CN103361016B - A kind of Underfill adhesive composition - Google Patents
A kind of Underfill adhesive composition Download PDFInfo
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- CN103361016B CN103361016B CN201210081595.9A CN201210081595A CN103361016B CN 103361016 B CN103361016 B CN 103361016B CN 201210081595 A CN201210081595 A CN 201210081595A CN 103361016 B CN103361016 B CN 103361016B
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- underfill adhesive
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Abstract
The invention discloses a kind of Underfill adhesive composition, belong to chemical industry adhesive field, it is by the raw material of following weight portion: hydrogenated epoxy resin 50 80 parts, modified resin 1 10 parts, toughened resin 10 30 parts, 15 parts of complexation firming agent combines, its preparation method is, production environment is transferred to temperature 15 28 DEG C, relative humidity is less than 70%, stir in hydrogenated epoxy resin is joined vacuum stirring still by formula order successively, it is uniformly added into modified resin, mix homogeneously adds firming agent, mix homogeneously, vacuum mix homogeneously, subpackage 20 DEG C of cold preservations of warehouse-in are filtered in deaeration.The filling adhesiveness of the present invention is low, during use without preheating, curing rate fast.
Description
Technical field
The present invention relates to a kind of adhesive, refer more particularly to the Underfill adhesive composition of a kind of flip-chip.
Background technology
Flip-chip is a kind of without pin configuration, typically contains circuit unit, and its principle is to deposit tin-lead on I/Opad
Ball, then combines the tin-lead ball that chip upset adds heat utilization melted with ceramic wafer, and flip-chip packaging techniques is with traditional
Lead key closing process is compared has many clear advantages, as eliminated the requirement connecting wire bonding, adds input/defeated
Going out the Connection Density of (I/O), the electricity thermal property etc. that package dimension is less and superior, therefore, this technology has replaced routine
Routing engage, be increasingly becoming the main flow of following encapsulation technology.
In flip chip technology (fct), the assembly material welded includes organic and inorganic different types of material, institute
Having these material thermal expansion coefficients the most inconsistent, thermal deformation somewhat all may result in the stress in assembly and concentrates, owing to falling
The solder joint of dress wafer assemblies is the least, it is easy to rupture in the process.
Therefore, in order to meet the requirement of electronic reliability, flip-chip typically uses underfill technology, just
Being that epoxy resin adhesive point is coated in flip-chip edge, by capillary effect, the offside that filling glue is drawn onto original paper is complete
Becoming underfill, then by the process of glue curing under conditions of heating, the material that underfill is used is by a kind of strong
The epoxide-resin glue of power adhesion type takes up, and reduces and redistributed stress, thus by chip, circuit board and pad it
Between thermal coefficient of expansion (coefficient of thermal expansion is called for short CTE) unmatched probability drop to
Low.When underfill in order to accelerate glue filling speed, often also need to substrate is preheated.
Underfill process for fill glue selection also by requiring, such as:
1, mobility to be got well, and has reasonable wettability simultaneously, it is possible to adapt to minimum gap, in flow process not
Easily produce bubble, have the ability preferably forming fillet；
2, condition of cure can match with the existing technological process of production, and longer hardening time may become production
The bottleneck of line；
3, good reliability, such as higher vitrification point (Tg), the thermal coefficient of expansion (CTE) matched with assembly
Deng；
4 and scaling powder have good compatibility.Sometimes due to material selection is improper, meeting between scaling powder and packing material
Produce cross reaction, make product reliability reduce rapidly；
5, after being completed, assembly can bear the most aging, and is exposed in wet steam function and reliability not
Impacted；
6, assembly can test (JEDEC, Level 3) by unleaded moisture sensitivity level.
CN102002209A discloses the compositions of a kind of flip-chip underfill, wherein have employed liquid epoxy
Resin, rubber toughening agent, modified organic silicone resin, multifunctional type epoxy resin, epoxide diluent, aromatic amine curing agent, silicon
Alkane coupling agent, silicon powder and pigment are as raw material so that the mobile performance filling glue has had certain improvement；CN101864147A
Disclose the compositions of the underfill of a kind of low viscosity, low linear expansion coefficient, with the addition of latent curing in the composition
Agent and surfactant so that the hardening time filling glue has shortened, and improves the stability of storage.
