CN101955678B - Flame retardant thermosetting resin composition and copper-clad plate - Google Patents
Flame retardant thermosetting resin composition and copper-clad plate Download PDFInfo
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- CN101955678B CN101955678B CN201010514530XA CN201010514530A CN101955678B CN 101955678 B CN101955678 B CN 101955678B CN 201010514530X A CN201010514530X A CN 201010514530XA CN 201010514530 A CN201010514530 A CN 201010514530A CN 101955678 B CN101955678 B CN 101955678B
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Abstract
The invention discloses a flame retardant thermosetting resin composition, which comprises thermosetting resin, curing agents, curing accelerators and solvents, and is characterized by also comprising an inorganic whisker which is one or a mixture of a magnesium carbonate whisker, a magnesium hydroxide whisker and a magnesium oxide whisker, and the inorganic whisker accounts for 10 to 80 weight percent of the solid content of the thermosetting resin composition. The composition formula contains an appropriate inorganic whisker, has excellent mechanical properties and electrical insulating property and stable chemical properties, can improve the shrinkage of a resin matrix, reduce the interface difference of the shrinkage between the matrix and fibers, and improve the interlayer performance of the thermosetting resin; meanwhile, the characteristics of high strength and high modulus of the whisker can further improve the strength and the modulus of the resin; and the composition has high flame retardance.
Description
Technical field
the invention belongs to technical field of electronic materials, relate to a kind of copper-clad plate, especially a kind of flame retardant type compositions of thermosetting resin and copper-clad plate thereof.
Background technology
in existing flame retardant type copper-clad plate was produced, the matrix resin that baseplate material is commonly used was a brominated epoxy resin.Brominated epoxy resin can be used as good reactive flame retardant, and still, the people in the industry generally believes brominated epoxy resin in combustion processes, can produce toxic gas, therefore need substitute with other not halogen-containing fire retardant.
a kind of replacement scheme is to add phosphide as fire retardant.Open 2005-187749 in japanese patent application laid, the spy opens among the 2004-197032, adopts phosphorus compound such as DOPO (9, the 10-dihydro-9-oxy is assorted-10-phosphorus phenanthryl-10-oxide compound) or its verivate to replace halogen compounds.In No. the 0384940th, European patent, also adopt the reaction of phosphorus compound and epoxy resin, form bifunctional or multi-functional epoxy resin.The cost of these phosphorous modified epoxies is quite high, in addition, and performances such as the water-absorbent of the interpolation regular meeting of phosphorus compound reduction compsn or sheet material tolerance.
another kind of replacement scheme is to add mineral filler at high proportion.In recent years, in copper-clad plate, use mineral filler, improved rigidity, flame retardant resistance, the thermal expansivity of sheet material, the technical study of insulativity has become the important topic in the copper-clad plate technological development.The filler that generally adopts has silicon-dioxide, white lake, aluminum oxide, talcum powder, nanoclay or the like.Publication number is the openly application of mineral filler in copper-clad plate in the Chinese invention patent application of CN101412840A and the Chinese invention patent that publication number is CN101039546A.Traditional copper-clad plate with resin combination in, generally add white lake, the method for mineral fillers such as silicon-dioxide reduces cost, improves flame retardant resistance, mechanical property etc., makes that the ratio of mineral filler in resin combination is increasing.Publication number discloses a kind of high performance copper clad laminate for the special Japanese patent application of opening 2001-316563 and Te Kai 2001-316564 in addition; This copper-clad plate is slim, stable, production cost is low; Insulation layer in the said copper-clad plate mainly is made up of thermosetting resin and magnesium borate crystal whisker or aluminium borate whisker; Improved the cohesiveness between Copper Foil and the insulation layer, reduce the thermal expansivity of insulation layer, but the heat decomposition temperature of magnesium borate or aluminium borate whisker has been high; Flame retardant effect is relatively poor, and therefore restriction is widely used in the flame retardant type copper-clad plate.
