A kind of flow model chip-level bottom filling adhesive and preparation method thereof
Technical field
The invention belongs to fill glue preparing technical field more particularly to a kind of flow model chip-level bottom filling adhesive and its system
Preparation Method.
Background technology
With the development that Electronic Packaging industry is maked rapid progress, harsher requirement is also proposed to electronic package material.
Since chip CTE made of silicon materials is far below substrate, in order to protect chip, tin ball and solder joint and enhance chip
Reliability, underfill are widely used in electronic package material.It is material that underfill, which usually selects epoxy-resin systems,
Material, it has the excellent performances such as high, corrosion-resistant, the sticky high and good insulating of toughness.But most of underfill is all at present
There are brittleness it is big, reliability is low, internal stress is big, poor heat resistance, poor moisture resistance the shortcomings of, be only capable of meeting second level package requirement.
Invention content
The present invention in view of the deficiency of the prior art, provides a kind of flow model chip-level bottom filling adhesive and its system
Preparation Method.
The technical solution that the present invention solves above-mentioned technical problem is as follows:A kind of flow model chip-level bottom filling adhesive, group
Divide and is formed by following parts by weight:18 parts~30 parts of epoxy resin, 1 part~3 parts of toughener, 0.1 part~1 part of wetting dispersing agent, idol
Join 8 parts~15 parts of 0.1 part~1 part of agent, 0.1 part~0.5 part of carbon black, 50 parts~70 parts of filler and curing agent.
Further, the epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, Ppolynuclear aromatic epoxy
Two or more mixing in resin, phenol aldehyde type epoxy resin.
Further, the bisphenol A type epoxy resin is E51, E44 or EPON 825;The bisphenol F type epoxy tree
Fat is EPIKOTE 862 or EPIKOTE 983U;The Ppolynuclear aromatic epoxy resin be EPICLON HP4700,
EPICLONHP4500 or EPICLONHP4032;The phenol aldehyde type epoxy resin is DEN 431, DEN 438 or DEN 439.
Advantageous effect using above-mentioned further scheme is that different types of epoxy resin is selected to coordinate, can be more effective
Performance various epoxy resin the advantages of so that thermal stability, coefficient of thermal expansion etc. reach an equalization point, excellent to obtain
Comprehensive performance.
Further, the toughener is liquid nbr carboxyl terminal, methyl vinyl silicone rubber, dimethylvinylsiloxy silicon
Rubber, methyl phenyl vinyl silicon rubber or methyldiphenyl base vinyl silicone gum.
Advantageous effect using above-mentioned further scheme is that the addition of toughener can adjust the toughness of solidfied material, effectively
Increase elasticity modulus, reduce coefficient of thermal expansion, meet shock proof requirement.
Further, the wetting dispersing agent is that fatty alcohol polyoxyethylene ether, aliphatic amine polyoxyethylene ether or alkyl phenol are poly-
Ethylene oxide ether.
Advantageous effect using above-mentioned further scheme is that the addition of wetting dispersing agent effectively reduces system viscosity, is increased
System is added to flow wetability.
Further, the coupling agent is that β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, γ-shrink are sweet
One or more kinds of mixing of oily oxygroup propyl trimethoxy silicane or γ mercaptopropyitrimethoxy silane.
Further, the carbon black is high-carbon black pigment.
Further, the filler is the ball-shaped silicon micro powder that grain size is less than that 15 μm and average grain diameter are 1.5 μm~7.5 μm.
Advantageous effect using above-mentioned further scheme is, 15 μm of silicon powder maximum particle diameter and average grain diameter 1.5 μm~
Between 7.5 μm, ensures the quickly good filling of small―gap suture chip energy, choose ball-shaped silicon micro powder so that the flowing of resin and filler
Property reaches consistent.
Further, the curing agent is modified amine compound or anhydride compound.
Further, the modified amine compound is modified aromatic amine, modified polyamide or modified dicyandiamine;It is described
Anhydride compound be tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride.
Second object of the present invention is to provide a kind of preparation method of flow model chip-level bottom filling adhesive, and step is such as
Under:
(1) 0.1 part~0.5 part of 18 parts~30 parts of epoxy resin and carbon black are weighed, puts into and stirs 0.5~1h in reaction kettle,
After mixing, it is put into reaction kettle after grinding;
(2) 0.1 part~1 part of 1 part~3 parts of toughener, 0.1 part~1 part of wetting dispersing agent and coupling agent are weighed, is put into
1~2h is stirred in reaction kettle, is uniformly mixed;
(3) 50 parts~70 parts of filler is weighed, is put into reaction kettle and is stirred 2~4 hours, is uniformly mixed, it is polished
It puts into reaction kettle again, temperature is controlled at 40~80 DEG C, stands 3~8h;
(4) temperature control weighs 8 parts~15 parts of curing agent, is put into reaction kettle and vacuumize stirring 1 at 20~25 DEG C
~2h is uniformly mixed to get filling glue.
Further, the speed of agitator in step (1)-(3) is 1000rpm;Speed of agitator in step (4) is 300rpm.
