CN103360621B - Filler in a kind of clad with metal foil plate with low thermal coefficient of expansion and preparation method thereof - Google Patents
Filler in a kind of clad with metal foil plate with low thermal coefficient of expansion and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to the amorphous eutectic powder stuffing of composite silicon dioxide in a kind of clad with metal foil plate, contain by weight percentage following component: silica 57～70wt%, alundum (Al2O3) 15～35wt%, magnesia+calcium oxide≤40wt%, sodium oxide molybdena+potassium oxide+lithia≤2wt%. Filler provided by the present invention not only improve the processability of electric substrate, make the clad with metal foil plate making there is lower thermal coefficient of expansion simultaneously.
Description
Technical field
The present invention relates to filler in a kind of clad with metal foil plate and preparation method thereof, relate in particular to one and cover metalAmorphous eutectic powder stuffing of composite silicon dioxide in paper tinsel plate and preparation method thereof.
Background technology
While for example, using filler in clad with metal foil plate (CEM-3), adopt aluminium hydroxide and hydroxide more in the pastMagnesium. But more than 200 degree Celsius, aluminium hydroxide just starts to decompose, thermo-labile impact, 230 DEG C, 300 DEG C, 530DEG C three phases discharges the crystallization water, easily causes plate material lamination to bubble, so, heat-treat; AndMagnesium hydroxide price is partially expensive.
Silica (SiO2) there is excellent physical characteristic, as have high-insulativity, high thermal conductivity,High thermal stability, resistance to acids and bases, wearability, low thermal coefficient of expansion, low-k etc., and lowerPrice advantage, have very much value of exploiting and utilizing. Along with the improvement of silica self surface treatment condition, changeBe apt to the compatibility of it and resin system, so the filler silicon powder of making as major ingredient with silica is applied toIn clad with metal foil plate, not only can reduce costs, can also improve some performance of clad with metal foil plate (as thermal expansionCoefficient, bending strength, dimensional stability etc.), therefore promise well.
Silicon powder is by natural quartz (SiO2) or vitreous silica (natural quartz through high-temperature fusion, cooling afterAmorphous Si O2) through broken, ball milling (or vibration, airflow milling), flotation, pickling purification, high purity water placeThe micro mist that the multiple tracks processes such as reason form.
Electron trade is unleaded has promoted the application of silicon powder filler at clad with metal foil plate. In the past have a kupper solderSn-Pb(37%Pb) lead welding material lowest total of the melting point is 183 DEG C, at present representative unleaded and canThe lowest total of the melting point of the scolder Sn-Ag-Cu system implementing etc. is 217 DEG C. The lifting of welding temperature, to various unitsDevice, printed circuit board (pcb) base material etc. have proposed higher heat resistance and reliability requirement. PCB withoutPlumbous processing procedure requires sheet material to have low thermal coefficient of expansion (CTE), for clad with metal foil plate, improves heat-resistingProperty main approach be to reduce the CTE of sheet material. And add filler be reduce at present CTE most economical, have mostThe method of effect. Reducing the most general method of sheet material CTE is at present in clad with metal foil plate, to introduce inorganic particle materialMaterial. The thermal coefficient of expansion of epoxy resin is (30-50) ppm/ DEG C, and the thermal coefficient of expansion of silica is (0.5-9)Ppm/ DEG C. In epoxy resin, add a large amount of silicon powders, so just can reduce the thermal coefficient of expansion of sheet material, withTime reduce water absorption rate, internal stress, shrinkage factor, thereby make the requirement of clad with metal foil plate adapted to leadless welding.
Silica, due to its excellent chemical stability, low thermal coefficient of expansion, is at present at clad with metal foilIn board industry, use maximum fillers. But it is high that the shortcoming of silica is hardness, Mohs' hardness is 7, to establishingStandby wearing and tearing are large. Especially affecting large is the obvious raising of the processing cost of downstream PCB producer, as boring, millingThe raising of plate cost and diel cost. In order to improve the processability of powder, changing powder composition becomesOne of method of considering.
