CN104817989B - A kind of Underfill adhesive composition and preparation method thereof - Google Patents
A kind of Underfill adhesive composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Underfill adhesive composition and preparation method thereof, said composition by weight percentage, includes following component：Modified epoxy 5wt% ~ 15wt%, modified bismaleimide 5wt% ~ 15wt%, filler 50wt% ~ 70wt%, curing agent 5wt% ~ 15wt%, curing agent accelerator 0.2wt% ~ 1wt%, diluent 5wt% ~ 10wt%, dispersant 2wt% ~ 8wt%, coupling agent 0.5wt% ~ 2wt%, ion adsorbent 0.1wt% ~ 2wt%；Wherein modified epoxy is polyester modified epoxy resin and/or carbonate-modified epoxy resin, and modified bismaleimide is acrylate modified BMI and/or organic-silicon-modified BMI.The Underfill adhesive composition has the good needs reprocessed performance, high reliability and high glass transition temperature, can meet packaging technology new at present.
Description
Technical field
The present invention relates to electronics and the underfill of microelectronic, more particularly to one kind can be used for smart mobile phone module
High-performance, the Underfill adhesive composition that can quickly repair and preparation method thereof.
Background technology
During chip package, because the thermal coefficient of expansion of chip and base material (CTE) has difference, usually cause connection
The Stress non-homogeneity that soldered ball between chip and base material is born, periphery cause chip when bearing thermal shock than broad in the middle, week
The soldered ball on side is easy to fall off and substantially reduces the reliability of connection.To make up this defect, generally add in the centre of chip and base material
Enter certain supporting material, disperse and absorb the stress that chip surface is born by supporting material, can so as to reach raising product
By the purpose of property.This supporting material is referred to as " underfill ".Underfill is mainly used in electronics and microelectronic
Encapsulation.
Underfill is a kind of chemical glue (Main Ingredients and Appearance is epoxy resin), is solidified by the form of heating.In core
In piece encapsulation, directly then underfill is heating and curing coated on chip or base material.Coating method mainly has capillary
Type underfill, help three kinds of weldering (non-current) type underfill and precoating.Most popular at present is that capillary bottom of the tube is filled out
Method is filled, the encapsulation requirement of flip-chip (FCIP) in its FCOB that is particularly suitable for use in (FCOB) and encapsulation.Capillary bottom
Portion's fill process can be described as：Underfill point is first coated in flip chip edge, glue can quickly be flowed by capillarity
Cross chip bottom and complete bottom filling process, finally complete the solidification of glue in case of heating.
With electronic product to miniaturization and multifunction direction develop, the packing forms of chip also change gradually
Become, ball grid array encapsulation (BGA), wafer-level package (CSP), wafer stage chip encapsulation (WLCSP), land grid array (LGA),
The advanced packing forms such as 3D chip packages (3DIC), silicon hole (TSV) arise at the historic moment.New packing forms solve more work(
Energy, high integration, high-speed low-power-consumption, the encapsulation problem of multilead IC chip, but it is also proposed to underfill
More harsh requirement, underfill is turned in high fluidity, high reliability, high glassy state in more advanced packing forms
The performance for changing temperature (Tg), low thermal coefficient of expansion (CTE) etc. proposes higher requirement.Existing underfill encapsulation
Part need to remove glue-line when reprocessing, when the underfill package parts glue-line using conventional epoxies as matrix destroys through processing
Easily divide blocking, residual silkgum content is big when removing glue-line, not easy to clean, reprocesses difficulty.Influenceed by self performance, using epoxy resin as base
The Tg and reliability of the underfill of body are relatively low.Therefore, existing underfill can not meet the needs of new technology.
The content of the invention
The present invention provides a kind of Underfill adhesive composition for reprocessing good performance, high reliability and high glass transition temperature
And preparation method thereof.
According to the first aspect of the invention, the present invention provides a kind of Underfill adhesive composition, and said composition is with weight hundred
Fraction meter, include following component：Modified epoxy 5wt%~15wt%, modified bismaleimide 5wt%~15wt%,
Filler 50wt%~70wt%, curing agent 5wt%~15wt%, curing agent accelerator 0.2wt%~1wt%, diluent 5wt%
~10wt%, dispersant 2wt%~8wt%, coupling agent 0.5wt%~2wt%, ion adsorbent 0.1wt%~2wt%；Its
In above-mentioned modified epoxy be polyester modified epoxy resin and/or carbonate-modified epoxy resin, above-mentioned modified span carrys out acyl
Imines is acrylate modified BMI and/or organic-silicon-modified BMI.
