CN113956617A - Preparation method of high-insulation low-temperature electronic packaging material - Google Patents
Preparation method of high-insulation low-temperature electronic packaging material Download PDFInfo
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- CN113956617A CN113956617A CN202111351812.7A CN202111351812A CN113956617A CN 113956617 A CN113956617 A CN 113956617A CN 202111351812 A CN202111351812 A CN 202111351812A CN 113956617 A CN113956617 A CN 113956617A
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- epoxy resin
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- boron nitride
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- 238000004100 electronic packaging Methods 0.000 title claims abstract description 41
- 239000005022 packaging material Substances 0.000 title claims abstract description 41
- 238000009413 insulation Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 62
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 62
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical class N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910052582 BN Inorganic materials 0.000 claims description 19
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical group [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004033 plastic Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Details Of Resistors (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a high-insulation low-temperature electronic packaging material, which relates to the field of electronic packaging materials, and is characterized in that modified epoxy resin and modified boron nitride are added into a high-speed mixer to be mixed to obtain a mixture, 4' -diamino diphenyl sulfone is added into the mixture, the mixture is stirred to be dissolved and then is solidified to obtain the high-insulation low-temperature electronic packaging material; according to the preparation method, the modified epoxy resin is used as a main material, and the modified epoxy resin has higher heat resistance, so that the adverse effect of the heat released by an electronic element on the performance of the electronic packaging material is avoided, the heat conductivity of the epoxy resin can be effectively improved by adding the modified boron nitride, the heat released by the electronic element can be rapidly led out, the electronic packaging material still has high insulating property under the high-temperature condition, and the requirement of electronic packaging development can be met.
Description
Technical Field
The invention relates to the field of electronic packaging materials, in particular to a preparation method of a high-insulation low-temperature electronic packaging material.
Background
The electronic packaging function is to protect microelectronic equipment (IC), the most important performance indexes of the electronic packaging material are thermal conductivity and thermal expansion coefficient, and heat generated by the IC with high integration level in the working process must be released in time so as to prevent the IC from working in an overheated state and influencing the service life and performance of the IC;
meanwhile, the Coefficient of Thermal Expansion (CTE) of the packaging material is kept consistent with that of the chip and the carrier as much as possible, and as the working temperature rises, thermal stress is inevitably generated between adjacent parts and at welding points, so that creep and fatigue at joints are caused to cause fracture, the rapid development of the electronic packaging technology promotes the development of the packaging material, namely, the traditional plastic packaging mainly adopts metal and ceramic packaging, and the plastic packaging has the advantages of relatively low price, simple molding process, suitability for mass production, equivalent reliability to that of the ceramic packaging and the like, and accounts for over 95 percent of the whole packaging material, and the most widely applied epoxy resin plastic packaging material is epoxy resin plastic packaging. The epoxy resin has excellent heat resistance, electric insulation, adherence, dielectricity and mechanical property, smaller shrinkage and chemical resistance, and has better processability and operability after the curing agent is added.
However, the high temperature resistance and thermal conductivity of the existing plastic electronic packaging material are still poor, which limits the development of the plastic electronic packaging material.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a preparation method of a high-insulation low-temperature electronic packaging material, which comprises the following steps: the high-insulativity low-temperature electronic packaging material is obtained by adding the modified epoxy resin and the modified boron nitride into a high-speed mixer for mixing to obtain a mixture, adding the 4, 4' -diamino diphenyl sulfone into the mixture, stirring until the mixture is dissolved, and then curing, so that the problem that the development of the plastic electronic packaging material is limited because the high-temperature resistance and the heat conductivity of the existing plastic electronic packaging material are still poor is solved.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the high-insulation low-temperature electronic packaging material comprises the following steps:
the method comprises the following steps: weighing 100-150 parts of modified epoxy resin, 5-25 parts of modified boron nitride and 10-15 parts of 4, 4' -diamino diphenyl sulfone according to the parts by weight for later use;
step two: adding the modified epoxy resin and the modified boron nitride into a high-speed mixer, and mixing for 4-6h at the stirring speed of 1200-2500r/min to obtain a mixture;
step three: adding 4, 4' -diaminodiphenyl sulfone into the mixture, heating to 130-.
