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A kind of halogen-free thermosetting resin composition, prepreg, laminate and printed circuit board using it

A resin composition, thermosetting technology, applied in the fields of laminates and printed circuit boards, halogen-free thermosetting resin compositions, and prepregs, which can solve the problems of peel strength, interlayer adhesion, low flexural strength, dielectric Poor performance, poor dielectric properties of cured products, etc., to achieve the effects of good processability, enhanced high heat resistance, and excellent flame retardant efficiency

Active Publication Date: 2022-06-28
GUANGDONG SHENGYI SCI TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Hydroxy-terminated phenoxyhydrocarbyl phosphine oxide is a reactive phosphorus-containing curing agent that can undergo a curing reaction with epoxy resin, but because its active group is a phenolic hydroxyl group, it will form a highly polar compound after reacting with epoxy resin. The secondary hydroxyl group leads to poor dielectric properties of the cured product
In CN103384674A, polyphosphonate with hydroxyl group and / or phosphonate-carbonate copolymer and epoxy composition are selected, and its active group is phenolic hydroxyl group, which also has the problem of poor dielectric properties; CN103694642A discloses Using epoxy resin, cyanate compound and / or cyanate prepolymer, polyphosphonate and / or phosphonate-carbonate copolymer to prepare halogen-free UL94V-0 with good dielectric properties and heat and humidity resistance Flame retardant prepreg and copper clad laminate, but its peel strength, interlayer adhesion and bending strength are low
CN108117633A discloses acid anhydrided phosphonate isocyanate resin and epoxy resin to make halogen-free copper clad laminates, but the excessive P-O bonds in the acid anhydrided phosphonate make the heat and humidity resistance slightly insufficient
Although the above resins have good dielectric properties, they all have defects such as difficult processing, poor heat resistance, poor peel strength and interlayer adhesion, and cannot meet the requirements of high-frequency, high-speed, halogen-free flame-retardant copper clad substrates.

Method used

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  • A kind of halogen-free thermosetting resin composition, prepreg, laminate and printed circuit board using it
  • A kind of halogen-free thermosetting resin composition, prepreg, laminate and printed circuit board using it
  • A kind of halogen-free thermosetting resin composition, prepreg, laminate and printed circuit board using it

Examples

Experimental program
Comparison scheme
Effect test

preparation example 1

[0084] Synthesis of DOPO-MAH Containing Phosphoric Anhydride

[0085] 49g of maleic anhydride and 108g of DOPO were stirred in a four-necked flask equipped with a stirrer and a thermometer, while nitrogen was introduced, and then the temperature was raised to 125°C, and the reaction was carried out at this temperature for 3h to obtain a product, numbered as DOPO-MAH. Its structure is:

[0086]

[0087] Characterized by infrared spectrometer Nicolet TR-460, such as figure 1 As shown in the infrared spectrum of DOPO-MAH, it can be seen that the P-H in the DOPO structure is at 2361 cm -1 , 2342cm -1 The characteristic absorption disappears, indicating that it has completely reacted; 1865cm -1 And 1787cm -1 In order to absorb the characteristics of the five-membered cyclic acid anhydride, it is explained that the newly generated structure contains the structure of the five-membered acid anhydride, and the phosphoric acid anhydride containing the above structure is synthesiz...

Embodiment 1-9

[0089] As shown in Table 1 and Table 2 (the amount of components is in parts by weight), the phosphoric anhydride, halogen-free epoxy resin, curing accelerator, halogen-free flame retardant and filler are mixed in a solvent in a certain proportion, and the control The solid content of the glue is 65%. The above glue is impregnated with 2116 glass fiber cloth to control the appropriate thickness, and then baked in an oven at 115 to 175 ° C for 2 to 15 minutes to make prepregs, and then several sheets of prepregs are stacked. Together, stack 18μRTF copper foil on both sides, the curing temperature is 170 ~ 250 ℃, and the curing pressure is 25 ~ 60kg / cm 2 , and the curing time is 60 to 300min to make a copper clad laminate. The composition of the resin composition and the performance test standard of the copper clad laminate are shown in Table 1 and Table 2.

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Abstract

The invention provides a halogen-free thermosetting resin composition, a prepreg, a laminate, and a printed circuit board using the same. The halogen-free thermosetting resin composition includes a halogen-free epoxy resin and a curing agent, and the curing agent includes The cyanate resin and the phosphoric anhydride-containing resin have the following components: 5-50 parts of cyanate resin, 30-60 parts of halogen-free epoxy resin and 15-40 parts of phosphoric anhydride-containing resin. In the present invention, cyanate ester and phosphoric anhydride are jointly used as the curing agent of halogen-free epoxy resin, and the two act synergistically to enhance the high heat resistance of the composition and have low dielectric loss value, and the three resins are mixed and cured, and the common The effect also brings the system to have excellent anti-peel strength and interlayer adhesion as well as excellent flame retardancy.

Description

technical field [0001] The invention belongs to the technical field of laminates, and relates to a halogen-free thermosetting resin composition, a prepreg using the same, a laminate and a printed circuit board. Background technique [0002] Traditional printed circuit laminates usually use brominated flame retardants to achieve flame retardancy, especially tetrabromobisphenol A epoxy resin. This brominated epoxy resin has good flame retardancy, but it is When burned, hydrogen bromide gas is produced. In addition, in recent years, carcinogens such as dioxins and dibenzofurans have been detected in the combustion products of electrical and electronic equipment wastes containing halogens such as bromine and chlorine, so the application of brominated epoxy resins has been limited. On July 1, 2006, the EU's two environmental protection directives "Directive on Scrap Electrical and Electronic Equipment" and "Directive on Restriction of the Use of Certain Hazardous Substances in E...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G59/42C08G59/40C08L63/00B32B17/04B32B15/14B32B15/20
CPCC08G59/4284C08G59/4014C08L63/00B32B5/02B32B15/14B32B15/20B32B2307/3065B32B2307/20B32B2307/7265B32B2457/08B32B2262/101B32B2260/021B32B2260/046
Inventor 罗成唐国坊
Owner GUANGDONG SHENGYI SCI TECH
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