According to the second aspect of the invention, the present invention provides a kind of method for the composition for preparing first aspect, this method
Including：At 65 DEG C~75 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator,
Diluent, dispersant, coupling agent, ion adsorbent add homogenizer stirring according to proportioning, and rotating speed is 700~1700r/
Min, time are 90~120min；Then stirring at low speed, rotating speed are 20~120r/min, and the time is 20~30min；Placement 18~
30h is cured；The glue of curing disperses 20~30min with 20~40KHz ultrasonic waves；Dispersion liquid is transferred to vacuum and taken off after filtering
Deaeration in bubble machine, finally gives above-mentioned composition.
The present invention Underfill adhesive composition using modified epoxy be used as matrix, assign underfill well
Reprocess performance；Use modified bismaleimide simultaneously so that underfill has high reliability and high glass transition temperature
The performance of degree.
In addition, filler does not settle for a long time in the Underfill adhesive composition of the present invention, storage stability is good, working life length；
The ability that underfill automatically forms fillet is strong, has good wettability to device substrate, good adhesion strength, low
Internal stress, low ion concentration, therefore the defects of effectively compensate for existing underfill.
Brief description of the drawings
Fig. 1 is that colloform texture change is former when existing underfill and the underfill package parts of the present invention are reprocessed
Reason figure；
Fig. 2 is the reliability and heavy industry of existing underfill (left figure) and the underfill (right figure) of the present invention
Graph of a relation；
Fig. 3 is the modified epoxy that one embodiment of the invention uses13C NMR spectras；
Fig. 4 is the modified epoxy that another embodiment of the present invention uses13C NMR spectras；
Fig. 5 is the modified bismaleimide that one embodiment of the invention uses13C NMR spectras；
Fig. 6 is the unmodified embodiment 9 (left figure) of a filler of the present invention and filler modified embodiment 1 (right figure)
Filling effect compares, it is seen that the former has cavity and streamline phenomenon, and the latter does not have；
Fig. 7 is SEM (SEM) image of the underfill of the embodiment of the present invention 1, shows uniform filling
It is scattered；
Fig. 8 is the condition of Underfill adhesive composition and traditional underfill in heating of one embodiment of the invention
Under, curve map that storage modulu diminishes with the rise of temperature.
Embodiment
The present invention is described in further detail below by embodiment combination accompanying drawing.
Existing underfill is primarily present problem points and is easily to reprocess and can only be chosen one of two with reliability, easily reprocesses
Usual reliability is not high, high generally not reworkable of reliability, it is impossible to meet the needs of new packaging technology, the main pin of the present invention
Contradictory relation with high reliability is easily reprocessed to existing underfill, the formula of underfill is improved, led to emphatically
Cross the modification to key component in formula such as epoxy resin and BMI and realize performance boost.
The Underfill adhesive composition of one embodiment of the invention, by weight percentage, include following component：It is modified
Epoxy resin 5wt%~15wt%, modified bismaleimide 5wt%~15wt%, filler 50%~70%, curing agent
5wt%~15wt%, curing agent accelerator 0.2wt%~1wt%, diluent 5wt%~10wt%, dispersant 2wt%~
8wt%, coupling agent 0.5wt%~2wt%, ion adsorbent 0.1wt%~2wt%；Wherein above-mentioned modified epoxy is poly-
Ester modified epoxy resin and/or carbonate-modified epoxy resin, above-mentioned modified bismaleimide are acrylate modified span
Come acid imide and/or organic-silicon-modified BMI.