Summary of the invention
the object of the invention provides a kind of flame retardant type compositions of thermosetting resin and copper-clad plate thereof; To overcome the defective of prior art; Improve the consistency of inorganic crystal whisker and thermosetting resin; The flame retardant resistance of raising copper-clad plate and hot expansibility, water absorption resistance, and significantly reduce production costs.
are for achieving the above object; The technical scheme that the present invention adopts is: a kind of flame retardant type compositions of thermosetting resin; Comprise thermosetting resin, solidifying agent, curing catalyst, solvent; Also comprise inorganic crystal whisker, said inorganic crystal whisker is selected from one or more the mixture in magnesium carbonate whisker, magnesium hydroxide crystal whisker, the magnesia crystal whisker, and the content range of its inorganic crystal whisker is 10～80%.
In
technique scheme; The consumption of said thermosetting resin, solidifying agent, curing catalyst and solvent is confirmed according to curing system; Belong to prior art, those skilled in the art can confirm the content ratio of thermosetting resin, solidifying agent, curing catalyst, solvent voluntarily according to the difference of thermosetting resin and curing system.
In
technique scheme; In order further to improve the effect of inorganic crystal whisker in the thermosetting resin combination; Inorganic crystal whisker is handled through surface treatment agent, and said surface treatment agent is selected from: silane series coupling agent, epoxy are that coupling agent, boron are a kind of in the coupling agent.
optimized technical scheme, said inorganic crystal whisker is a magnesium carbonate whisker.Magnesium carbonate whisker not only has higher mechanical characteristics, insulativity, and has the excellent fire retardant characteristic, under combustion conditions, generates activated magnesia, and this activated magnesia has stronger heat insulating function, and has stronger heat-conductive characteristic.
In
technique scheme, the mean diameter of said inorganic crystal whisker is 0.5～5 μ m.
The length of
said inorganic crystal whisker is greater than 10 times of diameter, and less than 100 μ m.
optimized technical scheme, by weight percentage, inorganic crystal whisker accounts for 30～60% of solids content in the compositions of thermosetting resin.
In the technique scheme, said thermosetting resin is selected from one or more the mixture in epoxy or modified epoxy, benzoxazine, cyanate ester resin, polyimide resin, ppe, the bimaleimide resin; Said solidifying agent is selected from one or more the mixture in Dyhard RU 100, resol, the anhydrides compound; Said curing catalyst is a glyoxaline compound, can select a kind of in glyoxal ethyline (2-MI), 2-ethyl-4-methylimidazole (2E4MI) or the 2-phenylimidazole (2-PI) for use; Said solvent is selected from one or more the mixture in acetone, butanone, toluene or the N.
the present invention asks for protection the copper-clad plate of a kind of flame retardant type thermosetting resin simultaneously; Made through the heating and pressurizing shaping by bonding sheet and the Copper Foil that covers the bonding sheet both side surface, said bonding sheet floods above-mentioned flame retardant type compositions of thermosetting resin after the product that oven dry is processed for adopting the E glasscloth.
wherein, the solids content of flame retardant type compositions of thermosetting resin is 10～60% by weight in the said bonding sheet.
The method of manufacture of above-mentioned flame retardant type thermosetting resin copper-clad plate is following:
first step: use the E glasscloth, the above-mentioned compositions of thermosetting resin of impregnation, baking is 3-6 minute in 140 ℃ ~ 170 ℃ baking ovens, processes bonding sheet, and the resin content of gained bonding sheet is 10～60%.
second step: get above-mentioned bonding sheet (prepreg); The two-sided electrolytic copper foil of mixing; Be placed between two blocks of mirror face stainless steel plates, place vacuum press then, under 150 ℃～200 ℃ of temperature, pressure 0.5MPa～3MPa; Suppressed 90～150 minutes, and processed copper-clad plate.
In
technique scheme, the quantity of bonding sheet can be adjusted according to the thickness of thickness, resin content scope and the required sheet material of the kind of used glasscloth, bonding sheet, and the thickness of institute's pressed sheet is different thus.For example, can use 8 bonding sheets superimposed neat, the two-sided electrolytic copper foil of mixing carries out above-mentioned pressing process.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
Selected suitable inorganic crystal whisker in
composite formula 1. of the present invention; Inorganic crystal whisker has excellent mechanical property, chemical property stabilizer pole; Electrical insulation capability, and can improve the shrinking percentage of resin matrix, the interface that reduces shrinking percentage between matrix and the fiber is poor; In addition; Whisker with certain length-to-diameter ratio can be pricked the interlayer at resin material as the nail riveting, and this pinning effect makes the connection between fiber and the resin matrix become the three-dimensional connection with steric effect from original simple interface connection (two dimension), thereby improves the interlayer performance of thermosetting resin; Simultaneously, high-strength, the high-modulus characteristic of whisker can further improve the intensity and the modulus of resin.
