CN-122011763-A - Thermosetting resin composition, prepreg and metal foil laminated plate thereof

Abstract

The invention discloses a thermosetting resin composition, a prepreg and a metal foil laminated plate thereof, wherein the thermosetting resin composition comprises, by weight, 30-90 parts of modified maleimide prepolymer and 5-60 parts of thermosetting resin. The modified maleimide prepolymer is prepared by prepolymerizing an amine modifier and maleimide resin. The invention has the advantages that the amino-substituted benzocyclobutene compound is introduced in the prepolymerization process of the modified maleimide resin, so that the crosslinking density and rigidity of a molecular chain are greatly enhanced, the curing temperature of a resin system is obviously reduced, the reaction completion of a reaction group is ensured, and the thermal expansion coefficient, the glass transition temperature and the Desmear tolerance of the resin composition are obviously improved.

Inventors

• HUANG RONGHUI
• HUANG DAXING

Assignees

• 科钛芯材(江苏)科技有限公司

Dates

Publication Date

20260512

Application Date

20260225

Claims (10)

1. 1. A thermosetting resin composition comprising, by weight: 30-90 parts of modified maleimide prepolymer; 5-60 parts of thermosetting resin; The modified maleimide prepolymer is prepared by prepolymerizing an amine modifier and maleimide resin.
2. 2. The thermosetting resin composition according to claim 1, wherein the amine modifier is amino-substituted benzocyclobutene or an amine compound containing no benzocyclobutene, and the reaction molar ratio of maleimide groups in the maleimide resin to primary amine groups in the amine modifier is 1:1-5:1.
3. 3. A thermosetting resin composition according to claim 1, wherein said maleimide resin contains at least 2 maleimide groups per molecular structure.
4. 4. A thermosetting resin composition according to claim 2, wherein said benzocyclobutene-free amine compound is one or more selected from the group consisting of an aromatic diamine compound, an aliphatic diamine compound and an amino silicone oil compound.
5. 5. A thermosetting resin composition according to claim 1, wherein said thermosetting resin is selected from one or more of a bis/polymaleimide resin, an epoxy resin, a cyanate ester resin, a benzoxazine resin, a polyphenylene ether resin, and a hydrocarbon resin.
6. 6. The thermosetting resin composition according to claim 1, further comprising an elastomer, wherein the elastomer is added in an amount of 5 to 40% by weight based on the thermosetting resin composition, and wherein the elastomer is one or more selected from hydrogenated or non-hydrogenated styrene-olefin copolymers, polyesters, polyurethanes, polyamides, polyethers, polyacrylates and silicones.
7. 7. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises a filler, the filler is added in an amount of 50% -90% by weight of the thermosetting resin composition, and the filler is an organic filler or an inorganic filler; The inorganic filler is selected from any one or more of obtuse-angle silica, acute-angle silica, spherical silica, hollow silica, aluminum hydroxide, boehmite, alumina, talcum powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, zinc molybdate, calcium molybdate, molybdenum disulfide and glass fiber powder; the organic filler is one or more selected from polytetrafluoroethylene powder, silicone resin powder, polymethacrylate powder, silicone rubber powder, styrene-butadiene rubber powder and polyacrylate rubber powder.
8. 8. The thermosetting resin composition according to claim 1, further comprising an accelerator, wherein the accelerator accounts for 0.01% -2% by weight of the thermosetting resin composition, and the accelerator is one or more selected from imidazoles, tertiary amines, organic ureas, thermal radicals, organic phosphorus, and metal carboxylates.
9. 9. A prepreg is characterized in that a resin composition according to any one of claims 1-8 is dissolved by a solvent, stirred uniformly, cured to prepare a resin composition glue solution, a reinforcing material is immersed in the resin composition glue solution, and the immersed reinforcing material is baked and dried to obtain the prepreg.
10. 10. A metal foil laminate characterized in that a metal foil is coated on one side or both sides of the prepreg according to claim 9 after the prepreg is laminated, and the metal foil laminate is obtained by hot press molding.