1st, modified epoxy
As shown in figure 1, existing underfill package parts need to remove glue-line when reprocessing, using conventional epoxies as base
The underfill package parts glue-line of body easily divides blocking when being destroyed through processing, residual silkgum content is big when removing glue-line, not easy to clean, returns
Repair difficulty.One embodiment of the invention is modified (i.e. polyester by introducing esters and/or carbon acidic groups to epoxy resin
Modified epoxy and/or carbonate-modified epoxy resin), solve the problems, such as that package parts reprocess difficulty.Encapsulation part
When part is reprocessed, underfill glue-line is destroyed at high temperature, and esters and/or carbon acidic groups will be replaced in mesogens molecules structure
Other feature segments decompose first.Now, although the adhesive strength rapid decrease of glue-line, can determine molecular conformation
Structure be not destroyed, glue-line still keeps complete network structure, and macro manifestations are an entirety, goes to be not easy during glue-line residual
Glue, cleaning are easy so that reprocessing for package parts is more convenient.In addition, also there is antistripping, cracking, punching in epoxy resin in itself
The shortcomings of hitting big poor performance, high temperature hygroscopicity, poor fire, the present invention can also be by introducing long-chain flexible group, ehter bond, third
The functional structures such as epoxide, it is effectively improved the impact flexibility and high temperature moisture pick-up properties of modified epoxy；P elements can be passed through
Introducing, improve its fire resistance.
Fig. 2 shows the reliability and again of existing underfill (left figure) and the underfill (right figure) of the present invention
The relation of work, it is seen that easily reprocessing for existing underfill can only choose one of two with reliability, and that easily reprocesses is usual reliable
Property it is not high, reliability it is high generally it is not reworkable；And the reliability and heavy industry of the underfill of the present invention are preferable.
Polyester modified epoxy resin alleged by the present invention and carbonate-modified epoxy resin are named with modified group.Contain
There are aliphatic ester, alicyclic ester, aromatic ester, the modified epoxy of group as carbamate to be properly termed as polyester and change
Property epoxy resin.A kind of above-mentioned group can be contained in modified epoxy can also contain two or more groups, example simultaneously
As simultaneously containing aliphatic ester and aromatic ester, simultaneously containing aromatic ester and carbamate, simultaneously containing aliphatic ester and
Carbamate etc..Modified epoxy containing group as carbonic ester is referred to as carbonate-modified epoxy resin, can also
It is polycarbonate modified epoxy resin.Carbonic ester is the hydrogen moiety of two hydroxyls (- OH) or all by alkane in carbonic acid molecule
Compound after base (R, R') substitution, its formula is RO-CO-OH or RO-CO-OR'.The modified epoxy of the present invention contains simultaneously
Have in aliphatic ester, alicyclic ester, aromatic ester, carbamate any one or it is two or more, and contain carbonic acid simultaneously
Ester is also possible.Refer to comprise only esters respectively as pure polyester modified epoxy resin or carbonate-modified epoxy resin
Or the modified epoxy of carbonic acid class, this is currently preferred modified epoxy.
Aliphatic ester alleged by the present invention, refers to the Ester containing aliphatic chain, wherein the length of aliphatic chain such as 2~
20 carbon atoms, and aliphatic chain can be the form of straight or branched, can be that saturation can also contain unsaturated bond such as
Double bond etc., can non-substituted can also contain substituent.Aliphatic ester generally refers to aliphatic acid and aliphatic alcohol passes through ester
Change the ester that reaction is formed, but it is not excluded that containing other atoms or group, such as contain phosphate group, contain phosphate group
Aliphatic ester can play obvious fire retardation, can be also crucial for inventive.As having into ring structure in fruit structure,
It can be described as alicyclic ester.
Aromatic ester alleged by the present invention, refer to the Ester containing aromatic group such as phenyl ring, naphthalene nucleus etc., wherein fragrance
The number of group such as 1~6, aromatic group can be substituted or non-substituted form.It is not excluded for containing beyond aromatic group
Other groups, such as alkane, alkene, alkynes hydrocarbyl group, and be also possible to containing phosphate group etc., the aromatic series containing phosphate group
Ester can play obvious fire retardation, can be also crucial for inventive.
Carbamate alleged by the present invention, refer to the Ester containing Carbamate groups, i.e. carbamic acid and alcohol
The ester that class is formed, wherein alcohols can be fatty alcohol or aromatic alcohol etc., and as the length such as 2~20 of its chain of fatty alcohol
Carbon atom, and aliphatic chain can be the form of straight or branched, can be that saturation can also contain unsaturated bond such as double bond
Deng can non-substituted can also contain substituent；As the number such as 1~6 of its aromatic group of aromatic alcohol, aromatic group
Can be substituted or non-substituted form, and other groups beyond being not excluded for containing aromatic group, such as alkane, alkene, alkynes hydrocarbon
Base group, and be also possible to containing phosphate group etc., the aromatic ester containing phosphate group can play obvious fire retardation,
Can be also crucial for inventive.
