CN104497494A - High stably dispersed nano-silica filled epoxy resin system, cured product and preparation method thereof - Google Patents
High stably dispersed nano-silica filled epoxy resin system, cured product and preparation method thereof Download PDFInfo
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- CN104497494A CN104497494A CN201410255167.2A CN201410255167A CN104497494A CN 104497494 A CN104497494 A CN 104497494A CN 201410255167 A CN201410255167 A CN 201410255167A CN 104497494 A CN104497494 A CN 104497494A
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Abstract
The invention discloses a high stably dispersed nano-silica filled epoxy resin system and a copper clad laminate prepreg prepared therefrom. The high stably dispersed nano-silica filled epoxy resin system comprises the following components by weight: 50-80 parts of epoxy resin, 30-60 parts of a curing agent, 0-3 parts of a curing accelerator, 1-20 parts of nano-silica, 0-5 parts of a dispersant, 0-3 parts of a defoaming agent and a proper amount of a solvent. After curing, the epoxy resin system provided by the invention has the advantages of low water absorption, low dielectric constant and dielectric loss, low thermal expansion coefficient, high glass transition temperature, high thermal reliability and mechanical properties, and good processability.
Description
Technical field
The present invention relates to nano-silica filled epoxy-resin systems and the cured article thereof of the dispersion of a kind of high stable.
Background technology
Along with the development of information science technology, electronics is to granular, high performance future development, ultra-large, ultra-high speed, the development trend that ultra-thin, superelevation fineness becomes unicircuit of new generation, therefore must improve the performance of the body material of copper-clad plate and semiconductor packages.The performance of these body materials is required to include substantially: high temperature resistant; In solidification process, shrinking percentage is little, and in use procedure, dimensional change is little; High strength, processes and mounting process requirement under adapting to high temperature.As can be seen here, as the epoxy resin of the resin of matrix, require that it after hardening, has low water absorption, lower specific inductivity and dielectric loss, higher glass transition temp, excellent mechanical property.
Summary of the invention
The object of the present invention is to provide a kind of nano-silica filled epoxy-resin systems, in this resin system, nanoparticle obtains high stable dispersion, and this resin system has high thermostability and humidity resistance.
Another object of the present invention is to provide a kind of prepreg made with nano-silica filled epoxy-resin systems, it has low water absorption, lower specific inductivity and dielectric loss, higher glass transition temp, excellent mechanical property.
For achieving the above object, the invention provides a kind of nano-silica filled epoxy-resin systems, its component and weight part are: epoxy resin 50-80 part, solidifying agent 30-60 part, curing catalyst 0-3 part, nano silicon 1-20 part, dispersion agent 0-5 part, defoamer 0-3 part and solvent are appropriate.
The nano-silica filled epoxy-resin systems of described a kind of high stable dispersion, it is characterized in that described epoxy resin is bisphenol f type epoxy resin, bisphenol A type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, resorcinol type epoxy, dicyclo penta epoxy resin, novolac epoxy, polyglycol type epoxy resins, isocyanate epoxy resin, 1, 1, 2, 2,-four (p-hydroxybenzene) ethane four tetraglycidel ether epoxy resin, polyfunctional epoxy resin, brominated epoxy resin, Glycide malcopimarate, triphenol methylmethane triglycidyl ether epoxy resin, 4, 4-diamino diphenyl methane tetraglycidyl ether, one or more mixture in glycolylurea epoxide resin.
The nano-silica filled epoxy-resin systems of described a kind of high stable dispersion, is characterized in that described solidifying agent is one or more the mixture in amine (as diphenylmethane diamine), resol or acid anhydride type curing agent.
The nano-silica filled epoxy-resin systems of described a kind of high stable dispersion, is characterized in that: described nano silicon particle diameter is 7-100nm, is preferably 12-50nm.
The nano-silica filled epoxy-resin systems of described a kind of high stable dispersion, it is characterized in that: described surface modification of silica agent is conventional coupling agents KH570, KH560, KH590, A151, hexamethyldisilazane, dimethyldichlorosilane(DMCS), the mixing of one or more in polydimethylsiloxane.
The nano-silica filled epoxy-resin systems of described a kind of high stable dispersion, is characterized in that: described dispersion agent is one or more the mixing in solvent-borne type or no-solvent type wetting dispersing agent.
The nano-silica filled epoxy-resin systems of described a kind of high stable dispersion, is characterized in that: described defoamer be organosilicon, inorganic silicon polysiloxane, without one or more the mixing in silicon froth breaking polyacrylic ester and polymers soln or polyethers.
