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CN-121975335-A - Hydrocarbon resin composition for prepreg and preparation method thereof

CN121975335ACN 121975335 ACN121975335 ACN 121975335ACN-121975335-A

Abstract

The invention belongs to the technical field of resin materials for copper-clad plates, and particularly relates to a hydrocarbon resin composition for prepregs and a preparation method thereof. The hydrocarbon resin composition is prepared from the following raw materials, by mass, 90-100 parts of hyperbranched modified prepolymer resin, 15-25 parts of inorganic filler, 0.2-0.4 part of silane coupling agent, 10-20 parts of cross-linking agent, 0.8-1.5 parts of initiator, 0.1-0.3 part of dibutyl tin dilaurate, 0.5-1 part of antioxidant and 50-80 parts of toluene. The hydrocarbon resin composition prepared by the invention has low dielectric property, high heat conduction, high heat resistance, high toughness and excellent processing formability.

Inventors

  • XU HONG
  • WANG MENG
  • ZHANG FENG
  • QIAN YOU
  • XI YAJUN

Assignees

  • 陕西泰信电子科技股份有限公司

Dates

Publication Date
20260505
Application Date
20260409

Claims (10)

  1. 1. The hydrocarbon resin composition for the prepreg is characterized by being prepared from the following raw materials in parts by mass: 90-100 parts of hyperbranched modified prepolymer resin, 15-25 parts of inorganic filler, 0.2-0.4 part of silane coupling agent, 10-20 parts of cross-linking agent, 0.8-1.5 parts of initiator, 0.1-0.3 part of dibutyl tin dilaurate, 0.5-1 part of antioxidant and 50-80 parts of toluene.
  2. 2. The hydrocarbon resin composition for prepregs according to claim 1, wherein the preparation method of the hyperbranched modified prepolymer resin comprises the following steps: (1) Uniformly mixing hydroxyl-terminated hyperbranched polyester, maleic anhydride, p-toluenesulfonic acid and N, N-dimethylformamide, and reacting for 3-5 hours at 60-90 ℃ under the protection of inert gas to obtain anhydride modified hyperbranched polyester; (2) The aromatic ring copolymerized polybutadiene, the anhydride modified hyperbranched polyester, the dicumyl peroxide and the dimethylbenzene are uniformly mixed, and react for 2-4 hours at 110-130 ℃ under the protection of inert gas, then the temperature is raised to 140-160 ℃ for 0.5-1 hour, and the hyperbranched modified prepolymer resin is obtained after cooling and filtering.
  3. 3. The hydrocarbon resin composition for prepregs according to claim 2, wherein in the step (1), the hydroxyl value of the hydroxyl terminated hyperbranched polyester is 100 to 300mgkoh/g, and the number average molecular weight is 2000 to 3000g/mol.
  4. 4. The hydrocarbon resin composition for prepregs according to claim 2, wherein in the step (1), the mass ratio of the hydroxyl-terminated hyperbranched polyester, the maleic anhydride, the p-toluenesulfonic acid and the N, N-dimethylformamide is (15-25) to (2-6) to (0.2-0.5) to (50-90).
  5. 5. The hydrocarbon resin composition for prepregs according to claim 2, wherein in the step (2), the mass ratio of the aromatic ring copolymerized polybutadiene, the acid anhydride modified hyperbranched polyester, the dicumyl peroxide and the xylene is 100:12-20:0.4-1:110-180.
  6. 6. The hydrocarbon resin composition for prepregs according to claim 2, wherein the preparation method of the aromatic ring-copolymerized polybutadiene comprises the following steps: In the presence of an inert atmosphere and an initiator, styrene, 1, 3-butadiene and maleic anhydride are polymerized in an organic solvent according to the mass ratio of (25-35) to (62-74) to (1-3) at 75-80 ℃ to obtain the aromatic ring copolymerized polybutadiene.
  7. 7. The hydrocarbon resin composition for prepregs according to claim 1, wherein the inorganic filler is prepared by mixing flaky boron nitride with a particle size of 10-20 μm, flaky boron nitride with a particle size of 1-2 μm and spherical boron nitride with a particle size of 1-3 μm according to a mass ratio of (4-5) to (2-3) to (3-4).
  8. 8. The hydrocarbon resin composition for prepregs according to claim 1, wherein the cross-linking agent is prepared by mixing divinylbenzene and hexamethylene diisocyanate trimer according to a mass ratio of (2-4) to 1.
  9. 9. The method for preparing a hydrocarbon resin composition for prepregs according to any one of claims 1 to 8, comprising the steps of: S1, uniformly mixing an inorganic filler, a silane coupling agent and 1/3 part of toluene to obtain inorganic filler slurry; S2, uniformly mixing hyperbranched modified prepolymer resin and 2/3 parts of toluene to obtain a resin solution; And S3, adding the inorganic filler slurry into the resin solution, uniformly mixing, sequentially adding the dibutyl tin dilaurate, the cross-linking agent and the antioxidant, uniformly mixing, and adding the initiator for reaction to obtain the hydrocarbon resin composition for the prepreg.
  10. 10. The preparation method of the hydrocarbon resin composition for the prepregs, according to claim 9, is characterized in that in the step S1, the mixing step is carried out at a rotating speed of 1000-1500 rpm for 15-30 min, and then grinding and dispersing are carried out for 1-2h, and in the step S3, the reaction temperature is 30-35 ℃, and the reaction time is 1-2 h.