In the preferred embodiments of the invention, modified epoxy has structural formula 1 or the chemical constitution shown in structural formula 2
Formula：
A kind of synthetic route of structural formula 1 is as follows：
A kind of synthetic route of structural formula 2 is as follows：
In structure above and synthetic line, R1、R2、R3And R4It is each independently selected from aliphatic ester, alicyclic ester, virtue
Fragrant race's ester, carbamate or carbonic ester.Aliphatic ester, alicyclic ester, aromatic ester, carbamate and carbonic ester have
Definitions as described above." independently of one another " R is meaned1、R2、R3And R4Substituent selection between do not limit, therefore R1、
R2、R3And R4May be each different, it is also possible to which it is identical to have two, three or four.If R1、R2、R3And R4It is
Selected from aliphatic ester, alicyclic ester, aromatic ester, carbamate, then the compound that structural formula 1 or structural formula 2 represent claims
For polyester modified epoxy resin；If R1、R2、R3And R4It is to be selected from carbonic ester, then the change that structural formula 1 or structural formula 2 represent
Compound is referred to as carbonate-modified epoxy resin.
Most preferably, above-mentioned R1、R2、R3And R4It is each independently selected from any one in structural formula 3 to structural formula 10：
Group shown in structure above 3 is referred to as carbamic acid propyl ester, has the activity of increase composition, reduces solidification receipts
Shrinkage and skin irritation and toxicity, the function of reducing moisture pick-up properties.
Group shown in structure above 4 is referred to as carbamic acid cyclohexyl ester, has the viscosity for reducing composition, increase stable
The function of property.
Group shown in structure above 5 is referred to as methacrylic acid phosphate monoester (PM1), it is possible to increase to base material (metal
Or plastics) adhesive force, improve curing rate, improve divergent function, improve anti-flaming function.
Group shown in structure above 6 is referred to as methacrylic acid phosphate diester (PM2), it is possible to increase to base material (metal
Or plastics) adhesive force, improve curing rate, increase is flexible, improves divergent function, improves anti-flaming function.
In order that the performance such as the impact flexibility of composition, reliability, anti-flammability further improves, for shown in structural formula 1
Chemical structural formula, R1、R2、R3And R4In at least one (such as one, two, three or four) be selected from structural formula 5 or knot
Group shown in structure formula 6；For the chemical structural formula shown in structural formula 2, R1And R2In at least one (such as one or two)
Selected from the group shown in structural formula 5 or structural formula 6.Present invention research is found, using containing shown in structural formula 5 or structural formula 6
The modified epoxy of group can obtain the optimal of various aspects of performance, such as reprocess performance, impact flexibility, reliability and anti-flammability
It is all very excellent.
Group shown in structure above 7 is referred to as lauryl methacrylate, and it has long flexible chain, is effectively improved modification
The impact flexibility of epoxy resin.
Group shown in structure above 8 is referred to as double (2- methacrylics) carbonic esters；Group shown in structure above 9
The referred to as carbonic ester of allyl diglycol two；Group shown in structure above 10 is referred to as isopropyl propyl carbonate.
The characteristic that group shown in structure above 3 to structural formula 10 is respectively provided with is that at high temperature, above-mentioned group will replace
Other feature segments in mesogens molecules structure are decomposed first.Therefore, although the adhesive strength rapid decrease of glue-line,
It can determine that the structure of molecular conformation is not destroyed, glue-line still keeps complete network structure, and macro manifestations are an entirety,
Go to be not easy cull during glue-line, cleaning is easy so that reprocessing for package parts is more convenient.
The modified epoxy that one embodiment of the invention uses has structure shown below formula：
The preparation method of compound shown in structural formula I is as follows：
10ml tetrachloromethanes are miscible in the absolute ethyl alcohol of 40ml Cymags, be added in 250ml flask, by flask
It is put into water-bath, is heated to 70 DEG C, reacts 30min.Add CO2Aqueous solution stirring 20min, the rear sodium carbonate that adds continues to stir
20min is mixed, obtains S0.
