CN102051025A - Halogen-free flame-retardant epoxy resin composition and application thereof - Google Patents
Halogen-free flame-retardant epoxy resin composition and application thereof Download PDFInfo
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Abstract
The invention discloses a halogen-free flame-retardant epoxy resin composition. The formula of the composition comprises the following components in parts by weight: 40 to 65 parts of phosphorus-containing epoxy resin solution, 35 to 65 parts of composite curing agent, 0 to 0.03 part of curing accelerant and 10 to 200 parts of filler, wherein the composite curing agent consists of benzoxazine, nitrogen-containing phenolic resin and diaminodiphenyl sulfone. The epoxy resin composition has the advantages of good operability, good flame-retardant performance, good reactivity and the like; and a copper-clad plate made from the epoxy resin composition has comprehensive performances of good heat resistance, good flame-retardant performance, low water absorption and the like.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, be specifically related to a kind of printed circuit copper-clad plate halogen-free flame retardant epoxy resin composition.
Background technology
Because the needs of environmental protection, from July 1st, 2006, the global electronic industry entered the pb-free solder epoch, because the raising of pb-free solder temperature is had higher requirement to thermotolerance, flame retardant resistance and the thermostability of printed circuit copper clad laminate.Original assembly weldprocedure is replaced by pb-free solder technology, welding temperature exceeds than in the past more than 20 ℃, this just proposes higher requirement to the over-all properties of printed circuit board and base material, such as: thermotolerance, the low water absorption of flame retardant resistance, excellence, therefore, the halogen-free flameproof copper-clad plate, for domestic copper-clad plate production, extremely urgent.
Over nearly 30 years, at the main baseplate material of printed circuit board---a large amount of chemical materialss such as tetrabromo-bisphenol, brominated epoxy resin that use in the copper-clad plate are in order to make copper-clad plate reach relevant flame retardant resistance performance demands.For many years, a large amount of research experiments prove: the copper-clad plate of adopting the brominated flame-retarded resin material of this class to manufacture in burning, when doing hot air leveling and assembly welding, can discharge the material that is pernicious to people; And when the printed circuit board of this copper-clad plate manufacturing being done waste treatment and carrying out recycling, also run into sizable difficulty.Therefore, although be not put into the row of the ban of above-mentioned rules by synthetic brominated epoxy resins such as tetrabromo-bisphenols, at present in most of complete machine design of electronic products such as Europe, Japan, produce, begin to adopt more and more non-halogen printed circuit board.
At present the halogen-free phosphorus-containing fire retardant resin all exist crisp firmly, water-intake rate big and defective such as thermotolerance deficiency, make to use to be very limited.Therefore, improve the defective that copper-clad plate is used, become one of emphasis problem of Halogen resin research.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art part, provide a kind of reactivity good halogen-free flame retardant epoxy resin composition, have over-all propertieies such as good heat resistance, flame retardant resistance is good, water-intake rate is low with its printed circuit copper-clad plate that makes.
Another object of the present invention provides the printed circuit copper-clad plate that is made by above-mentioned halogen-free flame retardant epoxy resin composition.
For achieving the above object, the present invention adopts following technical scheme:
A kind of halogen-free flame retardant epoxy resin composition is characterized in that: prescription calculates by weight and comprises:
Phosphorous epoxy resin solution 40～65 weight parts
Composite curing agent 35～65 weight parts
Curing catalyst 0～0.03 weight part
Filler 10～200 weight parts
Wherein, composite curing agent is made up of benzoxazine, nitrogenous resol, two amido sulfobenzides.
The solid content of described phosphorous epoxy resin solution is 65-85%.
Described phosphorous epoxy resin solution is prepared by following method: 20～35 weight part linear phenolic epoxy resins and 6～16 weight part response type P contained compounds are added reactive tank, add 0.010～0.020 weight part catalyst triphenyl phosphorus in 110-130 ℃, 165-185 ℃ of reaction 2-3 hour, sneaking into epoxy equivalent (weight) again is lower molecular weight bisphenol A type epoxy resin 5～10 weight parts of 180～200g/eq, epoxy equivalent (weight) is macromolecule bisphenol A type epoxy resin 5～10 weight parts and 2～6 weight parts, four phenol ethane, four glycidyl ethers of 2500～3300g/eq, is dissolved into solution with butanone again.