As a further scheme of the invention: the preparation method of the modified epoxy resin comprises the following steps:
s11: adding a saturated sodium carbonate solution into a three-neck flask provided with a stirrer and a constant-pressure dropping funnel, dropwise adding diphenyldichlorosilane while stirring under the conditions that the temperature is 20-30 ℃ and the stirring speed is 300-500r/min, controlling the dropwise adding speed to be 1 drop/s, continuously stirring and reacting for 10-30min after the dropwise adding is finished, washing a reaction product with distilled water until the pH value is 7, then carrying out vacuum filtration, and freeze-drying a filter cake to obtain an intermediate 1;
the reaction principle is as follows:
s12: adding epoxy resin and absolute ethyl alcohol into a three-neck flask provided with a stirrer, a condensation reflux pipe and a nitrogen guide pipe, introducing nitrogen for protection, stirring at the temperature of 20-30 ℃ and the stirring speed of 500-800r/min until the epoxy resin is completely dissolved, then adding an intermediate 1 and dibutyl tin dilaurate, continuing stirring for reaction for 3-4h, adjusting the pH of a reaction product to 7 by using a saturated sodium carbonate solution after the reaction is finished, and then rotationally evaporating the reaction product to obtain an intermediate 2;
the reaction principle is as follows:
s13: adding the intermediate 2 into a three-neck flask provided with a stirrer, a condensation reflux pipe and a nitrogen guide pipe, introducing nitrogen for protection, stirring at the temperature of 100-.
The reaction principle is as follows:
as a further scheme of the invention: the dosage ratio of the saturated sodium carbonate solution to the diphenyl dichlorosilane in the step S11 is 10-20 mL: 5-8 mL.
As a further scheme of the invention: the epoxy resin in the step S12 is epoxy resin E-44, and the usage ratio of the epoxy resin, the absolute ethyl alcohol, the intermediate 1 and the dibutyl tin dilaurate is 10 g: 50-100 mL: 0.5-1.0 g: 0.01-0.15 g.
As a further scheme of the invention: the mass ratio of the intermediate 2, DOPO and triphenylphosphine in the step S13 is 100-200: 1-5: 0.01-0.05.
As a further scheme of the invention: the preparation method of the modified boron nitride comprises the following steps:
s21: adding concentrated sulfuric acid and concentrated nitric acid into a three-neck flask provided with a stirrer, stirring for 10-20min under the condition that the stirring speed is 300-500r/min, then adding cubic boron nitride powder, stirring for 3-4h under the condition that the temperature is raised to 60-70 ℃, centrifugally treating a reaction product after the reaction is finished, washing the centrifugal product to be neutral by using distilled water, then placing the centrifugal product into a vacuum drying box, and drying the centrifugal product to constant weight under the condition that the temperature is 60-70 ℃ to obtain pretreated boron nitride;
s22: adding a silane coupling agent and an ethanol solution into a three-neck flask provided with a stirrer, stirring for 10-20min under the condition that the stirring speed is 300-500r/min, standing for 3-5h, then adding pretreated boron nitride, stirring for 1-3h under the condition that the stirring speed is 800-1000r/min, centrifuging a reaction product after the reaction is finished, washing the centrifuged product for 2-3 times by using absolute ethanol, then placing the product in a vacuum drying box, and drying to constant weight under the condition that the temperature is 60-70 ℃ to obtain the modified boron nitride.
As a further scheme of the invention: in the step S21, the mass fraction of the concentrated sulfuric acid is 95 to 98%, the mass fraction of the concentrated nitric acid is 65 to 68%, and the usage ratio of the concentrated sulfuric acid, the concentrated nitric acid, and the cubic boron nitride powder is 30 mL: 10mL of: 1-5 g.
