阅读说明：本技术 高导热高绝缘的热塑性树脂组合物及其制备方法和应用 (High-thermal-conductivity high-insulation thermoplastic resin composition and preparation method and application thereof ) 是由 李政 何志球 于 2019-11-22 设计创作，主要内容包括：本发明涉及集成电路互连介质材料技术领域,尤其涉及一种高导热高绝缘的热塑性树脂组合物及其制备方法和应用。一种高导热高绝缘的热塑性树脂组合物的制备方法,包括以下步骤：(1)端羧基聚硅氧烷改性环氧树脂的制备；(2)枝状三维氧化石墨烯的制备；(3)高导热高绝缘的热塑性树脂组合物的制备：将所述枝状三维氧化石墨烯加入所述端羧基聚硅氧烷改性环氧树脂中,混合搅拌得到所述高导热高绝缘的热塑性树脂组合物。本发明的目的在于提出一种高导热高绝缘的热塑性树脂组合物的制备方法,通过该制备方法制备得到的树脂组合物具有高导热性高绝缘性,其导热系数可根据配方进行调整,导热性能好,绝缘性能优异,适用范围广。(The invention relates to the technical field of integrated circuit interconnection dielectric materials, in particular to a high-thermal-conductivity high-insulation thermoplastic resin composition, and a preparation method and application thereof. A preparation method of a thermoplastic resin composition with high thermal conductivity and high insulation comprises the following steps: (1) preparing carboxyl-terminated polysiloxane modified epoxy resin; (2) preparing dendritic three-dimensional graphene oxide; (3) preparation of highly thermally conductive and highly insulating thermoplastic resin composition: and adding the dendritic three-dimensional graphene oxide into the carboxyl-terminated polysiloxane modified epoxy resin, and mixing and stirring to obtain the high-thermal-conductivity high-insulation thermoplastic resin composition. The invention aims to provide a preparation method of a high-thermal-conductivity high-insulation thermoplastic resin composition, and the resin composition prepared by the preparation method has high thermal conductivity and high insulation, the thermal conductivity coefficient of the resin composition can be adjusted according to a formula, and the resin composition has good thermal conductivity, excellent insulation performance and wide application range.)

1. A preparation method of a thermoplastic resin composition with high thermal conductivity and high insulation is characterized by comprising the following steps:

(1) preparation of carboxyl-terminated polysiloxane modified epoxy resin: stirring and heating hydroxyl-terminated polysiloxane to 100-150 ℃ under the vacuum condition of 0.05-0.1 Mpa, keeping for 2-3 h, dropwise adding an anhydride compound, and continuously reacting for 2-4 h to generate modified carboxyl-terminated polysiloxane; adding the modified carboxyl-terminated polysiloxane into epoxy resin, adding an accelerant for dispersing for 30-60 min, heating to 60-100 ℃ under a stirring state, and reacting for 2-3 h to generate thermoplastic carboxyl-terminated polysiloxane modified epoxy resin;

(2) preparing dendritic three-dimensional graphene oxide: adding zinc ion electrolyte into a mixed solution of absolute ethyl alcohol and deionized water, performing pre-dispersion for 30-60 min in a magnetic stirring manner to obtain a zinc ion electrolyte mixed solution, adding an ultrasonically dispersed carboxyl functionalized graphene oxide mixed solution into the zinc ion electrolyte mixed solution, and performing vacuum drying for 6-12 h under the conditions of 0.05-0.1 Mpa and 60-90 ℃ to obtain dendritic three-dimensional graphene oxide;

(3) preparation of highly thermally conductive and highly insulating thermoplastic resin composition: adding the dendritic three-dimensional graphene oxide into the carboxyl-terminated polysiloxane modified epoxy resin, and mixing and stirring to obtain the high-thermal-conductivity high-insulation thermoplastic resin composition;

in the step (3), the mass ratio of the dendritic three-dimensional graphene oxide to the carboxyl-terminated polysiloxane modified epoxy resin is 20: 80-70: 30.