Described response type P contained compound is selected from 9, and the 10-dihydro-9-oxy is assorted-one or both mixing in 10-phospho hetero phenanthrene-10-oxide compound or 10-(2, the 5-the dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound.
Described composite curing agent is made up of benzoxazine, nitrogenous resol, two amido sulfobenzides, and its mixed weight ratio is 5～10: 1～5: 1～15.
Described curing catalyst is an imidazoles promotor, is selected from one or more mixing in imidazoles, glyoxal ethyline, 1-benzyl benzene-2-ethyl imidazol(e) or the 2-ethyl-4-methylimidazole.
Described filler is mineral filler, is selected from one or more mixing in silicon-dioxide, aluminium hydroxide, aluminium sesquioxide, the magnesium oxide.
Composition epoxy resin of the present invention has good operability, good flame resistance and advantage such as reactive good; Be used to prepare printed circuit copper-clad plate, make this copper-clad plate have over-all propertieies such as copper-clad plate good heat resistance, flame retardant resistance is good, water-intake rate is low.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
The present invention is a kind of halogen-free flame retardant epoxy resin composition, and prescription calculates by weight and comprises: phosphorous epoxy resin solution 40～65 weight parts, composite curing agent 35～65 weight parts, curing catalyst 0～0.03 weight part, filler 10～200 weight parts.
Wherein, composite curing agent is made up of benzoxazine, nitrogenous resol, two amido sulfobenzides.Preferably, its mixed weight ratio is 5～10: 1～5: 1～15.Two amido sulfobenzides in the present invention, can improve the resistance to elevated temperatures and the flame retardant properties of cured article as curing agent for epoxy resin, have improved the performance of cured article greatly, and its combined influence sees Table 1.
The solid content of described phosphorous epoxy resin solution is 65-85%, prepare by following method: 20～35 weight part linear phenolic epoxy resins and 6～16 weight part response type P contained compounds are added reactive tank, add 0.010～0.020 weight part catalyst triphenyl phosphorus in 110-130 ℃, 165-185 ℃ of reaction 2-3 hour, sneaking into epoxy equivalent (weight) again is lower molecular weight bisphenol A type epoxy resin 5～10 weight parts of 180～200g/eq, epoxy equivalent (weight) is macromolecule bisphenol A type epoxy resin 5～10 weight parts and 2～6 weight parts, four phenol ethane, four glycidyl ethers of 2500～3300g/eq, is dissolved into solution with butanone again.Wherein the response type P contained compound is selected from 9, and the 10-dihydro-9-oxy is assorted-one or both mixing in 10-phospho hetero phenanthrene-10-oxide compound or 10-(2, the 5-the dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound.
Described curing catalyst is an imidazoles promotor, is selected from one or more mixing in imidazoles, glyoxal ethyline, 1-benzyl benzene-2-ethyl imidazol(e) or the 2-ethyl-4-methylimidazole.
Described filler is mineral filler, is selected from one or more mixing in silicon-dioxide, aluminium hydroxide, aluminium sesquioxide, the magnesium oxide.Add mineral filler and can reduce resin shared ratio in whole system, thereby reduce the thermal expansivity of resin system, can effectively suppress the generation of internal stress, can reduce cost simultaneously.
Embodiment 1
(1) preparation of phosphorous epoxy resin butanone solution:
27 weight part linear phenolic epoxy resins and 12 weight part response type P contained compounds are added reactive tank, add 0.012 weight part catalyst triphenyl phosphorus in 120 ℃, at 175 ℃ of reaction 2.5h, sneak into the low-molecular-weight bisphenol A type epoxy resin of 7 weight parts again, the bisphenol A type epoxy resin of 7 weight part macromolecules and 3.7 weight parts, four phenol ethane, four glycidyl ethers, being dissolved into solid content with butanone again is 75% solution.Above-mentioned consumption is parts by weight.
(2) preparation of composite curing agent: be made up of benzoxazine, nitrogenous resol, two amido sulfobenzides, its blended weight ratio is 6.2: 2.0: 2.3.
