A low dielectric epoxy resin for copper clad laminate and its processing technology

Abstract

The invention relates to the field of copper clad laminates and specifically discloses a low-dielectric epoxy resin for copper clad laminates and a processing technology thereof. The low-dielectric epoxy resin for copper clad laminates comprises a component A and a component B. Component A comprises the following raw materials, calculated in parts by mass: 100-150 parts of acetone, 250-300 parts of bisphenol A epoxy resin, and 50-100 parts of low-dielectric fillers; component B comprises the following raw materials, calculated in parts by mass: 150-250 parts of a low-dielectric curing agent, 20-30 parts of a curing agent, and 10-20 parts of a curing accelerator. The preparation of the low-dielectric curing agent comprises the following steps: taking a diamine modifier, 4,4'-diaminodiphenyl ether, 4,4'-oxydiphthalic anhydride, and meta-cresol, stirring under nitrogen protection, adding isoquinoline, stirring, cooling, adding meta-cresol, discharging the material while hot into ethanol, washing, filtering, extracting to remove the meta-cresol, and vacuum drying to obtain the low-dielectric curing agent.

Description

Technical Field

[0001] The invention relates to the field of copper clad laminates, and particularly discloses a low-dielectric epoxy resin for copper clad laminates and a processing technology thereof. Background Art

[0002] With the advancement of science and technology, people's requirements for information transmission and communication are getting higher and higher. 5G communication is gradually integrated into production and life. In order to pursue lower signal delay to meet the use requirements of equipment, various smart devices require low dielectricity to improve the fidelity of 5G communication.

[0003] Epoxy resins have excellent mechanical, electrical, dimensional, and adhesive properties. Epoxy resin-based copper-clad laminates offer many advantages, but their dielectric constants still need to be reduced. Furthermore, due to their chemical structure, epoxy resins are brittle without toughening treatment, limiting their application. Therefore, research on an epoxy resin for copper-clad laminates that combines low dielectric properties with high toughness and its processing technology is of great significance. Summary of the Invention

[0004] The object of the present invention is to provide a low dielectric epoxy resin for copper clad laminates and a processing technology thereof, so as to solve the problems raised in the above background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solution: a low-dielectric epoxy resin for copper-clad laminates, comprising component A and component B; component A comprises the following raw materials, calculated in parts by mass: 100-150 parts of acetone, 250-300 parts of bisphenol A epoxy resin, and 100-130 parts of low-dielectric filler; component B is a curing component, comprising the following raw materials, calculated in parts by mass: 150-250 parts of low-dielectric curing agent, 20-30 parts of curing agent, and 10-20 parts of curing accelerator.

[0006] Preferably, the bisphenol A epoxy resin includes but is not limited to epoxy resin E44; the curing agent contains an amino group, including but not limited to 2,4-diaminodiphenylamine; and the curing accelerator includes but is not limited to imidazole.

[0007] Preferably, the preparation of the low dielectric curing agent includes the following steps: taking a diamine modifier, 4,4'-diaminodiphenyl ether, 4,4'-oxydiphthalic anhydride, and m-cresol, stirring under nitrogen protection, adding isoquinoline, stirring, adding m-cresol after cooling, discharging the material while hot into ethanol, washing, filtering, extracting to remove m-cresol, and vacuum drying to obtain a low dielectric curing agent.

[0008] Preferably, the low dielectric curing agent comprises the following raw materials, calculated by mass: 3 to 8 parts of diamine modifier, 8 to 15 parts of 4,4'-diaminodiphenyl ether, 20 to 30 parts of 4,4'-oxydiphthalic anhydride, 200 to 300 parts of m-cresol, 10 to 20 parts of isoquinoline, and 600 to 800 parts of ethanol.

[0009] Preferably, the preparation of the diamine modifier comprises the following steps: S1: taking 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane, stirring evenly to prepare solution A; taking undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and propylene glycol, mixing evenly to prepare solution B; taking trichloronitrobenzene, potassium carbonate A, and methanol, mixing evenly, cooling to 0-1°C, adding solution A dropwise thereto under nitrogen protection, stirring and heating under reflux for 20-25h, adding potassium carbonate B, cooling to 0-1°C, adding solution B dropwise thereto under nitrogen protection, stirring and heating under reflux for 25-30h, cooling to room temperature, precipitating in saturated sodium chloride ice water solution, and collecting solid by filtration; recrystallizing the obtained solid from methanol, filtering and drying to obtain substance A;

[0010] S2: Take ammonium formate and ethanol, stir evenly to obtain solution C; add substance A, palladium carbon catalyst, and 1,4-dioxane, stir evenly, heat to reflux, slowly add solution C dropwise, reflux and stir for 20 to 25 hours, filter while hot to remove the palladium carbon catalyst, add saturated sodium chloride ice water solution, dry, and perform column chromatography to obtain a diamine modifier.

[0011] Preferably, the diamine modifier includes the following raw materials, calculated by mass: 20 to 30 parts of substance A, 0.5 to 2 parts of palladium-carbon catalyst, 80 to 150 parts of 1,4-dioxane, and 80 to 150 parts of solution C; in substance A, the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole is (1 to 1.5): (1 to 1.5): 1: 1, the mass of potassium carbonate A is 10 to 15% of the mass of trichloronitrobenzene, and the mass of methanol is 6 to 8 times that of trichloronitrobenzene; the mass of potassium carbonate B is 15 to 25% of the mass of undecyl alcohol.