10ml carbamates are taken, 10ml methacrylic acids phosphate monoester (PM1), 10ml acetylene alcohols, it is anhydrous to add 15ml
ZnCl2Dense HCl (be referred to as Lucas (Lucas) reagent) heating, be slowly added into 10ml tetrahydrofurans, be subsequently added into S0 stirrings,
Obtain S1.
By 10ml epoxy resin-base ERL-4269 (U.S. UCC), 25ml CH3Cl adds anhydrous ZnCl2Dense HCl (claim
For Lucas (Lucas) reagent) heating, it is rear to add S1 stirrings, 15ml NaOH ethanol solution is added, is eventually adding
5ml lauryl mercaptan sodium, with 20ml DMF (dimethylformamide) for solvent, react two hours, will obtain under the conditions of 190 DEG C
Solution add CO2Aqueous solution stirring 20min, the rear 8g sodium carbonate that adds continues to stir 20min, obtains S2.
10ml carbamic acid cyclohexyl esters are taken, 10ml lauryl methacrylates, add anhydrous 5ml ZnCl2Dense HCl (claim
For Lucas (Lucas) reagent) heating, obtain S3.
S2 and S3 is mixed into 30min, 8ml tetrahydrofurans is slowly added into and stirs 30min, it is rear to add 10ml's 5%
NaOH obtains final products.Analyze it13C NMR spectras are as shown in Figure 3.
The modified epoxy that another embodiment of the present invention uses has structure shown below formula：
The preparation method of compound shown in formula II is as follows：
Dicyclopentadiene is dissolved in NaOH ethanol solution, be heated to 70 DEG C stirring 60min, add solid-state or
Liquid CO2, reaction 12h~24h obtains S0 under conditions of MP about 190dc.
By 10ml epoxy resin-base ERL-4269 (U.S. UCC), 25ml CH3Cl adds anhydrous ZnCl2Dense HCl (claim
For Lucas (Lucas) reagent) heating, it is rear to add S0 stirrings, 15ml NaOH ethanol solution is added, is eventually adding
5ml lauryl mercaptan sodium, with 20ml DMF (dimethylformamide) for solvent, react two hours, will obtain under the conditions of 190 DEG C
Solution add CO2Aqueous solution stirring 20min, the rear 8g sodium carbonate that adds continues to stir 20min, obtains S1.
10ml carbamic acid cyclohexyl esters are taken, 10ml isopropyl propyl carbonates, add anhydrous 5ml ZnCl2Dense HCl (claim
For Lucas (Lucas) reagent) 70 DEG C of stirring 30min~60min are heated to, obtain S2.
S1 and S2 is mixed into 30min, 15ml tetrahydrofurans is slowly added into and stirs 30min, it is rear to add 10ml 5%
NaOH flow back and obtain final products 3~5 times.Analysis13C NMR spectras are as shown in Figure 4.
2nd, modified bismaleimide
Influenceed by self performance, it is relatively low as the Tg and reliability of the underfill of matrix using epoxy resin.This hair
It is bright that modified bismaleimide is added into matrix resin, effectively increase underfill Tg and its in use
Reliability.Bimaleimide resin typically exists in solid form, the poor compatibility with epoxy resin, is asked for this
Topic, the present invention introduces fats into BMI strand or alicyclic ring class group is modified to it.Modified tree
Fat is low viscosity liquid, good with epoxy resin compatibility, and the extent of interpenetration of two kinds of resins greatly improves in cured product, bottom
The Tg and its reliability in use for filling glue are also greatly improved.It is also possible to bimaleimide resin
Middle introducing P elements, improve its fire resistance.
Modified bismaleimide for the present invention is acrylate modified BMI and/or organic-silicon-modified
BMI.