Advantageous effect using above-mentioned further scheme is to reduce mixing speed, energy after curing agent is added in step (4)
Enough heats for reducing stirring and generating.
Further, the filler in step (3) in a kettle with other raw materials after mixing, ground by three-roll grinder
It adds in reaction kettle after mill, is stood at 40~80 DEG C.
Advantageous effect using above-mentioned further scheme is that hot conditions are conducive to resin and the abundant wetting and dispersing of filler.
Further, the vacuum degree vacuumized in step (4) is less than -0.095MPa, and when reaction kettle pressure release need to be passed through nitrogen guarantor
Shield.
The beneficial effects of the invention are as follows:Chip-level bottom filling adhesive produced by the present invention does not use any kind of dilution
Agent simultaneously has the characteristics that flowing velocity is fast, reliability is high, coefficient of thermal expansion is low, bending modulus is high, hygroscopicity is low, wetting dispersing agent
Addition effectively reduce viscosity, the effect for increasing flowing velocity is notable, significantly more efficient so that filler is uniformly dispersed, and ensure that
Encapsulate the reliability of component.
Specific implementation mode
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
It is further illustrated the present invention by embodiment and comparative example.The product that following embodiments and comparative example obtain is carried out
Test, tests its viscosity, mobile performance, water absorption rate, curing performance, coefficient of thermal expansion, elasticity modulus, shear strength seven respectively
Performance indicator.
Viscosity is tested, and TA companies of U.S. rheometer, rotating speed 1.5s are used-1, 25 DEG C of temperature, unit Pas.
Mobile performance is tested, and form gap by spacer shims and coverslip, glass slide (simulates between encapsulating component for 50 μm
Gap) device, at 100 DEG C test product flow 10mm the time required to, unit s.
Water absorption rate test tests (PCT), 121 DEG C, humidity 100%R.H., time 20h of temperature using saturated vapor.
Curing performance is tested, and using differential scanning calorimetry (DSC), required solidification is fully cured in 150 DEG C of products of constant temperature
Time, unit min.
Coefficient of thermal expansion tests (CTE), according to U.S.'s ASTM D696 standards, is tested using thermomechanical analysis (TMA),
Unit μm/m DEG C.
Elasticity modulus is tested, and according to U.S.'s ASTM E1142 standards, is tested using dynamic mechanical analyzer (DMA), unit
GPa。
Shear strength test, condition of cure is to cure 90min at 150 DEG C, according to the test sides GB/T7124-1986 of China
Method measures AL/AL shear strengths, units MPa.
Embodiment 1
A kind of preparation method of flow model chip-level bottom filling adhesive, steps are as follows:
(1) bisphenol A type epoxy resin E51 80g, phenol aldehyde type epoxy resin DEN 431 100g and carbon black 5g are weighed, is put into
0.5~1h is stirred with the speed of 1000rpm in reaction kettle, after mixing, is put into reaction kettle after grinding;
(2) liquid nbr carboxyl terminal 20g, fatty alcohol polyoxyethylene ether 10g and γ-mercaptopropyi trimethoxy are weighed
Base silane 5g is put into the speed in reaction kettle with 1000rpm and stirs 1~2h, is uniformly mixed;
(3) the silicon powder 700g for weighing 7.5 μm of average grain diameter is put into the speed stirring 2 with 1000rpm in reaction kettle
It~4 hours, is uniformly mixed, polished to put into reaction kettle again, temperature is controlled at 40~80 DEG C, stands 3~8h;
(4) temperature control at 20~25 DEG C, weigh four benzonitrile acid anhydride 80g of methyl, put into reaction kettle vacuumize, with
The speed of 300rpm stirs 1~2h, is uniformly mixed to get filling glue.
Embodiment 2
A kind of preparation method of flow model chip-level bottom filling adhesive, steps are as follows:
(1) bisphenol f type epoxy resin EPIKOTE 983U 120g, Ppolynuclear aromatic epoxy resin ICLON are weighed
HP4700 100g and carbon black 5g put into the speed in reaction kettle with 1000rpm and stir 0.5~1h, after mixing, after grinding
It puts into reaction kettle;
(2) methyl phenyl vinyl silicon rubber 30g, aliphatic amine polyoxyethylene ether 10g and β-(3,4- epoxy hexamethylenes are weighed
Base) ethyl trimethoxy silane 5g, 1~2h of stirring in reaction kettle is put into, is uniformly mixed;
(3) the silicon powder 630g for weighing 1.5 μm of average grain diameter is put into the speed stirring 2 with 1000rpm in reaction kettle
It~4 hours, is uniformly mixed, polished to put into reaction kettle again, temperature is controlled at 40~80 DEG C, stands 3~8h;
(4) temperature control at 20~25 DEG C, weigh modified aromatic amine 100g, put into reaction kettle vacuumize, with
The speed of 300rpm stirs 1~2h, is uniformly mixed to get filling glue.
