CN103242775B - Acrylic ester modified epoxy resin conductive chip adhesive - Google Patents
Acrylic ester modified epoxy resin conductive chip adhesive Download PDFInfo
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- CN103242775B CN103242775B CN201310181783.3A CN201310181783A CN103242775B CN 103242775 B CN103242775 B CN 103242775B CN 201310181783 A CN201310181783 A CN 201310181783A CN 103242775 B CN103242775 B CN 103242775B
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Abstract
The invention relates to an acrylic ester modified epoxy resin conductive chip adhesive and belongs to the technical field of adhesives applied to microelectronic packaging. The conductive chip adhesive consists of sheet-like silver powder, epoxy resin, acrylic ester modified epoxy resin, a curing agent, a coupling agent and a diluent, wherein the acrylic ester modified epoxy resin is a copolymerization product of glycidyl methacrylate and 2 to 3 types of acrylic ester monomers and/or olefin monomers; the coupling agent comprises a silane coupling agent KH-550 and the like; and the diluent is 1,4-butanediol diglycidyl ether. The acrylic ester modified epoxy resin conductive chip adhesive has the effects that the high temperature resistance, high humidity resistance and ageing resistance of the epoxy resin are improved; the volume resistivity is low; the bonding strength is high; the conductive chip adhesive is adapted to the electronic packaging requirement of lead-free, high-temperature and high-humidity environments; the packaging reliability is improved; and the service life of packaged devices is prolonged.
Description
Technical field
The invention belongs to the adhesive techniques field being applied to microelectronics Packaging, specifically disclose a kind of silver filling, acrylate modified epoxide resin conductive adhesive as LED and IC die adhesive.
Background technology
Tin-lead solder has widely used for many years in the electronics industry, due to the lead meeting contaminated soil in electron trade waste and underground water, finally causes poisoning at people's internal deposition.European Union is that the pollution that minimizing Electronic Wastes brings proposed WEEE/RoHS instruction cases in 1998 and came into effect in 2003.Epoxide resin conductive adhesive, as die adhesive, has been widely used in microelectronics and LED field at present.Along with the use of novel lead-free brazing metal, the Reflow Soldering temperature of Electronic Packaging improves, and common epoxy resin glue resistance to elevated temperatures is limited, cannot meet the new high temperature reliability needed for unleaded brazing metal.In order to adapt to this higher reliability requirement, in electron trade, numerous research is carried out to novel fire resistant modified epoxy conductive resin, wherein, some introducings more high-crosslinking-degree epoxy resin improve temperature tolerance (CN200910029251.1), have introduce in system heatproof group as maleimide (CN201210035153.0) or organosilicon (CN200910029251.1) modification such as organic boron, what have welds (CN200910194200.4 for circuit card etc. by the photosensitive conducting glue of epoxy resin and the acrylic ester copolymer of resistance to elevated temperatures excellence replacing solder, CN200510085609.4), but also there is no acrylate modified epoxy resin realization at present for the chip conductive caking agent of high-end field.
Summary of the invention
The object of this invention is to provide a kind of acrylate modified epoxy resin conductive chip caking agent, this conductive resin overcomes the shortcoming of conventional epoxy conductive resin non-refractory high humidity, keeps good bonding force in a variety of contexts.
The present invention relates to a kind of conductive chip adhesive, it contains flake silver powder, epoxy resin, acrylated epoxy, solidifying agent, coupling agent, thinner.
The present invention realizes by following technical scheme:
An acrylate modified epoxy resin conductive chip caking agent, forms and is by mass percentage:
Epoxy resin 5% ~ 20%;
Acrylated epoxy 5% ~ 20%;
Solidifying agent 1% ~ 5%;
Thinner 5% ~ 10%;
Coupling agent 0.1% ~ 1%;
Flake silver powder 60% ~ 80%.
Described acrylated epoxy, it consists of the copolymerization product of glycidyl methacrylate and 2-3 kind acrylic ester monomer and/or olefin monomer, wherein the mass percentage of glycidyl methacrylate in the modified epoxy of copolymerization is 20% ~ 35%, and other monomers (acrylic ester monomer and/or olefin monomer amount to) are 65% ~ 80%.Acrylic ester monomer comprises methyl methacrylate, butyl methacrylate, ethyl propenoate etc.; Olefin monomer comprises 4-methyl-1-pentene, vinyl acetate, vinylbenzene etc.Acrylated epoxy can free radical solution polymerization legal system conventionally standby, can take toluene as solvent, add acrylic ester monomer and/or olefin monomer and glycidyl methacrylate, be polymerized under the initiation of Diisopropyl azodicarboxylate.Acrylic ester monomer and/or olefin monomer consumption can mix by any mass ratio.