Acrylate modified BMI alleged by the present invention, refer to ester system (the i.e. propylene containing acrylic acid groups
Acid esters system) modified bismaleimide, wherein the ester system containing acrylic acid groups refers to the esters that acrylic acid and alcohol are formed, its
In to be used to form the alcohol of the esters can be fatty alcohol or aromatic alcohol etc., and as the length such as 2~20 of its chain of fatty alcohol
Individual carbon atom, and aliphatic chain can be the form of straight or branched, can be that saturation can also contain unsaturated bond as double
Key etc., can non-substituted can also contain substituent；As the number such as 1~6 of its aromatic group of aromatic alcohol, aromatic radical
Group can be substituted or non-substituted form, and other groups beyond being not excluded for containing aromatic group, such as alkane, alkene, alkynes
Hydrocarbyl group, and be also possible to containing phosphate group etc., the aromatic ester containing phosphate group can play obvious fire-retardant work
With can be also crucial for inventive.
In one embodiment of the invention, modified bismaleimide has the chemical structural formula shown in structural formula 11：
Wherein, R1、R2、R3And R4The group of acrylic ester or silicon-type is each independently selected from, R5 is selected from
Wherein, acrylic ester has definitions as described above.
Most preferably, the group of aforesaid propylene acid esters system has the change shown in structural formula 12, structural formula 13 or structural formula 14
Learn structural formula：
The group of above-mentioned silicon-type has the chemical structural formula shown in structural formula 15：
Wherein, n values are 0~3, such as 0,1,2 or 3；M values are 0~5, such as 0,1,2,3,4 or 5；P values be 0~5, such as 0,
1st, 2,3,4 or 5.
Group shown in structure above 12 is referred to as lauryl methacrylate；Group shown in structure above 13 is referred to as
Methacrylic acid diethyl ethylphosphate (DEMEP)；Group shown in structure above 14 is referred to as acrylic acid ethyl phosphonic acids diformazan
Ester (DAP).
In order that the anti-flammability of composition further improves, the R in modified bismaleimide shown in structural formula 111、
R2、R3And R4In at least one (such as one, two, three or four) be selected from structural formula 13 (DEMEP) or structural formula 14
(DAP).Due to containing phosphate group in structural formula 13 and structural formula 14, the anti-flammability of composition is greatly improved.
R in modified bismaleimide1、R2、R3And R4Substituent can be with different, it is possibility to have one of them, two
It is individual, three or four substituents it is identical.
The modified bismaleimide that one embodiment of the invention uses has structure shown below formula：
The preparation method of compound shown in formula II I is as follows：
Ethanol solution is added in 250ml vial and is preheated to 50 DEG C, adds 10ml R5Diamine, 10ml
Maleic anhydride (MA), 2g nickel acetates, 30min is stirred, then add 5ml acetic anhydrides, solvent 20ml DMF (N, the N diformazans of ' one
Base formamide), stir 30min.Add CO2Aqueous solution stirring 20min, the rear 5g sodium carbonate that adds is heated to 70 DEG C, reaction
30min, obtain S0.
Take 10ml methacrylic acids diethyl ethylphosphate, 20ml acrylic acid ethyls dimethyl phosphonate, 10ml isopropyls third
Base carbonic ester, add anhydrous 15ml ZnCl2Dense HCl (be referred to as Lucas (Lucas) reagent) be heated to 70 DEG C of stirring 30min
~60min, obtains S1.
S0 and S1 is mixed into 30min, 20ml tetrahydrofurans is slowly added into and stirs 30min, it is rear to add 10ml 5%
NaOH obtain final products.Analyze it13C NMR spectras are as shown in Figure 5.
3rd, filler
Filler in the present invention can be selected from aluminium skimmings, aluminium powder, aluminium borate whisker, aluminum oxide, anthracite, sodium antimonate, three oxygen
Change antimony, apatite, cigarette ash, Attagel, barium metaborate, barium sulfate, barium titanate, bentonite, bismuth oxide, boron oxide, calcium carbonate, hydrogen
Calcium oxide, calcium sulfate, carbon black, ceramic microsphere, clay, diatomite, ferrite, feldspar, bead, gold, graphite, silicate hydrate
Calcium, kaolin, magnesia, magnesium hydroxide, molybdenum, molybdenum disulfide, nickel, polymer filler, float stone, lardite, rubber grain, Hai Pao
At least one of stone, silica, silica gel, silver powder, talcum, titanium dioxide, zeolite, Firebrake ZB, zinc sulphide, preferably dioxy
SiClx, titanium dioxide or Attagel.
