Bio-based light-cured heat-conducting insulating composite material, preparation method and application

Abstract

The invention provides a bio-based light-cured heat-conducting and insulating composite material, a preparation method and application, and relates to the technical field of radiation curing, and the bio-based light-cured heat-conducting and insulating composite material comprises a bio-based oligomer, a reactive diluent, a modified heat-conducting filler, a free radical photoinitiator and an organic silicon defoaming agent. The bio-based oligomer is selected as a main component of the photocuring coating, and compared with a coating prepared from petroleum-based acrylic resin in the prior art, the coating has the green and environment-friendly functions, and meanwhile, the harm to the environment caused by exploitation and processing of petrochemical products can be reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of radiation curing, and in particular to a bio-based light-cured thermally conductive insulating composite material, a preparation method and uses thereof. Background Art

[0002] As electronic devices develop towards thinner, smaller, and more integrated designs, higher requirements are placed on the heat dissipation and other properties of electronic packaging materials. The development of high-thermal-conductivity composite materials can quickly transfer heat from electronic devices during operation, ensuring the normal operation of the devices.

[0003] Conventional high-thermal-conductivity composite materials are primarily made by thermally curing a petroleum-based acrylic resin coating. The solvents released during the curing process can pose serious health and environmental risks, resulting in a heavy reliance on fossil resources and potential health and environmental hazards. Therefore, there is an urgent need to develop a high-thermal-conductivity composite material that is both fossil-free and environmentally friendly. Summary of the Invention

[0004] The present invention aims to provide a bio-based light-cured thermally conductive insulating composite material, a preparation method and uses thereof, in order to at least partially solve at least one of the above-mentioned technical problems.

[0005] To solve the above technical problems, the first aspect of the present invention provides a bio-based light-cured thermally conductive insulating composite material, comprising: a bio-based oligomer, a reactive diluent, a modified thermally conductive filler, a free radical photoinitiator, and a silicone defoaming agent.

[0006] According to a preferred embodiment of the present invention, the mass parts of each component are as follows:

[0007]

[0008]

[0009] According to a preferred embodiment of the present invention, the bio-based oligomer is at least one of epoxy soybean oil acrylate, castor oil-based polyurethane acrylate, linseed oil-based acrylate, and cardanol-based acrylate.

[0010] According to a preferred embodiment of the present invention, the reactive diluent is: isobornyl acrylate, 2-phenoxyethyl acrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tris(2-hydroxyethyl)isocyanate triacrylate, dipentaerythritol hexaacrylate or a combination of several thereof.

[0011] According to a preferred embodiment of the present invention, the photoinitiator is: 2-hydroxy-2-methyl-1-phenylpropanone-1, 2-phenyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholinopropanone-1, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-difluoro-3-(1H-pyrrolyl-1)phenyl)titaniumocene, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-(3-benzoylphenyl)guanidine propionate, 9-anthramethyl N,1-(anthraquinone-2-yl)ethylimidazole carboxylate, N-diethylcarbamate, or a combination of the following.

[0012] According to a preferred embodiment of the present invention, the modified thermally conductive particle filler is a thermally conductive particle filler modified by a silane coupling agent or a titanate coupling agent.

[0013] According to a preferred embodiment of the present invention, the thermally conductive filler is at least one of artificial diamond, boron nitride, aluminum nitride, silicon nitride and aluminum oxide.

[0014] To solve the above technical problems, the second aspect of the present invention provides a method for preparing the above-mentioned bio-based light-cured thermally conductive and insulating composite material, comprising the following steps:

[0015] S1. Evenly mix the bio-based oligomer, the active diluent, the modified thermal conductive filler, the free radical photoinitiator, and the defoaming agent to obtain a mixed solution;

[0016] S2. The mixed solution is prepared into a film by a wet coating process, and then irradiated and cured under UV light.

[0017] According to a preferred embodiment of the present invention, before step S1, the method further includes:

[0018] Add a thermally conductive filler to an ethanol solution of KH-570, heat and stir at 80° C. for 1 hour, filter and dry to obtain a modified thermally conductive filler; the thermally conductive filler is at least one of artificial diamond, boron nitride, aluminum nitride, silicon nitride and aluminum oxide.

[0019] To solve the above technical problems, the third aspect of the present invention provides a use of the bio-based photocurable thermally conductive insulating composite material as described in any one of the above items, wherein the bio-based photocurable thermally conductive insulating composite material is used for microelectronic packaging.