Described epoxy resin is selected from bisphenol F epoxy resin, bisphenol A epoxide resin, the one in phenol aldehyde type epoxy resin.
Thinner is the BDDE of quality purity more than 90%.
Described solidifying agent, for amine curing agent (in Dyhard RU 100, two amido sulfobenzides, fenuron one or more), or/and imidazole curing agent (in 2-phenyl-4-methylimidazole, glyoxal ethyline, 1-cyanoethyl-2-ethyl-4-methylimidazole one or more).Amine curing agent is or/and imidazole curing agent can mix by any mass ratio.
Described coupling agent is one or more in silane resin acceptor kh-550, KH-560 and KH-792.
Flake silver powder used, it consists of the flake silver powder that diameter is less than 50 microns.
The preparation method of above-mentioned conductive resin is: solidifying agent and thinner are mixed by above-mentioned formula rate, add appropriate epoxy resin, acrylated epoxy and coupling agent again to stir, the last silver powder slowly adding formula rate again, continue to be stirred to evenly, last vacuum removal bubble, obtained conductive resin.
The invention has the beneficial effects as follows:
1 by acrylate to epoxy resin modification, and this modified epoxy is introduced epoxy resin conductive chip caking agent, improves the resistance to elevated temperatures of epoxy resin glue, high temperature resistant Du Keda more than 250 DEG C, adapted to unleaded Electronic Packaging requirement.
2 are introduced by the hydrophobicity of acrylate, and the resistance to height enhancing epoxy glue is moist, improve product and packaging thereof to the adaptive faculty of hot and humid environment..
3 ageing resistance utilizing acrylate, improve the weathering resistance of epoxy conducting.
4 uses combined, enhance the reliability that the promoter action of conductive resin to interfacial adhesion strength improves encapsulation, extend the work-ing life of packaging.
Accompanying drawing explanation
Fig. 1 is the typical dynamic mechanical analysis figure (DMA) of conductive resin of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited to these embodiments.
Embodiment 1
The composition of acrylate modified epoxy resin conductive chip caking agent and having in mass ratio:
Flake silver powder 70.0%;
Modified epoxy 12.0%;
Bisphenol F epoxy resin 10.0%;
Fenuron 0.5%;
Two amido sulfobenzides 2.0%;
KH-550 0.5%；
BDDE 5%.
Modified epoxy is wherein glycidyl methacrylate in mass ratio: methyl methacrylate: vinylbenzene=1: the product of 1.5: 1 copolymerization.
The preparation method of above-mentioned conductive resin is: by fenuron, two amido sulfobenzides and 1,4-butanediol diglycidyl ether mixes by above-mentioned formula rate, add KH-550, bisphenol F epoxy resin and modified epoxy again to stir, the last silver powder slowly adding formula rate again, continue to be stirred to evenly, last vacuum removal bubble, obtained conductive resin.
175 DEG C solidification 1 hour, recording volume specific resistance is 0.00006ohmcm, and horizontal shear force is 25MPa, through 85 DEG C/RH85% after aging 168 hours horizontal shear force be 20MPa, aging rear resistivity is constant.
Embodiment 2
The composition of acrylate modified epoxy resin conductive chip caking agent and having in mass ratio:
Flake silver powder 60.0%;
Modified epoxy 20.0%;
Bisphenol A epoxide resin 7.3%;
Glyoxal ethyline 0.5%;
Two amido sulfobenzides 4.5%;
KH-560 0.2%；
BDDE 7.5%.
Modified epoxy is wherein glycidyl methacrylate in mass ratio: 4-methyl-1-pentene: ethyl propenoate: vinylbenzene=1: the product of 1: 1.2: 1 copolymerization.
The preparation method of above-mentioned conductive resin is: by glyoxal ethyline, two amido sulfobenzides and 1,4-butanediol diglycidyl ether mixes by above-mentioned formula rate, add KH-560, bisphenol A epoxide resin and modified epoxy again to stir, the last silver powder slowly adding formula rate again, continue to be stirred to evenly, last vacuum removal bubble, obtained conductive resin.