Silicon is released and is improved the G2-C product of processability than section, and has applied for that this powder applies on copper clad laminateInvention CN102088820A. The filler of this disclosure of the invention is by silica 50-62wt%, alundum (Al2O3)11-19wt%, diboron trioxide 4-13wt%, calcium oxide 6-27wt%, magnesia < 6wt%, strontium oxide strontia <The amorphism network structure that 1.5wt% and barium monoxide < 0.1wt% form altogether. Although the filler wherein addingThere is lower hardness, but thermal coefficient of expansion is larger.
Summary of the invention
The object of the invention is to make after clad with metal foil plate for current use silicon powder filler thermal expansion systemThe problem that number is larger, provides a kind of composite silicon dioxide amorphous eutectic powder stuffing. Provided by the inventionFiller composite silicon dioxide eutectic powder not only improve the processability of electric substrate, what make to make covers simultaneouslyMetal foil plate has lower thermal coefficient of expansion.
In order to achieve the above object, the present invention has adopted following technical scheme:
The amorphous eutectic powder stuffing of composite silicon dioxide in clad with metal foil plate, by weight percentageContain following component: silica 57～70wt%, be for example 58wt%, 61wt%, 64wt%, 68wt%,69wt% etc., alundum (Al2O3) 15～35wt%, be for example 16wt%, 19wt%, 22wt%, 26wt%,29wt%, 32wt%, 34wt% etc., magnesia+calcium oxide≤40wt%, be for example 6wt%, 8wt%,10wt%、14wt%、16wt%、18wt%、22wt%、26wt%、29wt%、32wt%、34wt%Deng, sodium oxide molybdena+potassium oxide+lithia≤2wt%, be for example 0.1wt%, 0.5wt%, 0.8wt%, 1.1wt%,1.3wt%, 1.6wt%, 1.8wt%, 1.95wt% etc.
As optimal technical scheme, filler of the present invention, contains following component: two by weight percentageSilica 60～66wt%, alundum (Al2O3) 23～28wt%, magnesia+calcium oxide≤30wt%, sodium oxide molybdena+ potassium oxide+lithia≤1wt%.
Silica forms the skeleton structure of eutectic, if its content is less than 57wt%, eutectic powderThermal coefficient of expansion is high. If its content is higher than 70wt%, filler hardness enlarges markedly, and affects adding of PCBWork. Therefore, it is 57～70wt% that the present invention selects dioxide-containing silica, is preferably 60～66wt%.
If the alundum (Al2O3) content in eutectic powder is less than 15wt%, the resistance to water of eutectic powder is notGood, if higher than 35wt%, the thermal coefficient of expansion of fusant powder is high. Therefore, the present invention selects three oxidationsTwo aluminium content are 15～35wt%, are preferably 23～28wt%.
Contain under calcium oxide, magnesian filler moisture conditions and easily separate out calcium ion, magnesium ion, affect CAFPerformance (energy of resistance to ion transport), thereby the insulating properties of the sheet material of impact preparation. Therefore, by its content sumBe defined as≤40wt%, be preferably≤30wt%. Calcium oxide is in the preparation of filler of the present invention on the other handIn process, can also there is fluxing action.
Sodium oxide molybdena+potassium oxide+lithia water soluble in eutectic powder, precipitating metal ion, impact systemThe insulating properties of standby copper-clad plate, if its content higher than 2wt%, the copper-clad plate of the preparation of fusant powder is exhaustedEdge performance worsens. Therefore, the present invention, by be defined as≤2wt% of its content, is preferably≤1wt%.
As optimal technical scheme, filler of the present invention, contain by weight percentage di-iron trioxide≤0.6wt%, be for example 0.05wt%, 0.11wt%, 0.15wt%, 0.18wt%, 0.22wt%, 0.25wt%,0.28wt%, 0.33wt%, 0.36wt%, 0.39wt%,, 0.44wt%, 0.51wt%, 0.58wt% etc.,Be preferably≤0.2wt% more preferably≤0.1wt%. Di-iron trioxide is can conductive materials, by its limitFix in specific content range, the powder that can solve prior art provides is being made after substrate, insulating propertiesProblem that can be not enough.