2. The method for preparing a thermoplastic resin composition with high thermal conductivity and high insulation according to claim 1, wherein the hydroxyl-terminated polysiloxane has a viscosity of 3000 to 100000cps in the step (1).

3. The method for preparing a thermoplastic resin composition with high thermal conductivity and high insulation according to claim 1, wherein in the step (1), the acid anhydride compound is any one of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylendomethylenetetrahydrophthalic anhydride, and the mass ratio of the hydroxyl-terminated polysiloxane to the acid anhydride compound is 100: 5-30;

the epoxy resin is any one of bisphenol A epoxy resin, bisphenol F epoxy resin and phenolic aldehyde modified epoxy resin, and the mass ratio of the epoxy resin to the modified carboxyl-terminated polysiloxane is 100:20 to 40.

4. The method for preparing a thermoplastic resin composition with high thermal conductivity and high electrical insulation according to claim 1, wherein in the step (1), the accelerator is any one of dimethylimidazole and diethyltetramethylimidazole, and the mass ratio of the epoxy resin to the accelerator is 100: 0.1 to 2.

5. The method for preparing a thermoplastic resin composition with high thermal conductivity and high insulation according to claim 1, wherein in the step (2), the zinc ion electrolyte is a zinc acetate compound, and the mass ratio of the absolute ethyl alcohol to the deionized water is 1: 1, the mass ratio of the mixed solution of the absolute ethyl alcohol and the deionized water to the zinc ion electrolyte is 100: 20-60, and the pre-dispersion temperature of the zinc ion electrolyte is 60-90 ℃;

the mixed solution of the carboxyl functionalized graphene oxide is a mixture of the carboxyl functionalized graphene oxide and the absolute ethyl alcohol and deionized water, the mass ratio of the mixed solution of the absolute ethyl alcohol and the deionized water to the carboxyl functionalized graphene oxide is the same as that of the mixed solution of the absolute ethyl alcohol and the deionized water to the zinc ion electrolyte, the carboxyl functionalized graphene oxide is pre-dispersed under the conditions that the ultrasonic power is 150W 80% and the temperature is 30-40 ℃, and the ultrasonic time is 20-30 min;

the mass ratio of the zinc ion electrolyte mixed solution to the carboxyl functionalized graphene oxide mixed solution is 1: 40-80.

6. The preparation method of the thermoplastic resin composition with high thermal conductivity and high insulation according to claim 1, wherein in the step (3), the branched three-dimensional graphene oxide is added to the carboxyl-terminated polysiloxane modified epoxy resin in multiple steps, and before each step, a mixed solution of the branched three-dimensional graphene oxide and the carboxyl-terminated polysiloxane modified epoxy resin needs to be uniformly stirred for 3-4 hours.

7. The method for preparing a thermoplastic resin composition with high thermal conductivity and high electrical insulation according to claim 1, wherein the mixing and stirring manner in the step (3) is mechanical stirring.

8. A thermoplastic resin composition with high thermal conductivity and high insulation, which is prepared by the preparation method of any one of claims 1 to 7.

9. The thermoplastic adhesive film using the thermoplastic resin composition with high thermal conductivity and high insulation of claim 8, wherein the thermoplastic resin composition with high thermal conductivity and high insulation is prepared by adding a solvent, an epoxy curing agent and a curing accelerator into the thermoplastic resin composition with high thermal conductivity and high insulation to obtain a mixed adhesive solution, and then coating the mixed adhesive solution on a PI base film in a slit coating manner and drying the PI base film.

10. The thermoplastic adhesive film using the thermoplastic resin composition with high thermal conductivity and high insulation according to claim 9, wherein the coating thickness of the mixed adhesive solution is 10 to 30 μm, the drying temperature is 60 to 90 ℃, and the drying time is 6 to 9 hours.

Technical Field

The invention relates to the technical field of integrated circuit interconnection dielectric materials, in particular to a high-thermal-conductivity high-insulation thermoplastic resin composition, and a preparation method and application thereof.