[0012] Preferably, the solution A comprises 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane in a mass ratio of 1:(8-12); the solution B comprises undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and propylene glycol in an amount 8-12 times the total mass of undecyl alcohol and 4-hydroxy-3-tert-butyl-anisole; and the solution C comprises ammonium formate and ethanol in a mass ratio of 1:(4-5).

[0013] Preferably, the preparation of the low dielectric filler includes the following steps: adding hollow glass microspheres to a sodium hydroxide aqueous solution, reflux stirring and reacting for 1 to 2 hours, washing until neutral and drying, adding an ethanol aqueous solution and an aminosilane coupling agent, stirring at 70 to 80°C for 4 to 6 hours, filtering, washing with water, and drying to obtain an amino-modified filler; taking the amino-modified filler, acetone, and 1,6-hexanediol diglycidyl ether, mixing them evenly, refluxing for 6 to 8 hours, removing the solvent, washing, and drying to obtain a low dielectric filler.

[0014] Preferably, the concentration of the sodium hydroxide aqueous solution is 0.3 mol / L; in the ethanol aqueous solution, the volume ratio of ethanol to water is (6-8):1; and the aminosilane coupling agent is KH550.

[0015] Preferably, the low dielectric filler includes the following raw materials, calculated by mass: 10 to 20 parts of amino-modified filler, 100 to 150 parts of acetone, and 3 to 8 parts of 1,6-hexanediol diglycidyl ether; in the amino-modified filler, the amount of ethanol aqueous solution added is 8 to 12 times the mass of the hollow glass microspheres, and the amount of aminosilane coupling agent added is 5 to 10% of the mass of the hollow glass microspheres; the concentration of the hollow glass microspheres in the sodium hydroxide aqueous solution is 0.03 to 0.05 mg / mL.

[0016] Preferably, the processing technology of a low-dielectric epoxy resin for copper clad laminates described in any one of the above items comprises the following steps: taking acetone and bisphenol A epoxy resin, mixing them evenly, adding a low-dielectric filler, and stirring evenly to obtain component A; taking a low-dielectric curing agent, a curing agent, and a curing accelerator, stirring for 3 to 5 minutes to obtain component B; adding component B to component A, mixing evenly, and obtaining a low-dielectric epoxy resin for copper clad laminates.

[0017] Compared with the prior art, the present invention has the following beneficial effects: a low-dielectric epoxy resin for copper-clad laminates is prepared, comprising component A and component B; a low-dielectric filler is added to component A, wherein the filler is obtained by modifying hollow glass microspheres with amino groups with 1,6-hexanediol diglycidyl ether; the hollow glass microspheres have a hollow structure and can greatly reduce the dielectric constant of the epoxy resin after being added; 1,6-hexanediol diglycidyl ether is a reactive diluent, and its introduction can improve the processability of the epoxy resin; since it contains flexible chain segments, the toughness of the epoxy resin can be improved, while the polarization degree is reduced, which is conducive to reducing the dielectric constant; the modification also introduces epoxy groups into the hollow glass microspheres, thereby improving their compatibility with the epoxy resin and component B.

[0018] Component B includes a low dielectric curing agent, a curing agent, and a curing accelerator. The low dielectric curing agent is prepared from a diamine modifier, 4,4'-diaminodiphenyl ether, and 4,4'-oxydiphthalic anhydride. During the preparation process, a large amount of 4,4'-oxydiphthalic anhydride is added. Therefore, the two ends of the low dielectric modifier are active carboxylic acid anhydride groups. Compared with the amino-cured epoxy resin, the structure generated when the anhydride cures the epoxy resin has a lower polarity, which helps to reduce the dielectric constant; the raw materials of the diamine modifier include undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene, and 1-methyl-5-nitro-2-hydroxymethylimidazole in a molar ratio of (1 to 1.5): (1 to 1.5): 1:1. First, the -OH in 1-methyl-5-nitro-2-hydroxymethylimidazole reacts with a -Cl in trichloronitrobenzene, and then undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole and another The -Cl reaction is carried out to obtain substance A, and then -NO2 is converted into -NH2 through modification to obtain a diamine modifier; among them, the imidazole structure of 1-methyl-5-nitro-2-hydroxymethylimidazole can improve heat resistance and water resistance, and also has a positive effect on improving the toughness of epoxy resin and reducing the dielectric constant; 4-hydroxy-3-tert-butyl-anisole contains tert-butyl group, and the introduction of tert-butyl group can effectively reduce the dielectric constant. At the same time, the anisole structure also helps to improve the performance of epoxy resin; undecyl alcohol improves the fluidity and processability of epoxy resin, and its long chain helps to improve the brittleness of epoxy resin and improves tensile properties; the introduction of the above three substances in a certain proportion can effectively improve the toughness of epoxy resin and reduce the dielectric constant; the low dielectric curing agent prepared by this method is used in combination with traditional amino curing agent and curing accelerator, which not only gives epoxy resin excellent performance but also improves curing efficiency. DETAILED DESCRIPTION

[0019] The following describes preferred implementations of the present invention. Obviously, the described embodiments are only a portion of the embodiments of the present invention, not all of them. It will be apparent to those skilled in the art that all other implementations derived without inventive effort, without departing from the principles of the present invention, are within the scope of protection of the present invention.