[0020] In summary, the bio-based light-cured thermally conductive insulating composite material prepared by the present invention using bio-based oligomers, reactive diluents, modified thermally conductive fillers, free radical photoinitiators, and silicone defoaming agents has at least the following beneficial effects compared to the prior art:

[0021] 1. Bio-based oligomers are used as the main component of the photocurable coating. Compared with the coating prepared with petroleum-based acrylic resin used in the existing technology, it has the function of being green and environmentally friendly, and can also reduce the harm to the environment caused by the mining and processing of petrochemical products.

[0022] 2. The film is prepared using a light-curing process. Compared with existing heat-curing thermal conductive materials, it is 100% solid-containing and has the advantages of fast curing speed, energy saving and environmental protection. DETAILED DESCRIPTION

[0023] The features and exemplary embodiments of various aspects of the present invention will be described in detail below. In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail. It should be understood that the specific embodiments described herein are only configured to explain the present invention and are not configured to limit the present invention. For those skilled in the art, the present invention can be implemented without the need for some of these specific details. The following description of the embodiments is merely to provide a better understanding of the present invention by illustrating examples of the present invention.

[0024] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article, or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or elements inherent to such process, method, article, or device. In the absence of further limitations, the elements defined by the phrase "comprising..." do not exclude the presence of other identical elements in the process, method, article, or device comprising the elements.

[0025] An embodiment of the present invention provides a bio-based light-cured thermally conductive insulating composite material, comprising: a bio-based oligomer, a reactive diluent, a modified thermally conductive filler, a free radical photoinitiator, and an organosilicon defoaming agent.

[0026] In a preferred embodiment, the mass parts of each component are as follows:

[0027]

[0028] Optionally, the bio-based oligomer is at least one of epoxy soybean oil acrylate, castor oil-based (polyurethane) acrylate, linseed oil-based acrylate, and cardanol-based acrylate.

[0029] Optionally, the active diluent is: isobornyl acrylate, 2-phenoxyethyl acrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tris(2-hydroxyethyl)isocyanate triacrylate, dipentaerythritol hexaacrylate or a combination of several thereof.

[0030] Optionally, the photoinitiator is: 2-hydroxy-2-methyl-1-phenylpropanone-1, 2-phenyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholinopropanone-1, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-difluoro-3-(1H-pyrrolyl-1)phenyl)titanium ocene, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-(3-benzoylphenyl)guanidine propionate, 9-anthracenyl N,1-(anthraquinone-2-yl)ethylimidazole carboxylate, N-diethylcarbamate, or a combination of the following.

[0031] Optionally, the modified thermally conductive particle filler is a thermally conductive particle filler modified by a silane coupling agent or a titanate coupling agent.

[0032] Optionally, the thermally conductive filler is at least one of artificial diamond, boron nitride, aluminum nitride, silicon nitride and aluminum oxide.

[0033] An embodiment of the present invention further provides a method for preparing a bio-based light-cured thermally conductive insulating composite material, the method comprising the following steps:

[0034] S1. Evenly mix the bio-based oligomer, the active diluent, the modified thermal conductive filler, the free radical photoinitiator, and the defoaming agent to obtain a mixed solution;

[0035] For example, the material-based oligomer, reactive diluent, modified thermal conductive filler, free radical photoinitiator, and defoamer can be uniformly mixed in a homogenizing degassing machine or a sand mill under light-proof conditions to obtain a mixed solution.

[0036] Preferably, before this step, a thermally conductive filler can be added to the ethanol solution of KH-570, heated and stirred at 80°C for 1 hour, and then filtered and dried to obtain a modified thermally conductive filler; the thermally conductive filler is at least one of artificial diamond, boron nitride, aluminum nitride, silicon nitride and aluminum oxide.

[0037] S2. The mixed solution is prepared into a film by a wet coating process, and then irradiated and cured under UV light.

[0038] Preferably, the irradiation time is 3-10 min.

[0039] The bio-based light-cured thermally conductive insulating composite material of the present invention is prepared by Examples 1-5, and the existing high thermal conductive composite material is prepared by Comparative Examples 1-2.