Background

With the rapid development of microelectronic high-density assembly technology and integration technology, the assembly density of electronic devices can be rapidly increased, so that the volumes of electronic components and logic circuits are reduced by tens of millions of times, the heat generated by the electronic devices is rapidly increased, and the composite insulating material with high thermal conductivity is very important for ensuring that the electronic components can still normally work with high reliability at ambient temperature.

Epoxy resins are widely used resins, have excellent processability, good mechanical properties, high electrical insulation, corrosion resistance and low density, but the low thermal conductivity (0.2W/(m.K)) limits the application of the epoxy resins in electronic packaging, chemical heat exchange equipment and the like. Carbon-based materials are used to prepare thermally conductive composites because they exhibit excellent high thermal conductivity. The graphene has excellent heat-conducting property, has extremely high heat-conducting coefficient which can reach 5300W/(m.K), is 10-30 times of copper and aluminum, is light in weight, and meets the development direction of modern electronic device industry-the light, thin, short and small heat-radiating requirement. However, it has high conductivity while having high thermal conductivity, and in many cases, high insulation is required for adhesion in the electronics industry.

In addition, the adhesion between circuit board layers in the existing electronic industry uses a thermosetting insulating adhesive film, needs longer curing time, has higher requirements on storage conditions (generally needs higher requirements such as low temperature and low humidity), and is inconvenient to use; in addition, the heat conductivity of the formula of the system is poor, so that the heat conductivity coefficient of the adhesive film is generally not more than 0.2W/(m.K), and the application range of the adhesive film is limited.

Disclosure of Invention

In view of the problems of the background art, the present invention aims to provide a method for preparing a high thermal conductivity and high insulation thermoplastic resin composition, which changes the dispersion phase phenomenon of the common graphene oxide during filling, and can effectively improve the thermal conductivity of the resin composition by a continuous "thermal conductive chain" formed by dendritic three-dimensional graphene oxide under the condition of ensuring high insulation.

The invention also aims to provide a high-thermal-conductivity high-insulation thermoplastic resin composition, and the resin composition prepared by the preparation method has high thermal conductivity and high insulation property, the thermal conductivity coefficient of the resin composition can be adjusted according to a formula, and the resin composition has good thermal conductivity, excellent insulation property and wide application range.

Another object of the present invention is to provide a thermoplastic adhesive film using the highly thermally conductive and highly insulating thermoplastic resin composition, which has high thermal conductivity and high insulating property, can be stored at normal temperature, can ensure temperature transmission at the bonding interface and prevent electrical breakdown, and has thermoplasticity to improve production efficiency and simplify production requirements.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a thermoplastic resin composition with high thermal conductivity and high insulation comprises the following steps:

(1) preparation of carboxyl-terminated polysiloxane modified epoxy resin: stirring and heating hydroxyl-terminated polysiloxane to 100-150 ℃ under the vacuum condition of 0.05-0.1 Mpa, keeping for 2-3 h, dropwise adding an anhydride compound, and continuously reacting for 2-4 h to generate modified carboxyl-terminated polysiloxane; adding the modified carboxyl-terminated polysiloxane into epoxy resin, adding an accelerant for dispersing for 30-60 min, heating to 60-100 ℃ under a stirring state, and reacting for 2-3 h to generate thermoplastic carboxyl-terminated polysiloxane modified epoxy resin;

(2) preparing dendritic three-dimensional graphene oxide: adding zinc ion electrolyte into a mixed solution of absolute ethyl alcohol and deionized water, performing pre-dispersion for 30-60 min in a magnetic stirring manner to obtain a zinc ion electrolyte mixed solution, adding an ultrasonically dispersed carboxyl functionalized graphene oxide mixed solution into the zinc ion electrolyte mixed solution, and performing vacuum drying for 6-12 h under the conditions of 0.05-0.1 Mpa and 60-90 ℃ to obtain dendritic three-dimensional graphene oxide;

(3) preparation of highly thermally conductive and highly insulating thermoplastic resin composition: adding the dendritic three-dimensional graphene oxide into the carboxyl-terminated polysiloxane modified epoxy resin, and mixing and stirring to obtain the high-thermal-conductivity high-insulation thermoplastic resin composition;

in the step (3), the mass ratio of the dendritic three-dimensional graphene oxide to the carboxyl-terminated polysiloxane modified epoxy resin is 20: 80-70: 30.