As a further scheme of the invention: the silane coupling agent in the step S22 is a silane coupling agent KH-560, and the dosage ratio of the silane coupling agent to the ethanol solution to the pretreated boron nitride is 2-5 g: 50-70 mL: 1-3g, wherein the mass fraction of the ethanol solution is 90%.
The invention has the beneficial effects that:
the preparation method of the high-insulation low-temperature electronic packaging material comprises the steps of adding modified epoxy resin and modified boron nitride into a high-speed mixer for mixing to obtain a mixture, adding 4, 4' -diamino diphenyl sulfone into the mixture, stirring until the mixture is dissolved, and then curing to obtain the high-insulation low-temperature electronic packaging material; the preparation method uses the modified epoxy resin as a main material, the epoxy resin has excellent heat resistance, electrical insulation, adherence, dielectricity, mechanical property and smaller shrinkage rate and chemical resistance, the curing agent is added to have better processability and operability, the modified epoxy resin is suitable for being used as an electronic packaging material, the modified epoxy resin has higher heat resistance, thereby avoiding adverse effects of heat released by electronic elements on the performance of the electronic packaging material, the heat conductivity of the epoxy resin can be effectively improved by adding the modified boron nitride, thereby being convenient for rapidly guiding out the heat released by the electronic elements, the electronic packaging material still has high insulation performance under the high-temperature condition, and the requirement of electronic packaging development can be met.
The modified epoxy resin is prepared in the process of preparing the low-temperature electronic packaging material, diphenyl dichlorosilane is hydrolyzed to form an intermediate 1, then hydroxyl on the intermediate 1 reacts with hydroxyl on the epoxy resin, a silicon element and a benzene ring are introduced to obtain an intermediate 2, then a part of epoxy groups on the intermediate 2 react with DOPO, so that organic phosphorus and benzene rings are introduced to obtain the modified epoxy resin, the introduced benzene rings have good stability, and the introduced silicon element and phosphorus element have higher bond energy, so that the thermal stability of the epoxy resin can be improved, and the high stability of the epoxy resin is maintained.
The modified boron nitride is prepared in the process of preparing the low-temperature electronic packaging material, the hexagonal boron nitride is high in heat conductivity coefficient, good in mechanical property, strong in oxidation resistance, strong in neutron absorption capacity, good in electrical insulation performance and high in thermal conductivity and insulation performance, so that the modified boron nitride is suitable for modifying epoxy resin, but the surface of the hexagonal boron nitride is provided with unsaturated bonds and dangling bonds, so that the hexagonal boron nitride is difficult to disperse in the epoxy resin and the performance of the epoxy resin is affected, the cubic boron nitride powder is firstly acidified by concentrated sulfuric acid and concentrated nitric acid, so that hydroxyl or carboxyl is introduced to the surface of the cubic boron nitride powder, then the silane coupling agent is utilized to hydrolyze to form silanol, and then the silanol is dehydrated and condensed to form low polysiloxane, so that the dispersibility of the boron nitride powder in the epoxy resin is improved, the agglomeration of the epoxy resin is avoided, so that the purpose of improving the thermal conductivity of the epoxy resin and not reducing the insulating property of the epoxy resin is realized.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment is a preparation method of a modified epoxy resin, comprising the following steps:
s11: adding 10mL of saturated sodium carbonate solution into a three-neck flask provided with a stirrer and a constant-pressure dropping funnel, dropwise adding 5mL of diphenyldichlorosilane while stirring under the conditions that the temperature is 20 ℃ and the stirring rate is 300r/min, controlling the dropwise adding rate to be 1 drop/s, continuing stirring and reacting for 10min after the dropwise adding is finished, washing a reaction product with distilled water until the pH value is 7, then carrying out vacuum filtration, and freeze-drying a filter cake to obtain an intermediate 1;
s12: adding 10g of epoxy resin E-44 and 50mL of absolute ethyl alcohol into a three-neck flask provided with a stirrer, a reflux condenser and a nitrogen guide pipe, introducing nitrogen for protection, stirring at the temperature of 20 ℃ and the stirring speed of 500r/min until the epoxy resin is completely dissolved, then adding 0.5g of intermediate 1 and 0.01g of dibutyl tin dilaurate, continuing stirring for reaction for 3 hours, adjusting the pH of a reaction product to 7 by using a saturated sodium carbonate solution after the reaction is finished, and then rotationally evaporating the reaction product to obtain an intermediate 2;
s13: adding 100g of the intermediate 2 into a three-neck flask provided with a stirrer, a condensation reflux pipe and a nitrogen guide pipe, introducing nitrogen for protection, stirring at the temperature of 100 ℃ and the stirring speed of 500r/min until the intermediate 2 is completely molten, then adding 1g of DOPO, continuing stirring until the DOPO is completely dissolved after the addition is finished, then adding 0.01g of triphenylphosphine, then heating to 120 ℃ while stirring, controlling the heating speed to be 1 ℃/min, and then stirring at constant temperature for reaction for 6 hours to obtain the modified epoxy resin.