[0020] The following parts are by mass unless otherwise specified;

[0021] Example 1: S1: Take 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane in a mass ratio of 1:10, stir evenly, and configure to solution A; take undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and 10 times the mass of propylene glycol, mix evenly, and configure to solution B; take trichloronitrobenzene, potassium carbonate A, and methanol, cool to 0°C, add solution A dropwise thereto under nitrogen protection, stir and heat under reflux for 22h, add potassium carbonate B, cool to 0°C, add solution B dropwise thereto under nitrogen protection, stir and heat Reflux for 26 hours, cool to room temperature, precipitate in 500 parts of saturated sodium chloride ice water solution, and collect the solid by suction filtration; the obtained solid is recrystallized from methanol, filtered and dried to obtain substance A; the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole is 1.2:1.2:1:1, the mass of potassium carbonate A is 12% of the mass of trichloronitrobenzene, the mass of methanol is 7 times that of trichloronitrobenzene; the mass of potassium carbonate B is 24% of the mass of undecyl alcohol;

[0022] S2: Take ammonium formate and ethanol in a mass ratio of 1:5, stir evenly to obtain solution C; add 25 parts of substance A, 1 part of palladium carbon catalyst, and 120 parts of 1,4-dioxane, stir evenly, heat to reflux, slowly add 120 parts of solution C dropwise, and reflux and stir for 24 hours; filter while hot to remove the palladium carbon catalyst, add 500 parts of saturated sodium chloride ice water solution, dry, and then perform column chromatography with dichloromethane and ethyl acetate in a volume ratio of 1:1 to obtain a diamine modifier;

[0023] S3: Add 6 parts of diamine modifier, 12 parts of 4,4'-diaminodiphenyl ether, 25 parts of 4,4'-oxydiphthalic anhydride, and 250 parts of m-cresol, and stir at 80°C for 7 hours under nitrogen protection. Add 15 parts of isoquinoline, stir at 115°C for 8 hours, stir at 180°C for 12 hours, cool to 90°C, add 10 parts of m-cresol, discharge the material while hot into 800 parts of anhydrous ethanol, wash, filter, and extract to remove m-cresol, and dry in vacuo at 120°C for 20 hours to obtain a low dielectric curing agent;

[0024] S4: adding the hollow glass microspheres to a 0.3 mol / L sodium hydroxide aqueous solution, reflux stirring for 2 h, washing until neutral, and drying, adding an ethanol aqueous solution 12 times the mass of the hollow glass microspheres and KH550 8% of the mass of the hollow glass microspheres, stirring at 80°C for 6 h, filtering, washing with water, and drying to obtain an amino-modified filler; the volume ratio of ethanol to water in the ethanol aqueous solution is 8:1; the concentration of the hollow glass microspheres in the sodium hydroxide solution is 0.03 mg / mL;

[0025] S5: Take 15 parts of amino-modified filler, 150 parts of acetone, and 6 parts of 1,6-hexanediol diglycidyl ether, mix them evenly, reflux for 8 hours, remove the solvent, wash, and dry to obtain a low dielectric filler;

[0026] S6: Take 130 parts of acetone and 250 parts of bisphenol A epoxy resin, mix them evenly, add 120 parts of low dielectric filler, stir evenly to obtain component A; take 220 parts of low dielectric curing agent, 20 parts of curing agent 2,4-diaminodiphenylamine, and 10 parts of curing accelerator imidazole, stir to obtain component B; mix component B with component A to obtain a low dielectric epoxy resin for copper clad laminate.

[0027] Example 2: S1: Take 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane in a mass ratio of 1:10, stir evenly, and configure to solution A; take undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and 10 times the mass of propylene glycol, mix evenly, and configure to solution B; take trichloronitrobenzene, potassium carbonate A, and methanol, cool to 0°C, add solution A dropwise thereto under nitrogen protection, stir and reflux for 22h, add potassium carbonate B, cool to 0°C, add solution B dropwise thereto under nitrogen protection, stir and add The mixture was refluxed for 26 hours, cooled to room temperature, and precipitated in 500 parts of saturated sodium chloride ice water solution. The solid was collected by filtration; the obtained solid was recrystallized from methanol, filtered and dried to obtain substance A; the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole was 1:1.5:1:1, the mass of potassium carbonate A was 12% of the mass of trichloronitrobenzene, the mass of methanol was 7 times that of trichloronitrobenzene; the mass of potassium carbonate B was 24% of the mass of undecyl alcohol;

[0028] S2: Take ammonium formate and ethanol in a mass ratio of 1:5, stir evenly to obtain solution C; add 20 parts of substance A, 0.5 parts of palladium carbon catalyst, and 80 parts of 1,4-dioxane, stir evenly, heat to reflux, slowly add 80 parts of solution C dropwise, and reflux and stir for 24 hours; filter while hot to remove the palladium carbon catalyst, add 500 parts of saturated sodium chloride ice water solution, dry, and then perform column chromatography with dichloromethane and ethyl acetate in a volume ratio of 1:1 to obtain a diamine modifier;

[0029] S3: Add 3 parts of diamine modifier, 8 parts of 4,4'-diaminodiphenyl ether, 20 parts of 4,4'-oxydiphthalic anhydride, and 250 parts of m-cresol, stir at 80°C for 7 hours under nitrogen protection, add 10 parts of isoquinoline, stir at 115°C for 8 hours, stir at 180°C for 12 hours, cool to 90°C, add 10 parts of m-cresol, discharge the material while hot into 800 parts of anhydrous ethanol, wash, filter, extract to remove m-cresol, and dry in vacuo at 120°C for 20 hours to obtain a low dielectric curing agent;