[0040] Example 1

[0041] A method for preparing a bio-based light-cured thermally conductive and insulating composite material, comprising:

[0042] Step 1: Take 30 parts by weight of epoxy soybean oil acrylate, 20 parts of isobornyl acrylate, 5 parts of photoinitiator 2-hydroxy-2-methyl-1-phenylacetone, 80 parts of modified boron nitride filler and 1 part of BYK-A535 defoamer, stir and mix evenly in the dark, and degas to obtain a UV-curable composite solution;

[0043] Step 2: wet-coating the above-mentioned UV-curable composite solution on a PET film, and irradiating it with UV light with a wavelength of 405 nm for 10 minutes to obtain the bio-based light-curable thermally conductive insulating composite material.

[0044] The modified boron nitride filler is prepared as follows: boron nitride powder is added to a 3 wt% ethanol solution of KH-570, heated and stirred at 80°C for 1 hour, and then filtered and dried. The amount of KH-570 used is 1% of the mass of the boron nitride powder. The boron nitride powder has a particle size of 0.5-20 microns.

[0045] Example 2

[0046] A method for preparing a bio-based light-cured thermally conductive and insulating composite material, comprising:

[0047] Step 1: Take 30 parts by weight of epoxy soybean oil acrylate, 20 parts of isobornyl acrylate, 5 parts of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone, 80 parts of modified aluminum nitride filler, and 1 part of BYK-A 535 defoamer, stir and mix evenly in the dark, and degas to obtain a UV-curable composite solution;

[0048] Step 2: wet-coating the above-mentioned UV-curable composite solution on a PET film, and irradiating it with UV light with a wavelength of 405 nm for 10 minutes to obtain the bio-based light-curable thermally conductive insulating composite material.

[0049] The modified aluminum nitride filler is prepared as follows: aluminum nitride powder is added to a 3 wt% ethanol solution of KH-570, heated and stirred at 80°C for 1 hour, and then filtered and dried. The amount of KH-570 used is 1% of the weight of the aluminum nitride powder. The aluminum nitride powder has a particle size of 0.5-20 microns.

[0050] Example 3

[0051] A method for preparing a bio-based light-cured thermally conductive and insulating composite material, comprising:

[0052] Step 1: Take 30 parts by weight of epoxy soybean oil acrylate, 20 parts of isobornyl acrylate, 5 parts of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone, 80 parts of modified alumina filler, and 1 part of BYK-A 535 defoamer, stir and mix evenly in the dark, and degas to obtain a UV-curable composite solution;

[0053] Step 2: wet-coating the above-mentioned UV-curable composite solution on a PET film, and irradiating it with UV light with a wavelength of 405 nm for 10 minutes to obtain the bio-based light-curable thermally conductive insulating composite material.

[0054] The modified alumina filler is prepared as follows: alumina powder is added to a 3 wt% ethanol solution of KH-570, heated and stirred at 80°C for 1 hour, and then filtered and dried. The amount of KH-570 used is 1% of the mass of the alumina powder. The alumina powder has a particle size of 0.5-20 microns.

[0055] Example 4

[0056] A method for preparing a bio-based light-cured thermally conductive and insulating composite material, comprising:

[0057] Step 1: Take 30 parts by weight of epoxy soybean oil acrylate, 20 parts of isobornyl acrylate, 5 parts of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone, 80 parts of modified silicon nitride filler, and 1 part of BYK-A 535 defoamer, stir and mix evenly in the dark, and degas to obtain a UV-curable composite solution;

[0058] Step 2: wet-coating the above-mentioned UV-curable composite solution on a PET film, and irradiating it with UV light with a wavelength of 405 nm for 10 minutes to obtain the bio-based light-curable thermally conductive insulating composite material.

[0059] The modified silicon nitride filler is prepared as follows: silicon nitride powder is added to a 3 wt% ethanol solution of KH-570, heated and stirred at 80°C for 1 hour, and then filtered and dried. The amount of KH-570 used is 1% of the mass of the silicon nitride powder. The silicon nitride powder has a particle size of 0.5-20 microns.

[0060] Example 5

[0061] A method for preparing a bio-based light-cured thermally conductive and insulating composite material, comprising:

[0062] Step 1: Take 30 parts by weight of epoxy soybean oil acrylate, 20 parts of isobornyl acrylate, 5 parts of photoinitiator 2-hydroxy-2-methyl-1-phenylacetone, 80 parts of modified artificial diamond filler, and 1 part of BYK-A 535 defoamer, stir and mix them evenly in the dark, and degas to obtain a UV-curable composite solution;

[0063] Step 2: wet-coating the above-mentioned UV-curable composite solution on a PET film, and irradiating it with UV light with a wavelength of 405 nm for 10 minutes to obtain the bio-based light-curable thermally conductive insulating composite material.

