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CN-121978866-A - Photosensitive low-dielectric resin composition and preparation method thereof

CN121978866ACN 121978866 ACN121978866 ACN 121978866ACN-121978866-A

Abstract

The application belongs to the technical field of electronic materials, and discloses a photosensitive low-dielectric resin composition and a preparation method thereof, wherein the preparation method comprises the steps of heating and reacting an elastomer with a modified compound to obtain a modified elastomer; heating and reacting maleimide monomer and triazine compound to obtain maleimide-triazine reactant, activating filler, adding the activated filler into solution containing hyperbranched monomer, heating and reacting, filtering and drying to obtain modified filler, mixing resin with modified elastomer and maleimide-triazine reactant to obtain prepolymer, adding functional auxiliary agent into the prepolymer, and stirring and mixing the modified filler to obtain the photosensitive low dielectric resin composition. The photosensitive low-dielectric resin composition prepared by the method has higher photosensitive sensitivity and lower dielectric constant.

Inventors

  • WANG DAOQUN
  • Xie Daizhong
  • CHEN ZHENWEN

Assignees

  • 惠州市则成技术有限公司

Dates

Publication Date
20260505
Application Date
20260304

Claims (10)

  1. 1. A method for preparing a photosensitive low dielectric resin composition, comprising the steps of: s1, heating and reacting an elastomer with a modified compound to obtain a modified elastomer, wherein the elastomer and the modified compound contain carbon-carbon double bonds, and the modified compound is used for introducing furan groups and tertiary amine groups into the elastomer; s2, heating and reacting a maleimide monomer with a triazine compound to obtain a maleimide-triazine reactant; S3, adding the filler into a strong alkali solution for activation treatment to obtain an activated filler, adding the activated filler into a solution containing hyperbranched monomers, heating for reaction, filtering and drying to obtain a modified filler, wherein the hyperbranched monomers at least contain one carboxyl group and two hydroxyl groups; s4, mixing the resin with the modified elastomer and the maleimide-triazine reactant to obtain a prepolymer, and adding the functional auxiliary agent and the modified filler into the prepolymer to be stirred and mixed to obtain the photosensitive low-dielectric resin composition.
  2. 2. The method for producing a photosensitive low dielectric resin composition according to claim 1, wherein the elastomer in step S1 comprises at least one of a styrene-butadiene-styrene block copolymer, a polybutadiene rubber, a natural rubber, and a styrene-butadiene rubber, and the modifying compound comprises at least one of N-allyl-2- (dimethylaminomethyl) furan, 4- (2-furanethyl) -1- (vinyl phenyl) piperazine, and N- (2-furanethyl) -N-allylmorpholine.
  3. 3. The method for producing a photosensitive low dielectric resin composition according to claim 1, wherein step S1 comprises: S1.1, dissolving a tertiary amine monomer and a base catalyst in anhydrous tetrahydrofuran, dropwise adding a furan monomer under stirring, stirring and reacting for 6-24 hours at 40-50 ℃, washing the mixture to be neutral in a water phase by sequentially using dilute hydrochloric acid, saturated sodium bicarbonate and deionized water to obtain an organic phase, performing vacuum fractionation, and collecting a fraction at 85-120 ℃ to obtain a modified compound, wherein the tertiary amine monomer comprises at least one of N-allylmethylamine, 1- (4-vinyl phenyl) piperazine and N-allylmorpholine, the furan monomer is at least one of 2-chloromethylfuran, 2-bromomethylfuran and 2- (2-bromoethyl) furan, the base catalyst comprises at least one of triethylamine, pyridine and 4-dimethylaminopyridine, and the mass ratio of the tertiary amine monomer to the base catalyst to the anhydrous tetrahydrofuran is 1 (1.05-1.10) (1.0-1.2) (8-12); S1.2, heating the elastomer, a modified compound, azodiisobutyronitrile and anhydrous toluene to 70-80 ℃ for stirring reaction for 5-7 hours to obtain a modified solution, wherein the mass ratio of the elastomer to the modified compound to the anhydrous toluene is 1 (0.05-0.30) (2-4), and the mass of the azodiisobutyronitrile is 0.5-2wt% of the modified compound; S1.3, adding a impurity removing agent into the modified solution, stirring for 30-90 min at room temperature, and filtering to obtain the modified elastomer, wherein the impurity removing agent comprises at least one of neutral and/or alkaline alumina, weak alkaline hydroxyapatite and zirconia, and the adding amount of the impurity removing agent is 3-8wt% of the mass of the modified solution.
  4. 4. A method for producing a photosensitive low dielectric resin composition according to claim 3, wherein step S1.2 further comprises: S1.2, mixing an elastomer with a first correcting compound, a first batch of azodiisobutyronitrile and anhydrous toluene, stirring at 50-60 ℃ for 2-3 hours, adding a second correcting compound and a second batch of azodiisobutyronitrile, heating to 70-80 ℃ for 3-4 hours, stirring, and obtaining a modified elastomer, wherein the mass ratio of the elastomer to the anhydrous toluene is 1 (0.05-0.30): 2-4), the mass ratio of the first correcting compound to the second correcting compound is 0.3-0.5): 0.7-0.5, the mass ratio of the first batch of azodiisobutyronitrile is 0.2-0.5 wt% of the mass of the first correcting compound, and the total mass of the azodiisobutyronitrile is 0.5-2 wt% of the total mass of the modified compound.
