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CN-121991610-A - Low-modulus high-thermal-conductivity acrylate-based chip mounting adhesive and preparation method thereof

CN121991610ACN 121991610 ACN121991610 ACN 121991610ACN-121991610-A

Abstract

The invention belongs to the technical field of adhesives, and in particular relates to a low-modulus high-heat-conductivity acrylic ester-based chip mounting adhesive and a preparation method thereof, wherein the mounting adhesive is prepared by taking acrylic ester as a base material and modified diamond and the like as additives through mixing, wherein the modified diamond is prepared by modifying a flexible polymer chain segment on the surface of the diamond, and the flexible polymer chain segment structure contains a large number of hydroxyl substituents generated by ring opening reaction, so that the adhesive can participate in the subsequent curing process of the acrylic ester mounting adhesive, therefore, the diamond and the acrylate adhesive can generate good interface effect, so that a small amount of more uniform dispersing agent is added in the acrylate, the effect of forming a complete heat conduction path can be achieved, the heat conduction performance of the acrylate adhesive is greatly improved, in addition, the flexible polymer chain segments are introduced into the acrylate structure in the curing process, the flexibility of the flexible polymer chain segments can be utilized, and the modulus of the adhesive can be effectively reduced.

Inventors

  • XU CUN
  • HUANG JUNDA
  • ZHANG HONGXIA

Assignees

  • 昆山石梅新材料科技有限公司

Dates

Publication Date
20260508
Application Date
20260226

Claims (10)

  1. 1. The low-modulus high-thermal-conductivity acrylate-based chip mounting adhesive is characterized by comprising the following raw materials in parts by weight: 26-34 parts of soft monomer, 10-16 parts of hard monomer, 3-6 parts of internal plasticizing monomer, 80-100 parts of ethyl acetate, 0.05-0.15 part of initiator, 2-4.5 parts of modified diamond and 1-3 parts of curing agent; The modified diamond is prepared by modifying a flexible molecular chain segment containing a silicon-oxygen bond on the surface of the diamond.
  2. 2. The low-modulus high-heat-conductivity acrylate-based chip mounting adhesive according to claim 1 is characterized in that the soft monomer is at least one of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate or lauryl acrylate, the hard monomer is at least one of methyl methacrylate, styrene, acrylonitrile or methyl acrylate, the internal plasticizing monomer is hydroxyethyl acrylate or hydroxypropyl acrylate, the initiator is azobisisobutyronitrile or azobisisoheptonitrile, and the curing agent is isocyanate curing agent.
  3. 3. The low modulus, high thermal conductivity acrylate based chip attach adhesive of claim 1, wherein the modified diamond is made by the steps of: Adding diamond into an ethanol water solution with the volume fraction of 60-70%, continuously adding an epoxidation modifying reagent after uniform dispersion, adjusting the pH to 3-4 after finishing addition, continuously preserving heat for 3-6 hours, cooling and discharging, collecting a solid material, and washing and vacuum drying to obtain the epoxidized diamond; Dispersing the epoxidized diamond in 1, 4-dioxane, adding polytetrahydrofuran ether glycol and a catalyst into the formed uniform mixed solution, stirring uniformly after adding, raising the temperature to 60-70 ℃, preserving heat for 2-4 hours, continuing to add a silicon-containing bridging agent, raising the temperature to 75-85 ℃ after adding, preserving heat for 12-18 hours, stopping heating, cooling and discharging, collecting solid materials, and washing and drying in vacuum to obtain the modified diamond.
  4. 4. The low-modulus high thermal conductivity acrylate-based chip attach adhesive according to claim 3, wherein in step one, the epoxidation modifying agent is 3-glycidoxypropyl trimethoxysilane or 3-glycidoxypropyl triethoxysilane.
  5. 5. The low-modulus, high thermal conductivity acrylate-based chip attach adhesive of claim 3, wherein in step two, the polytetrahydrofuran ether glycol has a number average molecular weight of 1000.
  6. 6. The low-modulus high-thermal-conductivity acrylate-based chip attach adhesive according to claim 3, wherein in the second step, the catalyst is boron trifluoride diethyl ether complex.
  7. 7. The low-modulus high-thermal-conductivity acrylate-based chip mounting adhesive according to claim 3, wherein in the second step, the silicon-containing bridging agent is prepared by the following method: adding decamethyl penta hydrogen siloxane, glycidyl methacrylate and absolute ethyl alcohol into a reaction kettle, introducing nitrogen for protection, then heating to 70-75 ℃ under stirring, then continuously adding a platinum catalyst, continuously preserving heat for 4-6 hours after the addition, distilling under reduced pressure to remove a solvent, naturally cooling, collecting a product, and purifying to obtain the silicon-containing bridging agent.
  8. 8. The low modulus, high thermal conductivity acrylate based chip attach adhesive of claim 7 wherein said molar ratio of decamethyipenta-penta-hydro-siloxane to glycidyl methacrylate is 1:2-2.05.
  9. 9. The low-modulus high-thermal-conductivity acrylate-based chip attach adhesive according to claim 3, wherein the mass ratio of the epoxidized diamond to the polytetrahydrofuran ether glycol to the silicon-containing bridging agent is 1:0.3-0.6:0.2-0.4.
  10. 10. The method for preparing the low-modulus high-thermal-conductivity acrylate-based chip mounting adhesive according to claim 1, which is characterized by comprising the following steps: Firstly, weighing and preparing raw materials according to parts by weight, adding a soft monomer, a hard monomer, an internal plasticization monomer and an initiator into ethyl acetate, stirring and mixing uniformly, starting heating, raising the temperature to 75-76 ℃, continuously preserving heat for 6-8 hours, stopping heating, cooling and discharging to obtain a polymer; and secondly, adding the modified diamond into the polymer, stirring and mixing, and then continuously adding the curing agent and stirring uniformly to obtain the chip mounting adhesive.

