Phosphorus-containing flame retardant composition, and phosphorus-containing polyphenyl ether resin composition, prepreg and laminated board using the same

Abstract

The invention provides a phosphorus-containing flame retardant composition, including: a hypophosphite compound, a DOPO derivative and a polyphosphazene compound. The composition as a flame retardant can play a synergistic effect of several phosphorus-containing compounds, realizes halogen-free flame retardance under small addition amount and reaches level V-0. The invention also provides a contains a polyphenyl ether resin composition containing the above phosphorus-containing flame retardant compositions and a prepreg and a copper clad laminated board prepared from the same. After curing, the polyphenyl ether resin composition achieves flame retardance of V-0 grade under the condition to which the halogen flame retardant does not apply and keeps good dielectric property and heat resistance of polyphenyl ether resin; the prepreg and copper clad laminated board made from the composition have good dielectric property and heat resistance, and realize halogen-free flame retardance to UL 94-V0 grade while ensuring excellent heat resistance and dielectric property; and the composition is applicable to the field of high speed and high frequency printed circuit board, and is in line with the future requirements of green and environmental protection.

Description

technical field [0001] The invention belongs to the technical field of copper-clad laminates, and relates to a phosphorus-containing composition, a phosphorus-containing polyphenylene ether resin composition, a prepreg and a laminate using the composition. Background technique [0002] In recent years, with the development of high-performance, high-functionality and networking of computers and information communication equipment, in order to transmit high-speed and process large-capacity information, the operating signal tends to be high-frequency, so the material of the circuit board is required. In particular, there is a rapid development in those electronic devices using broadband such as mobile communication devices. [0003] Among conventional printed circuit board materials, epoxy resins excellent in adhesive properties are widely used. However, epoxy resin circuit substrates generally have high dielectric constant and dielectric loss tangent (dielectric constant is g...

AI Technical Summary

Problems solved by technology

For a long time, those skilled in the art have studied thermosetting cyanate esters, bismaleimide resins, hydrocarbon resins, etc. with good dielectric properties; in addition, polyphenylene ether resins have good dielectric properties, Heat resistance has also been studied as a high-frequency and high-speed material by many technicians, but due to its high melting point and poor fluidity, it is subject to many restrictions in application, and the melt viscosity of prepregs is large, which cannot meet the requirements of multi-layer printing. Process requirements for circuit boards

By reducing the molecular weight of polyphenylene ether resin, it can effectively reduce its melting temperature and improve fluidity, but this also sacrifices the heat resistance of polyphenylene ether resin

[0004] CN1745142A uses a polyphenylene ether resin whose end group contains vinylphenyl and m-vinylphenyl as the main resin, uses trienyl isocyanurate as a crosslinking curing agent, and can also add inorganic fillers and flame retardants if necessary Obtain a polyphenylene ether resin composition, and then impregnate NE type glass fiber fabrics to obtain prepregs and laminates with excellent dielectric properties and higher glass transition temperatures, but due to the use of isocyanurate in the composition Acid trienyl ester is used as a cross-linking curing agent, its molecular weight is low, and it is very easy to volatilize during the prepreg production process, which is not conducive to the stable production of prepregs and laminates

[0006] WO2006 / 023371A1 provides a composition of a bifunctional polyphenylene ether resin and an unsaturated olefin monomer, which can improve the fluidity and cured properties of the polyphenylene ether resin, but does not point out that the bifunctional polyphenylene ether resin Performance advantages when used in the field of laminated boards, and the unsaturated olefin monomers used are low molecular weight compounds, which are easy to volatilize at high temperatures and have poor manufacturability

[0007] It can be seen from the above that the problem of heat resistance drop caused by the decrease of polyphenylene ether molecular weight can be solved by functionalizing low molecular weight, but for the specific application in the laminate field, how to choose the appropriate curing crosslinking and embody The performance advantages of functionalized polyphenylene ether resins need further research

[0008] In addition, with the strengthening of the society's awareness of environmental protection, the environmental protection problems of electronic products are becoming more and more prominent. Therefore, how to realize the halogenation of substrate materials is also the focus of research by personnel in this technical field this year. Phosphorous elements are introduced for flame retardancy. Common substances include phosphorus-containing epoxy resins, phosphorus-containing phenolic resins, phosphate compounds, polyphosphate compounds, phosphazene compounds, and hypophosphite compounds. However, due to the limitations of the characteristics of these materials , used alone cannot meet the requirements of heat resistance and dielectric properties in the field of high-speed materials, such as phosphorus-containing epoxy resins and phosphorus-containing phenolic resins. The performance is not good, and at the same time, the introduction of too much phosphorus will lead to the deterioration of the resistance to heat and humidity, which cannot meet the reliability requirements of high-layer PCBs; the flame retardant effect of the added phosphinate alone is not good, especially in carbon Lower resin system; polyphosphazene compounds have a relatively low melting point and strong plasticity, and a large amount of addition will bring about a sharp drop in heat resistance, such as a decrease in glass transition temperature. At the same time, when used alone, even if a large amount of addition is very It is difficult to achieve the level of flame retardant V-0

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