  5. 5. The method for producing a photosensitive low dielectric resin composition according to claim 1, wherein the maleimide monomer in step S2 comprises at least one of 4,4' -bismaleimide diphenylmethane, 1, 3-bis (maleimido) benzene, 1, 6-bismaleimidohexane, and the triazine compound comprises melamine and/or 2,4, 6-triphenylamino-1, 3, 5-triazine.
  6. 6. The method for producing a photosensitive low dielectric resin composition according to claim 1, wherein step S2 comprises: S2.1, dissolving maleimide, a triazine compound and a catalyst 2-ethyl-4 methylimidazole in dimethylacetamide, and heating to 90-110 ℃ in an inert atmosphere, stirring and reacting for 3-5 hours to obtain a maleimide-triazine prepolymer, wherein the mass ratio of maleimide to triazine compound to 2-ethyl-4 methylimidazole to dimethylacetamide is (100-110): 70-85): 0.5-1.5): 200-300; S2.2, adding polycyclic aromatic hydrocarbon into cyclohexanone solution, and stirring for 1.5-2.5 hours at 60-70 ℃ to obtain a polycyclic ring solution, wherein the polycyclic aromatic hydrocarbon is pyrene-4, 5,9, 10-tetraone and/or coronene-5, 6,11, 12-tetraone, and the concentration of the polycyclic aromatic hydrocarbon in the polycyclic ring solution is 5-15wt%; S2.3, dropwise adding the condensed ring solution into the maleimide-triazine prepolymer under the stirring condition, and stirring and reacting for 2-3 hours at 130-150 ℃ to obtain a maleimide-triazine reactant, wherein the mass ratio of the condensed ring solution to the maleimide-triazine prepolymer is (3-5).
  7. 7. The method for preparing a photosensitive low dielectric resin composition according to claim 1, wherein the filler in step S3 is spherical silica containing nano-pore size or solid, and the hyperbranched monomer comprises at least one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, 2-dimethylolvaleric acid, and trimethylol acetic acid, and step S3 comprises: S3.1, adding the filler into a strong alkali solution with the strong alkali concentration of 1-1.5 mol/L, stirring at 60-80 ℃ for 1-2 hours, filtering, washing with deionized water to be neutral, and obtaining a pretreated filler, wherein the strong alkali is sodium hydroxide and/or potassium hydroxide, and the mass ratio of the filler to the strong alkali solution is (5-20); S3.2, adding the pretreated filler into a high-pressure reaction kettle containing deionized water, heating to 120-150 ℃ at 2-3 ℃ per minute, carrying out constant-pressure stirring treatment for 1-2 hours, releasing pressure when the treated system is hot, rapidly carrying out hot filtration separation, immediately washing the obtained filter cake with hot deionized water above 80 ℃ for 4-8 times, and drying to obtain the activated filler, wherein the mass ratio of the pretreated filler to the deionized water is (15-20); S3.3, adding the activated filler into a solution containing hyperbranched monomers, heating to 100-150 ℃ in an inert atmosphere, stirring and reacting for 6-24 hours, filtering, washing with N, N-dimethylformamide, washing with ethanol, and drying to obtain the modified filler, wherein the solution is N, N-dimethylformamide or dimethyl sulfoxide, the concentration of the hyperbranched monomers in the solution is 5-30wt%, and the mass ratio of the activated filler to the hyperbranched monomers is 1 (0.5-3).
  8. 8. The method for preparing a photosensitive low dielectric resin composition according to claim 1, wherein the resin in the step S4 is a vinyl-containing resin, the vinyl-containing resin comprises at least one of hydrogenated dicyclopentadiene divinyl ether, hydrogenated dicyclopentadiene diacrylate and vinyl norbornene, the functional auxiliary agent is a composition of a photoacid generator, a flame retardant and a thermal free radical initiator, the photoacid generator comprises at least one of triarylsulfonium salts, diaryl iodonium salts and N-hydroxyimide sulfonate compounds, the flame retardant is a bromine-containing flame retardant and/or a phosphorus-containing flame retardant, and the thermal free radical initiator comprises at least one of dicumyl peroxide, benzoyl peroxide and azobisisobutyronitrile.
  9. 9. The method for producing a photosensitive low dielectric resin composition according to claim 1 or 8, wherein step S4 comprises: S4.1, adding a modified elastomer into resin at 80-90 ℃ under stirring conditions, stirring for 0.5-1.5 h, then heating to 100-120 ℃, adding a maleimide-triazine reactant, and stirring for 1-2 h in a pulse ultrasonic wave with the power of 400-600W and the frequency of 22-28 kHz to obtain a prepolymer, wherein the mass ratio of the modified elastomer to the maleimide-triazine reactant is (15-30): 10-22): 10-23; S4.2, adding a functional auxiliary agent and a modified filler into the prepolymer, and stirring and mixing at 40-60 ℃ for 0.5-2 hours to obtain the photosensitive low-dielectric resin composition, wherein the mass ratio of the functional auxiliary agent to the modified filler is (35-75): (5-23): (5-50), and the mass ratio of the photoacid generator, the flame retardant and the thermal free radical initiator in the functional auxiliary agent is (0.5-4): (4-15): (0.5-4).
  10. 10. A photosensitive low dielectric resin composition, characterized in that it is produced by a process for producing a photosensitive low dielectric resin composition according to any one of claims 1 to 9.