Stain is the black impurity in composite silicon dioxide eutectic powder, and by analysis, stain major part isBlack can conductive materials, and therefore, stain not only can affect the apparent of base material, and more affects the insulation of base materialProperty. Therefore, the stain number of amorphous described composite silicon dioxide eutectic powder is less than 20 by the present invention/ 300g is for example 3/300g, 5/300g, 8/300g, 11/300g, 14/300g, 16Individual/300g, 18/300g etc., be preferably less than 15/300g, is further preferably less than 10/300g.
As optimal technical scheme, the electrical conductivity≤200 μ s/cm of filler of the present invention, be for example 5 μ s/cm,10μs/cm、15μs/cm、20μs/cm、26μs/cm、34μs/cm、39μs/cm、45μs/cm、55μs/cm、60μs/cm、68μs/cm、76μs/cm、88μs/cm、105μs/cm、124μs/cm、136μs/cm、145μs/cm、157 μ s/cm, 165 μ s/cm, 174 μ s/cm, 186 μ s/cm, 198 μ s/cm etc., be preferably≤100 μ s/cm.Electrical conductivity is the electric conductivity of powder, the insulating properties of the higher sheet material of electrical conductivity are poorer, in order to ensure sheet materialInsulating properties, are defined as the electrical conductivity of filler≤200 μ s/cm.
As optimal technical scheme, filler of the present invention is through surface treatment. Due to described in the present inventionPowder stuffing is inorganic material, bad with organic resin matrix compatibility, therefore, need to use surface treatmentAgent is done surface treatment to it, to increase the compatibility of itself and matrix.
Preferably, the surface conditioning agent that described surface treatment is used is silane coupler, titanate ester processingAgent, aluminate, zirconates, cationic surface active agent, anionic surfactant, amphoteric surfaceActivating agent, neutral surface active agent, stearic acid, oleic acid, laurate and their metallic salt, phenolic aldehyde treeOne kind or two or more mixture in fat, organic silicone oil, HMDS, polyethylene glycol, excellentElect a kind or 2 in silane coupler, titanate ester inorganic agent, organic silicone oil, HMDS asMixture more than kind.
As optimal technical scheme, the average grain diameter of filler of the present invention is 1-20 μ m, be for example 2 μ m,4 μ m, 6 μ m, 7 μ m, 9 μ m, 12 μ m, 15 μ m, 17 μ m, 19 μ m etc., maximum particle diameter≤35 μ m;Being preferably average grain diameter is 1-6 μ m, maximum particle diameter≤25 μ m.
One of object of the present invention is also to provide the preparation method of described filler, comprises the steps:
(a) mineral that comprise quartz sand, kaolin, bauxite, lime stone are mixed by raw material proportioning;
(b), by the mixture high temperature melting of step (a), obtain the amorphous eutectic of composite silicon dioxide;
(c) eutectic of step (b) is through grinding the amorphous eutectic powder of acquisition composite silicon dioxideDescribed filler;
Optionally carry out (d) the eutectic powder of step (c) is carried out to surface treatment.
As optimal technical scheme, the high temperature melting temperature described in described preparation method's step (b) is1000-2500 DEG C is for example 1050 DEG C, 1110 DEG C, 1150 DEG C, 1180 DEG C, 1250 DEG C, 1360 DEG C, 1420℃、1490℃、1560℃、1700℃、1950℃、2050℃、2100℃、2200℃、2350℃、2460 DEG C, 2490 DEG C etc., be preferably 1300-1600 DEG C.
As optimal technical scheme, the average grain diameter of the eutectic powder described in described preparation method's step (c)For 1-20 μ m, be for example 1.5 μ m, 2.2 μ m, 3 μ m, 5 μ m, 7 μ m, 9 μ m, 11 μ m, 14 μ m, 16 μ m,19 μ m etc., maximum particle diameter≤35 μ m; Being preferably average grain diameter is 1-6 μ m, maximum particle diameter≤25 μ m.