But, flip-chip underfill of the prior art mainly there is also following defect:
1, viscosity is higher, and typically under about 3000cps, room temperature, mobility is very poor, is easy to produce in flow process
Bubble, it is therefore desirable to be preheated to 50-80 DEG C and improve its mobility；
2, hardening time is longer, and more than 150 DEG C need within 15-30 minute, could solidify, easily become the bottleneck of production line；
3, considering from energy cost, the consumption to the energy is bigger.
Summary of the invention
It is an object of the invention to provide a kind of Underfill adhesive composition, to solve above-mentioned present in prior art asking
Topic, this filling glue composition of the present invention, not only there is all properties of existing product, and there is relatively low viscosity, make
Used time, curing rate was fast without preheating.
For solving the problems referred to above, the present invention is achieved through the following technical solutions:
A kind of Underfill adhesive composition, described compositions is made up of the raw material of following weight portion: hydrogenated epoxy resin 50-
80 parts, modified resin 1-10 part, toughened resin 5-30 part, complexation firming agent 1-10 part.
In the present invention, described hydrogenated epoxy resin be hydrogenated bisphenol A, 3,4-epoxycyclohexyl-methyl-3,4-epoxide ring
Hexyl formic acid esters, double [7-oxabicyclo (4.1.0) heptane-3-methyl] adipate ester, because their viscosity is respectively less than
1000cps, especially 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl formic acid esters and double [7-oxabicyclo (4.1.0) heptan
Alkane-3-methyl] viscosity of adipate ester is all between 200-800cps, and there is good manufacturability, thermostability height, cure shrinkage
The feature such as little, good electrical property, UV resistant and good weatherability, can meet the low-viscosity of high performance electronic packaging material, height especially
The requirements such as thermostability, low water absorbable and excellent electrical.
In the present invention, weight portion preferred 55-80 part of described hydrogenated epoxy resin.
In the present invention, described modified resin is nano-organosilicon resin and polyurethane modified epoxy resin, and polyurethane changes
Property epoxy resin.Wherein, polyurethane modified epoxy resin can form inierpeneirating network structure or Semi-IPN with hydrogenated epoxy resin
Network structure, thus reach to improve the purpose of epoxy resin toughness, its intensity and thermostability will not be reduced again simultaneously；Nanometer is organic
Silicones not only has the adhesive force of excellence, wearability, resistance to water, aging-resistant characteristic, also has environment friendly.
In the present invention, weight portion preferred 1.1-10 part of described modified resin, because when the weight portion of modified resin is little
In 1.1 parts time, it is inconspicuous to the toughening effect of epoxy resin, and time between 1.1 to 10 parts, toughening effect is significantly increased,
When the weight portion of modified resin is more than 10 parts, toughening effect is again without significantly improving.
In the present invention, described toughened resin is polyether polyol toughened resin or PEPA toughened resin, such tree
Fat has good toughness, usual and hydrogenated bisphenol A use, can improve its fragility, and the impact improving glue-line is strong, polyethers therein
Pluracol 1016, the Voranol 3010 of DOW company of polyhydric alcohol toughened resin preferred Bayer company, Bayer company
The Fomrez1066-560 of Multranol 9158, PEPA toughened resin preferred Uniroyal company.
In the present invention, described toughened resin weight portion preferred 5.5-30 part, experiment shows, toughened resin weight portion is at this
In the range of time best to the toughening effect of hydrogenated bisphenol A.
In the present invention, described complexation firming agent is boron triflouride-mono aminoethane complex, boron trifluoride-triethanolamine network
Compound and boron trifluoride-piperidines complex, wherein, boron triflouride-mono aminoethane complex is epoxy resin lalent solidifying agent, uses
The resin of its solidification has half latency feature, it is adaptable to leaching part is carried out various machining, and this firming agent before curing
More ehter bond can produced in the solidification of epoxy resin, increasing toughness and the adhesive force of product, utilize such firming agent
The product obtained also has higher heat distortion temperature, up to about 230 DEG C.
