CN101704991B - Thermosetting epoxy resin composition - Google Patents
Thermosetting epoxy resin composition Download PDFInfo
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- CN101704991B CN101704991B CN2009102236728A CN200910223672A CN101704991B CN 101704991 B CN101704991 B CN 101704991B CN 2009102236728 A CN2009102236728 A CN 2009102236728A CN 200910223672 A CN200910223672 A CN 200910223672A CN 101704991 B CN101704991 B CN 101704991B
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Abstract
The invention discloses a thermosetting epoxy resin composition, which contains modified silicon dioxide and therefore can be used in the preparation of epoxy resin laminated boards with a low expansion coefficient property and excellent drilling processability. The modified silicon dioxide does not contain crystal water, has a low expansion coefficient property and comprises 40 to 80 weight percent of silicon dioxide and 60 to 20 percent of inorganic additive. And the modified silicon dioxide is prepared by sintering and melting at a high temperature above 1,000 DEG C and crushing.
Description
Technical field
The present invention relates to a kind of thermosetting epoxy resin composition, particularly a kind of thermosetting epoxy resin composition that comprises modified form silicon-dioxide, it can be applicable to prepare the epoxy laminate that has low-expansion coefficient characteristic and good boring processibility concurrently.
Background technology
Two important instructions of European Union: " useless motor electronics instruction (WEEE) " and " the motor electronics objectionable impurities limits the use of instruction (RoHS) " in formal enforcement on July 1st, 2006, in the instruction specified in more detail motor electronic product ban use of and contain Pb, Cd, Hg, Cr
6+, objectionable impurities, especially Qian forbiddings such as PBB, PBDE, will make global electronic march toward the unleaded epoch.
The fusing point of tinsel is 183 ℃, is the minimum alloy of industrial fusing point.After changing to unleaded preparation process, the fusing point of other alloy will promote more than 20 ℃, make the reflow temperature of unleaded preparation process will be promoted to 265 ℃ or higher.
Under the higher condition of preparation process temperature requirement, epoxy laminate is in order to reduce the dimensional change amount under the high temperature, and regular meeting adds a certain amount of aluminium hydroxide (Al (OH) in resin formula
3) or silicon-dioxide (SiO
2) inorganic filling material.
When epoxy laminate uses natural aluminium hydroxide as packing material, because aluminium hydroxide contains crystal water, and only 250 ℃～270 ℃ of cracking temperatures, in the high temperature preparation process or carry out thermotolerance when test, the crystal water of aluminium hydroxide can be cracked into the steam loss and come out, but the vapour pressure of steam that loss is come out and generation easily makes Resins, epoxy overstock plate generation layering plate bursting.
Silicon-dioxide has good thermostability, but hardness is too high, and Mohs' hardness is up to 7～7.5.When epoxy laminate uses native silicon dioxide as packing material, because the hardness of silicon-dioxide is too high, the processing that is unfavorable for holing, and can become crisp firmly after the epoxy laminate interpolation silicon-dioxide, inconvenience is arranged during use more.For example, the boring of carrying out epoxy laminate adds man-hour, and the wearing and tearing of drill bit are too big, and the quality of boring processing is not good; Even bestow plating, the borehole wall quality of epoxy laminate is still not good, easily causes the finished product of printed circuit board (PCB) electrically unusual.
Summary of the invention
Main purpose of the present invention is to provide a kind of modified form silicon-dioxide, it does not contain crystal water and has low expansion character, can be used for promoting the boring processibility of epoxy laminate or printed circuit board (PCB), its composition comprises the silicon-dioxide of 40～80wt% and the inorganic additive of 60-20wt%, and pulverizes after high temperature sintering melting more than 1000 ℃ again and make; Described inorganic additive is selected from the group of being made up of aluminium sesquioxide, boron trioxide, calcium oxide and magnesium oxide one or more.
The average particle size range of described modified form silicon-dioxide is between 0.1 micron to 20 microns, but is good with median size between 0.5 micron to 5.0 microns.
The coefficient of expansion of described modified form silicon-dioxide is about 3～5ppm/ ℃.