[0030] S4: adding the hollow glass microspheres to a 0.3 mol / L sodium hydroxide aqueous solution, reflux stirring for 2 h, washing until neutral, and drying, adding an ethanol aqueous solution 12 times the mass of the hollow glass microspheres and KH550 5% of the mass of the hollow glass microspheres, stirring at 80°C for 6 h, filtering, washing with water, and drying to obtain an amino-modified filler; the volume ratio of ethanol to water in the ethanol aqueous solution is 8:1; the concentration of the hollow glass microspheres in the sodium hydroxide solution is 0.03 mg / mL;

[0031] S5: Take 10 parts of amino-modified filler, 150 parts of acetone, and 3 parts of 1,6-hexanediol diglycidyl ether, mix them evenly, reflux for 8 hours, remove the solvent, wash, and dry to obtain a low dielectric filler;

[0032] S6: Take 130 parts of acetone and 250 parts of bisphenol A epoxy resin, mix them evenly, add 120 parts of low dielectric filler, stir evenly to obtain component A; take 220 parts of low dielectric curing agent, 20 parts of curing agent 2,4-diaminodiphenylamine, and 10 parts of curing accelerator imidazole, stir to obtain component B; mix component B with component A to obtain a low dielectric epoxy resin for copper clad laminate.

[0033] Example 3: S1: Take 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane in a mass ratio of 1:10, stir evenly, and configure to solution A; take undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and propylene glycol 10 times the mass of both, mix evenly, and configure to solution B; take trichloronitrobenzene, potassium carbonate A, and methanol, cool to 0°C, add solution A dropwise thereto under nitrogen protection, stir and reflux for 22h, add potassium carbonate B, cool to 0°C, add solution B dropwise thereto under nitrogen protection, stir and add The mixture was refluxed for 26 hours, cooled to room temperature, and precipitated in 500 parts of saturated sodium chloride ice water solution. The solid was collected by filtration; the obtained solid was recrystallized from methanol, filtered and dried to obtain substance A; the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole was 1.5:1:1:1, the mass of potassium carbonate A was 12% of the mass of trichloronitrobenzene, the mass of methanol was 7 times that of trichloronitrobenzene; the mass of potassium carbonate B was 24% of the mass of undecyl alcohol;

[0034] S2: Take ammonium formate and ethanol in a mass ratio of 1:5, stir evenly to obtain solution C; add 30 parts of substance A, 2 parts of palladium carbon catalyst, and 150 parts of 1,4-dioxane, stir evenly, heat to reflux, slowly add 150 parts of solution C dropwise, and reflux and stir for 24 hours; filter while hot to remove the palladium carbon catalyst, add 500 parts of saturated sodium chloride ice water solution, dry, and then perform column chromatography with dichloromethane and ethyl acetate in a volume ratio of 1:1 to obtain a diamine modifier;

[0035] S3: Add 8 parts of diamine modifier, 15 parts of 4,4'-diaminodiphenyl ether, 30 parts of 4,4'-oxydiphthalic anhydride, and 250 parts of m-cresol, and stir at 80°C for 7 hours under nitrogen protection. Add 20 parts of isoquinoline, stir at 115°C for 8 hours, and stir at 180°C for 12 hours. Cool to 90°C, add 10 parts of m-cresol, and discharge the hot material into 800 parts of anhydrous ethanol, wash, filter, and extract to remove m-cresol. Dry in a vacuum at 120°C for 20 hours to obtain a low dielectric curing agent.

[0036] S4: adding the hollow glass microspheres to a 0.3 mol / L sodium hydroxide aqueous solution, reflux stirring for 2 h, washing until neutral, and drying, adding an ethanol aqueous solution 12 times the mass of the hollow glass microspheres and KH550 10% of the mass of the hollow glass microspheres, stirring at 80°C for 6 h, filtering, washing with water, and drying to obtain an amino-modified filler; the volume ratio of ethanol to water in the ethanol aqueous solution is 8:1; the concentration of the hollow glass microspheres in the sodium hydroxide solution is 0.03 mg / mL;

[0037] S5: Take 20 parts of amino-modified filler, 150 parts of acetone, and 8 parts of 1,6-hexanediol diglycidyl ether, mix them evenly, reflux for 8 hours, remove the solvent, wash, and dry to obtain a low dielectric filler;

[0038] S6: Take 130 parts of acetone and 250 parts of bisphenol A epoxy resin, mix them evenly, add 120 parts of low dielectric filler, stir evenly to obtain component A; take 220 parts of low dielectric curing agent, 20 parts of curing agent 2,4-diaminodiphenylamine, and 10 parts of curing accelerator imidazole, stir to obtain component B; mix component B with component A to obtain a low dielectric epoxy resin for copper clad laminate.

[0039] Comparative Example 1 (changing the amount of diamine modifier, 4,4'-diaminodiphenyl ether, and 4,4'-oxydiphthalic anhydride, and the other method steps are consistent with Example 1): S1: Take 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane in a mass ratio of 1:10, stir evenly, and configure to solution A; take undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and 10 times the mass of propylene glycol, mix evenly, and configure to solution B; take trichloronitrobenzene, potassium carbonate A, and methanol, cool to 0°C, add solution A dropwise thereto under nitrogen protection, stir and heat under reflux for 22h, and add potassium carbonate B , cooled to 0°C, solution B was added dropwise thereto under nitrogen protection, stirred and heated under reflux for 26 hours, cooled to room temperature, precipitated in 500 parts of saturated sodium chloride ice water solution, and the solid was collected by filtration; the obtained solid was recrystallized from methanol, filtered and dried to obtain substance A; the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole was 1.2:1.2:1:1, the mass of potassium carbonate A was 12% of the mass of trichloronitrobenzene, the mass of methanol was 7 times that of trichloronitrobenzene; the mass of potassium carbonate B was 24% of the mass of undecyl alcohol;