Magnesium carbonate whisker is preferably adopted in
2. the present invention; Because magnesium carbonate whisker not only has higher mechanical characteristics, insulativity; Also has stronger flame retardant resistance; The activated magnesia that under combustion conditions, generates has stronger heat insulating function, thereby has improved the flame retardant resistance of copper-clad plate, and effectively improves hot expansibility, rigidity, cohesiveness and cost.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one
The preparation of
1, thermoset resin components: take by weighing 80 weight part epoxy resin; The phosphorous modified epoxy of 20 weight parts; 67 weight part resol; 0.5 the 2-ethyl-4-methylimidazole of weight part, 72 weight parts are through surface-treated magnesium carbonate whisker (mean diameter is 0.8 μ m, and mean length is 20 μ m); Surface treatment agent is a silane coupling agent, and being added in an amount of butanone solvent and stirring, to mix the system solids content is 70% compositions of thermosetting resin (whisker content 30%).
2, to use 8 models be that 7628 E glasscloth immerses in the above-mentioned compositions of thermosetting resin that contains Carbon Dioxide magnesium whisker, carries out gluing, and baking is 3 minutes in 155 ℃ of baking ovens, processes the bonding sheet of semi-cured state.
3, again with above-mentioned 8 bonding sheets stack alignment, the Copper Foil of respectively joining 1 18 μ m up and down, in vacuum press, by 190 ℃ of temperature, the condition of pressure 0.034Pa, the copper-clad plate that thickness is 1.6mm is processed in hot pressing 90 minutes.
Embodiment two
The preparation of
1, thermoset resin components: take by weighing 90 weight part epoxy resin; The phosphorous modified epoxy of 10 weight parts; 67 weight part resol, the 2-ethyl-4-methylimidazole of 0.5 weight part, (mean diameter is 0.8 μ m to 112 weight parts through surface-treated magnesium carbonate whisker; Mean length is 20 μ m); Surface treatment agent is a silane coupling agent, is added in an amount of butanone solvent to stir, and mixed system solids content is 70% compositions of thermosetting resin (whisker content 40%).
2, immerse in the above-mentioned compositions of thermosetting resin that contains Carbon Dioxide magnesium whisker with 8 7628 E glasscloths, carry out gluing, baking is 3 minutes in 155 ℃ of baking ovens, processes the bonding sheet of semi-cured state.
3, again with above-mentioned 8 bonding sheets stack alignment, respectively join 1 18 μ m Copper Foil up and down, in vacuum press, by 190 ℃ of temperature, the condition of pressure 0.034Pa, the copper-clad plate that thickness is 1.6mm is processed in hot pressing 90 minutes.
Embodiment three
The preparation of
1, thermoset resin components: take by weighing 100 weight part epoxy resin; 67 weight part resol, the 2-ethyl-4-methylimidazole of 0.5 weight part, (mean diameter is 0.8 μ m to 168 weight parts through surface-treated magnesium carbonate whisker; Mean length is 20 μ m); Surface treatment agent is a silane coupling agent, is added in an amount of butanone solvent to stir, and mixed system solids content is 70% compositions of thermosetting resin (whisker content 50%).
2, immerse in the above-mentioned compositions of thermosetting resin that contains Carbon Dioxide magnesium whisker with 8 7628 E glasscloths, carry out gluing, baking is 3 minutes in 155 ℃ of baking ovens, processes the bonding sheet of semi-cured state.
3, again with above-mentioned 8 bonding sheets stack alignment, respectively join 1 18 μ m Copper Foil up and down, in vacuum press, by 190 ℃ of temperature, the condition of pressure 0.034Pa, the copper-clad plate that thickness is 1.6mm is processed in hot pressing 90 minutes.
Embodiment four
The preparation of
1, thermoset resin components: take by weighing 90 weight part epoxy resin, 20 weight part benzoxazine resins, 57 weight part resol; 0.5 the glyoxal ethyline of weight part; 72 weight parts are through surface-treated magnesium carbonate whisker (mean diameter is 0.8 μ m, and mean length is 20 μ m), and surface treatment agent is an epoxy coupling agents; Be added in an amount of butanone solvent and stir, mixed system solids content is 70% compositions of thermosetting resin (whisker content 30%).