[0064] The modified synthetic diamond filler is prepared as follows: synthetic diamond powder is added to an ethanol solution of KH-570 (concentration: 3 wt%), heated and stirred at 80°C for 1 hour, and then filtered and dried. The amount of KH-570 used is 1% of the weight of the synthetic diamond. The synthetic diamond powder has a particle size of 0.5-20 microns.

[0065] Comparative Example 1

[0066] A method for preparing a high thermal conductivity composite material, comprising:

[0067] Step 1: Take 30 parts of epoxy resin, 20 parts of acetone, 5 parts of curing agent dicyandiamide, 80 parts of modified boron nitride filler and 1 part of BYK-A 535 defoamer according to weight parts, stir and mix evenly and degas to obtain a composite solution;

[0068] Step 2: Pour the above composite solution into a polytetrafluoroethylene mold, first evaporate the acetone solvent at 50°C for 6 hours, and then cure it according to a curing procedure of 170°C / 1 hour + 180°C / 2 hours + 190°C / 1 hour to obtain a high thermal conductivity insulation composite material.

[0069] The modified boron nitride filler is prepared as follows: boron nitride powder is added to a 3 wt% ethanol solution of KH-570, heated and stirred at 80°C for 1 hour, and then filtered and dried. The amount of KH-570 used is 1% of the mass of the boron nitride powder. The boron nitride powder has a particle size of 0.5-20 microns.

[0070] Comparative Example 2

[0071] A method for preparing a high thermal conductivity composite material, comprising:

[0072] Step 1: Take 30 parts by weight of epoxy soybean oil acrylate, 20 parts of isobornyl acrylate, 5 parts of photoinitiator 2-hydroxy-2-methyl-1-phenylacetone, 80 parts of modified boron nitride filler and 1 part of BYK-A535 defoamer, stir and mix evenly in the dark, and degas to obtain a UV-curable composite solution;

[0073] Step 2: wet-coating the above-mentioned UV-curable composite solution on a PET film, and irradiating it with UV light with a wavelength of 405 nm for 10 minutes to obtain the bio-based light-curable thermally conductive insulating composite material.

[0074] The modified boron nitride filler is prepared as follows: boron nitride powder is added to a 3 wt% ethanol solution of KH-570, heated and stirred at 80°C for 1 hour, and then filtered and dried. The amount of KH-570 used is 1% of the mass of the boron nitride powder. The boron nitride powder has a particle size of 0.5-20 microns.

[0075] The following performance tests were performed on the bio-based light-cured thermally conductive insulating composite materials prepared in Examples 1-5 and the high thermal conductivity composite materials prepared in Comparative Examples 1-2:

[0076] 1. Thermal Conductivity: The thermal diffusivity (α) of Examples 1-5 and Comparative Examples 1-2 was measured using an LFA467 laser scattering thermal conductivity meter from NETZSCH, Germany, in m² / s. The bulk density (ρ) of the materials was measured using the displacement method and an electronic balance in g / cm³. The thermal conductivity (λ) of the composite materials was calculated using the formula λ = α × ρ × Cp (W / (m·K)).

[0077] 2. Insulation strength: Taiwan Chroma 19073 is used to test the insulation strength of the implementation case and the comparison case.

[0078] The test results are shown in Table 1.

[0079] Table 1 Test results of composite material properties of Examples 1-5 and Comparative Examples 1-2

[0080] sample Thermal conductivity (W / mK) Dielectric strength (kV / mm) Example 1 3.5 25.3 Example 2 3.6 24.7 Example 3 1.6 25.1 Example 4 3.4 26.1 Example 5 6.4 26.3 Comparative Example 1 3.5 24.8 Comparative Example 2 3.4 25.2

[0081] The performance test results of the various examples and comparative examples in Table 1 indicate that the improvement in thermal conductivity is related to the filler's inherent properties. At the same filler loading, the diamond composite material exhibits the highest thermal conductivity. Comparing Example 1 with Comparative Example 1 reveals that photocuring is energy-efficient and environmentally friendly, contains no volatile solvents, and significantly reduces curing time. Comparing Example 1 with Comparative Example 2 reveals that bio-based oligomers can serve as alternatives to petroleum-based polymers without compromising the thermal conductivity and insulation properties of the cured material.