[0040] S2: Take ammonium formate and ethanol in a mass ratio of 1:5, stir evenly to obtain solution C; add 25 parts of substance A, 1 part of palladium carbon catalyst, and 120 parts of 1,4-dioxane, stir evenly, heat to reflux, slowly add 120 parts of solution C dropwise, and reflux and stir for 24 hours; filter while hot to remove the palladium carbon catalyst, add 500 parts of saturated sodium chloride ice water solution, dry, and then perform column chromatography with dichloromethane and ethyl acetate in a volume ratio of 1:1 to obtain a diamine modifier;

[0041] S3: Add 12 parts of diamine modifier, 24 parts of 4,4'-diaminodiphenyl ether, 10 parts of 4,4'-oxydiphthalic anhydride, and 250 parts of m-cresol, and stir at 80°C for 7 hours under nitrogen protection. Add 15 parts of isoquinoline, stir at 115°C for 8 hours, and stir at 180°C for 12 hours. Cool to 90°C, add 10 parts of m-cresol, and discharge the hot material into 800 parts of anhydrous ethanol, wash, filter, and extract to remove m-cresol. Dry in a vacuum at 120°C for 20 hours to obtain a low dielectric curing agent.

[0042] S4: adding the hollow glass microspheres to a 0.3 mol / L sodium hydroxide aqueous solution, reflux stirring for 2 h, washing until neutral, and drying, adding an ethanol aqueous solution 12 times the mass of the hollow glass microspheres and KH550 8% of the mass of the hollow glass microspheres, stirring at 80°C for 6 h, filtering, washing with water, and drying to obtain an amino-modified filler; the volume ratio of ethanol to water in the ethanol aqueous solution is 8:1; the concentration of the hollow glass microspheres in the sodium hydroxide solution is 0.03 mg / mL;

[0043] S5: Take 15 parts of amino-modified filler, 150 parts of acetone, and 6 parts of 1,6-hexanediol diglycidyl ether, mix them evenly, reflux for 8 hours, remove the solvent, wash, and dry to obtain a low dielectric filler;

[0044] S6: Take 130 parts of acetone and 250 parts of bisphenol A epoxy resin, mix them evenly, add 120 parts of low dielectric filler, stir evenly to obtain component A; take 220 parts of low dielectric curing agent, 20 parts of curing agent 2,4-diaminodiphenylamine, and 10 parts of curing accelerator imidazole, stir to obtain component B; mix component B with component A to obtain a low dielectric epoxy resin for copper clad laminate.

[0045] Comparative Example 2 (changing the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole, and the remaining method steps are consistent with Example 1): S1: Take 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane in a mass ratio of 1:10, stir evenly, and prepare solution A; take undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and propylene glycol 10 times the mass of both, mix evenly, and prepare solution B; take trichloronitrobenzene, potassium carbonate A, and methanol, cool to 0°C, add solution A dropwise thereto under nitrogen protection, stir and heat under reflux for 2 minutes, and stir. 2h, potassium carbonate B was added, cooled to 0°C, solution B was added dropwise thereto under nitrogen protection, stirred and heated under reflux for 26h, cooled to room temperature, precipitated in 500 parts of saturated sodium chloride ice water solution, and the solid was collected by filtration; the obtained solid was recrystallized from methanol, filtered and dried to obtain substance A; the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole was 1:2:1:2, the mass of potassium carbonate A was 12% of the mass of trichloronitrobenzene, the mass of methanol was 7 times that of trichloronitrobenzene; the mass of potassium carbonate B was 24% of the mass of undecyl alcohol;

[0046] S2: Take ammonium formate and ethanol in a mass ratio of 1:5, stir evenly to obtain solution C; add 25 parts of substance A, 1 part of palladium carbon catalyst, and 120 parts of 1,4-dioxane, stir evenly, heat to reflux, slowly add 120 parts of solution C dropwise, and reflux and stir for 24 hours; filter while hot to remove the palladium carbon catalyst, add 500 parts of saturated sodium chloride ice water solution, dry, and then perform column chromatography with dichloromethane and ethyl acetate in a volume ratio of 1:1 to obtain a diamine modifier;

[0047] S3: Add 6 parts of diamine modifier, 12 parts of 4,4'-diaminodiphenyl ether, 25 parts of 4,4'-oxydiphthalic anhydride, and 250 parts of m-cresol, and stir at 80°C for 7 hours under nitrogen protection. Add 15 parts of isoquinoline, stir at 115°C for 8 hours, stir at 180°C for 12 hours, cool to 90°C, add 10 parts of m-cresol, discharge the material while hot into 800 parts of anhydrous ethanol, wash, filter, and extract to remove m-cresol, and dry in vacuo at 120°C for 20 hours to obtain a low dielectric curing agent;

[0048] S4: adding the hollow glass microspheres to a 0.3 mol / L sodium hydroxide aqueous solution, reflux stirring for 2 h, washing until neutral, and drying, adding an ethanol aqueous solution 12 times the mass of the hollow glass microspheres and KH550 8% of the mass of the hollow glass microspheres, stirring at 80°C for 6 h, filtering, washing with water, and drying to obtain an amino-modified filler; the volume ratio of ethanol to water in the ethanol aqueous solution is 8:1; the concentration of the hollow glass microspheres in the sodium hydroxide solution is 0.03 mg / mL;

[0049] S5: Take 15 parts of amino-modified filler, 150 parts of acetone, and 6 parts of 1,6-hexanediol diglycidyl ether, mix them evenly, reflux for 8 hours, remove the solvent, wash, and dry to obtain a low dielectric filler;

[0050] S6: Take 130 parts of acetone and 250 parts of bisphenol A epoxy resin, mix them evenly, add 120 parts of low dielectric filler, stir evenly to obtain component A; take 220 parts of low dielectric curing agent, 20 parts of curing agent 2,4-diaminodiphenylamine, and 10 parts of curing accelerator imidazole, stir to obtain component B; mix component B with component A to obtain a low dielectric epoxy resin for copper clad laminate.

