-conducting slurry.
Comparative example 1
The comparative example provides an insulating heat-conducting slurry which comprises, by mass, 3% of liquid bisphenol A epoxy resin, 5% of liquid bisphenol F epoxy resin, 0.6% of curing agent (Japanese Ajinomoto PN-40, imidazoles), 79.5% of modified spherical alumina (the maximum particle size is less than or equal to 15 mu m), 10% of modified flaky alumina (D50 is less than or equal to 7 mu m), 2% of flaky boron nitride (the average particle size is less than or equal to 1 mu m), and 1.9% of p-tert-butylphenyl glycidyl ether.
The preparation method comprises the following steps:
1. weighing bisphenol A type epoxy resin, bisphenol F type epoxy resin, a curing agent, all modified spherical alumina, modified flaky alumina, flaky boron nitride and p-tert-butylphenyl glycidyl ether according to the formula, preliminarily mixing, then performing roller milling on a three-roller machine, and performing roller milling by controlling gaps among rollers to obtain preliminary slurry, wherein the fineness of the roller milling is less than 15 micrometers for three times;
2. transferring the slurry to a planetary stirrer for vacuum stirring for 2 h;
3. and (3) setting a defoaming program in the revolution and rotation defoaming machine for vacuum defoaming of the stirred slurry to obtain the heat-conducting slurry.
Comparative example 2
The embodiment provides an insulating and heat-conducting slurry, which comprises the following components in percentage by mass: 10% of liquid novolac epoxy resin (dow), 0.8% of curing agent (japanese gourmet PN-40, imidazoles), 84% of modified spherical alumina (D100 ═ 15 μm), 4.2% of flake boron nitride (D50 ═ 3 μm), and 1% of butanediol diglycidyl ether.
1. Weighing the liquid novolac epoxy resin, the imidazole curing agent and the flaky boron nitride according to the content in the formula, uniformly mixing, then performing roller milling on a three-roller machine, and performing roller milling for three times by controlling gaps among rollers to obtain a base material with the fineness of less than 15 micrometers;
2. sequentially adding butanediol diglycidyl ether and the modified spherical heat-conducting powder into the base material while stirring for high-speed stirring, and transferring the stirred slurry into a vacuum stirrer for vacuum stirring for 2 hours;
3. and (3) setting a defoaming program in the revolution and rotation defoaming machine for vacuum defoaming of the vacuum-stirred slurry to obtain the heat-conducting slurry.
Example 2
The embodiment provides an insulating and heat-conducting slurry, which comprises the following components in percentage by mass: 10% of liquid novolac epoxy resin (dow), 0.8% of curing agent (japanese gourmet PN-40, imidazoles), 84% of modified spherical alumina (D50 ═ 13 μm), 4.2% of flake boron nitride (D50 ═ 3 μm), and 1% of butanediol diglycidyl ether.
1. Weighing the liquid novolac epoxy resin, the imidazole curing agent and the flaky boron nitride according to the content in the formula, uniformly mixing, then performing roller milling on a three-roller machine, and performing roller milling three times by controlling gaps among rollers, wherein the fineness is less than 15 microns, so as to obtain a base material;
2. sequentially adding butanediol diglycidyl ether and the modified spherical heat-conducting powder into the base material while stirring for high-speed stirring, and transferring the stirred slurry into a vacuum stirrer for vacuum stirring for 2 hours;
3. and (3) setting a defoaming program in the revolution and rotation defoaming machine for vacuum defoaming of the vacuum-stirred slurry to obtain the heat-conducting slurry.
Example 3
The embodiment provides an insulating and heat-conducting slurry, which comprises the following components in percentage by mass: 6% of bisphenol A epoxy resin, 3% of special bifunctional epoxy resin, 0.6% of curing agent (Japanese monosodium glutamate PN-40, imidazoles), 85.3% of modified spherical alumina (D50 ═ 10 micrometers), 4.1% of flake boron nitride (D50 ═ 3 micrometers) and 1% of ethylene glycol diglycidyl ether (south Asia).
The preparation method comprises the following steps:
1. weighing bisphenol A type epoxy resin, special bifunctional epoxy resin, imidazole curing agent and flaky boron nitride according to the content in the formula, uniformly mixing, and then performing roller milling on a three-roller mill, wherein the fineness is less than 15 microns by controlling the gap between the rollers and performing roller milling for three times to obtain a base material;
2. sequentially adding tert-butylphenyl glycidyl ether and the modified spherical alumina large-particle-size heat-conducting powder into the base material while stirring, stirring at a high speed, transferring the stirred slurry into a vacuum stirrer, and stirring for 2 hours in vacuum;
3. and (3) setting a defoaming program in the revolution and rotation defoaming machine for vacuum defoaming of the vacuum-stirred slurry to obtain the heat-conducting slurry.