Example 2:
the embodiment is a preparation method of a modified epoxy resin, comprising the following steps:
s11: adding 20mL of saturated sodium carbonate solution into a three-neck flask provided with a stirrer and a constant-pressure dropping funnel, dropwise adding 8mL of diphenyldichlorosilane while stirring under the conditions that the temperature is 30 ℃ and the stirring rate is 500r/min, controlling the dropwise adding rate to be 1 drop/s, continuing stirring for reacting for 30min after the dropwise adding is finished, washing a reaction product with distilled water until the pH value is 7, then carrying out vacuum filtration, and freeze-drying a filter cake to obtain an intermediate 1;
s12: adding 10g of epoxy resin E-44 and 100mL of absolute ethyl alcohol into a three-neck flask provided with a stirrer, a condensation reflux pipe and a nitrogen guide pipe, introducing nitrogen for protection, stirring at the temperature of 30 ℃ and the stirring speed of 800r/min until the epoxy resin is completely dissolved, then adding 1.0g of intermediate 1 and 0.15g of dibutyl tin dilaurate, continuing stirring for reaction for 4 hours, adjusting the pH of a reaction product to 7 by using a saturated sodium carbonate solution after the reaction is finished, and then rotationally evaporating the reaction product to obtain an intermediate 2;
s13: adding 200g of the intermediate 2 into a three-neck flask provided with a stirrer, a condensation reflux pipe and a nitrogen guide pipe, introducing nitrogen for protection, stirring at the temperature of 110 ℃ and the stirring speed of 800r/min until the intermediate 2 is completely molten, then adding 5g of DOPO, continuing stirring until the DOPO is completely dissolved after the addition is finished, then adding 0.05g of triphenylphosphine, heating to 130 ℃ while stirring, controlling the heating speed to be 1 ℃/min, and then stirring at constant temperature for reaction for 8 hours to obtain the modified epoxy resin.
Example 3:
the embodiment is a preparation method of modified boron nitride, which comprises the following steps:
s21: adding 30mL of 98% concentrated sulfuric acid and 10mL of 68% concentrated nitric acid into a three-neck flask provided with a stirrer, stirring for 20min at a stirring speed of 500r/min, then adding 5g of cubic boron nitride powder, stirring for 4h at a temperature of 70 ℃, carrying out centrifugal treatment on a reaction product after the reaction is finished, washing the centrifugal product to be neutral by using distilled water, then placing the centrifugal product into a vacuum drying box, and drying the centrifugal product to constant weight at a temperature of 70 ℃ to obtain pretreated boron nitride;
s22: adding 5g of silane coupling agent KH-560 and 70mL of 90 mass percent ethanol solution into a three-neck flask provided with a stirrer, stirring for 20min under the condition of stirring speed of 500r/min, standing for 5h, adding 3g of pretreated boron nitride, stirring for 3h under the condition of stirring speed of 1000r/min, centrifuging a reaction product after the reaction is finished, washing the centrifuged product for 3 times by absolute ethanol, then placing the product in a vacuum drying oven, and drying to constant weight under the condition of temperature of 70 ℃ to obtain the modified boron nitride.