Another object of the present invention is to provide a kind of thermosetting epoxy resin composition, it is applied to prepare the epoxy laminate that has low-expansion coefficient characteristic and good boring processibility concurrently, and its main component that comprises is:
(a) novolac epoxy accounts for 0～100PHR of all resins composition solid and the about 160～250g/eq of epoxy equivalent (weight) (EEW);
(b) Resins, epoxy accounts for 0～100PHR of all resins composition solid and the about 300～460g/eq of epoxy equivalent (weight) (EEW);
(c) stiffening agent is phenolic aldehyde stiffening agent or dicyandiamide hardener, accounts for 4.47～48PHR of all resins composition solid;
(d) modified form silicon-dioxide accounts for 13.4～181.5PHR of all resins composition solid.
Embodiment
Under the influence of printed circuit board (PCB) multiple stratification and unleaded preparation process, more and more strict for the coefficient of expansion and the stable on heating requirement of copper-clad laminate.Under the high temperature preparation process, can not rupture for guaranteeing the circuit on the printed circuit board (PCB), even cause line short because of the expansion of copper-clad laminate, need reduce the coefficient of expansion of copper-clad laminate again.
The invention provides a kind of modified form silicon-dioxide, it does not contain crystal water, and has low expansion character, can be used for promoting the boring processibility of printed circuit board (PCB).And described modified form silicon-dioxide comprises the silicon-dioxide of 40～80wt%, and is mixed with the inorganic additive of 60-20wt%, and pulverizes behind high temperature sintering more than 1000 ℃ again and make.Wherein the median size of silicon-dioxide is between 0.1 micron to 20 microns, but is good for 0.5 micron to 5.0 microns with particle diameter.Described inorganic additive is selected from one or more ores in the group of being made up of aluminium sesquioxide, boron trioxide, calcium oxide and magnesium oxide.
The blending ratio of silicon-dioxide also can be 5～40wt% or 80～99wt% in the described modified form silicon-dioxide.But the blending ratio of silicon-dioxide is crossed when hanging down in the described modified form silicon-dioxide, and is more not obvious for the effect that reduces the coefficient of expansion when being used in epoxy laminate or preimpregnation material, and also relatively poor for thermostability; Otherwise when the blending ratio of silicon-dioxide was too high in the described modified form silicon-dioxide, because hardness is higher, it was more not obvious to improve effect for the boring processibility of epoxy laminate.Therefore, modified form silicon-dioxide of the present invention is most preferred embodiment to contain silicon-dioxide 40～80wt%.
When if modified form silicon-dioxide of the present invention uses particle diameter less than 0.1 micron silicon-dioxide, because surface-area causes viscosity excessive more greatly, the viscosity that contains novolac epoxy varnish that can make preparation be used to make epoxy laminate and preimpregnation material significantly promotes, and causes the operation inconvenience of impregnation preparation process.Therefore, when modified form silicon-dioxide of the present invention contained than the silicon-dioxide of fine grain size, its adding proportion needed to reduce again.
In addition, the trend that electronic product is lightening, make the thickness of epoxy laminate and preimpregnation material will be reduced to 30～50 microns, if when using particle diameter, will cause the problem that novolac epoxy varnish can't cover silicon-dioxide fully that contains that is used to make epoxy laminate and preimpregnation material greater than 20 microns silicon-dioxide.Therefore, modified form silicon-dioxide of the present invention is preferred embodiment to contain particle diameter between 0.1 micron to 20 microns silicon-dioxide, is most preferred embodiment to contain particle diameter between 0.5 micron to 5.0 microns silicon-dioxide.
Modified form silicon-dioxide of the present invention does not have crystal water, can not emit crystal water in the high temperature preparation process and influence thermotolerance, and the coefficient of expansion is also low than native silicon dioxide.The proportion of general native silicon dioxide is 2.65, and the coefficient of expansion is about 5.0ppm/ ℃.Modified form silicon-dioxide of the present invention, because mix one or more ore, proportion will reduce to 2.3～2.5, and have the lower coefficient of expansion is arranged, its coefficient of expansion is about 3～5ppm/ ℃.
In addition, general native silicon dioxide is a powdered quartz, after the high-temperature fusion more than 1000 ℃, again through quick cooling, can make powdered quartz become non-crystalline type silicon-dioxide, and its Mohs' hardness will reduce to 6～6.5 from 7～7.5.
Modified form silicon-dioxide of the present invention is non-crystalline type silicon-dioxide, and adds one or more other kind ore before fusion, Mohs' hardness can be reduced to 4～6 again, so can effectively improve the boring processibility of printed circuit board (PCB).
Modified form silicon-dioxide of the present invention can be arranged in pairs or groups and use the silane surface treatment agent to carry out surface treatment, with addition and the dispersion effect that promotes described modified form silicon-dioxide.