Preferably, the surface conditioning agent that the described surface treatment of step (d) is used is silane coupler, titanate estersClass inorganic agent, aluminate, zirconates, cationic surface active agent, anionic surfactant, twoSurfacant, neutral surface active agent, stearic acid, oleic acid, laurate and their metallic salt,One kind or two or more mixing in phenolic resins, organic silicone oil, HMDS, polyethylene glycolThing, is preferably 1 in silane coupler, titanate ester inorganic agent, organic silicone oil, HMDSPlant or mixture of more than two kinds.
The amorphous eutectic powder of composite silicon dioxide, as the special quartzy silicon powder of a class performance, adopts intoIn point, alkali metal oxide content is less than 2%, aluminoborosilicate quartz-like compound carries out extra-fine grinding, precisionThe serial deep processing such as classification, being prepared into average grain diameter is 1～20 μ m, is that one can be applied to large-scale integratedThe novel green electronic powder material of circuit substrate. Powder stuffing provided by the present invention not only has traditional siliconHeat-resisting, the high moisture-proof of height that micro mist possesses, high filler loading capacity, low bulk, low stress, low-friction coefficient etc. are excellentMore performance, and there is lower thermal coefficient of expansion compared with common composite silicon dioxide filler. With compoundThe powder filled large-scale circuit substrate of the amorphous eutectic of silica can increase substantially large-scale integrated electricityThe combination property of base board.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment. Those skilled in the art should understand,Described embodiment only, for helping to understand the present invention, should not be considered as concrete restriction of the present invention.
As no specific instructions, various raw material of the present invention all can obtain by commercially available; Or according to this areaConventional method prepares. Unless otherwise defined or described herein, all specialties used herein and science are usedThe language meaning familiar with those skilled in the art is identical. In addition any similar to described content or equalDeng method and material all can be applicable in the inventive method.
The experimental technique of unreceipted actual conditions in the following example, measures according to national standard conventionally. If not yetThere is corresponding national standard, according to general international standard, normal condition or build according to manufacturerThe condition of view is carried out. Unless otherwise indicated, otherwise all umbers are weight portion, and all percentages are attached most importance toAmount percentage.
The preparation of embodiment 1 filler A1-A4
Get different raw material proportioning batch mixings by the constituent content of filler of the present invention, utilize system provided by the inventionPreparation Method makes filler A1-A4, and its composition and quality percentage composition are in table 1.
Comparative example: its composition and quality percentage composition are in the filler B of table 1.
Table 1
| Composition | Filler A1 | Filler A2 | Filler A3 | Filler A4 | Filler B |
| Silica | 64 | 61 | 70 | 57 | 55 |
| Alundum (Al2O3) | 29 | 11 | 18 | 23 | 14 |
| Calcium oxide+magnesia | 4 | 26 | 11 | 18 | 6 |
| Diboron trioxide | -- | -- | -- | -- | 10 |
| Sodium oxide molybdena+potassium oxide+lithia | 1.8 | 0.1 | 0.5 | -- | -- |
| Di-iron trioxide | 0.6 | 0.3 | -- | 0.05 | -- |
The appraisal procedure that filler to the invention described above and the filler of comparative example carry out stain and electrical conductivity is as follows.
1, the assessment of powder stuffing stain
A) take sample 300g, put into the clean beaker of 1000mL;
B) with cleaned by ultrasonic vibration 400 eye mesh screens, cleaner by pure water rinsing;
C) sample in beaker is slowly poured in off-the-shelf clean test sieve, then added pure water dilution to rinseIn beaker, remain sample, vibration is rocked residue sample is all poured in test sieve gently;
D) to pouring the test sieve pure water rinsing of sample into, then residue on sieve is poured to clean beaker with pure waterMiddle observation, number stain number.
2, the assessment of powder electrical conductivity
10g powder adds in 100ml water fully and stirs, and tests electrical conductivity of water with conductivity measurement.