[0082] Based on the above-mentioned preparation method of the bio-based light-cured thermally conductive insulating composite material, the present invention also provides a use of the bio-based light-cured thermally conductive insulating composite material prepared by the above-mentioned method, and the bio-based light-cured thermally conductive insulating composite material is used for microelectronic packaging.

[0083] It should be understood that the present invention is not limited to the specific structures and processes described above. For the sake of brevity, a detailed description of known methods is omitted here. In the above embodiments, several specific steps are described and illustrated as examples. However, the method process of the present invention is not limited to the specific steps described and illustrated. Those skilled in the art can make various changes, modifications, and additions, or change the order of the steps after understanding the spirit of the present invention.

[0084] It should also be noted that the exemplary embodiments described herein describe methods or systems based on a series of steps or devices. However, the present invention is not limited to the order of the steps described above. In other words, the steps may be performed in the order described in the embodiments, or in a different order, or several steps may be performed simultaneously.

[0085] The above description is only a specific embodiment of the present invention. Those skilled in the art will clearly understand that for the convenience and brevity of description, the specific working processes of the systems, modules and units described above can refer to the corresponding processes in the aforementioned method embodiments, and will not be repeated here. It should be understood that the protection scope of the present invention is not limited to this. Any person skilled in the art can easily think of various equivalent modifications or replacements within the technical scope disclosed by the present invention, and these modifications or replacements should be included in the protection scope of the present invention.

Claims

1. A bio-based light-cured thermally conductive insulating composite material, characterized in that: include: Bio-based oligomers, reactive diluents, modified thermally conductive fillers, free radical photoinitiators, silicone defoamers.

2. The bio-based light-cured thermally conductive insulating composite material according to claim 1, characterized in that: The mass parts of each component are as follows:

3. The bio-based light-cured thermally conductive insulating composite material according to claim 1, characterized in that: The bio-based oligomer is at least one of epoxy soybean oil acrylate, castor oil-based polyurethane acrylate, linseed oil-based acrylate, and cardanol-based acrylate.

4. The bio-based light-cured thermally conductive insulating composite material according to claim 1, characterized in that: The active diluent is one or a combination of the following: isobornyl acrylate, 2-phenoxyethyl acrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tris(2-hydroxyethyl)isocyanate triacrylate, and dipentaerythritol hexaacrylate.

5. The bio-based light-cured thermally conductive insulating composite material according to claim 1, characterized in that: The photoinitiator is one or a combination of 2-hydroxy-2-methyl-1-phenylpropanone-1, 2-phenyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholinopropanone-1, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-difluoro-3-(1H-pyrrolyl-1)phenyl)titanium ocene, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-(3-benzoylphenyl)guanidine propionate, 9-anthramethyl N,1-(anthraquinone-2-yl)ethylimidazole carboxylate, and N-diethylcarbamate.

6. The bio-based light-cured thermally conductive insulating composite material according to claim 1, characterized in that: The modified thermally conductive particle filler is a thermally conductive particle filler modified by a silane coupling agent or a titanate coupling agent.

7. The bio-based light-cured thermally conductive insulating composite material according to claim 5, characterized in that: The thermal conductive filler is at least one of artificial diamond, boron nitride, aluminum nitride, silicon nitride and aluminum oxide.

8. A method for preparing the bio-based light-cured thermally conductive and insulating composite material according to any one of claims 1 to 7, characterized in that: The preparation method of the bio-based light-cured thermally conductive insulating composite material comprises the following steps: S1. Evenly mix the bio-based oligomer, the active diluent, the modified thermal conductive filler, the free radical photoinitiator, and the defoaming agent to obtain a mixed solution; S2. The mixed solution is prepared into a film by a wet coating process, and then irradiated and cured under UV light.

9. The method according to claim 8, characterized in that Before step S1, the method further includes: Add a thermally conductive filler to an ethanol solution of KH-570, heat and stir at 80° C. for 1 hour, filter and dry to obtain a modified thermally conductive filler; the thermally conductive filler is at least one of artificial diamond, boron nitride, aluminum nitride, silicon nitride and aluminum oxide.

10. A use of the bio-based light-cured thermally conductive and insulating composite material according to any one of claims 1 to 7, characterized in that: The bio-based light-cured thermally conductive insulating composite material is used for microelectronic packaging.

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