Description

Low-modulus high-thermal-conductivity acrylate-based chip mounting adhesive and preparation method thereof Technical Field The invention belongs to the technical field of adhesives, and particularly relates to a low-modulus high-heat-conductivity acrylate-based chip mounting adhesive and a preparation method thereof. Background Die attach adhesives are critical materials in microelectronic packaging for securing semiconductor chips to a substrate or leadframe. Its performance directly affects the mechanical stability, heat dissipation efficiency, and long-term reliability of the packaged device. With the development of semiconductor technology to high density, high power and miniaturization, the adhesive needs to meet more severe comprehensive performance requirements. The acrylic acid ester adhesive is a polymer material formed by copolymerizing acrylic acid ester monomers, has wide application in the field of chip mounting, has distinct characteristics, has multiple advantages of mild curing conditions, good process adaptability, high adhesive strength, electric insulation and the like, and can be used as a base material of the chip mounting adhesive, however, the acrylic acid ester adhesive has poor heat conducting property, is difficult to meet the high-efficiency heat dissipation requirement of a high-power chip, has relatively high modulus and is poor in performance in terms of relieving thermal stress, so that the development of the acrylic acid ester adhesive with low modulus and high heat conducting property has important significance in the field of chip mounting adhesive. At present, the improvement of the heat conducting performance of the acrylate adhesive is generally realized by adding a heat conducting additive, however, the problem of a natural interface between an inorganic heat conducting additive and an acrylate matrix becomes a major defect of the scheme, on one hand, a stable heat conducting path cannot be formed by a small adding amount, the heat conducting modification of the acrylate adhesive is realized, and on the other hand, the modulus of the acrylate adhesive becomes high due to the excessively high adding amount. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a low-modulus high-heat-conductivity acrylate-based chip mounting adhesive and a preparation method thereof. The invention provides a low-modulus high-heat-conductivity acrylate-based chip mounting adhesive, which comprises the following raw materials in parts by weight: 26-34 parts of soft monomer, 10-16 parts of hard monomer, 3-6 parts of internal plasticizing monomer, 80-100 parts of ethyl acetate, 0.05-0.15 part of initiator, 2-4.5 parts of modified diamond and 1-3 parts of curing agent; The modified diamond is prepared by modifying a flexible molecular chain segment containing a silicon-oxygen bond on the surface of the diamond. According to the preferable technical scheme, the soft monomer is at least one of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate or lauryl acrylate, the hard monomer is at least one of methyl methacrylate, styrene, acrylonitrile or methyl acrylate, the internal plasticizing monomer is hydroxyethyl acrylate or hydroxypropyl acrylate, the initiator is azo-bis-isobutyronitrile or azo-bis-isoheptanenitrile, and the curing agent is isocyanate curing agent. As a preferred technical scheme of the invention, the modified diamond is prepared by the following steps: Adding diamond into an ethanol water solution with the volume fraction of 60-70%, continuously adding an epoxidation modifying reagent after uniform dispersion, adjusting the pH to 3-4 after finishing addition, continuously preserving heat for 3-6 hours, cooling and discharging, collecting a solid material, and washing and vacuum drying to obtain the epoxidized diamond; Dispersing the epoxidized diamond in 1, 4-dioxane, adding polytetrahydrofuran ether glycol and a catalyst into the formed uniform mixed solution, stirring uniformly after adding, raising the temperature to 60-70 ℃, preserving heat for 2-4 hours, continuing to add a silicon-containing bridging agent, raising the temperature to 75-85 ℃ after adding, preserving heat for 12-18 hours, stopping heating, cooling and discharging, collecting solid materials, and washing and drying in vacuum to obtain the modified diamond. As a preferred embodiment of the present invention, in step one, the epoxidation modifying reagent is 3-glycidol ether oxygen propyl tri-component methoxy silane or 3-glycidoxy propyl triethoxy silane. In a preferred embodiment of the present invention, in the second step, the polytetrahydrofuran ether glycol has a number average molecular weight of 1000. In the second step, the catalyst is boron trifluoride diethyl etherate. In the second step, as a preferred technical scheme of the invention, the silicon-containing bridging agent is prepared by the following method: adding decamethyl penta hy