Example 4
The embodiment provides an insulating and heat-conducting slurry, which comprises the following components in percentage by mass: 10% of an organosilicon-modified epoxy resin, 0.1% of a curing agent (japanese gourmet PN-40, imidazole), 0.6% of isocyanate, 78.3% of modified angular alumina (D50 ═ 14 μm), 8% of lamellar boron nitride (D50 ═ 3 μm), and 3% of butanediol diglycidyl ether.
1. Weighing the organic silicon modified epoxy resin, the imidazole curing agent and the flaky boron nitride according to the content in the formula, uniformly mixing, then performing roller milling on a three-roller machine, and performing roller milling for three times by controlling gaps among rollers to obtain the base material with the fineness of less than 15 micrometers;
2. adding butanediol diglycidyl ether and modified angular alumina (D50 is 14 microns) large-particle-size heat-conducting powder into the base material while stirring, stirring at high speed, transferring the stirred slurry into a vacuum stirrer, and stirring for 2 hours in vacuum;
3. and (3) setting a defoaming program in the revolution and rotation defoaming machine for vacuum defoaming of the vacuum-stirred slurry to obtain the heat-conducting slurry.
Example 5
The embodiment provides an insulating and heat-conducting slurry, which comprises the following components in percentage by mass: 6% of bisphenol F epoxy resin, 4% of amino bifunctional epoxy resin, 0.6% of curing agent (Japan monosodium glutamate PN-40, imidazoles), 63.4% of modified angular alumina (D50 ═ 14 micrometers), 25% of flake boron nitride (D50 ═ 3 micrometers), and 1% of polypropylene glycol diglycidyl ether.
1. Weighing bisphenol F type epoxy resin, amino bifunctional epoxy resin, imidazole curing agent and flaky boron nitride (D50 is 3 microns) according to the content in the formula, uniformly mixing, then performing roller milling on a three-roller mill, and performing roller milling three times by controlling gaps among rollers, wherein the fineness is less than 15 microns, thus obtaining the base material;
2. adding polypropylene glycol diglycidyl ether and modified angular alumina (D50 is 14 microns) large-particle-size heat-conducting powder into the base material while stirring, stirring at high speed, transferring the stirred slurry into a vacuum stirrer, and stirring for 2 hours in vacuum;
3. and (3) setting a defoaming program in the revolution and rotation defoaming machine for vacuum defoaming of the vacuum-stirred slurry to obtain the heat-conducting slurry.
Example 6
The embodiment provides an insulating and heat-conducting slurry, which comprises the following components in percentage by mass: 6% of amino phenol trifunctional epoxy resin, 0.7% of curing agent (Japanese gourmet PN-40, imidazole), 68.3% of modified spherical alumina (D50 is 14 microns), 17% of modified angle-type alumina (D50 is 14 microns), 5% of flake aluminum nitride (D50 is 3 microns) and 3% of double-head epoxy resin.
1. Weighing the aminophenol trifunctional epoxy resin, the imidazole curing agent and the flaky aluminum nitride according to the content in the formula, uniformly mixing, then performing roller milling on a three-roller machine, and performing roller milling three times by controlling gaps among rollers to obtain a base material with the fineness of less than 15 micrometers;
2. adding double-end-enclosure epoxy resin, spheroidal alumina and modified angular alumina into the base material while stirring, stirring at a high speed, transferring the stirred slurry into a vacuum stirrer, and stirring for 2 hours in vacuum;
3. and (3) setting a defoaming program in the revolution and rotation defoaming machine for vacuum defoaming of the vacuum-stirred slurry to obtain the heat-conducting slurry.
The insulating and thermally conductive pastes of examples 1 to 6 and comparative examples 1 to 2 were subjected to a plug hole treatment. The hole plugging treatment mode adopts a vacuum screen printing process to plug the insulating heat-conducting slurry into the holes on the PCB.
The plugged PCB was baked under the baking conditions of 110 ℃x0.5 h +130 ℃x1 h +150 ℃x0.5 h, and the performance verification experiment was performed after baking and curing. The thermal expansion rates are data measured at 40-300 deg.C and are detailed in Table 1.