The present invention also provides a kind of thermosetting epoxy resin composition, said composition contains modified form silicon-dioxide of the present invention, through being modulated into the thermosetting epoxy resin varnish of making veneer sheet or laminating material use, can be applicable to prepare epoxy laminate, to improve the boring processibility of epoxy laminate or printed circuit board (PCB) with low-expansion coefficient characteristic.Described thermosetting epoxy resin composition comprises following main component:
(a) novolac epoxy accounts for 0～100PHR of all resins composition solid and the about 160～250g/eq of epoxy equivalent (weight) (EEW);
(b) Resins, epoxy accounts for 0～100PHR of all resins composition solid and the about 300～460g/eq of epoxy equivalent (weight) (EEW);
(c) stiffening agent can be phenolic aldehyde stiffening agent or dicyandiamide hardener, accounts for 4.47～48PHR of all resins composition solid;
(d) modified form silicon-dioxide accounts for 13.4～181.5PHR of all resins composition solid;
Wherein, the addition of described modified form silicon-dioxide is if consider dispersed and when reducing the effect of the coefficient of expansion, the 30.3～121PHR that accounts for all resins composition solid is better.When the addition of described modified form silicon-dioxide hanged down, the coefficient of expansion amplitude that can reduce was less; When the addition of modified form silicon-dioxide is higher,, all have negative impact for dispersed and boring processibility though can significantly reduce the Z-direction coefficient of expansion.Therefore, can adjust the addition of described modified form silicon-dioxide according to the end-use of different printing circuit card.
Embodiment:
Below with preferred embodiment in detail the present invention is described in detail, each code name and composition thereof used in embodiment and the comparative example are as follows:
Resins, epoxy A; The novolac epoxy of representing Nanya Plastic Cement Industry Co., Ltd to produce, commodity are called NPPN-431A70, and its epoxy equivalent (weight) is between 160～250g/eq.
Resins, epoxy B; The Resins, epoxy of representing Nanya Plastic Cement Industry Co., Ltd to produce, commodity are called NPEB-454A80, and its epoxy equivalent (weight) is between 300～460g/eq.
Stiffening agent A; The resol stiffening agent of representing Nanya Plastic Cement Industry Co., Ltd to produce, commodity are called NPEH710.
Stiffening agent B; Represent Dyhard RU 100 (DICYANDIAMIDE).
Promotor 2MI; Represent glyoxal ethyline, 14.2% is dissolved in DMF.
Packing material A; The native silicon dioxide of representing Bao Lin company to produce, trade(brand)name 925.
Packing material B; Represent the clear aluminium hydroxide that the electrician produces that closes, commodity are called H42M.
The veneer sheet of following examples and comparative example is according to following measuring method, measures the coefficient of expansion, 288 ℃ of anti-scolding tin thermotolerances, boring property and dispersivenesses.
1, the coefficient of expansion (Coefficient of thermal expension)
Behind the stripping of the veneer sheet etching after pressing copper, with the diamond clipper sample is cut length * wide * thick 4 * 4 * 0.8mm of being size, measure the coefficient of expansion of veneer sheet with TMA (Thermomechanical Analysis).
2,288 ℃ of anti-scolding tin thermotolerances
Testing method is that (121 ℃ of conditions 2atm) were handled 1/2 hour, immersed in 288 ℃ of solder furnace record testing plate plate bursting layering required time through pressure cooker with testing plate earlier.
3, boring property
Veneer sheet after the pressing is made borehole test in three one folded modes with drilling machine, and the boring aperture that uses is 0.25mm, and the boring number is 2000 holes, again position, the hole precision (Cpk) of relatively holing.
4, dispersiveness
Veneer sheet etching after the pressing is divested Copper Foil, visual veneer sheet outward appearance, inhomogeneous as appearance color, then be judged to be and disperse inequality.
[embodiment 1～8]
In embodiment 1～8, use Resins, epoxy A, Resins, epoxy B, stiffening agent A or the stiffening agent B and the promotor of same ratio, but add modified form silicon-dioxide (the Bao Lin company of different ratios, product code name G2C), its prescription composition sees table 1 for details, and utilize acetone to be modulated into and make the thermosetting epoxy resin varnish that veneer sheet uses, wherein solid accounts for 75%.