The nano-silica filled epoxy-resin systems of described a kind of high stable dispersion, is characterized in that: described curing catalyst is imidazoles promotor: glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-ethyl-4-phenylimidazole, cyanoethyl-2-ethyl-4-methylimidazole, 2-undecyl imidazole; Primary, secondary with quaternary amine, quaternary ammonium salt and phosphamidon salt: benzyldimethylamine, butyltriphenylphosphonium phosphonium salt and 4,4 '-and 3,3 '-diaminodiphenylsulfone(DDS); Peroxidation class initiator, azo-initiator and organic metal salt or complex compound; Or Lewis acid; The mixture of one or more in above promotor.
The nano-silica filled epoxy-resin systems of described a kind of high stable dispersion, is characterized in that: described solvent is one or more in butanone, acetone or pimelinketone.
The nano-silica filled epoxy-resin systems of described a kind of high stable dispersion, is characterized in that: its preparation method comprises the steps:
Step one, epoxy resin, nano-powder, dispersion agent and appropriate solvent are carried out pre-dispersed 10-30min
Step 2, above-mentioned mixed solution is proceeded to sand mill disperse 10min-3h further
Step 3, the ultrasonic 10min-1h of mixed solution that will epoxy resin and nano-powder be isolated
Step 4, in the mixed solution of epoxy resin and nano-powder, add solidifying agent, curing catalyst, defoamer mixes the nano-silica filled epoxy-resin systems namely obtaining the dispersion of a kind of high stable.
The nano-silica filled epoxy resin of a kind of high stable dispersion provided by the invention prepares cured article.
Accompanying drawing explanation
Fig. 1 KH570-SiO
2/ EP loading level 5wt%(a, b) and 10wt%(c, d) time TEM figure.
Embodiment
The invention process is described in detail as follows, but the present invention is not confined to scope of embodiments.
embodiment 1
Get bisphenol f type epoxy resin 60 parts, the nano silicon (50nm) 2 parts of KH570 modification, dispersion agent 0.15 part, the pre-dispersed 10min of pimelinketone 10ml high speed dispersor, then proceeds to sand mill grinding 1h, is separated the mixing solutions obtaining epoxy resin and silicon-dioxide, methyl hexahydrophthalic anhydride 44 parts is added after ultrasonic disperse 30min, glyoxal ethyline 0.1 part, defoamer 0.5 part and pimelinketone in right amount, stir, are made into the resin solution that solid content is 65%.
embodiment 2
Get bisphenol-s epoxy resin 60 parts, the nano silicon (50nm) 10 parts of KH570 modification, dispersion agent 0.3 part, the pre-dispersed 10min of acetone 10ml high speed dispersor, then proceeds to sand mill grinding 1h, is separated the mixing solutions obtaining epoxy resin and silicon-dioxide, methyl hexahydrophthalic anhydride 44 parts is added after ultrasonic disperse 30min, glyoxal ethyline 0.1 part, defoamer 0.5 part and acetone in proper, stir, be made into the resin solution that solid content is 65%.
embodiment 3
Get novolac epoxy 60 parts, the nano silicon (12nm) 20 parts of dimethyldichlorosilane(DMCS) modification, dispersion agent 0.1 part, the pre-dispersed 10min of butanone 10ml high speed dispersor, then proceeds to sand mill grinding 1h, is separated the mixing solutions obtaining epoxy resin and silicon-dioxide, methyl hexahydrophthalic anhydride 35 parts is added after ultrasonic disperse 30min, glyoxal ethyline 0.1 part, defoamer 0.5 part and butanone in right amount, stir, are made into the resin solution that solid content is 65%.
embodiment 4
Get bisphenol A type epoxy resin 80 parts, the nano silicon (12nm) 50 parts of dimethyldichlorosilane(DMCS) modification, dispersion agent 0.15 part, the pre-dispersed 10min of butanone 10ml high speed dispersor, then proceeds to sand mill grinding 1h, is separated the mixing solutions obtaining epoxy resin and silicon-dioxide, methyl hexahydrophthalic anhydride 58 parts is added after ultrasonic disperse 30min, glyoxal ethyline 0.1 part, defoamer 0.5 part and butanone in right amount, stir, are made into the resin solution that solid content is 65%.
comparative example 1
Get bisphenol A type epoxy resin 60 parts, add methyl hexahydrophthalic anhydride 44 parts, glyoxal ethyline 0.1 part, defoamer 0.5 part and butanone in right amount, stir, are made into the resin solution that solid content is 65%.
comparative example 2
Get novolac epoxy 60 parts, silicon-dioxide (50nm) 10 parts, dispersion agent 1.2 parts, the pre-dispersed 10min of butanone 10ml high speed dispersor, then proceeds to sand mill grinding 1h, is separated the mixing solutions obtaining epoxy resin and silicon-dioxide, methyl hexahydrophthalic anhydride 35 parts is added after ultrasonic disperse 30min, glyoxal ethyline 0.1 part, defoamer 0.5 part and butanone in right amount, stir, are made into the resin solution that solid content is 65%.