2, immerse in the above-mentioned compositions of thermosetting resin that contains Carbon Dioxide magnesium whisker with 8 7628 E glasscloths, carry out gluing, baking is 3 minutes in 155 ℃ of baking ovens, processes the bonding sheet of semi-cured state.
3, again with above-mentioned 8 bonding sheets stack alignment, respectively join 1 18 μ m Copper Foil up and down, in vacuum press, by 190 ℃ of temperature, the condition of pressure 0.034Pa, the copper-clad plate that thickness is 1.6mm is processed in hot pressing 90 minutes.
Embodiment five
The preparation of
1, thermoset resin components: take by weighing 90 weight part bimaleimide resins; 57 weight part cyanate ester resins; 20 weight part resol, the glyoxal ethyline of 0.5 weight part, (mean diameter is 0.8 μ m to 72 weight parts through surface-treated magnesium carbonate whisker; Mean length is 20 μ m); Surface treatment agent is an epoxy coupling agents, is added in an amount of butanone solvent to stir, and mixed system solids content is 70% compositions of thermosetting resin (whisker content 30%).
2, immerse in the above-mentioned compositions of thermosetting resin that contains Carbon Dioxide magnesium whisker with 8 7628 E glasscloths, carry out gluing, baking is 3 minutes in 155 ℃ of baking ovens, processes the bonding sheet of semi-cured state.
3, again with above-mentioned 8 bonding sheets stack alignment, respectively join 1 18 μ m Copper Foil up and down, in vacuum press, by 190 ℃ of temperature, the condition of pressure 0.034Pa, the copper-clad plate that thickness is 1.6mm is processed in hot pressing 90 minutes.
Comparative Examples one:
The preparation of
1, thermoset resin components: take by weighing the phosphorous modified epoxy of 100 weight parts; 3.0 weight part Dyhard RU 100; 0.5 weight part 2-phenylimidazole, 72 weight parts are through surface-treated silicon-dioxide, surface treatment agent is an epoxy coupling agents; Be added in an amount of butanone solvent and stir, mixed system solids content is 70% compositions of thermosetting resin.
2, immerse in the resin matching fluid of above-mentioned boronic acid containing magnesium whisker with 8 7628 E glasscloths, carry out gluing, baking is 3 minutes in 155 ℃ of baking ovens, processes the bonding sheet of semi-cured state.
3, again with above-mentioned 8 bonding sheets stack alignment, respectively join 1 18 μ m Copper Foil up and down, in vacuum press, by 190 ℃ of temperature, the condition of pressure 0.034Pa, the metal foil laminate that thickness is 1.6mm is processed in hot pressing 90 minutes.
this example adds common silicon-dioxide as filler, compares with embodiments of the invention.
Comparative Examples two:
The preparation of
1, thermoset resin components: take by weighing 20 weight part epoxy resin; 80 weight part phosphorus modified epoxies; 67 weight part resol; 0.5 weight part 2-phenylimidazole is added in an amount of butanone solvent and stirs, mixed system solids content is 70% compositions of thermosetting resin (not filled).
2, immerse in the above-mentioned compositions of thermosetting resin with 8 7628 E glasscloths, carry out gluing, baking is 3 minutes in 155 ℃ of baking ovens, processes the bonding sheet of semi-cured state.
3, again with above-mentioned 8 bonding sheets stack alignment, respectively join 1 18 μ m Copper Foil up and down, in vacuum press, by 190 ℃ of temperature, the condition of pressure 0.034Pa, the copper-clad plate that thickness is 1.6mm is processed in hot pressing 90 minutes.
this example is not filled, compares with embodiments of the invention.
Product to the foregoing description and Comparative Examples carries out performance test, and method is:
thermally stratified layer time T-288, testing method adopts hot mechanical decomposition method (TMA).
Copper Foil stripping strength adopts 90 ℃ of peeling strength test machines to measure.
thermal expansivity (CTE), testing method adopts hot mechanical decomposition method (TMA).
The test of
water-intake rate is with reference to IPC-TM-650 2.6.2.1.
incendivity is measured by U.S. UL94 vertical combustion method.