In the present invention, weight portion preferred 1.1-10 part of described complexation firming agent because in this range time, gained
Fill adhesive curing shortest time, and adhesion property is unaffected.
The preparation method of the flip-chip underfill of the present invention is: production environment is transferred to temperature 15-28 DEG C, phase
To humidity less than 70%, stir in successively hydrogenated epoxy resin, modified resin, toughened resin being joined vacuum stirring still by formula
Mixing, add complexation firming agent, mix homogeneously, vacuum mix homogeneously after mix homogeneously, deaeration filtration, subpackage is put in storage, cold at-20 DEG C
Hide.
Owing to have employed above technical scheme, compared with prior art, the present invention has the advantage that
1, viscosity is the lowest, about 300-800cps；
2, curing rate is faster, solidification in 1-2 minute at 150 DEG C；
3, flowing velocity is fast, without preheating during use.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawings and the present invention is further described below by specific embodiment:
Embodiment 1
Compositions is:
Hydrogenated bisphenol A: 375kg；
3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl formic acid esters: 1000kg；
Polyurethane modified epoxy resin: 12.5kg；
Nano-organosilicon resin: 15kg；
Pluracol 1016:137.5kg；
Boron triflouride-mono aminoethane complex: 10kg；
Boron trifluoride-zirconium triethanolamine complex: 17.5kg.
Embodiment 2
Compositions is:
3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl formic acid esters: 650kg；
Double [7-oxabicyclo (4.1.0) heptane-3-methyl] adipate ester: 725kg；
Polyurethane modified epoxy resin: 10.5kg；
Nano-organosilicon resin: 17kg；
Multranol 9158:120kg；
Boron triflouride-mono aminoethane complex: 12kg；
Boron trifluoride-piperidines complex: 15.5kg.
Embodiment 3
Compositions is:
Hydrogenated bisphenol A: 275kg；
Double [7-oxabicyclo (4.1.0) heptane-3-methyl] adipate ester: 1100kg；
Polyurethane modified epoxy resin: 10.5kg；
Nano-organosilicon resin: 17kg；
Voranol 3010:120kg；
Boron triflouride-mono aminoethane complex: 12kg；
Boron trifluoride-piperidines complex: 15.5kg.
Embodiment 4
Compositions is:
Hydrogenated bisphenol A: 1300kg；
Polyurethane modified epoxy resin: 7.5kg；
Nano-organosilicon resin: 20kg；
Fomrez1066-560:120kg；
Boron triflouride-mono aminoethane complex: 12kg；
Boron trifluoride-piperidines complex: 15.5kg.
Embodiment 5
Compositions is:
Hydrogenated bisphenol A: 275kg；
Double [7-oxabicyclo (4.1.0) heptane-3-methyl] adipate ester: 800kg；
3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl formic acid esters: 300kg；
Nano-organosilicon resin: 27.5kg；
Pluracol 1016:60kg；
Fomrez1066-56060kg；
Boron triflouride-mono aminoethane complex: 12kg；
Boron trifluoride-piperidines complex: 15.5kg.
Embodiment 6
Compositions is:
Hydrogenated bisphenol A: 275kg；
Double [7-oxabicyclo (4.1.0) heptane-3-methyl] adipate ester: 1100kg；
Polyurethane modified epoxy resin: 10.5kg；
Nano-organosilicon resin: 17kg；
Multranol 9158:80kg；
Voranol 3010:40kg；
Boron triflouride-mono aminoethane complex: 12kg；
Boron trifluoride-piperidines complex: 5.5kg
Boron trifluoride-zirconium triethanolamine complex: 10kg.
Embodiment 7
Compositions is:
Hydrogenated bisphenol A: 775kg；
Double [7-oxabicyclo (4.1.0) heptane-3-methyl] adipate ester: 600kg；
Polyurethane modified epoxy resin: 27.5kg；
Pluracol 1016:100kg；
Multranol 9158 20kg；
Fomrez1066-560 20kg；
Boron triflouride-mono aminoethane complex: 27.5kg.
According to any one dispensing in embodiment 1-7, production environment being transferred to temperature 15-28 DEG C, relative humidity is less than
70%, stir in successively hydrogenated epoxy resin, modified resin, toughened resin being joined vacuum stirring still, add after mix homogeneously
Entering complexation firming agent, mix homogeneously, vacuum mix homogeneously, deaeration filtration, subpackage is put in storage ,-20 DEG C of cold preservations.