The carboxyl-terminated polysiloxane modified epoxy resin (thermoplastic block compound) can be formed by modifying hydroxyl-terminated polysiloxane through an anhydride compound, and can be subjected to condensation reaction with epoxy resin, so that normal-temperature storage can be realized; in addition, the high heat resistance of the polysiloxane resin per se imparts performance stability to the synthetic product at high soldering temperatures; meanwhile, as the main resin epoxy resin has high insulation property and is used as a system continuous phase, the composition can be ensured to continuously maintain the high insulation property;

the high thermal conductivity of the graphene oxide is higher than that of the larger grain size, the high flatness and other factors, and the dendritic three-dimensional graphene oxide can enable phonons participating in heat transfer to be rapidly transmitted in a channel due to the formation of a conductive heat transfer channel and the increase of an effective contact area, so that the thermal conductivity of the dendritic three-dimensional graphene oxide is higher than that of the common graphene oxide, the thermal conductivity coefficient is increased from original 120W/(m.K) to 190W/(m.K), and the dendritic three-dimensional graphene oxide has the advantages of high porosity, high thermal conductivity, good thermal stability and the like;

therefore, the dendritic three-dimensional graphene oxide is filled in the carboxyl-terminated polysiloxane modified epoxy resin system, the carboxyl-terminated polysiloxane modified epoxy resin is a continuous phase, and the dendritic three-dimensional graphene oxide fills the carboxyl-terminated polysiloxane modified epoxy resin by utilizing the formed continuous heat conduction chain and also forms the continuous phase.

Preferably, in the step (1), the hydroxyl-terminated polysiloxane has a viscosity of 3000 to 100000 cps.

The polymerization degree is indirectly characterized by viscosity, the viscosity of the hydroxyl-terminated polysiloxane is limited to 3000-100000 cps, if the viscosity is lower than 3000cps, the molecular weight of the hydroxyl-terminated polysiloxane is too low, the polymer is easy to produce excessive branched chains, if the viscosity is higher than 100000cps, the molecular weight of the hydroxyl-terminated polysiloxane is too high, the hydroxyl-terminated polysiloxane is difficult to disperse in a mixing reaction, and meanwhile, the phenomenon of uneven reaction is easy to generate, and the service performances such as the heat conductivity, the heat resistance and the like of the composition are influenced.

Preferably, in the step (1), the acid anhydride compound is any one of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylendomethylenetetrahydrophthalic anhydride, and the mass ratio of the hydroxyl-terminated polysiloxane to the acid anhydride compound is 100: 5-30;

the epoxy resin is any one of bisphenol A epoxy resin, bisphenol F epoxy resin and phenolic aldehyde modified epoxy resin, and the mass ratio of the epoxy resin to the modified carboxyl-terminated polysiloxane is 100:20 to 40.

The hydroxyl-terminated polysiloxane is modified by an anhydride compound to generate anhydride modified polysiloxane with terminal carboxyl, and then the anhydride modified polysiloxane reacts with epoxy resin under the action of an accelerant to generate thermoplastic polysiloxane modified epoxy resin, so that the problem that a composition prepared by using conventional thermosetting epoxy resin needs high storage conditions such as low temperature and low humidity is solved, and the composition can be stored at normal temperature.

Preferably, in the step (1), the accelerator is any one of dimethylimidazole and diethyltetramethylimidazole, and the mass ratio of the epoxy resin to the accelerator is 100: 0.1 to 2.

