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CN-122011680-A - Glass cloth-based epoxy prepreg sheet pressed without gumming and preparation method thereof

CN122011680ACN 122011680 ACN122011680 ACN 122011680ACN-122011680-A

Abstract

The invention relates to the technical field of high-performance composite materials, in particular to a glass cloth-based epoxy prepreg sheet pressed without gummosis and a preparation method thereof. The glass cloth-based epoxy prepreg is prepared by impregnating glass fiber cloth with glue solution and performing semi-curing treatment, wherein the glue solution comprises, by weight, 35-45 parts of tetrafunctional epoxy resin, 30-40 parts of biphenyl epoxy resin, 10-20 parts of hydrogenated bisphenol A epoxy resin, 40-55 parts of phenolic resin, 10-20 parts of surface epoxy functionalized PES micro powder, 30-40 parts of spherical silica, 0.3-0.8 part of curing accelerator, 0.5-1.5 parts of KH-560, an organic solvent, a toughening agent and a flame retardant. The three-stage sectional drying is used for constructing a step curing process, the reaction degree of the semi-curing stage is accurately controlled, and the glass cloth-based epoxy prepreg is prepared, has uniform flow characteristics and storage stability, and realizes the performance balance effect of three integration of flame retardance, flow inhibition and toughness.

Inventors

  • ZENG ZHAOFENG
  • ZHANG XIAOQING
  • CAO ZHENGLIN
  • HUA GUOQING

Assignees

  • 俊萱新材料(杭州)有限公司

Dates

Publication Date
20260512
Application Date
20260325

Claims (10)