150 DEG C solidification 1.5 hours, recording volume specific resistance is 0.0003ohmcm, and horizontal shear force is 28MPa, through 85 DEG C/RH85% after aging 168 hours horizontal shear force be 22MPa, aging rear resistivity is constant.
Embodiment 3
The composition of acrylate modified epoxy resin conductive chip caking agent and having in mass ratio:
Flake silver powder 80.0%;
Modified epoxy 8.9%;
Bisphenol F epoxy resin 5.0%;
Dyhard RU 100 0.1%;
Two amido sulfobenzides 0.9%;
KH-550 0.1%；
BDDE 5.0%
Modified epoxy is wherein glycidyl methacrylate in mass ratio: butyl methacrylate: ethyl propenoate: vinylbenzene=1: the product of 2: 1: 1 copolymerization.
The preparation method of above-mentioned conductive resin is: by Dyhard RU 100, two amido sulfobenzides and 1,4-butanediol diglycidyl ether mixes by above-mentioned formula rate, add KH-550, bisphenol F epoxy resin and modified epoxy again to stir, the last silver powder slowly adding formula rate again, continue to be stirred to evenly, last vacuum removal bubble, obtained conductive resin.
180 DEG C solidification 0.5 hour, recording volume specific resistance is 0.0005ohmcm, and horizontal shear force is 24MPa, through 85 DEG C/RH85% after aging 168 hours horizontal shear force be 20MPa, aging rear resistivity is constant.
Embodiment 4
The composition of acrylate modified epoxy resin conductive chip caking agent and having in mass ratio:
Flake silver powder 61.0%;
Modified epoxy 5.0%;
Phenol aldehyde type epoxy resin 20.0%;
2-phenyl-4-methylimidazole 0.4%;
Two amido sulfobenzides 2.6%;
KH-792 1.0%；
BDDE 10.0%.
Modified epoxy is wherein glycidyl methacrylate in mass ratio: ethyl propenoate: 4-methyl-1-pentene=1: the product of 1: 0.9 copolymerization.
The preparation method of above-mentioned conductive resin is: by 2-phenyl-4-methylimidazole, two amido sulfobenzides and 1,4-butanediol diglycidyl ether mixes by above-mentioned formula rate, add KH-792, phenol aldehyde type epoxy resin and modified epoxy again to stir, the last silver powder slowly adding formula rate again, continue to be stirred to evenly, last vacuum removal bubble, obtained conductive resin.
160 DEG C solidification 1 hour, recording volume specific resistance is 0.0002ohmcm, and horizontal shear force is 26MPa, through 85 DEG C/RH85% after aging 168 hours horizontal shear force be 21MPa, aging rear resistivity is constant.
Embodiment 5
Modified epoxy is wherein glycidyl methacrylate in mass ratio: butyl methacrylate: vinyl acetate: vinylbenzene=1: the product of 1: 0.7: 1 copolymerization.
The composition of acrylate modified epoxy resin conductive chip caking agent and having in mass ratio:
Flake silver powder 67.5%;
Modified epoxy 10.7%;
Bisphenol F epoxy resin 13.0%;
1-cyanoethyl-2-ethyl-4-methylimidazole 0.3%;
Two amido sulfobenzides 2.0%;
KH-550 0.5%；
BDDE 6.0%.
Modified epoxy is wherein glycidyl methacrylate in mass ratio: butyl methacrylate: vinyl acetate: vinylbenzene=1: the product of 1: 0.7: 1 copolymerization.
The preparation method of above-mentioned conductive resin is: by 1-cyanoethyl-2-ethyl-4-methylimidazole, two amido sulfobenzides and 1,4-butanediol diglycidyl ether mixes by above-mentioned formula rate, add KH-550, bisphenol F epoxy resin and modified epoxy again to stir, the last silver powder slowly adding formula rate again, continue to be stirred to evenly, last vacuum removal bubble, obtained conductive resin.
160 DEG C solidification 1 hour, recording volume specific resistance is 0.0001ohmcm, and horizontal shear force is 26MPa, through 85 DEG C/RH85% after aging 168 hours horizontal shear force be 20MPa, aging rear resistivity is constant.