The mass ratio of the epoxy resin to the accelerator is defined as 100: 0.1-2, the addition of the accelerator is beneficial to reducing the activation energy of the reaction, reducing the temperature required by the reaction and reducing the time required by the reaction, if the addition amount is too small, the purpose cannot be achieved, if the addition amount exceeds 2%, the reaction is over-accelerated, excessive branched chains are produced under the condition that the resin does not form a complete crosslinking system, and the mechanical property and the heat resistance of the carboxyl-terminated polysiloxane modified epoxy resin are reduced, so that the mechanical property, the heat resistance and other properties of the composition are reduced.

Preferably, in the step (2), the zinc ion electrolyte is a zinc acetate compound, and the mass ratio of the absolute ethyl alcohol to the deionized water is 1: 1, the mass ratio of the mixed solution of the absolute ethyl alcohol and the deionized water to the zinc ion electrolyte is 100: 20-60, and the pre-dispersion temperature of the zinc ion electrolyte is 60-90 ℃;

the mixed solution of the carboxyl functionalized graphene oxide is a mixture of the carboxyl functionalized graphene oxide and the absolute ethyl alcohol and deionized water, the mass ratio of the mixed solution of the absolute ethyl alcohol and the deionized water to the carboxyl functionalized graphene oxide is the same as that of the mixed solution of the absolute ethyl alcohol and the deionized water to the zinc ion electrolyte, the carboxyl functionalized graphene oxide is pre-dispersed under the conditions that the ultrasonic power is 150W 80% and the temperature is 30-40 ℃, and the ultrasonic time is 20-30 min;

the mass ratio of the zinc ion electrolyte mixed solution to the carboxyl functionalized graphene oxide mixed solution is 1: 40-80.

Preferably, the zinc ion electrolyte is any one of anhydrous zinc acetate and zinc acetate dihydrate.

The method comprises the steps of using a zinc ion electrolyte for providing a hybrid framework fulcrum, forming an ionic bond with a carboxyl in carboxyl functionalized graphene oxide by using zinc ions as a connecting point in a reaction, so that the carboxyl functionalized graphene oxide is connected, forming a graphene oxide material with a dendritic three-dimensional structure by using the zinc ions as the connecting point, and enabling phonons participating in heat transfer to be rapidly transmitted in a channel due to the formation of a conductive heat transfer channel and the increase of effective contact area, so that the heat conduction effect of the graphene oxide material is higher than that of common graphene oxide.

Preferably, in the step (3), the branched three-dimensional graphene oxide is added into the carboxyl-terminated polysiloxane modified epoxy resin in multiple steps, and before each step, a mixed solution of the branched three-dimensional graphene oxide and the carboxyl-terminated polysiloxane modified epoxy resin is added and uniformly stirred, wherein the mixing and stirring time is 3-4 hours.

The dendritic three-dimensional graphene oxide is added into the carboxyl-terminated polysiloxane modified epoxy resin in multiple steps, a continuous heat conducting chain formed by the dendritic three-dimensional graphene oxide is uniformly filled in the carboxyl-terminated polysiloxane modified epoxy resin system, and the formed thermoplastic resin composition has high heat conductivity and high insulation.

Preferably, in the step (3), the mixing and stirring manner is mechanical stirring.

Mechanical stirring and mixing are adopted in the preparation method of the composition, ultrasonic dispersion and grinding and other modes cannot be used, the dendritic structure of the dendritic three-dimensional graphene oxide can be protected, the structure is not easy to damage, the phenomenon that the dendritic three-dimensional graphene oxide is re-dispersed into particles in the mixing process is avoided, and therefore the thermal conductivity of the obtained composition is protected from being damaged.

A thermoplastic resin composition with high thermal conductivity and high insulation is prepared by the preparation method.

The thermoplastic resin composition with high thermal conductivity and high insulation, which is prepared by the preparation method of the thermoplastic resin composition with high thermal conductivity and high insulation, has high thermal conductivity and high insulation, the thermal conductivity coefficient of the thermoplastic resin composition can reach more than 5W/(m.K) according to the addition amount of the dendritic three-dimensional graphene oxide, the volume resistivity of the thermoplastic resin composition is more than or equal to 1012 (omega. cm), the thermal conductivity is good, and the insulation performance is excellent.