[0051] Comparative Example 3 (amino-modified filler instead of low dielectric filler, the rest of the method steps are consistent with Example 1): S1: Take 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane in a mass ratio of 1:10, stir evenly, and configure to solution A; take undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and 10 times the mass of propylene glycol, mix evenly, and configure to solution B; take trichloronitrobenzene, potassium carbonate A, and methanol, cool to 0°C, add solution A dropwise thereto under nitrogen protection, stir and heat under reflux for 22h, add potassium carbonate B, cool to 0°C, and protect with nitrogen Solution B was added dropwise thereto, the mixture was stirred and heated under reflux for 26 hours, cooled to room temperature, and precipitated in 500 parts of saturated sodium chloride ice water solution, and the solid was collected by filtration; the resulting solid was recrystallized from methanol, filtered and dried to obtain substance A; the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole was 1.2:1.2:1:1, the mass of potassium carbonate A was 12% of the mass of trichloronitrobenzene, the mass of methanol was 7 times that of trichloronitrobenzene; the mass of potassium carbonate B was 24% of the mass of undecyl alcohol;

[0052] S2: Take ammonium formate and ethanol in a mass ratio of 1:5, stir evenly to obtain solution C; add 25 parts of substance A, 1 part of palladium carbon catalyst, and 120 parts of 1,4-dioxane, stir evenly, heat to reflux, slowly add 120 parts of solution C dropwise, and reflux and stir for 24 hours; filter while hot to remove the palladium carbon catalyst, add 500 parts of saturated sodium chloride ice water solution, dry, and then perform column chromatography with dichloromethane and ethyl acetate in a volume ratio of 1:1 to obtain a diamine modifier;

[0053] S3: Add 6 parts of diamine modifier, 12 parts of 4,4'-diaminodiphenyl ether, 25 parts of 4,4'-oxydiphthalic anhydride, and 250 parts of m-cresol, and stir at 80°C for 7 hours under nitrogen protection. Add 15 parts of isoquinoline, stir at 115°C for 8 hours, stir at 180°C for 12 hours, cool to 90°C, add 10 parts of m-cresol, discharge the material while hot into 800 parts of anhydrous ethanol, wash, filter, and extract to remove m-cresol, and dry in vacuo at 120°C for 20 hours to obtain a low dielectric curing agent;

[0054] S4: adding the hollow glass microspheres to a 0.3 mol / L sodium hydroxide aqueous solution, reflux stirring for 2 h, washing until neutral, and drying, adding an ethanol aqueous solution 12 times the mass of the hollow glass microspheres and KH550 8% of the mass of the hollow glass microspheres, stirring at 80°C for 6 h, filtering, washing with water, and drying to obtain an amino-modified filler; the volume ratio of ethanol to water in the ethanol aqueous solution is 8:1; the concentration of the hollow glass microspheres in the sodium hydroxide solution is 0.03 mg / mL;

[0055] S5: Take 130 parts of acetone and 250 parts of bisphenol A epoxy resin, mix them evenly, add 120 parts of low dielectric filler, stir evenly to obtain component A; take 220 parts of low dielectric curing agent, 20 parts of curing agent 2,4-diaminodiphenylamine, and 10 parts of curing accelerator imidazole, stir to obtain component B; mix component B with component A to obtain a low dielectric epoxy resin for copper clad laminate.

[0056] Comparative Example 4 (changing the amount of raw materials in component A and component B, the rest of the method steps are consistent with Example 1): S1: Take 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane in a mass ratio of 1:10, stir evenly, and configure to solution A; take undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and 10 times the mass of propylene glycol, mix evenly, and configure to solution B; take trichloronitrobenzene, potassium carbonate A, and methanol, cool to 0°C, add solution A dropwise thereto under nitrogen protection, stir and reflux for 22h, add potassium carbonate B, cool to 0°C, and nitrogen protection Solution B was added dropwise thereto under protection, and the mixture was stirred, heated and refluxed for 26 hours, cooled to room temperature, and precipitated in 500 parts of saturated sodium chloride ice water solution. The solid was collected by filtration; the obtained solid was recrystallized from methanol, filtered and dried to obtain substance A; the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole was 1.2:1.2:1:1, the mass of potassium carbonate A was 12% of the mass of trichloronitrobenzene, the mass of methanol was 7 times that of trichloronitrobenzene; the mass of potassium carbonate B was 24% of the mass of undecyl alcohol;

[0057] S2: Take ammonium formate and ethanol in a mass ratio of 1:5, stir evenly to obtain solution C; add 25 parts of substance A, 1 part of palladium carbon catalyst, and 120 parts of 1,4-dioxane, stir evenly, heat to reflux, slowly add 120 parts of solution C dropwise, and reflux and stir for 24 hours; filter while hot to remove the palladium carbon catalyst, add 500 parts of saturated sodium chloride ice water solution, dry, and then perform column chromatography with dichloromethane and ethyl acetate in a volume ratio of 1:1 to obtain a diamine modifier;