Example 4:
the embodiment is a preparation method of a high-insulation low-temperature electronic packaging material, which comprises the following steps:
the method comprises the following steps: weighing 100 parts of modified epoxy resin from example 1, 5 parts of modified boron nitride from example 3 and 10 parts of 4, 4' -diaminodiphenyl sulfone according to parts by weight for later use;
step two: adding the modified epoxy resin and the modified boron nitride into a high-speed mixer, and mixing for 4 hours at a stirring speed of 1200r/min to obtain a mixture;
step three: adding 4, 4 '-diamino diphenyl sulfone into the mixture, heating to 130 ℃, stirring until the 4, 4' -diamino diphenyl sulfone is completely dissolved, vacuumizing for 3h, curing at 130 ℃ for 1h, and curing at 200 ℃ for 1h to obtain the high-insulation low-temperature electronic packaging material.
Example 5:
the embodiment is a preparation method of a high-insulation low-temperature electronic packaging material, which comprises the following steps:
the method comprises the following steps: weighing 150 parts by weight of the modified epoxy resin obtained in example 2, 25 parts by weight of the modified boron nitride obtained in example 3 and 15 parts by weight of 4, 4' -diaminodiphenyl sulfone for later use;
step two: adding the modified epoxy resin and the modified boron nitride into a high-speed mixer, and mixing for 6 hours at a stirring speed of 2500r/min to obtain a mixture;
step three: adding 4, 4 '-diamino diphenyl sulfone into the mixture, heating to 140 ℃, stirring until the 4, 4' -diamino diphenyl sulfone is completely dissolved, vacuumizing for 4h, curing at 140 ℃ for 2h, and curing at 210 ℃ for 2h to obtain the high-insulation low-temperature electronic packaging material.
Comparative example 1:
comparative example 1 differs from example 5 in that epoxy resin E-44 was used instead of the modified epoxy resin, and no modified boron nitride was added.
Comparative example 2:
comparative example 2 differs from example 5 in that epoxy resin E-44 is used instead of the modified epoxy resin.
The performance of the high-insulation low-temperature electronic packaging materials of the examples 4-5 and the comparative examples 1-2 is tested, and the test results are as follows:
| sample (I) | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Resistivity at 25 deg.C/omega.m | 1.56×1015 | 2.13×1015 | 6.48×1014 | 7.22×1014 |
| Resistivity at 400 deg.C/omega.m | 8.23×1012 | 1.04×1013 | 7.21×1010 | 2.14×1011 |
| Thermal conductivity coefficient/(W/m.K) | 0.768 | 0.847 | 0.175 | 0.626 |
Referring to the data in the table, it can be seen that the high-insulation low-temperature electronic packaging material shows high insulation and high thermal conductivity under the action of the modified epoxy resin and the modified boron nitride according to the comparison of the example and the comparative example 1, the modified epoxy resin E-44 has higher high temperature resistance and can still maintain high resistivity under a high-temperature environment according to the comparison of the example and the comparative example 2, so that high insulation performance is achieved, and it can be seen that the thermal conductivity of the epoxy resin E-44 can be obviously improved and a certain heat resistance is improved according to the comparison of the comparative example 1 and the example 2.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The preparation method of the high-insulation low-temperature electronic packaging material is characterized by comprising the following steps of:
the method comprises the following steps: weighing 100-150 parts of modified epoxy resin, 5-25 parts of modified boron nitride and 10-15 parts of 4, 4' -diamino diphenyl sulfone according to the parts by weight for later use;
step two: adding the modified epoxy resin and the modified boron nitride into a high-speed mixer, and mixing for 4-6h at the stirring speed of 1200-2500r/min to obtain a mixture;
step three: adding 4, 4' -diaminodiphenyl sulfone into the mixture, heating to 130-.