The thermoplastic adhesive film using the high-thermal-conductivity and high-insulation thermoplastic resin composition is prepared by adding a solvent, an epoxy curing agent and a curing accelerator into the high-thermal-conductivity and high-insulation thermoplastic resin composition to obtain a mixed adhesive solution, and then coating the mixed adhesive solution on a PI base film in a slit coating manner and drying.

The adhesive film prepared from the high-thermal-conductivity and high-insulation thermoplastic resin composition has high thermal conductivity and high insulation property, can be stored at normal temperature, can ensure the temperature transmission of a bonding interface and prevent electric breakdown, and has thermoplasticity which can improve the production efficiency and simplify the production requirement.

Preferably, the coating thickness of the mixed glue solution is 10-30 μm, the drying temperature is 60-90 ℃, and the drying time is 6-9 h.

Preferably, the solvent is any one or a combination of more of benzene, toluene, acetone, butanone, dimethylformamide, propylene glycol methyl ether and propylene glycol methyl ether acetate, and the mass ratio of the thermoplastic resin composition with high thermal conductivity and high insulation to the solvent is 100: 30-80 parts;

the epoxy curing agent is any one of dicyandiamide, organic urea, triphenyl phosphorus, diaminodiphenyl sulfone and polyamide, and the mass ratio of the high-thermal-conductivity high-insulation thermoplastic resin composition to the epoxy curing agent is 100: 5-20;

the curing accelerator is any one of dimethyl imidazole and diethyl tetramethyl imidazole, and the mass ratio of the high-thermal-conductivity high-insulation thermoplastic resin composition to the curing accelerator is 100: 0.01 to 1.

The coating thickness of the mixed glue solution is limited to 10-30 microns, if the coating thickness of the glue solution is too thin, the situation that the surface of the glue layer is not flat due to the exposure of heat conducting particles is easy to occur, and if the coating thickness of the glue solution is too thick, the heat conducting performance of the glue film is poor due to the fact that the heat conducting channel is lengthened and the transfer distance of heat flow is increased.

Compared with the prior art, the invention has the following beneficial effects:

1. the dendritic three-dimensional graphene oxide is filled in the carboxyl-terminated polysiloxane modified epoxy resin system, the carboxyl-terminated polysiloxane modified epoxy resin is a continuous phase, and the dendritic three-dimensional graphene oxide fills the carboxyl-terminated polysiloxane modified epoxy resin by utilizing a formed continuous heat conduction chain and also forms the continuous phase.

2. The hydroxyl-terminated polysiloxane is modified by an anhydride compound to generate anhydride modified polysiloxane with terminal carboxyl, and then the anhydride modified polysiloxane reacts with epoxy resin under the action of an accelerant to generate thermoplastic polysiloxane modified epoxy resin, so that the problem that a composition prepared by using conventional thermosetting epoxy resin needs high storage conditions such as low temperature and low humidity is solved, and the composition can be stored at normal temperature.

3. The adhesive film prepared from the high-thermal-conductivity and high-insulation thermoplastic resin composition has high thermal conductivity and high insulation property, can be stored at normal temperature, can ensure the temperature transmission of a bonding interface and prevent electric breakdown, has thermoplasticity, can improve the production efficiency and simplify the production requirement, and has a wide application range.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

And (3) performance testing:

1. and (3) measuring the heat conductivity coefficient: the method is characterized in that the method adopts an ASTM D5470 standard to carry out measurement, a steady-state heat flow method is adopted, a certain heat flow, pressure, the thickness of a test sample and the temperature difference between a hot plate and a cold plate are applied to the sample, and the heat conductivity coefficient of the sample is obtained.

2. And (3) volume resistivity measurement: the volume resistivity and the surface resistivity of the solid insulating material are measured by adopting a GBT 1410-2006 test method.