  1. 1. The glass cloth-based epoxy prepreg is characterized in that the prepreg is prepared by impregnating glass fiber cloth with glue solution and performing semi-curing treatment; The glue solution comprises, by weight, 35-45 parts of tetrafunctional epoxy resin, 30-40 parts of biphenyl epoxy resin, 10-20 parts of hydrogenated bisphenol A epoxy resin, 40-55 parts of phenolic resin, 10-20 parts of surface epoxy functionalized PES micro powder, 30-40 parts of spherical silicon dioxide, 0.3-0.8 part of curing accelerator, 0.5-1.5 parts of KH-560 and an organic solvent.
  2. 2. The laminated non-gummed glass cloth-based epoxy prepreg according to claim 1, wherein the preparation of the surface epoxy functionalized PES micro powder comprises the following steps: (1) Pretreating raw materials, namely placing PES micro powder into a vacuum drying oven, drying for 4-6 hours at 100-120 ℃, removing water physically adsorbed on the surface, and cooling for later use; (2) Adding KH-560 into a first part of absolute ethyl alcohol to obtain a mixed solution A, mixing deionized water and glacial acetic acid to obtain a mixed solution B with a pH value of 4-5, slowly dripping the mixed solution B into the mixed solution A, stirring for 30-60 minutes at room temperature to fully hydrolyze the mixed solution B, and obtaining a clear and transparent pre-hydrolyzed solution; (3) Adding a second part of absolute ethyl alcohol into a reaction container, starting stirring, slowly adding PES micro powder pretreated in the step S1, uniformly dispersing to form suspension, heating the reaction container to 50-60 ℃, slowly dripping the pre-hydrolyzed solution in the step S2 into the PES micro powder suspension in a stirring state, heating the reaction system to 75-85 ℃ after dripping, and continuously reacting for 4-6 hours in a reflux state; (4) And (3) post-treatment and drying, namely cooling to room temperature after the reaction is finished, centrifugally separating a reaction product, collecting a solid material, washing the solid material for a plurality of times by using absolute ethyl alcohol until the washing liquid is clear, transferring the washed wet filter cake to a vacuum drying oven for drying to constant weight, and sieving the dried product to obtain the PES micropowder with the surface functionalized by epoxy.
  3. 3. The laminated adhesive-free glass cloth-based epoxy prepreg according to claim 2, wherein the surface epoxy functionalized PES micro powder is prepared from, by weight, 90-110 parts of PES micro powder, 3-8 parts of KH-560, 100 parts of first absolute ethyl alcohol, 1.5-3 parts of deionized water and 200 parts of second absolute ethyl alcohol.
  4. 4. The laminated non-gumming glass cloth-based epoxy prepreg according to claim 1, wherein the spherical silica comprises the following raw materials, by weight, 20-25 parts of submicron spherical silica and 10-15 parts of amino silanization-treated nanoscale spherical silica.
  5. 5. The laminated non-gumming glass cloth-based epoxy prepreg according to claim 1, wherein the curing accelerator is an imidazole accelerator and triphenylphosphine in a weight ratio of 1 (2-5), and the imidazole accelerator is any one selected from 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
  6. 6. The laminated non-gumming glass cloth-based epoxy prepreg according to claim 1, further comprising 5-12 parts of a toughening agent, wherein the toughening agent is a core-shell structured acrylate polymer.
  7. 7. The laminated non-gumming glass cloth-based epoxy prepreg according to claim 1, further comprising 10-20 parts of a flame retardant, wherein the flame retardant is any one of DOPO and DOPO derivatives.
  8. 8. A method for preparing the laminated non-gumming glass cloth-based epoxy prepreg according to any one of claims 1 to 7, which is characterized by adopting the following technical scheme: S1, dipping, namely pre-treating the glass fiber cloth to remove surface moisture and impurities, passing the pre-treated glass cloth through a dipping tank containing glue solution at a stable speed through a dipping-extrusion process to fully soak the glue solution, extruding the dipped material through a metering roller to remove redundant glue solution, and controlling the resin content to obtain a prepreg wet material; S2, semi-curing, namely placing the prepreg wet material obtained in the step S2 into a drying box for sectional drying to obtain a semi-cured prepreg; S3, rolling and storing, namely cooling the semi-cured prepreg obtained in the step S3 to room temperature by a cooling roller, coating a polyethylene isolating film on the surface, rolling, and sealing and packaging the product and storing the product in a clean environment.
  9. 9. The method for preparing the laminated non-gummed glass cloth-based epoxy prepreg according to claim 8, wherein the gum solution in the step S1 is prepared according to the following method: S11, adding the tetrafunctional epoxy resin, the biphenyl epoxy resin and the hydrogenated bisphenol A type epoxy resin into a reaction kettle, stirring and mixing, heating to 70-80 ℃, stirring at a constant temperature until the resin is completely melted and uniformly mixed, enabling the system to be in a transparent uniform state, and then cooling to 40-60 ℃ for standby; S12, sequentially adding surface epoxy functionalized polyether sulfone micro powder, submicron spherical silica and amino silanization treated nanometer spherical silica into the resin mixture obtained in the step S11, increasing the stirring rotation speed, and dispersing at a high speed under a vacuum condition to ensure that the powder is sufficiently wet, uniformly dispersed and free of agglomerated particles; s13, cooling the mixture obtained in the step S12 to 40-50 ℃, adding phenolic resin and a curing accelerator under stirring, reducing the stirring rotation speed, and continuously mixing under vacuum condition to completely dissolve and uniformly disperse the curing agent; s14, adjusting the viscosity of the glue solution to 1800-2200 mPa.s by using an organic solvent, sieving the glue solution with a 150-250 mesh sieve, discharging, standing and defoaming for standby.
  10. 10. The method for preparing the laminated non-gumming glass cloth-based epoxy prepreg according to claim 8, wherein the step S2 is characterized in that the step S2 is carried out by sectional drying, namely, a first area is 100-120 ℃, the second area is 135-145 ℃, the third area is 2-4 minutes, and the third area is 150-160 ℃ and the third area is 1-2 minutes.