The stain of filler and the assessment result of electrical conductivity are in table 2.
Table 2
The preparation of embodiment 2 resin combinations
The filler that the embodiment of the present invention 1 and comparative example are made utilizes butanone to be modulated into copper coated foil plate tree usedFat glue, wherein solid constituent accounts for 65%, and its component and content are in table 3.
Table 3
Material and composition thereof used in embodiment are as follows:
Thermosetting resin A is the bisphenol A type epoxy resin that DOW Chemical is produced, and commodity are called DER530,Epoxide equivalent 435g/eq.
Thermosetting resin B is Hexion Specialty Chemicals company (Bowden chemical company of the former U.S. and German BerletCompany) novolac epoxy resin produced, commodity are called EPR627-MEK80, its epoxide equivalent between 160～250g/eq。
Curing agent is the phenolic resins curing agent that Hexion Specialty Chemicals company produces, and commodity are by namePHL6635M65。
Promoter is that Japanese four countries change into the 2MI that company produces.
The filler that embodiment 3 utilizes filler that the present invention makes and comparative example to make is prepared copper coated foil plate
(1) glue: solvent is added in proportion container, add respectively thermosetting resin, curing agent under stirringThe solution of solution and curing accelerator; Stir after 2 hours, add filler, continue to stir after 4-8 hour,The gel time (170 DEG C of constant temperature hot plates) of sampling and testing glue is 200～300 seconds.
(2) impregnation: by the layers of reinforcement of soaking glue by vertical or horizontal type impregnation machine, by controlThe conditions such as extruding wheel speed, linear speed, wind-warm syndrome and furnace temperature, specifically taking vertical impregnation machine demonstration example as squeegee rollerSpeed :-1.3～-2.5 ± 0.1M/min; Main line speed: 4～18m/min; Wind-warm syndrome: 120～170 DEG C; Furnace temperature:130～220 DEG C, make prepreg.
(3) compacting: after the prepreg of having reduced and Copper Foil are combined, put into vacuum hotpressing machine, pressCertain temperature, time and pressure also finally make copper coated foil plate.
The concrete demonstration example of the laminate compacting that 1.6mm is thick is:
Temperature formula: 130 DEG C/30min+155 DEG C/30min+190 DEG C/90min+220 DEG C/60min;
Pressure formula:
25Kgf.cm-2/30min+50Kgf.cm-2/30min+90Kgf.cm-2/120min+30Kgf.cm-2/90min；
Vacuum formula: 30mmHg/130min+800mmHg/130min.
Under these conditions, adopt the prepreg that 8 thickness are 0.2mm to be stacked layer by layer in 35 μ m thickBetween Copper Foil, after hot pressing, can make the copper-clad laminate that 1.6mm is thick.
Embodiment 4 carries out performance test to copper-clad laminate
The assessment of thermal expansion size changing rate: utilize etching solution to remove the Copper Foil of substrate, cut into the large of 5mmLittle. Use TMA device (TA company) to heat up with 10 DEG C/min, measure sample at the thickness of 50-260 DEG CDirection expansion rate. The plate property of table 4 for utilizing the present invention to make filler and utilize the filler of comparative example to makeContrast.
Table 4
As can be seen from Table 4, compare and add the copper coated foil plate that common dioxide composite silicon powder makes, incite somebody to action thisThe composite silicon dioxide eutectic powder stuffing that invention makes adds the copper coated foil plate of making in glue to be hadLow thermal coefficient of expansion.
The above, be only preferred embodiment of the present invention, not the content of composition of the present invention appointedWhat restriction, for the person of ordinary skill of the art, can be according to technical scheme of the present invention and technologyOther various corresponding changes and distortion are made in design, and every foundation technical spirit of the present invention or composition becomeAny trickle amendment, equivalent variations and modification that part or content are done above embodiment, all belong to the present inventionIn the scope of technical scheme.
