Thermosetting resin composition and application

A resin composition and thermosetting technology, which is applied in the field of thermosetting resin compositions, can solve the problems of low dielectric properties, poor processability of copper clad laminates, and high cost, and achieve the goal of improving dielectric properties, good thermal reliability, and good dielectric properties Effect

Active Publication Date: 2009-12-16
ITEQ DONGGUAN
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  • Abstract
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AI Technical Summary

Problems solved by technology

[0002] Epoxy resin has been widely used in various electronic insulating materials, mainly because it has good heat resistance, chemical resistance and good insulation and dielectric properties. Commonly used curing agents include amines, acid anhydrides and Phenolic or phenolic, especially in the application of copper clad laminates, dicyandiamide (amine) and phenolic resin (phenolic) are commonly used as curing agents for epoxy resins, which have good processability, heat resistance, and Chemical and insulating properties, but its dielectric properties cannot meet the requirements of high-frequency signal transmission integrity because of its high dielectric constant (Dk for short) and dielectric loss factor (Df for short), especially In the field of high-frequency (2GHz and above) communications such as radio frequency base stations and radar antennas, higher requirements are placed on signal transmission loss and signal transmission delay. Since signal transmission loss is mainly related to the dielectric loss of materials, the lower the dielectric loss, the lower the dielectric loss. The lower the signal transmission loss, the signal transmission delay is mainly related to the dielectric constant of the material. The lower the dielectric constant, the smaller the signal transmission delay. Therefore, only materials with extremely low dielectric constant and dielectric loss can meet high frequency requirements. (especially above 10GHz) applications in the field of communication
For example, the Dk / Df of polytetrafluoroethylene (PTFE) at 1MHz is about 2.1 / 0.0004, and the Dk / Df of polyphenylene ether (PPE) at 1MHz is about 2.45 / 0.0007. Copper clad laminates made of PTFE or PPE have been applied In the field of high-frequency communication, but its cost is too high, and its copper clad laminate and PCB formability are poor
[0003] Using styrene-maleic anhydride copolymer (SMA for short) to replace traditional dicyandiamide and phenolic resin to cure epoxy resin can avoid the generation of OH polar groups, and can greatly reduce the dielectric constant and dielectric loss of cured resin , but currently technically limited to the application of SMA copolymers with a S (styrene) / MA (maleic anhydride) molar ratio of 1:1 to 4:1, due to the styrene structure with low dielectric properties in the molecular structure The ratio is not high enough, and its Dk and Df are not low enough. The Dk and Df at 1GHz frequency of the copper clad laminate made of E-glass glass cloth are generally 3.7-4.2 and 0.008-0.012 respectively, such as in patents WO9818845, WO9607683, CN1935896A, CN1955217A , CN1955219A mentions that the dielectric properties of the copper-clad laminate made of the SMA / epoxy resin composition are not low enough, and its Dk / Df generally falls in the interval of 3.7-4.2 / 0.008-0.012, while the SMA / epoxy resin mentioned in other patents The resin composition has poor PCB processability and is not suitable for PCB applications, or the heat resistance such as Tg and Td is reduced

Method used

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  • Thermosetting resin composition and application
  • Thermosetting resin composition and application
  • Thermosetting resin composition and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1~5

[0045] When the acid anhydride equivalent and phenolic hydroxyl equivalent change compared with the epoxy equivalent, the Tg and other properties of the copper clad laminate produced by the above experimental method of the resin composition will change accordingly. The specific Tg changes are shown in the data in Table 1. When the equivalence ratio is 0.9:1.0-1.1:1, the corresponding Tg of the copper clad laminate is relatively the highest.

[0046] Table 1

[0047] Example number

1

2

3

4

5

Anhydride equivalent + phenolic hydroxyl equivalent

1.6

1.3

1.1

0.9

0.6

epoxy equivalent

1

1

1

1

1

Tg(DSC)(℃)

131

138

149

142

133

[0048] Note: (1) The ratio of each component in the above table is calculated as solid.

[0049] (2) The S:MA molar ratio of SMA is 8:1, which is represented by SMA (S:MA=8:1), and the same below.

Embodiment 6

[0050] Embodiment 6 (comparative example)

[0051] Configure the resin composition according to the following formula: first adopt 192g of butanone (abbreviated as MEK) solvent to dissolve 156g of SMA3000 and 40g of TBBA, then add 185g of BET-535A80 (solid content is 80%, 20% is acetone solvent) and 93.3 g of BET-400T60 (solid content is 60%, 40% is toluene solvent), then add 0.12g of 2-ethyl-4-methylimidazole (2E4Mz for short), stir for 2 hours and mix well, according to the above Implementation method Copper clad laminates were fabricated and tested for their physical and electrical properties. In this embodiment, the ratio of acid anhydride equivalents plus phenolic hydroxyl equivalents to epoxy equivalents is 1.1:1

Embodiment 7

[0053] Configure the resin composition according to the following formula: first adopt 272g of butanone (abbreviated as MEK) solvent to dissolve 220g of SMA (S:MA=5:1) and 20g of TBBA, then add 25g of BET-535A80 (solid content is 80% , 20% is acetone solvent) and 233.3g of BET-400T60 (solid content is 60%, 40% is toluene solvent), then add 0.36g of 2-ethyl-4-methylimidazole (2E4Mz for short), stir for 2 Mix evenly after 1 hour, manufacture copper clad laminates according to the implementation method described above and test its physical properties and electrical properties. In this embodiment, the ratio of acid anhydride equivalents plus phenolic hydroxyl equivalents to epoxy equivalents is 1.1:1.

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Abstract

The invention discloses a thermosetting resin composition, which comprises the following components: bifunctional or multifunctional epoxy resin, styrene-maleic anhydride copolymer SMA as a curing agent with styrene/maleic anhydride molar ratio of 5-12:1, low-bromine or high-bromine BPA type epoxy resin or tetrabromo bisphenol A as a fire retardant, an accelerator and a solvent. The resin composition after curing has quite low dielectric property, higher heat reliability and better toughness, has quite low dielectric constant and dielectric loss coefficient, high Td, better toughness and excellent PCB processability with a copper-clad plate made of glass fiber cloth and other reinforcing materials, is suitable for manufacturing a copper-clad plate and a semi-cured plate for PCB, and can also be used in common application of the epoxy resin, such as molding resin, composite materials for buildings, automobiles and aviation, and the like.

Description

technical field [0001] The invention relates to a thermosetting resin composition, which is suitable for making copper-clad laminates and prepregs for PCBs, and is used in common uses of epoxy resins such as molding resins and composite materials for construction, automobiles and aviation. Background technique [0002] Epoxy resin has been widely used in various electronic insulating materials, mainly because it has good heat resistance, chemical resistance and good insulation and dielectric properties. Commonly used curing agents include amines, acid anhydrides and Phenolic or phenolic, especially in the application of copper clad laminates, dicyandiamide (amine) and phenolic resin (phenolic) are commonly used as curing agents for epoxy resins, which have good processability, heat resistance, and Chemical and insulating properties, but its dielectric properties cannot meet the requirements of high-frequency signal transmission integrity because of its high dielectric consta...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08L63/00C08G59/42C08G59/62C08K13/02
Inventor 贺育方张伦强
Owner ITEQ DONGGUAN
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