Description

Photosensitive low-dielectric resin composition and preparation method thereof Technical Field The application relates to the technical field of electronic materials, in particular to a photosensitive low-dielectric resin composition and a preparation method thereof. Background Positive photosensitive resin is used as a key material in advanced packaging of integrated circuits and high-density interconnection (HDI) substrate manufacturing, and has the core advantage that fine patterning can be directly realized through an efficient and accurate photoetching process, so that urgent requirements of modern electronic equipment on high wiring density and complex interconnection structures are met. The material can selectively dissolve an exposure area through an alkaline aqueous solution after exposure due to excellent photosensitivity and development characteristics, and realizes high-resolution pattern transfer completely consistent with mask patterns, and the characteristics obviously improve the efficiency and precision of a patterning process and avoid the complexity and material loss of the traditional etching process. However, the traditional resin system faces serious interface regulation and control challenges in multi-component compounding and graphic processing, namely, on one hand, the compatibility difference between the toughened elastomer and the rigid resin matrix is easy to induce microscopic phase separation to form a weak bonding interface with abrupt electrical property changes, the phase separation structure can seriously scatter and attenuate exposure light and prevent the photoacid generator and reaction products thereof from diffusing, so that the photochemical reaction efficiency is reduced, the photosensitivity is obviously reduced, and on the other hand, the inorganic filler and the organic matrix are easy to generate infiltration defects due to surface energy mismatch to form nano-scale micropores and an adsorption water layer. These interface defects can cause free charges to accumulate in large amounts at the heterogeneous interface, exacerbating the frequency dispersion phenomenon of the dielectric loss factor. Meanwhile, interfacial stress concentration in the curing process can promote migration and enrichment of polar small molecules to an interface region to form a local high-polarization domain, so that the electromagnetic field uniformity of the dielectric layer is further damaged. Disclosure of Invention The invention aims to solve the technical problems of low sensitivity and high dielectric constant of resin caused by interface polarization due to poor compatibility among multiple components in photosensitive resin. In order to solve the technical problems, the invention provides a preparation method of a photosensitive low-dielectric resin composition, which comprises the following preparation steps: s1, heating and reacting an elastomer with a modified compound to obtain a modified elastomer, wherein the elastomer and the modified compound contain carbon-carbon double bonds, and the modified compound is used for introducing furan groups and tertiary amine groups into the elastomer; s2, heating and reacting a maleimide monomer with a triazine compound to obtain a maleimide-triazine reactant; S3, activating the filler, adding the activated filler into a solution containing hyperbranched monomers, heating for reaction, filtering and drying to obtain modified filler, wherein the hyperbranched monomers contain one carboxyl group and at least two hydroxyl groups; s4, mixing the resin with the modified elastomer and the maleimide-triazine reactant to obtain a prepolymer, and adding the functional auxiliary agent and the modified filler into the prepolymer to be stirred and mixed to obtain the photosensitive low-dielectric resin composition. In some embodiments, the elastomer in step S1 comprises at least one of a styrene-butadiene-styrene block copolymer, polybutadiene rubber, natural rubber, styrene-butadiene rubber, and the modifying compound comprises at least one of N-allyl-2- (dimethylaminomethyl) furan, 4- (2-furanethyl) -1- (vinyl phenyl) piperazine, N- (2-furanethyl) -N-allylmorpholine. In some embodiments, step S1 comprises: S1.1, dissolving a tertiary amine monomer and a base catalyst in anhydrous tetrahydrofuran, dropwise adding a furan monomer under stirring, stirring and reacting for 6-24 hours at 40-50 ℃, washing the mixture to be neutral in a water phase by sequentially using dilute hydrochloric acid, saturated sodium bicarbonate and deionized water to obtain an organic phase, performing vacuum fractionation, and collecting a fraction at 85-120 ℃ to obtain a modified compound, wherein the tertiary amine monomer comprises at least one of N-allylmethylamine, 1- (4-vinyl phenyl) piperazine and N-allylmorpholine, the furan monomer is at least one of 2-chloromethylfuran, 2-bromomethylfuran and 2- (2-bromoethyl) furan, the base catalyst comprises at least one of triet