(3) preparation of halogen-free flame retardant epoxy resin composition:
Press and take by weighing the composite curing agent that the phosphorous epoxy resin butanone solution that obtains of (1) step and (2) step obtain, and add mineral filler, curing catalyst, mix:
Phosphorous epoxy resin butanone solution 55 weight parts
Composite curing agent 45 weight parts
Glyoxal ethyline 0.015 weight part
Aluminium hydroxide+silicon-dioxide 20+25 weight part
(4) preparation of the curing of resin combination and substrate:
Above composition epoxy resin is made prepreg PP 170 ℃ of baking oven bakings, reusable heat press pressing and forming, hot pressing condition is: 170 ℃ of * 35kg/cm
2* 23min.The flame resistivity of this substrate (UL94) is V-0.
Embodiment 2
(1) preparation of phosphorous epoxy resin butanone solution:
22 weight part linear phenolic epoxy resins and 15 weight part response type P contained compounds are added reactive tank, add 0.012 weight part catalyst triphenyl phosphorus in 120 ℃, at 175 ℃ of reaction 2.5h, sneak into the low-molecular-weight bisphenol A type epoxy resin of 9 weight parts again, the bisphenol A type epoxy resin of 9 weight part macromolecules and 4.4 weight parts, four phenol ethane, four glycidyl ethers, being dissolved into solid content with butanone again is 75% solution.Above-mentioned consumption is parts by weight.
(2) preparation of composite curing agent: be made up of benzoxazine, nitrogenous resol, two amido sulfobenzides, its blended weight ratio is 7.1: 2.5: 10.0.
(3) preparation of halogen-free flame retardant epoxy resin composition:
Press and take by weighing the composite curing agent that the phosphorous epoxy resin butanone solution that obtains of (1) step and (2) step obtain, and add mineral filler, curing catalyst, mix:
Phosphorous epoxy resin butanone solution 65 weight parts
Composite curing agent 45 weight parts
Glyoxal ethyline 0.015 weight part
Aluminium hydroxide 50 weight parts
(4) preparation of the curing of resin combination and substrate:
Above composition epoxy resin is made prepreg PP 170 ℃ of baking oven bakings, reusable heat press pressing and forming, hot pressing condition is: 170 ℃ of * 35kg/cm
2* 23min.The flame resistivity of this substrate (UL94) is V-0.
Embodiment 3
(1) preparation of phosphorous epoxy resin butanone solution:
30 weight part linear phenolic epoxy resins and 8 weight part response type P contained compounds are added reactive tank, add 0.020 weight part catalyst triphenyl phosphorus in 120 ℃, at 175 ℃ of reaction 2.0h, sneak into the low-molecular-weight bisphenol A type epoxy resin of 10 weight parts again, the bisphenol A type epoxy resin of 6 weight part macromolecules and 3.3 weight parts, four phenol ethane, four glycidyl ethers, being dissolved into solid content with butanone again is 75% solution.Above-mentioned consumption is parts by weight.
(2) preparation of composite curing agent: be made up of benzoxazine, nitrogenous resol, two amido sulfobenzides, its blended weight ratio is 8.0: 2.4: 1.7.
(3) preparation of halogen-free flame retardant epoxy resin composition:
Press and take by weighing the composite curing agent that the phosphorous epoxy resin butanone solution that obtains of (1) step and (2) step obtain, and add mineral filler, curing catalyst, mix:
Phosphorous epoxy resin butanone solution 50 weight parts
Composite curing agent 45 weight parts
Glyoxal ethyline 0.016 weight part
Aluminium hydroxide+magnesium dioxide 40+25 weight part
(4) preparation of the curing of resin combination and substrate:
Above composition epoxy resin is made prepreg PP 170 ℃ of baking oven bakings, reusable heat press pressing and forming, hot pressing condition is: 170 ℃ of * 35kg/cm
2* 23min.The flame resistivity of this substrate (UL94) is V-0.
Embodiment 4
(1) preparation of phosphorous epoxy resin butanone solution:
33 weight part linear phenolic epoxy resins and 14 weight part response type P contained compounds are added reactive tank, add 0.019 weight part catalyst triphenyl phosphorus in 120 ℃, at 175 ℃ of reaction 2.5h, sneak into the low-molecular-weight bisphenol A type epoxy resin of 7 weight parts again, the bisphenol A type epoxy resin of 7 weight part macromolecules and 4.7 weight parts, four phenol ethane, four glycidyl ethers, being dissolved into solid content with butanone again is 75% solution.Above-mentioned consumption is parts by weight.