Description

Hydrocarbon resin composition for prepreg and preparation method thereof Technical Field The invention belongs to the technical field of resin materials for copper-clad plates, and particularly relates to a hydrocarbon resin composition for prepregs and a preparation method thereof. Background The copper-clad plate is used as one of the core materials for electronic communication, and has higher and higher performance requirements based on the rapid development of high-speed information processing and high-frequency signal transmission at present. The traditional epoxy resin/glass cloth-based prepreg can generate serious signal attenuation and heating at high frequency due to higher dielectric constant and dielectric loss, and is not applicable. Therefore, the resin material for copper-clad laminate is required to have better dielectric properties, heat resistance and dimensional stability. The material represented by polytetrafluoroethylene has extremely low dielectric constant and dielectric loss, but polytetrafluoroethylene has the problems of large difference of thermal expansion coefficient and copper foil, weak bonding force, poor processability, high cost and the like, and limits the application of the polytetrafluoroethylene in high-frequency and high-speed electronic materials with complex and high reliability requirements. Hydrocarbon resin systems typified by modified polybutadiene, styrene-butadiene copolymer, cycloolefin polymer, etc. have been developed in order to balance properties, manufacturability and cost. The molecular main chain of the material is composed of nonpolar carbon-carbon bonds and carbon-hydrogen bonds, has natural low polarity characteristics, and has good compatibility with the traditional epoxy resin system, thus becoming the main stream choice of the current copper-clad plate. The Chinese patent application document with the application publication number of CN115651128A discloses a hydrocarbon resin polymer and a preparation method of a copper-clad plate containing the hydrocarbon resin polymer, the proposal synthesizes the hydrocarbon resin polymer with low molecular weight, introduces a benzene ring structure, ensures that a resin system is solidified more stably, reduces the thermal expansion coefficient of the copper-clad plate, but uses inorganic filler compounded by silicon dioxide, hollow zirconium dioxide and hollow aluminum oxide according to the ratio of 1:1:1 in the resin composition, and the surface wettability of the hollow powder filler is poor, the hollow powder filler is easy to agglomerate, the binding force with a resin matrix is weak, the uniformity of glue solution is easy to be reduced, and the mechanical property and dielectric property of the copper-clad plate are influenced. Disclosure of Invention The invention provides a hydrocarbon resin composition for prepregs and a preparation method thereof, aiming at solving the problem that the existing hydrocarbon resin composition has poor compatibility of inorganic filler and hydrocarbon resin. In order to achieve the purpose of the invention, the invention adopts the following technical scheme: in a first aspect, the invention provides a hydrocarbon resin composition for prepregs, which is prepared from the following raw materials in parts by mass: 90-100 parts of hyperbranched modified prepolymer resin, 15-25 parts of inorganic filler, 0.2-0.4 part of silane coupling agent, 10-20 parts of cross-linking agent, 0.8-1.5 parts of initiator, 0.1-0.3 part of dibutyl tin dilaurate, 0.5-1 part of antioxidant and 50-80 parts of toluene. By adopting the technical scheme, the advantages of low dielectric property and high toughness of the hyperbranched modified prepolymer resin are fully exerted, the short performance board of a single component is made up by the accurate proportion of the components such as the inorganic filler, the cross-linking agent and the like, and the effects of improving the compatibility of the filler, controlling the cross-linking reaction and enhancing the heat resistance and oxidation resistance are realized by adding the silane coupling agent, the dibutyl tin dilaurate and the antioxidant, so that the proportion of the raw materials is scientific and reasonable, and the synergistic effect is obvious. Further, the preparation method of the hyperbranched modified prepolymer resin comprises the following steps: (1) Uniformly mixing hydroxyl-terminated hyperbranched polyester, maleic anhydride, p-toluenesulfonic acid and N, N-dimethylformamide, and reacting for 3-5 hours at 60-90 ℃ under the protection of inert gas to obtain anhydride modified hyperbranched polyester; (2) The aromatic ring copolymerized polybutadiene, the anhydride modified hyperbranched polyester, the dicumyl peroxide and the dimethylbenzene are uniformly mixed, and react for 2-4 hours at 110-130 ℃ under the protection of inert gas, then the temperature is raised to 140-160 ℃ for 0.5-1 hour, and the hyperbranched mod