Prepare epoxy laminate with currently known methods, with the above-mentioned varnish resin liquid of 7628 glasscloth impregnations, descended dry several minutes in 170 ℃ of temperature (impregnation machine temperature) then, by adjusting and control time of drying, with the melting viscosity of adjusting dried prepreg is 4000～10000 pools, at last 4 films are folded layer by layer mutually between the thick Copper Foil of two 35 μ m, at 25kg/cm
2Under the pressure, control intensification temperature and time can make the thick veneer sheet of 0.8mm after hot pressing.
[comparative example 1～2]
The prescription composition sees table 1 for details, Resins, epoxy A, Resins, epoxy B, stiffening agent A and promotor that comparative example 1～2 uses same ratio, but add packing material A and packing material B respectively in varnish, the filling ratio is 121PHR (50wt%), and utilize acetone to be modulated into and make the thermosetting epoxy resin varnish that veneer sheet uses, wherein solid accounts for 75%; Utilize the method prepared layer pressing plate identical again with embodiment 1～8 prepared layer pressing plate.
[embodiment 9～11]
The prescription composition sees table 2 for details, Resins, epoxy A, Resins, epoxy B, stiffening agent A and promotor that embodiment 9～11 uses same ratio, and add 121PHR to the silica-filled material of the surface treated improvement of 282.2PHR (Bao Lin company, product code name G2CARI), and utilize acetone to be modulated into and make the thermosetting epoxy resin varnish that veneer sheet uses, wherein solid accounts for 75%; Utilize the method prepared layer pressing plate identical again with embodiment 1～8 prepared layer pressing plate.
[comparative example 3～5]
The prescription composition sees table 2 for details, Resins, epoxy A, Resins, epoxy B, stiffening agent A and promotor that comparative example 3～5 uses same ratio, and add surface treated packing material A (Bao Lin company, product code name 925ARI) in varnish, the filling ratio by 121PHR to 282.2PHR, and utilize acetone to be modulated into and make the thermosetting epoxy resin varnish that veneer sheet uses, wherein solid accounts for 75%; Utilize the method prepared layer pressing plate identical again with embodiment 1～8 prepared layer pressing plate.
Table 1 normal temperature is the composition of the thermosetting epoxy resin composition that contains modified form silicon-dioxide of preparation down
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 | Comparative example 2 | |
| Resins, epoxy A | 80 PHR | 80 PHR | 80 PHR | 80 PHR | 80 PHR | 0 PHR | 100 PHR | 80 PHR | 80 PHR | 80 PHR |
| Resins, epoxy B | 20 PHR | 20 PHR | 20 PHR | 20 PHR | 20 PHR | 100 PHR | 0 PHR | 20 PHR | 20 PHR | 20 PHR |
| Stiffening agent A | 21 PHR | 21 PHR | 21 PHR | 21 PHR | 21 PHR | 23 PHR | 48 PHR | 0 | 21 PHR | 21 PHR |
| Stiffening agent B | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 4.47 PHR | 0 | 0 |
| Modified form silicon-dioxide | 0 | 13.4 PHR | 80.6 PHR | 121 PHR | 181.5 PHR | 123 PHR | 148 PHR | 104.47 PHR | 0 | 0 |
| Packing material A | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 121 PHR | 0 |
| Packing material B | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 121 PHR |
PHR:parts per hundreds of rubber (or resin), the umber that expression is added per 100 parts of (in mass) rubber (or resin).
Table 2 preparation contains the composition of the thermosetting epoxy resin composition of surface treated modified form silicon-dioxide
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Resins, epoxy A | 80 PHR | 80 PHR | 80 PHR | 80 PHR | 80 PHR | 80 PHR |
| Resins, epoxy B | 20 PHR | 20 PHR | 20 PHR | 20 PHR | 20 PHR | 20 PHR |
| Stiffening agent A | 21 PHR | 21 PHR | 21 PHR | 21 PHR | 21 PHR | 21 PHR |
| Surface treated modified form silicon-dioxide | 121 PHR | 181.5 PHR | 282.2 PHR | 0 | 0 | 0 |
| Surface treated packing material A | 0 | 0 | 0 | 121 PHR | 181.5 PHR | 282.2 PHR |
PHR: the umber that expression is added per 100 parts of (in mass) rubber (or resin).
The veneer sheet characteristic evaluation of each prescription of table 3
Table 4 uses the characteristic of each veneer sheet of filling a prescription of surface treatment packing material
The result:
By the result of table 3 and table 4 as can be known:
When 1, veneer sheet used modified form silicon-dioxide of the present invention, its coefficient of expansion descended along with the raising of addition, and the coefficient of expansion to use native silicon dioxide and aluminium hydroxide be low.