Above-mentioned dispersion system through except desolventizing, obtains cured article by 100 DEG C/1h+110 DEG C/1h+120 DEG C/2h+160 DEG C/4h temperature programming solidification.
The testing method of above characteristic is as follows:
1. glass transition temp (Tg): according to dsc, measures according to the DSC method of IPC-TM-650 2.4.25 defined.
2. flexural strength: according to the method for IPC-TM-650 2.4.4 defined, at room temperature puts on the flexural strength on specified dimension and shape sample load.
[0027]
Be illustrated in figure 1 TEM picture in example 1 and example 2, be uniformly dispersed as seen, soilless sticking.Table two is placement three months sedimentation information slips, without demixing phenomenon.
Claims (11)
1. high stable dispersion nano-silica filled epoxy-resin systems, it is characterized in that contained component and weight part as follows: epoxy resin 50-80 part, solidifying agent 30-60 part, curing catalyst 0-3 part, nano silicon 1-20 part, dispersion agent 0-5 part, defoamer 0-3 part and solvent are appropriate.
2. the nano-silica filled epoxy-resin systems of high stable dispersion as claimed in claim 1, is characterized in that described epoxy resin is bisphenol f type epoxy resin, bisphenol A type epoxy resin, one or more mixture of bisphenol-s epoxy resin.
3. the nano-silica filled epoxy-resin systems of a kind of high stable dispersion as claimed in claim 1, it is characterized in that described solidifying agent is one or more the mixture in amine, resol or acid anhydride type curing agent, described amine is diphenylmethane diamine.
4. the nano-silica filled epoxy-resin systems of high stable dispersion as claimed in claim 1, is characterized in that described nano silicon particle diameter is 7-100nm, is preferably 10-50nm.
5. the nano-silica filled epoxy-resin systems of high stable dispersion as claimed in claim 1, it is characterized in that described surface modification of silica agent is conventional coupling agents KH570, KH560, KH590, A151, hexamethyldisilazane, dimethyldichlorosilane(DMCS), the mixing of one or more in polydimethylsiloxane.
6. the nano-silica filled epoxy-resin systems of high stable dispersion as claimed in claim 1, is characterized in that: described dispersion agent is one or more the mixing in solvent-borne type or no-solvent type wetting dispersing agent.
7. the nano-silica filled epoxy-resin systems of high stable dispersion as claimed in claim 1, is characterized in that: described defoamer be organosilicon, inorganic silicon polysiloxane, without one or more the mixing in silicon froth breaking polyacrylic ester and polymers soln or polyethers.
8. the nano-silica filled epoxy-resin systems of high stable dispersion as claimed in claim 1, is characterized in that: described curing catalyst is imidazoles promotor: glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-ethyl-4-phenylimidazole, cyanoethyl-2-ethyl-4-methylimidazole, 2-undecyl imidazole; Primary, secondary with quaternary amine, quaternary ammonium salt and phosphamidon salt: benzyldimethylamine, butyltriphenylphosphonium phosphonium salt and 4,4 '-and 3,3 '-diaminodiphenylsulfone(DDS); Peroxidation class initiator, azo-initiator and organic metal salt or complex compound; Or Lewis acid; The mixture of one or more in above promotor.
9. the nano-silica filled epoxy-resin systems of high stable dispersion as claimed in claim 1, is characterized in that: described solvent is butanone, acetone or pimelinketone.
10. the nano-silica filled epoxy-resin systems of high stable dispersion as claimed in claim 1, is characterized in that: its preparation method comprises the steps:
Step one, epoxy resin, nano-powder, dispersion agent and appropriate solvent are carried out pre-dispersed 10-30min
Step 2, above-mentioned mixed solution is proceeded to sand mill disperse 10min-3h further
Step 3, the ultrasonic 10min-1h of mixed solution that will epoxy resin and nano-powder be isolated
Step 4, in the mixed solution of epoxy resin and nano-powder, add solidifying agent, curing catalyst, defoamer mixes the nano-silica filled epoxy-resin systems namely obtaining high stable dispersion.