The effect of filler in the present invention：The thermal coefficient of expansion of resin cured matter is reduced, reduces the water imbibition of resin cured matter,
Improve the resistance to ag(e)ing and chemical-resistant of solidfied material；Reduce the shrinkage of resin cured matter；Improve the resistance to electricity of resin cured matter
Arc and the other electrical properties of raising；Improve the wear resistance of resin cured matter；Compatibilization, cost is reduced, improve product in city
Competitiveness on field.
In order to further improve the dispersiveness of the performance of composition, especially filler, the present invention is changed using silane coupler
The filler of property, the wherein typical but non-limiting example of silane coupler can be HMDS, hexamethyl vinyl
At least one of silazane and vinylethoxysilane.One kind of the present invention is typical but filler is changed in non-limiting manner
Property processing method be：First by filler be placed in drying box (100 DEG C~120 DEG C) it is drying for one day, then with absolute ethyl alcohol, go from
Sub- water is according to 1：1：1 volume ratio mixes, and stand-by with the scattered 2h of 30KHz ultrasonic waves；By coupling agent (such as the silicon nitrogen of hexamethyl two
Alkane, hexamethyl vinyl silazane or vinylethoxysilane) add in absolute ethyl alcohol that (the quality accounting of coupling agent is
5%) mixed after, being sufficiently stirred with aforementioned ultrasonic dispersion liquid, 2~3h is sufficiently stirred at 70 DEG C, rotating speed is 1200 ± 300r/
Min, finally it is centrifuged at a high speed, ultrasonic disperse, 4~5 times repeatedly, obtains modified filler.The particle diameter 7 of general modified filler~
40nm, preferably 10~25nm, average grain diameter 20nm, accounting more than 85%, 5~80m of specific surface area2/g。
Filler in the present invention typically has tridimensional network characteristic, and there is unsaturated bond and different bonding shapes on surface
The hydroxyl of state so that there is very high activity, with silane coupler obtained dispersity nano-particle modified to its surface
The compatibility with resin can be improved, improves insulating properties, reduces hygroscopicity, surface good sphericity, smooth densification.If filler is not
Modified, then surface porosity, can there is negative effect to viscosity, such as during high temperature forms fused silica, titanium dioxide
Silicon can be oxidized, and oxygen is run into during cooling and forms ultramicro powder on surface, causes surface flatness to decline, dispersiveness drop
It is low, influence to flow.
4th, curing agent
Curing agent preferably uses LCM, if using solid curing agent, it is desirable to 3~8 μm of particle diameter, the μ of average grain diameter 5
10 μm of m, maximum particle diameter ＜.
Available curing agent is in the present invention：Maleic anhydride (MA), phthalic anhydride (PA) and its derivative,
Trimellitic anhydride (TMA), pyromellitic dianhydride (PMDA), methyl tetrahydro phthalic anhydride, HHPA, THPA, 3,3,4,4-
Benzophenone tetracarboxylic dianhydride (BTDA), dodecenylsuccinic acid acid anhydride (DDSA), methylcyclohexene tetracarboxylic dianhydride (MCTC), methyl hexahydro
Phthalic anhydride (MHHPA), methylnadic anhydride (MNA), benzoyl hydrazine, sebacic dihydrazide (SPH), 2-methylimidazole, methyl miaow
Azoles, 1- methylimidazoles, 2- heptadecyl imidazoles, 2- undecyl imidazoles, 2-ethyl-4-methylimidazole, 1- cyanoethyl -2- second
At least one of base -4-methylimidazole, three second hydroxylamines, 3,4- 3,5-dimethylphenyl subotituted dicyardiamides；Commodity can also be selected
CAPCURE3-800, CAPCURE WR-6, EPOMATE QX-10, EPOMATE QX-11 or the EPIKURE QX-40 of change.
5th, curing agent accelerator
Curing agent accelerator can be selected from benzyltrimethylammonium chloride, triethanolamine borate, triethanol amine titanate, pungent
Sour tin, quaternary alkylphosphonium salts, dicyandiamide, DBU carbonate, imidazoles metal salt, diethylaminopropylamine, benzyl dimethylamine (BDMA), N, N-
Dimethylaniline, 2-ethyl-4-methylimidazole, three-(2 ethyl hexanoic acid) salt of 2,4,6- tri- (dimethylamino methyl) phenol, 2,
Three oleates of 4,6- tri- (dimethylamino methyl) phenol, three (dimethylamino methyl) phenol 2 ethyl hexanoic acid salt at least
It is a kind of.