2. The method for preparing a high-insulation low-temperature electronic packaging material according to claim 1, wherein the modified epoxy resin is prepared by the following steps:
s11: adding a saturated sodium carbonate solution into a three-neck flask, dropwise adding diphenyldichlorosilane while stirring, continuously stirring for reaction after dropwise adding is finished, washing a reaction product with distilled water until the pH value is 7, then performing vacuum filtration, and freeze-drying a filter cake to obtain an intermediate 1;
s12: adding epoxy resin and absolute ethyl alcohol into a three-neck flask, stirring until the epoxy resin is completely dissolved, then adding an intermediate 1 and dibutyl tin dilaurate, continuously stirring for reaction, adjusting the pH of a reaction product to 7 after the reaction is finished, and then carrying out rotary evaporation on the reaction product to obtain an intermediate 2;
s13: adding the intermediate 2 into a three-neck flask, stirring until the intermediate 2 is completely molten, then adding DOPO, stirring until the DOPO is completely dissolved, then adding triphenylphosphine, heating, and stirring at constant temperature for reaction to obtain the modified epoxy resin.
3. The method for preparing a high-insulation low-temperature electronic packaging material according to claim 2, wherein the saturated sodium carbonate solution and the diphenyldichlorosilane are used in a ratio of 10-20mL in step S11: 5-8 mL.
4. The method for preparing a high-insulation low-temperature electronic packaging material as claimed in claim 2, wherein the epoxy resin in step S12 is epoxy resin E-44, and the ratio of the epoxy resin, absolute ethanol, intermediate 1 and dibutyl tin dilaurate is 10 g: 50-100 mL: 0.5-1.0 g: 0.01-0.15 g.
5. The method as claimed in claim 2, wherein the mass ratio of the intermediate 2, DOPO and triphenylphosphine in step S13 is 100-200: 1-5: 0.01-0.05.
6. The method for preparing a high-insulation low-temperature electronic packaging material according to claim 1, wherein the method for preparing the modified boron nitride comprises the following steps:
s21: adding concentrated sulfuric acid and concentrated nitric acid into a three-neck flask, stirring, adding cubic boron nitride powder, heating and stirring, centrifugally treating a reaction product after the reaction is finished, washing the centrifugal product to be neutral, and drying to constant weight to obtain pretreated boron nitride;
s22: adding a silane coupling agent and an ethanol solution into a three-neck flask, stirring, standing, adding pretreated boron nitride, stirring, centrifuging a reaction product after the reaction is finished, washing the centrifuged product, and drying to constant weight to obtain the modified boron nitride.
7. The method for preparing a high-insulation low-temperature electronic packaging material according to claim 6, wherein the mass fraction of the concentrated sulfuric acid in step S21 is 95-98%, the mass fraction of the concentrated nitric acid is 65-68%, and the usage ratio of the concentrated sulfuric acid, the concentrated nitric acid and the cubic boron nitride powder is 30 mL: 10mL of: 1-5 g.
8. The method for preparing a high-insulation low-temperature electronic packaging material according to claim 6, wherein the silane coupling agent in step S22 is a silane coupling agent KH-560, and the ratio of the silane coupling agent to the ethanol solution to the pretreated boron nitride is 2-5 g: 50-70 mL: 1-3g, wherein the mass fraction of the ethanol solution is 90%.
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| PCT/CN2022/089223 WO2022156832A2 (en) | 2021-10-27 | 2022-04-26 | Preparation method for high-insulativity low-temperature electronic packaging material |
| ZA2022/05995A ZA202205995B (en) | 2021-10-27 | 2022-05-30 | Preparation method of high-insulation low-temperature electronic packaging material |
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Cited By (2)
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| WO2022156832A3 (en) * | 2021-10-27 | 2022-09-22 | 江苏拜富科技股份有限公司 | Preparation method for high-insulativity low-temperature electronic packaging material |
| CN117467243A (en) * | 2023-12-05 | 2024-01-30 | 昆山兴凯半导体材料有限公司 | High-heat-conductivity and high-insulativity epoxy composition and application thereof |
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Also Published As
| Publication number | Publication date |
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| ZA202205995B (en) | 2022-10-26 |
| WO2022156832A3 (en) | 2022-09-22 |
| WO2022156832A2 (en) | 2022-07-28 |
| WO2022156832A9 (en) | 2022-12-01 |
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