[0058] S3: Add 6 parts of diamine modifier, 12 parts of 4,4'-diaminodiphenyl ether, 25 parts of 4,4'-oxydiphthalic anhydride, and 250 parts of m-cresol, and stir at 80°C for 7 hours under nitrogen protection. Add 15 parts of isoquinoline, stir at 115°C for 8 hours, stir at 180°C for 12 hours, cool to 90°C, add 10 parts of m-cresol, discharge the material while hot into 800 parts of anhydrous ethanol, wash, filter, and extract to remove m-cresol, and dry in vacuo at 120°C for 20 hours to obtain a low dielectric curing agent;

[0059] S4: adding the hollow glass microspheres to a 0.3 mol / L sodium hydroxide aqueous solution, reflux stirring for 2 h, washing until neutral, and drying, adding an ethanol aqueous solution 12 times the mass of the hollow glass microspheres and KH550 8% of the mass of the hollow glass microspheres, stirring at 80°C for 6 h, filtering, washing with water, and drying to obtain an amino-modified filler; the volume ratio of ethanol to water in the ethanol aqueous solution is 8:1; the concentration of the hollow glass microspheres in the sodium hydroxide solution is 0.03 mg / mL;

[0060] S5: Take 15 parts of amino-modified filler, 150 parts of acetone, and 6 parts of 1,6-hexanediol diglycidyl ether, mix them evenly, reflux for 8 hours, remove the solvent, wash, and dry to obtain a low dielectric filler;

[0061] S6: Take 130 parts of acetone and 250 parts of bisphenol A epoxy resin, mix them evenly, add 150 parts of low dielectric filler, stir evenly to obtain component A; take 260 parts of low dielectric curing agent, 20 parts of curing agent 2,4-diaminodiphenylamine, and 10 parts of curing accelerator imidazole, stir to obtain component B; mix component B with component A to obtain a low dielectric epoxy resin for copper clad laminate.

[0062] In the above examples, the test methods used are conventional methods unless otherwise specified; the raw materials used are commercially available unless otherwise specified, and the sources of the raw materials are as follows: ethanol (CAS: 64-17-5); 1-methyl-5-nitro-2-hydroxymethylimidazole (CAS: 936-05-0); dichloromethane (CAS: 75-09-2); undecyl alcohol (CAS: 112-42-5); 4-hydroxy-3-tert-butyl-anisole (CAS: 121-00-6); propylene glycol (CAS: 57-55-6); trichloronitrobenzene (CAS: 29595-61-7); methanol (CAS: 67-56-1); ammonium formate (CAS: 540-69-2); palladium-carbon catalyst (5%, Xi'an Kaili New Materials Co., Ltd.); 1,4-dioxane (CAS: 123-91-1); ethyl acetate ( CAS: 141-78-6); 4,4'-diaminodiphenyl ether (CAS: 101-80-4); 4,4'-oxydiphthalic anhydride (CAS: 1823-59-2); m-cresol (CAS: 108-39-4); isoquinoline (CAS: 119-65-3); hollow glass microspheres (~40 μm, Kramar); silane coupling agents (KH550, S15028, Shanghai Yuanye) ; 1,6-Hexanediol diglycidyl ether (CAS: 16096-31-4); bisphenol A epoxy resin (E44, epoxy equivalent 210-240 g / eq, Nanjing Bermuda Biotechnology Co., Ltd.); 2,4-diaminodiphenylamine (CAS: 136-17-4); Imidazole (CAS: 288-32-4); potassium carbonate (S3039, Shanghai Yuanye); acetone (CAS: 67-64-1).

[0063] Experiment: Component B and component A prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were mixed; (1) the mixture was cured in a mold with a diameter of 11 cm and a thickness of 5 mm under the following curing conditions: 70° C. for 1 hour and 150° C. for 4 hours; the dielectric constant was then tested using an Aiyi QBG-3D tester; (2) after curing according to the above steps, the tensile strength was tested in accordance with the GB / T1843-2008 standard; the specific data are shown in the table below.

[0064]

[0065]

[0066] Conclusion: In Comparative Example 1, the amount of diamine modifier, 4,4'-diaminodiphenyl ether, and 4,4'-oxydiphthalic anhydride was changed. Since the amount of 4,4'-oxydiphthalic anhydride was reduced, the end of the low-dielectric curing agent was an amino group, and the dielectric constant was increased compared with the epoxy resin cured with anhydride in the embodiment; Comparative Example 2 changed the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene and 1-methyl-5-nitro-2-hydroxymethylimidazole, resulting in a reduction in the amount of undecyl alcohol introduced, and the reduction in long chains led to a decrease in toughness, so the tensile strength was significantly decreased; Comparative Example 3 replaced the low-dielectric filler with an amino-modified filler, that is, 1,6-hexanediol diglycidyl ether was not introduced, and the performance was not as good as the embodiment; Comparative Example 4 increased the amount of low-dielectric filler and low-dielectric curing agent added, and the tensile properties decreased significantly; in summary, the low-dielectric epoxy resin for copper clad laminate prepared by the present invention has a low dielectric constant, good tensile properties, and has good practical value.

[0067] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention, but the scope of protection of this application is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the spirit and principles of the present invention and within the technical scope disclosed in this application should be included in the scope of protection of this application. The embodiments and features of the embodiments of this application can be combined with each other unless there is a conflict. Therefore, the scope of protection of this application should be based on the scope of protection of the claims.