When 2, veneer sheet uses modified form silicon-dioxide of the present invention, have good boring, when being added into 181.5PHR, borehole accuracy still can be greater than Cpk 1.33, and the scolding tin thermotolerance can not influence to some extent because of the interpolation of modified form silicon-dioxide.But when addition promoted, dispersiveness had not good phenomenon.
3, the modified form silicon-dioxide of embodiment 9～11 uses after surface treatment can promote optimum filling amount to 181.5PHR.
When 4, veneer sheet uses modified form silicon-dioxide of the present invention, has the boring processibility that reduces coefficient of expansion effect and improve veneer sheet.And can use the surface treatment of collocation silane to promote the loading level of improvement silicon-dioxide of the present invention.
Claims (4)
1. a thermosetting epoxy resin composition is applied to prepare the epoxy laminate with low-expansion coefficient characteristic, it is characterized in that, said composition comprises following main component:
(a) novolac epoxy account for 0～100PHR of all resins composition solid, and epoxy equivalent (weight) is 160～250g/eq;
(b) Resins, epoxy account for 0～100PHR of all resins composition solid, and epoxy equivalent (weight) is 300～460g/eq;
(c) stiffening agent is phenolic aldehyde stiffening agent or dicyandiamide hardener, accounts for 4.47～48PHR of all resins composition solid;
(d) modified form silicon-dioxide, median size is 0.1～20 micron, accounts for 13.4～181.5PHR of all resins composition solid;
Wherein, described modified form silicon-dioxide comprises the silicon-dioxide of 40～80wt% and the inorganic additive of 60-20wt%, and pulverizes after high temperature sintering melting more than 1000 ℃ again and make; Described inorganic additive is selected from one or more in the group of being made up of aluminium sesquioxide, boron trioxide, calcium oxide and magnesium oxide.
2. thermosetting epoxy resin composition as claimed in claim 1 is characterized in that, 30.3～121PHR of described modified form silica comprises all resins composition solid.
3. thermosetting epoxy resin composition as claimed in claim 1 is characterized in that, the median size of described modified form silicon-dioxide is 0.5～5.0 micron.
4. thermosetting epoxy resin composition as claimed in claim 1 is characterized in that, the coefficient of expansion of described modified form silicon-dioxide is 3～5ppm/ ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102236728A CN101704991B (en) | 2009-11-23 | 2009-11-23 | Thermosetting epoxy resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102236728A CN101704991B (en) | 2009-11-23 | 2009-11-23 | Thermosetting epoxy resin composition |
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| CN101704991A CN101704991A (en) | 2010-05-12 |
| CN101704991B true CN101704991B (en) | 2011-08-17 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002187937A (en) * | 2000-12-19 | 2002-07-05 | Matsushita Electric Works Ltd | Epoxy resin composition, prepreg, and metal-clad laminate |
| JP2003013002A (en) * | 2001-07-03 | 2003-01-15 | Denki Kagaku Kogyo Kk | Epoxy resin varnish for resin substrate |
| CN1890325A (en) * | 2003-12-15 | 2007-01-03 | 积水化学工业株式会社 | Thermosetting resin composition, material for substrate and film for substrate |
| JP2009007469A (en) * | 2007-06-28 | 2009-01-15 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg, laminate and semiconductor device |
| JP2009185170A (en) * | 2008-02-06 | 2009-08-20 | Kyocera Chemical Corp | Prepreg, metal-clad laminate and printed wiring board |
-
2009
- 2009-11-23 CN CN2009102236728A patent/CN101704991B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002187937A (en) * | 2000-12-19 | 2002-07-05 | Matsushita Electric Works Ltd | Epoxy resin composition, prepreg, and metal-clad laminate |
| JP2003013002A (en) * | 2001-07-03 | 2003-01-15 | Denki Kagaku Kogyo Kk | Epoxy resin varnish for resin substrate |
| CN1890325A (en) * | 2003-12-15 | 2007-01-03 | 积水化学工业株式会社 | Thermosetting resin composition, material for substrate and film for substrate |
| JP2009007469A (en) * | 2007-06-28 | 2009-01-15 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg, laminate and semiconductor device |
| JP2009185170A (en) * | 2008-02-06 | 2009-08-20 | Kyocera Chemical Corp | Prepreg, metal-clad laminate and printed wiring board |
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