(2) preparation of composite curing agent: be made up of benzoxazine, nitrogenous resol, two amido sulfobenzides, its blended weight ratio is 7.1: 3.4: 14.8.
(3) preparation of halogen-free flame retardant epoxy resin composition:
Press and take by weighing the composite curing agent that the phosphorous epoxy resin butanone solution that obtains of (1) step and (2) step obtain, and add mineral filler, curing catalyst, mix:
Phosphorous epoxy resin butanone solution 65 weight parts
Composite curing agent 48 weight parts
Glyoxal ethyline 0.015 weight part
Aluminium hydroxide+silicon-dioxide 40+25 weight part
(4) preparation of the curing of resin combination and substrate:
Above composition epoxy resin is made prepreg PP 170 ℃ of baking oven bakings, reusable heat press pressing and forming, hot pressing condition is: 170 ℃ of * 35kg/cm
2* 23min.The flame resistivity of this substrate (UL94) is V-0.
Embodiment 5
(1) preparation of phosphorous epoxy resin butanone solution:
35 weight part linear phenolic epoxy resins and 15 weight part response type P contained compounds are added reactive tank, add 0.020 weight part catalyst triphenyl phosphorus in 120 ℃, at 175 ℃ of reaction 2.5h, sneak into the low-molecular-weight bisphenol A type epoxy resin of 9 weight parts again, the bisphenol A type epoxy resin of 8 weight part macromolecules and 3.7 weight parts, four phenol ethane, four glycidyl ethers, being dissolved into solid content with butanone again is 75% solution.Above-mentioned consumption is parts by weight.
(2) preparation of composite curing agent: be made up of benzoxazine, nitrogenous resol, two amido sulfobenzides, its blended weight ratio is 8.2: 3.0: 7.0.
(3) preparation of halogen-free flame retardant epoxy resin composition:
Press and take by weighing the composite curing agent that the phosphorous epoxy resin butanone solution that obtains of (1) step and (2) step obtain, and add mineral filler, curing catalyst, mix:
Phosphorous epoxy resin butanone solution 65 weight parts
Composite curing agent 45 weight parts
Glyoxal ethyline 0.012 weight part
Aluminium hydroxide+silicon-dioxide 55+35 weight part
(4) preparation of the curing of resin combination and substrate:
Above composition epoxy resin is made prepreg PP 170 ℃ of baking oven bakings, reusable heat press pressing and forming, hot pressing condition is: 170 ℃ of * 35kg/cm
2* 23min.The flame resistivity of this substrate (UL94) is V-0.
Embodiment 6
(1) preparation of phosphorous epoxy resin butanone solution:
27 weight part linear phenolic epoxy resins and 15 weight part response type P contained compounds are added reactive tank, add 0.010 weight part catalyst triphenyl phosphorus in 120 ℃, at 175 ℃ of reaction 2.5h, sneak into the low-molecular-weight bisphenol A type epoxy resin of 10 weight parts again, the bisphenol A type epoxy resin of 5 weight part macromolecules and 4.9 weight parts, four phenol ethane, four glycidyl ethers, being dissolved into solid content with butanone again is 75% solution.Above-mentioned consumption is parts by weight.
(2) preparation of composite curing agent: be made up of benzoxazine, nitrogenous resol, two amido sulfobenzides, its blended weight ratio is 5.1: 2.8: 5.1.
(3) preparation of halogen-free flame retardant epoxy resin composition:
Press and take by weighing the composite curing agent that the phosphorous epoxy resin butanone solution that obtains of (1) step and (2) step obtain, and add mineral filler, curing catalyst, mix:
Phosphorous epoxy resin butanone solution 45 weight parts
Composite curing agent 45 weight parts
Glyoxal ethyline 0.010 weight part
Aluminium hydroxide 80 weight parts
(4) preparation of the curing of resin combination and substrate:
Above composition epoxy resin is made prepreg PP 170 ℃ of baking oven bakings, reusable heat press pressing and forming, hot pressing condition is: 170 ℃ of * 35kg/cm
2* 23min.The flame resistivity of this substrate (UL94) is V-0.
The characteristic of the printed circuit copper-clad plate substrate that the foregoing description obtains sees Table 1.
