Poly(amino bimaleimide) resin composition, preparation and use thereof in copper clad laminate

A technology of polyurethane bismaleimide resin and bismaleimide is applied in the field of high temperature resistant halogen-free flame retardant polyurethane bismaleimide composition, which can solve the problem that organic flame retardants are easily destroyed by organic compounds. Solvent dissolution or extraction, reduction in moisture resistance, heat resistance and electrical properties, difficulty in meeting heat-resistant materials, etc., to achieve the effects of short curing time at high temperature, high flexural strength and peel strength, and excellent heat resistance

Inactive Publication Date: 2011-01-19
SHENZHEN TONGXIN CIRCUIT ELECTRONICS
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the additive-type organic phosphorus-containing flame retardants inevitably have some disadvantages, such as organic flame retardants are easily dissolved or extracted by organic solvents during processing; the addition of organic phosphorus flame retardants will lead to some performance degradation of copper clad laminates , such as moisture resistance, heat resistance and electrical performance reduction, etc.
[0006] Chinese Patent Publication No. CN 1297618C, published on January 31, 2007, the name of the invention is a halogen-free flame-retardant adhesive for laminates. The application discloses a composition of benzoxazine, phosphorous epoxy resin, Adhesives composed of phenolic resins and / or cyanate resins and inorganic fillers have good heat resistance and meet the requirements of halogen-free flame retardancy. However, their glass transition temperature is about 180°C, which is difficult to meet the requirements of higher heat-resistant materials. need
Japanese patent JP 2001294689 discloses a halogen-free flame-retardant adhesive composed of bismaleimide, cyanate resin and inorganic flame-retardant filler, which has high heat resistance and excellent electrical properties, but must meet UL94V-0 A large amount of inorganic flame retardant fillers need to be added for the flame retardant effect of the grade. Due to the low viscosity of bismaleimide and cyanate resin and the presence of a large amount of inorganic fillers, the wettability of the adhesive to the glass fiber cloth is poor, and a large amount of Inorganic fillers can also make PCB processability worse

Method used

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  • Poly(amino bimaleimide) resin composition, preparation and use thereof in copper clad laminate
  • Poly(amino bimaleimide) resin composition, preparation and use thereof in copper clad laminate
  • Poly(amino bimaleimide) resin composition, preparation and use thereof in copper clad laminate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0056] Embodiment 1 gets bismaleimide 50 grams (in the bismaleimide structural formula, R 1 for -O-, R 2 , R 3 Both are -H), 17.4 grams of aromatic diamine (in the structural formula of aromatic diamine, R 4 for -O-, R 5 , R 6 Both are -H) and 60 grams of toluene, after being heated to transparency in a 500 milliliter three-necked bottle with a stirrer, a condenser and a temperature sensor (industry can be enlarged to 50-500 liters of reactor production), Reflux temperature was reacted for 30 minutes, discharged after cooling, in batching container with 134.8 gram phosphorus-containing epoxy resin (phosphorus content is 2.55%), 67.4 gram novolac polyglycidyl ether (polymerization degree is 4), 179.7 gram bisphenol Type A cyanate, 100 grams of silicon dioxide, 79.7 grams of aluminum hydroxide, 4.5 grams of 2-methylimidazole, and finally add 290 grams of acetone and 600 grams of propylene glycol methyl ether and mix well to obtain a polyurethane with a solid content of 40%. ...

Embodiment 2

[0057] Embodiment 2 gets 2 kilograms of bismaleimide (in the bismaleimide structural formula, R 1 for -CH 2 -, R 2 , R 3 Both are -H), 559 grams of aromatic diamine (in the structural formula of aromatic diamine, R 4 for -O-, R 5 , R 6 Be all-H) and 2.5 kilograms of toluene, after being heated to transparent in 10 liters of three-neck bottles with stirrer, condenser, temperature sensor, react 45 minutes at reflux temperature, discharge after cooling, mix in batching container 3.41 kilograms of phosphorus-containing epoxy resin (phosphorus content is 3.66%), 0.43 kilograms of linear cresol formaldehyde polyglycidyl ether (polymerization degree is 3), 2.13 kilograms of novolac cyanate, 1.71 kilograms of silicon dioxide, 171 grams of 2- Ethylimidazole, finally add 3 kilograms of acetone and 4.9 kilograms of dimethylformamide and mix uniformly to obtain a polyurethane bismaleimide resin composition with a solid content of 50%, impregnate the glass fiber cloth with the composi...

Embodiment 3

[0058] Embodiment 3 gets 1 kilogram of bismaleimide (in the bismaleimide structural formula, R 1 for -CH 2 -, R 2 , R 3 Both are -C 2 h 5 ), 191 grams of aromatic diamine (in the structural formula of aromatic diamine, R 4 for -CH 2 -, R 5 , R 6 Be all-H) and 2 kilograms of toluene, after being heated to transparent in 5 liters of three-neck bottles with stirrer, condenser, temperature sensor, react at reflux temperature for 55 minutes, discharge after cooling, mix in batching container 2.14 kilograms of phosphorus-containing epoxy resin (phosphorus content is 4.52%), 0.48 kilograms of linear bisphenol A type novolac epoxy resin (polymerization degree is 2), 0.95 kilograms of bisphenol M type cyanate, 1 kilogram of silicon dioxide, 0.67 One kilogram of aluminum oxide, 24 grams of 2-phenylimidazole, finally add 3 kilograms of methyl ethyl ketone and 2.89 kilograms of dimethylacetamide and mix uniformly to obtain a polyamide bismaleimide resin composition with a solid co...

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Abstract

The invention relates to a poly-amino-bismaleimide resin composite, a preparation method and the application thereof in copper clad plates. The composite essentially consists of a poly-amino-bismaleimide resin, a phosphoric epoxy resin, a cyanate resin, a novolac epoxy resin, an inorganic stuffing, a curing catalyst and a solvent. The poly-amino-bismaleimide resin in use is pre-polymerized from bismaleimide and aromatic amine under the reflow temperature with toluene as the solvent. The poly-amino-bismaleimide resin composite used in copper clad plates has good processing properties, low curing temperature (195 DEG C) and short high temperature curing time (1 to 1.5 hours). The prepared copper clad plates have excellent heat resistance, good fire retardant effect, comparatively high peeling strength, bending strength and comparatively low water absorption ratio, with the vitrification transition temperature ranging from 204 DEG C to 230 DEG C.

Description

technical field [0001] The invention relates to a polyurethane bismaleimide resin composition and a preparation method thereof in the field of polymer materials, in particular to a high-temperature resistant halogen-free flame-retardant polyurethane bismaleimide composition applied to copper-clad laminates thing. technical background [0002] With the rapid development of the electronics industry, electronic products tend to develop in the direction of short, thin, high density and high reliability, which not only puts forward higher requirements for the heat resistance of printed circuit It also puts forward environmental protection requirements for the flame retardancy of printed circuit boards. [0003] In recent years, some patents and publications have reported some high-temperature-resistant flame-retardant adhesive formulations, such as European patent EP 424135, which discloses copolymerization of bismaleimide, aromatic diamine and tribromophenyl monomaleimide The ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08L63/00C08K3/26C08K3/22C08K5/3445C08K3/38C08G73/10C08G73/02C08K3/36C08J5/24C08L79/08
Inventor 赵三平徐卫林
Owner SHENZHEN TONGXIN CIRCUIT ELECTRONICS
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