Embodiment 3
A kind of preparation method of flow model chip-level bottom filling adhesive, steps are as follows:
(1) bisphenol A type epoxy resin E44 160g, Ppolynuclear aromatic epoxy resin ICLON HP4500 100g are weighed
With carbon black 5g, puts into 0.5~1h of speed stirring in reaction kettle with 1000rpm and put into reaction kettle after grinding after mixing
In;
(2) 3,5-dimethylphenyl vinyl silicone gum 20g, aliphatic amine polyoxyethylene ether 5g and β-(3,4- epoxy hexamethylenes are weighed
Base) ethyl trimethoxy silane 10g, it is put into the speed in reaction kettle with 1000rpm and stirs 1~2h, be uniformly mixed;
(3) the silicon powder 560g for weighing 5 μm of average grain diameter, put into reaction kettle speed stirring 2 with 1000rpm~
It 4 hours, is uniformly mixed, polished to put into reaction kettle again, temperature is controlled at 40~80 DEG C, stands 3~8h;
(4) temperature control at 20~25 DEG C, weigh modified dicyandiamine 140g, put into reaction kettle vacuumize, with
The speed of 300rpm stirs 1~2h, is uniformly mixed to get filling glue.
Embodiment 4
A kind of preparation method of flow model chip-level bottom filling adhesive, steps are as follows:
(1) 862 epoxy resin 150g of bisphenol f type epoxy resin EPIKOTE, phenol aldehyde type epoxy resin DEN 439 are weighed
150g and carbon black 5g puts into the speed in reaction kettle with 1000rpm and stirs 0.5~1h, after mixing, reaction put into after grinding
In kettle;
(2) methyl phenyl vinyl silicon rubber 30g, alkyl phenol polyoxyethylene ether 5g and γ-glycidoxypropyl are weighed
Trimethoxy silane 10g is put into the speed in reaction kettle with 1000rpm and stirs 1~2h, is uniformly mixed;
(3) the silicon powder 500g for weighing 3 μm of average grain diameter, put into reaction kettle speed stirring 2 with 1000rpm~
It 4 hours, is uniformly mixed, polished to put into reaction kettle again, temperature is controlled at 40~80 DEG C, stands 3~8h;
(4) temperature control at 20~25 DEG C, weigh hexahydrophthalic anhydride 150g, put into reaction kettle vacuumize, with
The speed of 300rpm stirs 1~2h, is uniformly mixed to get filling glue.
Comparative example 1
A kind of preparation method of chip-level bottom filling adhesive, steps are as follows:
(1) bisphenol f type epoxy resin EPIKOTE 983U 120g, Ppolynuclear aromatic epoxy resin ICLON are weighed
HP4700 100g and carbon black 5g put into the speed in reaction kettle with 1000rpm and stir 0.5~1h, after mixing, after grinding
It puts into reaction kettle;
(2) methyl phenyl vinyl silicon rubber 30g and β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane 5g is weighed,
It is put into the speed in reaction kettle with 1000rpm and stirs 1~2h, be uniformly mixed;
(3) 1.5 μm of silicon powder 630g of average grain diameter are weighed, put into reaction kettle speed stirring 2 with 1000rpm~
It 4 hours, is uniformly mixed, polished to put into reaction kettle again, temperature is controlled at 40~80 DEG C, stands 3~8h;
(4) temperature control at 20~25 DEG C, weigh hexahydrophthalic anhydride 150g, put into reaction kettle vacuumize, with
The speed of 300rpm stirs 1~2h, is uniformly mixed to get filling glue.
Comparative example 2
A kind of preparation method of chip-level bottom filling adhesive, steps are as follows:
(1) 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters 400g, bis- (7- oxabicyclos are weighed
[4.1.0] 3- methyl in heptan) adipate ester 400g and hexafluoro antimonate 5g, it puts into the speed in reaction kettle with 1000rpm and stirs 0.5
~1h is put into after grinding in reaction kettle after mixing;
(2) control temperature weighs acrylic acid epoxy resin 100g, butyl acrylate 50g, Isosorbide-5-Nitrae-fourth two at 15 DEG C~20 DEG C
Alcohol 30g, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane 10g, benzoyl peroxide 3g and carbon black 2g input reactions
It is vacuumized in kettle, 2~4h is stirred with the speed of 500rpm, be uniformly mixed to get filling glue.
Glue will be filled made from above-described embodiment 1-4 carries out testing performance index, number with filling glue prepared by comparative example 1-2
According to the results are shown in Table 1.
1 performance indicator of table compares
Chip-level bottom filling adhesive produced by the present invention is can be seen that from the data of table 1, two level is longer than on hardening time
Underfill is faster than two level underfill on flowing time so that glue is formed less in filling and solidification process
Internal flaw;Coefficient of thermal expansion, water absorption rate, bending modulus, shear strength etc. all compared with second level package underfill
It has a clear superiority.This just determines that chip-level bottom filling adhesive produced by the present invention has higher reliability, meets level-one height
The requirement of density chip grade encapsulation.In addition, in the present invention wetting dispersing agent addition, effectively reduce viscosity, increase flowing speed
The effect of degree is notable.Since the chip-level bottom filling adhesive does not use any diluent, there is higher reliability.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.