Claims

1. A low dielectric epoxy resin for copper clad laminate, characterized in that: The invention comprises component A and component B; component A comprises the following raw materials, calculated by weight: 100-150 parts of acetone, 250-300 parts of bisphenol A epoxy resin, and 100-130 parts of low-dielectric filler; component B is a curing component, comprising the following raw materials, calculated by weight: 150-250 parts of low-dielectric curing agent, 20-30 parts of curing agent, and 10-20 parts of curing accelerator; The preparation of the low dielectric curing agent comprises the following steps: taking a diamine modifier, 4,4'-diaminodiphenyl ether, 4,4'-oxydiphthalic anhydride, and m-cresol, stirring under nitrogen protection, adding isoquinoline, stirring, adding m-cresol after cooling, discharging the material while hot into ethanol, washing, filtering, extracting to remove m-cresol, and vacuum drying to obtain a low dielectric curing agent; The low dielectric curing agent includes the following raw materials, calculated by mass: 3 to 8 parts of diamine modifier, 8 to 15 parts of 4,4'-diaminodiphenyl ether, 20 to 30 parts of 4,4'-oxydiphthalic anhydride, 200 to 300 parts of m-cresol, 10 to 20 parts of isoquinoline, and 600 to 800 parts of ethanol; The preparation of the diamine modifier includes the following steps: S1: taking 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane, stirring them evenly to prepare solution A; taking undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and propylene glycol, mixing them evenly to prepare solution B; taking trichloronitrobenzene, potassium carbonate A, and methanol, mixing them evenly, cooling them to 0-1°C, adding solution A dropwise thereto under nitrogen protection, stirring and heating under reflux for 20-25 hours, adding potassium carbonate B, cooling them to 0-1°C, adding solution B dropwise thereto under nitrogen protection, stirring and heating under reflux for 25-30 hours, cooling them to room temperature, precipitating them in a saturated sodium chloride ice water solution, and collecting solids by suction filtration; recrystallizing the obtained solids with methanol, filtering and drying them, and obtaining substance A; S2: Take ammonium formate and ethanol, stir evenly to obtain solution C; add substance A, palladium carbon catalyst, and 1,4-dioxane, stir evenly, heat to reflux, slowly add solution C dropwise, reflux and stir for 20-25 hours, filter while hot to remove the palladium carbon catalyst, add saturated sodium chloride ice water solution, dry, and perform column chromatography to obtain a diamine modifier; The diamine modifier includes the following raw materials, calculated by mass: 20 to 30 parts of substance A, 0.5 to 2 parts of palladium-carbon catalyst, 80 to 150 parts of 1,4-dioxane, and 80 to 150 parts of solution C; in substance A, the molar ratio of undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, trichloronitrobenzene, and 1-methyl-5-nitro-2-hydroxymethylimidazole is (1 to 1.5): (1 to 1.5): 1: 1, the mass of potassium carbonate A is 10 to 15% of the mass of trichloronitrobenzene, the mass of methanol is 6 to 8 times that of trichloronitrobenzene; and the mass of potassium carbonate B is 15 to 25% of the mass of undecyl alcohol; The solution A comprises 1-methyl-5-nitro-2-hydroxymethylimidazole and dichloromethane in a mass ratio of 1:(8-12); the solution B comprises undecyl alcohol, 4-hydroxy-3-tert-butyl-anisole, and propylene glycol in an amount 8-12 times the total mass of the undecyl alcohol and 4-hydroxy-3-tert-butyl-anisole; and the solution C comprises ammonium formate and ethanol in a mass ratio of 1:(4-5).

2. The low dielectric epoxy resin for copper clad laminate according to claim 1, wherein: The preparation of the low dielectric filler includes the following steps: adding hollow glass microspheres to a sodium hydroxide aqueous solution, reflux stirring and reacting for 1 to 2 hours, washing until neutral, drying, adding an ethanol aqueous solution and an aminosilane coupling agent, stirring at 70 to 80° C. for 4 to 6 hours, filtering, washing with water, and drying to obtain an amino-modified filler; and taking the amino-modified filler, acetone, and 1,6-hexanediol diglycidyl ether, mixing them uniformly, reflux reacting for 6 to 8 hours, removing the solvent, washing, and drying to obtain the low dielectric filler.

3. The low dielectric epoxy resin for copper clad laminate according to claim 2, wherein: The low dielectric filler includes the following raw materials, calculated by mass: 10 to 20 parts of amino-modified filler, 100 to 150 parts of acetone, and 3 to 8 parts of 1,6-hexanediol diglycidyl ether; in the amino-modified filler, the amount of ethanol aqueous solution added is 8 to 12 times the mass of the hollow glass microspheres, and the amount of aminosilane coupling agent added is 5 to 10% of the mass of the hollow glass microspheres; the concentration of the hollow glass microspheres in the sodium hydroxide aqueous solution is 0.03 to 0.05 mg / mL.

4. The processing technology of a low dielectric epoxy resin for copper clad laminate according to any one of claims 1 to 3, characterized in that: The following steps are involved: Take acetone and bisphenol A epoxy resin, mix them evenly, add low dielectric filler, stir evenly to obtain component A; take low dielectric curing agent, curing agent, and curing accelerator, stir for 3 to 5 minutes to obtain component B; add component B to component A, mix evenly to obtain low dielectric epoxy resin for copper clad laminate.

Images