Cured article prepared by the nano-silica filled epoxy resin that 11. high stables as claimed in claim 1 disperse.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237954A (en) * | 2015-10-29 | 2016-01-13 | 景旺电子科技(龙川)有限公司 | Epoxy resin composition for plugging holes and blending method for epoxy resin composition |
| CN105601982A (en) * | 2016-02-04 | 2016-05-25 | 中南大学 | Preparation method of nano silicon dioxide-epoxy resin porous composite material |
| CN106336617A (en) * | 2016-08-22 | 2017-01-18 | 中国科学院合肥物质科学研究院 | Room temperature low-thermal-expansion epoxy resin material and preparation method thereof |
| CN106589464A (en) * | 2016-11-28 | 2017-04-26 | 深圳先进技术研究院 | Preparation method for vinyl polymer coated nano-silica microsphere and modified epoxy resin |
| CN107043520A (en) * | 2017-01-19 | 2017-08-15 | 景旺电子科技(龙川)有限公司 | A kind of composition epoxy resin of large aperture metal base printed circuit board consent and preparation method thereof |
| CN108511584A (en) * | 2018-03-12 | 2018-09-07 | 合肥同佑电子科技有限公司 | A kind of special encapsulating material of light emitting diode and preparation method thereof |
| CN110845825A (en) * | 2019-10-22 | 2020-02-28 | 艾森半导体材料(南通)有限公司 | Nano-silica modified epoxy resin composition for LED packaging |
| CN111233395A (en) * | 2020-01-18 | 2020-06-05 | 杭州申华混凝土有限公司 | High-strength pervious concrete and preparation method thereof |
| CN113185804A (en) * | 2020-01-14 | 2021-07-30 | 广东生益科技股份有限公司 | Resin composition, bonding sheet containing same and application thereof |
| WO2022239708A1 (en) * | 2021-05-13 | 2022-11-17 | デンカ株式会社 | Silica powder in which aggregation is reduced, resin composition, and semiconductor sealing material |
| WO2024055946A1 (en) * | 2022-09-15 | 2024-03-21 | 华为技术有限公司 | Resin composition, method for preparing same, and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408904A (en) * | 2013-07-04 | 2013-11-27 | 东莞上海大学纳米技术研究院 | Modified nanometer silicon dioxide filling epoxy resin composition as well as preparation method and product thereof |
-
2014
- 2014-06-10 CN CN201410255167.2A patent/CN104497494A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408904A (en) * | 2013-07-04 | 2013-11-27 | 东莞上海大学纳米技术研究院 | Modified nanometer silicon dioxide filling epoxy resin composition as well as preparation method and product thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237954A (en) * | 2015-10-29 | 2016-01-13 | 景旺电子科技(龙川)有限公司 | Epoxy resin composition for plugging holes and blending method for epoxy resin composition |
| CN105601982A (en) * | 2016-02-04 | 2016-05-25 | 中南大学 | Preparation method of nano silicon dioxide-epoxy resin porous composite material |
| CN106336617A (en) * | 2016-08-22 | 2017-01-18 | 中国科学院合肥物质科学研究院 | Room temperature low-thermal-expansion epoxy resin material and preparation method thereof |
| CN106589464A (en) * | 2016-11-28 | 2017-04-26 | 深圳先进技术研究院 | Preparation method for vinyl polymer coated nano-silica microsphere and modified epoxy resin |
| CN107043520A (en) * | 2017-01-19 | 2017-08-15 | 景旺电子科技(龙川)有限公司 | A kind of composition epoxy resin of large aperture metal base printed circuit board consent and preparation method thereof |
| CN108511584A (en) * | 2018-03-12 | 2018-09-07 | 合肥同佑电子科技有限公司 | A kind of special encapsulating material of light emitting diode and preparation method thereof |
| CN110845825A (en) * | 2019-10-22 | 2020-02-28 | 艾森半导体材料(南通)有限公司 | Nano-silica modified epoxy resin composition for LED packaging |
| CN110845825B (en) * | 2019-10-22 | 2022-06-14 | 艾森半导体材料(南通)有限公司 | Nano-silica modified epoxy resin composition for LED packaging |
| CN113185804A (en) * | 2020-01-14 | 2021-07-30 | 广东生益科技股份有限公司 | Resin composition, bonding sheet containing same and application thereof |
| CN111233395A (en) * | 2020-01-18 | 2020-06-05 | 杭州申华混凝土有限公司 | High-strength pervious concrete and preparation method thereof |
| CN111233395B (en) * | 2020-01-18 | 2021-11-30 | 杭州申华混凝土有限公司 | High-strength pervious concrete and preparation method thereof |
| WO2022239708A1 (en) * | 2021-05-13 | 2022-11-17 | デンカ株式会社 | Silica powder in which aggregation is reduced, resin composition, and semiconductor sealing material |
| WO2024055946A1 (en) * | 2022-09-15 | 2024-03-21 | 华为技术有限公司 | Resin composition, method for preparing same, and use thereof |
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