Table 1 insulation plug hole paste performance test data table
It can be seen from table 1 that the technical solution provided by the present invention adopts the compounding of different types of powders with different particle sizes, which can ensure proper printing process viscosity and reduce interface thermal resistance, thereby improving thermal conductivity; the technical scheme provided by the invention can solve the sagging phenomenon in the vertical baking process of the slurry, and greatly improves the easy grinding performance; meanwhile, the stability in the storage process can be improved and the service life of the slurry can be prolonged by adjusting the components of the formula.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The easily-ground high-thermal-conductivity insulation hole plugging slurry is characterized by comprising the following components in percentage by weight:
80-93 wt% of insulating heat-conducting powder;
6-15 wt% resin;
0.2-2 wt% of a curing agent;
0.8-3 wt% of auxiliary agent.
2. The easily-milled high-thermal-conductivity insulation plug hole paste according to claim 1, wherein the insulation and thermal-conductivity powder is selected from at least any two of boron nitride, aluminum oxide and aluminum nitride, preferably from aluminum oxide and aluminum nitride or from aluminum oxide and boron nitride.
3. The easily-grinded high-thermal-conductivity insulation plug hole paste as claimed in claim 1 or 2, wherein the shape of the insulation and thermal-conductivity powder is a combination of at least any two of a sheet shape, a sphere-like shape, a spherical shape or an angular shape; preferably, the insulating heat-conducting powder is spherical, spheroidal or angular alumina powder and flaky boron nitride powder; more preferably, the alumina powder is modified aiming at a resin system, and the mass ratio of the alumina powder to the boron nitride powder is 80: 1-10: 1.
4. The easily-milled high thermal conductivity insulation plug hole paste according to claim 3, wherein the insulation thermal conductive powder comprises small insulation thermal conductive powder with average particle size of 0.5-1 μm and large insulation thermal conductive powder with average particle size of 10-15 μm, and the maximum particle size of the insulation thermal conductive powder is not more than 40 μm; preferably, the mass ratio of the small-particle insulating heat-conducting powder to the large-particle insulating heat-conducting powder is 5:1-50: 1.
5. The easily-grinded high-thermal-conductivity insulation plug hole paste according to claim 1, wherein the resin is a liquid epoxy resin without organic solvent, preferably at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, silicone modified epoxy resin, and multifunctional epoxy resin; more preferably one or a combination of more of liquid bisphenol A epoxy resin, bisphenol F epoxy resin or special polyfunctional epoxy resin.
6. The easily-grinded high-thermal-conductivity insulation plug hole paste according to claim 1, wherein the curing agent is at least one selected from amino resins, imidazoles, organic acid anhydrides, and dicyandiamide; imidazoles and dicyandiamide are preferred.
7. The easily milled, highly thermally conductive insulating via plug paste according to claim 1, wherein said adjuvants comprise wetting dispersants, diluents; preferably, the wetting and dispersing agent is selected from one or two combinations of modified polysiloxane or polyurethane compounds; the diluent is epoxy reactive diluent, preferably one or a combination of more of monofunctional glycidyl ether or multifunctional glycidyl ether.
8. The method for preparing the easily-milled high-thermal-conductivity insulation plug hole paste according to any one of claims 1 to 7, comprising the following steps:
1) uniformly mixing resin, a curing agent and insulating heat-conducting powder with the granularity not more than 15 mu m in a certain proportion by a high-speed mixer to obtain a primary base material;
2) grinding the base material preliminarily dispersed in the step 1) by using a three-roller mill to obtain a heat-conducting base material;
3) and sequentially adding an auxiliary agent and insulating heat-conducting powder with the granularity larger than 15 mu m into the heat-conducting base material, and uniformly stirring in a planetary stirring device to form the final easily-ground high-heat-conducting insulating hole plugging slurry.
9. The preparation method of claim 8, wherein the rotation speed of the roller mill in the step 2) is 200r/min-300r/min, and the roller mill is carried out until the fineness is below 15 microns; preferably, the rotation speed of stirring in the step 3) is 1500r/min-2000r/min, and the time duration is 2-5 hours.
10. Use of the easily milled high thermal conductivity insulating plug hole paste according to any one of claims 1 to 7 or the easily milled high thermal conductivity insulating plug hole paste prepared by the preparation method according to any one of claims 8 to 9 for plug holes in ceramic substrates and 5G high-frequency or high-power plates.
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| CN202210802794.8A CN115083660A (en) | 2022-07-07 | 2022-07-07 | Easily-ground high-thermal-conductivity insulation hole plugging slurry, preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116694275A (en) * | 2023-04-26 | 2023-09-05 | 湖北三选科技有限公司 | Liquid epoxy plastic package material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116694275A (en) * | 2023-04-26 | 2023-09-05 | 湖北三选科技有限公司 | Liquid epoxy plastic package material and preparation method thereof |
| CN116694275B (en) * | 2023-04-26 | 2024-03-08 | 湖北三选科技有限公司 | Liquid epoxy plastic package material and preparation method thereof |
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