Table 1.
From above data as can be seen: the operability of composition epoxy resin of the present invention, thermotolerance (T
288Reach more than the 30min, decomposition temperature Td is more than 340 ℃), water-intake rate and flame retardant resistance etc. have clear improvement.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, all comprise within protection scope of the present invention.
Claims (8)
1. halogen-free flame retardant epoxy resin composition is characterized in that: prescription calculates by weight and comprises:
Phosphorous epoxy resin solution 40～65 weight parts
Composite curing agent 35～65 weight parts
Curing catalyst 0～0.03 weight part
Filler 10～200 weight parts
Wherein, composite curing agent is made up of benzoxazine, nitrogenous resol, two amido sulfobenzides.
2. halogen-free flame retardant epoxy resin composition according to claim 1 is characterized in that: the solid content of described phosphorous epoxy resin solution is 65-85%.
3. halogen-free flame retardant epoxy resin composition according to claim 1, it is characterized in that: described phosphorous epoxy resin solution is prepared by following method: 20～35 weight part linear phenolic epoxy resins and 6～16 weight part response type P contained compounds are added reactive tank, add 0.010～0.020 weight part catalyst triphenyl phosphorus in 110-130 ℃, 165-185 ℃ of reaction 2-3 hour, sneaking into epoxy equivalent (weight) again is lower molecular weight bisphenol A type epoxy resin 5～10 weight parts of 180～200g/eq, epoxy equivalent (weight) is macromolecule bisphenol A type epoxy resin 5～10 weight parts and 2～6 weight parts, four phenol ethane, four glycidyl ethers of 2500～3300g/eq, is dissolved into solution with butanone again.
4. halogen-free flame retardant epoxy resin composition according to claim 3, it is characterized in that: described response type P contained compound is selected from 9, the 10-dihydro-9-oxy is assorted-one or both mixing in 10-phospho hetero phenanthrene-10-oxide compound or 10-(2, the 5-the dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound.
5. halogen-free flame retardant epoxy resin composition according to claim 1 is characterized in that: described composite curing agent is made up of benzoxazine, nitrogenous resol, two amido sulfobenzides, and its mixed weight ratio is 5～10: 1～5: 1～15.
6. halogen-free flame retardant epoxy resin composition according to claim 1, it is characterized in that: described curing catalyst is an imidazoles promotor, is selected from one or more mixing in imidazoles, glyoxal ethyline, 1-benzyl benzene-2-ethyl imidazol(e) or the 2-ethyl-4-methylimidazole.
7. halogen-free flame retardant epoxy resin composition according to claim 1 is characterized in that: described filler is mineral filler, is selected from one or more mixing in silicon-dioxide, aluminium hydroxide, aluminium sesquioxide, the magnesium oxide.
8. the described halogen-free flame retardant epoxy resin composition of arbitrary claim among the claim 1-7 is applied to prepare printed circuit copper-clad plate.
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| CN102585440A (en) * | 2012-01-16 | 2012-07-18 | 广州宏仁电子工业有限公司 | High-CTI (comparative tracking index) halogen-free flame retardant resin composition for copper-clad laminate |
| CN103059266A (en) * | 2013-01-17 | 2013-04-24 | 中山联成化学工业有限公司 | Preparation method of phosphorus-containing cresol novolac epoxy resin |
| CN103214794A (en) * | 2013-05-17 | 2013-07-24 | 宏昌电子材料股份有限公司 | Halogen-free epoxy resin composition for copper-clad plate and application thereof |
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| CN103059266A (en) * | 2013-01-17 | 2013-04-24 | 中山联成化学工业有限公司 | Preparation method of phosphorus-containing cresol novolac epoxy resin |
| CN103059266B (en) * | 2013-01-17 | 2015-10-14 | 中山联成化学工业有限公司 | A kind of preparation method of phosphorous cresol novolac epoxy resins |
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| CN104015461B (en) * | 2014-05-27 | 2016-06-15 | 铜陵浩荣华科复合基板有限公司 | A kind of Halogen Tg130 method for manufacturing cover clad laminate |
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| CN106218136A (en) * | 2016-07-27 | 2016-12-14 | 重庆德凯实业股份有限公司 | The preparation method of environment-friendly type CEM 3 copper-clad plate |
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