Claims (3)
1. an acrylate modified epoxy resin conductive chip caking agent, form and be by mass percentage: epoxy resin 5% ~ 20%, acrylated epoxy 5% ~ 20%, solidifying agent 1% ~ 5%, thinner 5% ~ 10%, coupling agent 0.1% ~ 1%, flake silver powder 60% ~ 80%, described acrylated epoxy, it is the copolymerization product of glycidyl methacrylate and acrylic ester monomer and olefin monomer, wherein the content of glycidyl methacrylate in acrylated epoxy accounts for 20% ~ 35% by quality, acrylic ester monomer and the olefin monomer content in acrylated epoxy accounts for 65% ~ 80% by quality, described acrylic ester monomer is methyl methacrylate, butyl methacrylate, 1 ~ 2 kind in ethyl propenoate, described olefin monomer is 4-methyl-1-pentene, vinyl acetate, 1 ~ 2 kind in vinylbenzene, described solidifying agent is 1 ~ 4 kind in Dyhard RU 100, two amido sulfobenzides, fenuron, 2-phenyl-4-methylimidazole, glyoxal ethyline, 1-cyanoethyl-2-ethyl-4-methylimidazole.
2. acrylate modified epoxy resin conductive chip caking agent according to claim 1, it is characterized in that, described epoxy resin, is bisphenol F epoxy resin, bisphenol A epoxide resin or phenol aldehyde type epoxy resin; Described coupling agent is the 1-3 kind in silane resin acceptor kh-550, KH-560, KH-792; Described thinner is the BDDE that quality purity is greater than 90%.
3. acrylate modified epoxy resin conductive chip caking agent according to claim 1 and 2, it is characterized in that, described flake silver powder, diameter is less than 50 microns.
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| CN201310181783.3A CN103242775B (en) | 2013-05-16 | 2013-05-16 | Acrylic ester modified epoxy resin conductive chip adhesive |
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| CN201310181783.3A CN103242775B (en) | 2013-05-16 | 2013-05-16 | Acrylic ester modified epoxy resin conductive chip adhesive |
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| CN103242775B true CN103242775B (en) | 2015-06-10 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540285B (en) * | 2013-10-14 | 2016-03-02 | 长春永固科技有限公司 | A kind of epoxyn for Intelligent card package |
| CN103709311B (en) * | 2013-11-18 | 2016-01-20 | 长春永固科技有限公司 | For the preparation method of the modified epoxy of die adhesive |
| CN103627357A (en) * | 2013-11-18 | 2014-03-12 | 长春永固科技有限公司 | Large-power conductive chip adhesive |
| CN103555250A (en) * | 2013-11-18 | 2014-02-05 | 长春永固科技有限公司 | High-transparency ultraviolet aging-resistant non-conductive chip adhesive |
| CN104530989B (en) * | 2014-12-10 | 2016-09-14 | 南通瑞达电子材料有限公司 | A kind of aluminium cell ramming paste binding agent and preparation method thereof |
| CN105860906B (en) * | 2016-06-21 | 2018-10-23 | 上海远沙电子科技有限公司 | A kind of conducting resinl for LED chip bonding |
| CN107418491A (en) * | 2017-09-21 | 2017-12-01 | 通号工程局集团有限公司 | A kind of conducting resinl and preparation method thereof |
| CN109326665B (en) * | 2017-09-28 | 2020-07-31 | 长春永固科技有限公司 | Solar cell string, solar cell module and preparation method thereof |
| CN109301003B (en) * | 2017-09-28 | 2020-10-09 | 长春永固科技有限公司 | Solar cell, solar cell module, solar cell system and method for preparing solar cell |
| CN110105902B (en) * | 2019-05-16 | 2021-08-03 | 湖南工业大学 | Multipurpose high-solid-content double-component composite adhesive and preparation method and application thereof |
| CN111440575B (en) * | 2020-03-27 | 2021-07-27 | 顺德职业技术学院 | Special low-dielectric high-thermal-conductivity underfill adhesive for chip packaging |
| CN112300740A (en) * | 2020-11-16 | 2021-02-02 | 上海汉司实业有限公司 | Room-temperature-cured high-heat-resistance high-peel-strength bi-component epoxy adhesive |
| CN113322023A (en) * | 2021-05-28 | 2021-08-31 | 陕西科技大学 | Epoxy resin conductive adhesive based on organic silicon modification and preparation method thereof |
| CN114181653B (en) * | 2022-01-13 | 2023-01-10 | 北京理工大学 | MXenes modified conductive adhesive and preparation method thereof |
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