Description

Thermosetting resin composition, prepreg and metal foil laminated plate thereof Technical Field The invention relates to the technical field of copper-clad plates, in particular to a thermosetting resin composition, a prepreg and a metal foil laminated plate. Background The low XY axis thermal expansion coefficient of the package substrate is a core requirement for guaranteeing the reliability of the package structure. In the high-temperature packaging process and the cold and hot cycle process of long-term working of electronic devices, if the difference between the XY axis thermal expansion coefficient of the base material and the chip is too large, obvious thermal stress can be generated, so that the packaging structure has the problems of warping, layering, welding spot cracking and the like, and finally, circuit failure is caused. The current solution for effectively reducing the XY axis CTE of the package substrate is to introduce a molecular structure having a stress absorbing function into the molecular structure by chemical prepolymerization. Meanwhile, adverse effects such as reduced adhesion, reduced toughness, poor fluidity and the like caused by the prior scheme of excessively increasing the proportion of the inorganic filler or the crosslinking density can be avoided. However, with the development of advanced packaging forms or processes such as SoC, ETS, FCBGA, etc., to higher densification, thinner, larger size, and more layers, higher requirements are also put on performances such as thermal expansion coefficient, ultra-thin carrier copper adhesion, glass transition temperature, resin flowability, etc., which are often difficult to meet or compromise in the current technical scheme. In addition, in the manufacturing process of the package substrate, if the adhesive residues generated by mechanical drilling are not removed effectively on the hole wall, the conductivity of through hole electroplating can be blocked, and interlayer interconnection failure can be caused. Therefore, the process of removing the glue residue (desmear) is an indispensable link. The currently common desmear treatment modes include chemical liquid medicine (such as potassium permanganate solution) treatment, plasma etching and the like, wherein the chemical liquid medicine treatment is widely adopted due to mature process and low cost. The packaging substrate is required to have excellent desmear liquid medicine biting resistance, so that the problems of excessive corrosion of resin on the surface of the substrate, exposure of fibers, overlarge roughness of the hole wall and the like in the desmear process are avoided, the bonding strength of an electroplated layer and the substrate is reduced, and hidden trouble of interconnection reliability is caused. Disclosure of Invention The invention aims to provide a thermosetting resin composition, a prepreg and a metal foil laminated plate thereof, wherein an amino-substituted benzocyclobutene compound is introduced in the process of prepolymerizing modified maleimide resin, so that the crosslinking density and rigidity of a molecular chain are greatly enhanced, the curing temperature of a resin system is obviously reduced, the reaction completion of a reaction group is ensured, and the thermal expansion coefficient, the glass transition temperature and the Desmear resistance of the resin composition are obviously improved. The technical aim of the invention is realized by the following technical scheme: A thermosetting resin composition comprising, by weight: 30-90 parts of modified maleimide prepolymer; 5-60 parts of thermosetting resin; The modified maleimide prepolymer is prepared by prepolymerizing an amine modifier and maleimide resin. Preferably, the preparation method of the modified maleimide prepolymer comprises the step of reacting an amine modifier and maleimide resin for 2-6 hours at 80-160 ℃ to obtain the modified maleimide prepolymer. Preferably, the amine modifier is amino-substituted benzocyclobutene or an amine compound free of benzocyclobutene. The structural formula of the amino-substituted benzocyclobutene is shown in the formula I: A formula I; wherein R is H or alkyl with 1-3 carbon atoms. Preferably, the reaction molar ratio of the maleimide groups in the maleimide resin to the primary amine groups in the amine modifier is 1:1-5:1. Preferably, the maleimide resin contains at least 2 maleimide groups in each molecular structure, and the structural formula of the maleimide groups is shown in formula II: A formula II; wherein R 1 is H or alkyl with 1-3 carbon atoms. Preferably, the maleimide resin is selected from one or more of the structures shown in formula III, formula IV, formula V, formula VI or formula VII: the structural formula III is as follows: Formula III; the structural formula IV is as follows: A formula IV; The structural formula of the formula V is as follows: A formula V; The structural formula VI is as follows: formula VI; Wherein R 2