Detected result sees the following form:
| Embodiment | One | Two | Three | Four | Five | Comparative Examples one | Comparative Examples two |
| Thermally stratified layer time T-288 min | ≥30 | ≥30 | ≥30 | ≥30 | ≥30 | ≥30 | ≥30 |
| Copper Foil stripping strength kN/m | 1.2 | 1.3 | 1.1 | 1.5 | 0.9 | 1.6 | 1.1 |
| Thermal expansivity ppm/ ℃ | 42 | 38 | 39 | 38 | 40 | 48 | 56 |
| Water-intake rate % | 0.15 | 0.12 | 0.10 | 0.14 | 0.15 | 0.28 | 0.26 |
| Flame retardant resistance UL94 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 |
can learn from above-mentioned detected result: the flame retardant type copper-clad plate the present invention has high heat resistance, low thermal coefficient of expansion (CTE), low water absorption, high flame retardant characteristic.Halogen contained compound not only compared with prior art, and reduced the phosphorus content in the prescription, thus improve the water-intake rate of copper-clad plate and reduce material cost, reach flame retardant resistance UL94 V-0 rank simultaneously, satisfy the halogen-free environmental requirement.
Claims (5)
1.
a kind of flame retardant type compositions of thermosetting resin; Comprise thermosetting resin, solidifying agent, curing catalyst, solvent; It is characterized in that: also comprise inorganic crystal whisker; Said inorganic crystal whisker is a magnesium carbonate whisker, and by weight percentage, inorganic crystal whisker accounts for 10～80% of solids content in the compositions of thermosetting resin; Said thermosetting resin is selected from one or more the mixture in epoxy or modified epoxy, benzoxazine, cyanate ester resin, polyimide resin, ppe, the bimaleimide resin; Said solidifying agent is selected from one or more the mixture in Dyhard RU 100, resol, the anhydrides compound; Said curing catalyst is a glyoxaline compound; Said solvent is selected from one or more the mixture in acetone, butanone, toluene or the N.
2.
flame retardant type compositions of thermosetting resin according to claim 1, it is characterized in that: the mean diameter of said inorganic crystal whisker is 0.5～5 μ m.
3.
flame retardant type compositions of thermosetting resin according to claim 1 is characterized in that: the length of said inorganic crystal whisker is greater than 10 times of diameter, and less than 100 μ m.
4.
flame retardant type compositions of thermosetting resin according to claim 1 is characterized in that: by weight percentage, inorganic crystal whisker accounts for 30～60% of solids content in the compositions of thermosetting resin.
5.
a kind of flame retardant type thermosetting resin copper-clad plate; Made through the heating and pressurizing shaping by bonding sheet and the Copper Foil that covers the bonding sheet both side surface, it is characterized in that: said bonding sheet is for adopting the E glasscloth dipping said flame retardant type compositions of thermosetting resin of claim 1 after the product that oven dry is processed.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102140239B (en) * | 2011-05-16 | 2012-03-21 | 刘立文 | Calcium sulfate whisker modified polyphenyl ether composite material and preparation method thereof |
| CN103582677B (en) * | 2011-06-09 | 2017-11-28 | 住友精化株式会社 | Non-ignitable film, non-ignitable film dispersion liquid, the manufacture method of non-ignitable film, solar cell backboard, flexible base board and solar cell |
| CN102888078B (en) * | 2011-07-20 | 2015-08-19 | 深圳光启高等理工研究院 | Matrix material and prepare the method for base material based on matrix material |
| CN103304949B (en) * | 2013-06-08 | 2016-03-23 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and the prepreg using it to make and veneer sheet |
| CN104277444A (en) * | 2014-09-25 | 2015-01-14 | 苏州长盛机电有限公司 | Flame-retardant nano material and preparation method thereof |
| CN104844801B (en) * | 2015-04-23 | 2017-04-12 | 东华大学 | Silicon-containing polyimide copper-clad plate and preparation method thereof |
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| CN101275010B (en) * | 2007-03-26 | 2012-08-08 | 上海金发科技发展有限公司 | Flame-proof reinforced Valox compound and preparation thereof |
| CN101550264A (en) * | 2009-04-30 | 2009-10-07 | 苏州生益科技有限公司 | Resin matching fluid used for metal foil laminated board |
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