Claims (10)
1. the amorphous eutectic powder stuffing of the composite silicon dioxide in clad with metal foil plate, is characterized in that,Contain by weight percentage following component: silica 57～70wt%, alundum (Al2O3) 15～35wt%,Magnesia+calcium oxide≤40wt%, sodium oxide molybdena+potassium oxide+lithia≤2wt%;
The stain number of described filler is less than 20/300g, and the electrical conductivity of described filler is≤200 μ s/cm;
The average grain diameter of described filler is 1-20 μ m, maximum particle diameter≤35 μ m.
2. filler according to claim 1, is characterized in that, contains by weight percentage following component:Silica 60～66wt%, alundum (Al2O3) 23～28wt%, magnesia+calcium oxide≤30wt%, oxidationSodium+potassium oxide+lithia≤1wt%.
3. filler according to claim 1, is characterized in that, contains by weight percentage three oxidations twoIron≤0.6wt%.
4. filler according to claim 3, is characterized in that, contains by weight percentage three oxidations twoIron≤0.2wt%.
5. filler according to claim 1, is characterized in that, the stain number of described filler is less than15/300g.
6. filler according to claim 1, is characterized in that, the electrical conductivity of described filler is≤100μs/cm。
7. filler according to claim 1, is characterized in that, described filler is through surface treatment.
8. filler according to claim 7, is characterized in that, the surface that described surface treatment is usedInorganic agent is silane coupler, titanate ester inorganic agent, aluminate, zirconates, cationic surface-activeAgent, anionic surfactant, amphoteric surfactant, neutral surface active agent, stearic acid, oleic acid,Laurate and their metallic salt, phenolic resins, organic silicone oil, HMDS, polyethylene glycolIn one kind or two or more mixture.
9. filler according to claim 8, is characterized in that, the surface that described surface treatment is usedInorganic agent is a kind in silane coupler, titanate ester inorganic agent, organic silicone oil, HMDSOr mixture of more than two kinds.
10. according to the filler described in claim 1-9 any one, it is characterized in that described filler averageParticle diameter is 1-6 μ m, maximum particle diameter≤25 μ m.
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| CN105968713B (en) * | 2015-11-23 | 2018-01-23 | 苏州海旭新材料科技有限公司 | A kind of preparation method of copper-clad plate filler, copper-clad plate resin combination and copper-clad plate |
| CN105802186B (en) * | 2016-03-18 | 2018-12-14 | 苏州海旭新材料科技有限公司 | A kind of copper-clad plate filler, resin combination and its application in copper-clad plate |
| CN108164151A (en) * | 2017-12-23 | 2018-06-15 | 江苏联瑞新材料股份有限公司 | A kind of preparation method of ic substrate micro-scale surface modified glass powder |
| CN113754979A (en) * | 2020-06-05 | 2021-12-07 | 浙江华正新材料股份有限公司 | Prepreg composition, prepreg, circuit board and printed circuit board |
| CN114526595B (en) * | 2022-03-17 | 2022-10-04 | 湖南亿胜新材料有限公司 | Preparation device and preparation method of low-dielectric-constant silicon micro powder |
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| CN101857735A (en) * | 2009-04-07 | 2010-10-13 | 台光电子材料股份有限公司 | Silicon dioxide eutectic filling material and preparation method of laminate |
| CN102088820A (en) * | 2009-12-03 | 2011-06-08 | 新加坡商矽比科亚洲有限公司 | Copper clad laminate and impregnation liquid for making same |
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| KR20070021925A (en) * | 2005-08-19 | 2007-02-23 | 쇼오트 아게 | METHOD FOR PRODUCING FLOATING ALLUMINOSILICATE GLASS USING SCOURING AGENT CONTAINING As2O3 AND SnO2 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101857735A (en) * | 2009-04-07 | 2010-10-13 | 台光电子材料股份有限公司 | Silicon dioxide eutectic filling material and preparation method of laminate |
| CN102088820A (en) * | 2009-12-03 | 2011-06-08 | 新加坡商矽比科亚洲有限公司 | Copper clad laminate and impregnation liquid for making same |
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