Description

Glass cloth-based epoxy prepreg sheet pressed without gumming and preparation method thereof Technical Field The invention relates to the technical field of high-performance composite materials, in particular to a glass cloth-based epoxy prepreg sheet pressed without gummosis and a preparation method thereof. Background Glass cloth-based epoxy prepregs are core base materials for the manufacture of multilayer printed circuit boards and high performance electrical insulation components. In general, it refers to a sheet-like composite material formed by impregnating a glass fiber cloth with an epoxy resin system in a semi-cured state by a specific process and then drying the same. The material has certain operability at normal temperature, and in the subsequent heating and pressurizing lamination process, the resin system further generates a crosslinking reaction to realize complete solidification, so that the multi-layer circuit pattern or the insulating layer is bonded into a whole. In the lamination process of the multilayer board, the flow characteristics of the resin in the prepreg are key factors in determining the quality of the product. Proper fluidity is a precondition for ensuring that the resin is able to sufficiently fill the gaps between the wires, eliminate interlayer air bubbles, and achieve firm adhesion with the inner layer copper foil or core board. However, if the fluidity of the resin is too high, the phenomenon of "gumming" is generated, which not only causes a great amount of resin loss and uncontrolled thickness of the medium, but also causes interlayer slippage, hidden trouble of short circuit and appearance defect due to resin overflow. To effectively control the gumming problem during lamination, the prior art has generally focused on adjusting the formulation composition of the resin system and its physical state. The common technical means comprises adding various tackifiers or high molecular tougheners into an epoxy resin matrix to improve the melt viscosity of the resin, changing the gelation time and fluidity of a resin system by controlling the baking conditions in the manufacturing process of the prepreg, and precisely regulating and controlling the resin content in the prepreg. These methods have somewhat constrained the flow behavior of the resin. However, the above methods often have contradictions that are difficult to reconcile between the inhibition of bleeding and the ensuring of good filling and interlayer bonding forces. In order to pursue extremely low amounts of gumming, the prior art generally tends to excessively increase the melt viscosity of the resin system at the lamination temperature or to accelerate its rate of gel reaction. This, while limiting macroscopic lateral flow of the resin, tends to significantly impair the microscopic wetting ability of the resin to the tows within the fiberglass cloth and to the roughened copper foil surface. As a result, minute voids or weak points of bonding force are easily generated at the interface of the laminate after curing, resulting in a decrease in interlayer peel strength, severely affecting the reliability and service life of the product. Therefore, there is an urgent need to develop a laminated non-gumming glass cloth-based epoxy prepreg and a preparation method thereof, so that under standard lamination process conditions, excellent resin fluidity can be maintained to fully infiltrate a fine interface and fill gaps, thereby ensuring high interface bonding strength, and macroscopic lateral flow of resin can be controlled at an extremely low level, thus truly realizing the effect of 'lamination non-gumming' or 'near zero gumming', and meeting the requirements of manufacturing high-density and high-reliability multilayer boards. Disclosure of Invention In order to meet the requirements of glass cloth-based epoxy prepreg on manufacturing of high-density and high-reliability multilayer plates, the application provides the glass cloth-based epoxy prepreg which is pressed without glue and a preparation method thereof, wherein the glass cloth-based epoxy prepreg can maintain excellent resin fluidity under standard lamination process conditions to fully infiltrate a fine interface and fill gaps, ensure high interface bonding strength, and can control macroscopic transverse flow of resin at an extremely low level, so that the effect of pressing without glue or near zero glue is truly realized. In a first aspect, the application provides a glass cloth-based epoxy prepreg which is pressed and not gummed, wherein the prepreg is prepared by dipping glass fiber cloth in a gum solution and performing semi-curing treatment; The glue solution comprises, by weight, 35-45 parts of tetrafunctional epoxy resin, 30-40 parts of biphenyl epoxy resin, 10-20 parts of hydrogenated bisphenol A epoxy resin, 40-55 parts of phenolic resin, 10-20 parts of surface epoxy functionalized PES micro powder, 30-40 parts of spherical silicon dioxide, 0.3