Halogen-free resin composite and use thereof

Abstract

Disclosed in the present invention is a halogen-free composition and prepreg material and laminate made thereof; based on organic solid matter parts by weight, said halogen-free resin composition comprises: (A) 40-80 parts by weight of allyl modified benzoxazine resin; (B) 10-20 parts by weight of hydrocarbon resin; (C) 10-40 parts by weight of allyl modified polyphenylene ether resin; (D) 10-20 parts by weight of allyl modified bismaleimide resin; (E) 0.01-3 parts by weight of initiator agent; (F) 10-100 parts by weight of filler; and (G) 0-80 parts by weight of phosphorus-containing flame retardants. Prepreg material and laminate made using the present halogen-free resin composition have a low dielectric constant and dielectric loss tangent value, high peel strength, a high glass transition temperature, good thermal resistance, and good flame retardancy.

Description

technical field [0001] The invention belongs to the technical field of preparation of copper-clad laminates, relates to a halogen-free resin composition and its application, in particular to a halogen-free resin composition, resin glue and prepreg prepared by using the halogen-free resin composition , laminates and copper clad laminates. Background technique [0002] Traditional copper-clad laminates for printed circuits mainly use brominated epoxy resin, and bromine is used to realize the flame-retardant function of the board. However, in recent years, carcinogens such as dioxin and dibenzofuran have been detected in the combustion products of electronic and electrical equipment wastes containing halogens such as bromine and chlorine, and highly toxic substances may be released during the combustion process of halogen-containing products hydrogen halide. In addition, on July 1, 2006, two environmental directives of the European Union, the Directive on Waste Electrical and...

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Problems solved by technology

[0004] WO97 / 38564 uses a non-polar tetrapolymer of styrene, butadiene and divinylbenzene to add magnesium aluminosilicate fillers, and a circuit substrate made of glass fiber cloth as a reinforcing material. Although the dielectric properties are excellent, but The heat resistance of the substrate is very poor, the glass transition temperature is only about 100°C, and the thermal expansion coefficient is very large, it is difficult to meet the high temperature (above 240°C) requirements of the lead-free process in the PCB manufacturing process

[0005] US5571609 uses low molecular weight 1,2-polybutadiene resin or polyisobutadiene with molecular weight less than 5000, and high molecular weight butadiene and styrene copolymer, and adds a large amount of silica powder as filler to Although the circuit substrate made of glass fiber cloth as a reinforcing material has excellent dielectric properties, because the patent uses high molecular weight components to improve the stickiness of the prepreg, the process performance of the process of making the prepreg is deteriorated; and because the entire The proportion of rigid structural benzene rings in the resin molecules of the resin system is very small, and most of the chain segments after crosslinking are composed of methylene groups with very low rigidity, so the rigidity of the board produced is not good, and the bending strength is very low

[0006] US6569943 uses amino-modified liquid polybutadiene resin with vinyl groups at the molecular ends, adds a large amount of low-molecular-weight monomer dibromostyrene as a curing agent and diluent, and impregnates a circuit board made of glass fiber cloth. Although the dielectric properties are very good, because the resin system is liquid at room temperature, it cannot be made into a non-sticky prepreg. Therefore, it is difficult to use the general prepreg stacking process when pressing and forming the board, and the process operation is relatively difficult.

[0007] CN1280337C uses polyphenylene ether resin with unsaturated double bonds at the molecular end, adopts low molecular weight vinyl monomers (such as dibromostyrene) as curing agent, but because these low molecular weight monomers have low boiling point, in It will be volatilized during the drying process of impregnated glass fiber cloth to make prepreg, so it is difficult to ensure sufficient curing agent dosage

In addition, although this patent mentions that polybutadiene resins can be used to modify the viscosity of the system, it does not clearly propose the use of polybutadiene resins with polar groups and the use of polybutadiene resins with polar groups. Diene resin to improve peel strength

[0008] CN101544841B uses a hydrocarbon resin with a molecular weight of less than 11000 and a vinyl content of more than 60% as the main body, and uses an allyl-modified phenolic resin to improve the sticky characteristics of the prepreg, and the peel strength has a certain increase, but the heat resistance of the system after curing is low. Copper clad laminates have a higher risk of delamination failure during PCB processing

[0009] The system mainly based on hydrocarbon resin has low adhesion to metal and heat resistance of the system, which brings a greater probability of failure risk to the PCB processing process downstream of the copper clad laminate

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