Last it is noted that above example only in order to the present invention is described and and unrestricted technology described in the invention
Scheme；Therefore, although this specification with reference to each above-mentioned embodiment to present invention has been detailed description, but, this
Field it is to be appreciated by one skilled in the art that still the present invention can be modified or equivalent；And all are without departing from this
The technical scheme of the spirit and scope of invention and improvement thereof, it all should be contained in scope of the presently claimed invention.
Claims (7)
1. a Underfill adhesive composition, it is characterised in that described compositions is made up of the raw material of following weight portion: 50-80
The hydrogenated epoxy resin of part, the modified resin of 1-10 part, the toughened resin of 5-30 part, the complexation firming agent of 1-10 part；
Described hydrogenated epoxy resin is hydrogenated bisphenol A, 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexyl formic acid esters, double [7-
Oxabicyclo (4.1.0) heptane-3-methyl] one or more in adipate ester, the range of viscosities of described hydrogenated epoxy resin
All between 200-800cps；
Described modified resin is the one in nano-organosilicon resin, polyurethane modified epoxy resin, or their mixture.
A kind of Underfill adhesive composition the most according to claim 1, it is characterised in that described toughened resin is that polyethers is many
Unit's alcohol toughened resin or PEPA toughened resin.
A kind of Underfill adhesive composition the most according to claim 1, it is characterised in that described complexation firming agent is trifluoro
Change one or more in boron-mono aminoethane complex, boron trifluoride-zirconium triethanolamine complex, boron trifluoride-piperidines complex.
A kind of Underfill adhesive composition the most according to claim 1, it is characterised in that each raw material in described compositions
Weight portion is: hydrogenated epoxy resin 55-80 part, modified resin 1.1-10 part, toughened resin 5.5-30 part, complexation firming agent 1.1-
10 parts.
A kind of Underfill adhesive composition the most according to claim 1, it is characterised in that described Underfill adhesive composition
Encapsulation field for flip-chip.
A kind of Underfill adhesive composition the most according to claim 2, it is characterised in that the toughness reinforcing tree of described polyether polyol
Fat is the Voranol 3010 of the Pluracol 1016 of Bayer company, DOW company, the Multranol 9158 of Bayer company
In one or more, described PEPA toughened resin is the Fomrez1066-560 of Uniroyal company.
7. the preparation method of a Underfill adhesive composition as claimed in claim 4, it is characterised in that described preparation method
For: production environment is transferred to temperature 15-28 DEG C, and relative humidity 20-70%, successively by the hydrogenation of 55-80 part by weight
Epoxy resin, 1.1-10 part modification resin, 5.5-30 part toughened resin join stirring in vacuum stirring still, add after mix homogeneously
Enter 1.1-10 part complexation firming agent, mix homogeneously, vacuum mix homogeneously, deaeration filters, and subpackage is put in storage, subzero 10 DEG C-subzero
40 DEG C of cold preservations.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210081595.9A CN103361016B (en) | 2012-03-26 | 2012-03-26 | A kind of Underfill adhesive composition |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210081595.9A CN103361016B (en) | 2012-03-26 | 2012-03-26 | A kind of Underfill adhesive composition |
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| CN103361016A CN103361016A (en) | 2013-10-23 |
| CN103361016B true CN103361016B (en) | 2016-08-03 |
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| CN113897164B (en) * | 2021-10-26 | 2023-04-25 | 江苏大力士投资有限公司 | Marble adhesive with high adhesiveness and high toughness and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362848A (en) * | 2008-09-24 | 2009-02-11 | 常熟佳发化学有限责任公司 | Filler resin composition for adjusting high backing plate by filling and preparation method |
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| US20070293603A1 (en) * | 2006-06-19 | 2007-12-20 | Ashland Licensing And Intellectual Property Llc | Epoxy adhesive composition and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362848A (en) * | 2008-09-24 | 2009-02-11 | 常熟佳发化学有限责任公司 | Filler resin composition for adjusting high backing plate by filling and preparation method |
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