The effect of curing agent accelerator is embodied in, and curing agent accelerator can speed up epoxy resin cure, reduces solidification temperature
Degree, shorten hardening time.Due to forming the hexatomic ring transition of charge discrepancy between curing agent accelerator, curing agent, epoxy radicals
State implements facilitation, therefore electrophilicity accelerator is effective to nucleophilicity curing agent, and nucleophilic promotor solidifies to electrophilicity
Agent is effective.
6th, diluent
Diluent can be selected from 1,2- cylohexanediol diglycidyl ethers, 1,4- butanediol diglycidyl ethers, 1,4- rings
Hexane dimethanol diglycidyl ether, neopentylglycol diglycidyl ether, ethylene glycol diglycidylether, 1,6-HD two shrink
Glycerin ether, diethylene glycol diglycidyl glycerin ether, diethylene glycol (DEG) diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether
At least one of (TMPEG).
7th, dispersant
Dispersant can be selected from waterglass, sodium tripolyphosphate, calgon, sodium pyrophosphate, triethyl group hexyl phosphoric acid, ten
In sodium dialkyl sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum and fatty acid polyethylene glycol ester extremely
Few one kind.
The effect of dispersant is embodied in, and dispersant adsorption forms adsorption layer on surface, make solid in the surface of solid particle
Particle surface forms bilayer structure, and outer layer dispersant polar end has compared with strong affinity with water, adds solids by water
The degree of wetting.It is remote because of electrostatic repulsion between solid particle, improve the intergranular reaction force for forming steric hindrance, drop
Interfacial tension between low liquid-liquid or solid-liquid, the solid particles surface of cohesion are easy to moisten, and make system uniform, and suspendability increases
Add, there are long-term not precipitative properties.
8th, coupling agent
The effect of coupling agent is：Particle filled composite surface is modified；By organo-functional group and resin-bonded, pass through inorganic official
The reaction of energy base and material interface, improves its cohesive force；Improve the electric property and mechanical property under wet environment.
Coupling agent can be selected from silane coupler and/or titanate coupling agent.Preferably, above-mentioned silane coupler is selected from
Gamma-aminopropyl-triethoxy-silane, 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, γ-methacryloxypropyl
Trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl methyl diethoxy
Silane, N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, γ-piperazine
Base hydroxypropyl methyl dimethoxysilane, vinyl three (2- methoxy ethoxies) silane, γ-methacryloxypropyl front three
At least one of TMOS and β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane；Preferably, above-mentioned titanate esters are even
Join agent and be selected from three iso stearate isopropyl titanates, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, double (two octyloxies Jiao
It is phosphate-based) ethylene titanate esters, two (octyl phenol APEO) phosphides, (the dioctyl phosphito acyl-oxygen of tetra isopropyl two
At least one of base) titanate esters, monoalkoxy unrighted acid titanate esters and pyrophosphoric acid type monoalkoxy class titanate esters.
9th, ion adsorbent
Ion adsorbent can absorb free acid ion, improve the heat resistance and water resistance of composition, prevent from producing
Product turn to be yellow.The DHT-4A of for example Japanese Kyowa Chemical Industry Co., Ltd of the ion adsorbent that can be selected (is a kind of acid-acceptor
Or heat stabilizer), a kind of IXE500 (being inorganic anion exchanger) of Toagosei Co., Ltd.The particle diameter of ion adsorbent
1.0~5.0 μm, average grain diameter 3 μm, accounting 85% it is preferable.
10th, other components
The Underfill adhesive composition of the present invention mainly includes above component, can also include other components as needed,
Such as dyestuff, antioxidant.
11st, Underfill adhesive composition
The Underfill adhesive composition of the present invention, by weight percentage, includes following component：Modified epoxy
5wt%~15wt%, modified bismaleimide 5wt%~15wt%, filler 50wt%~70wt%, curing agent 5wt%~
15wt%, curing agent accelerator 0.2wt%~1wt%, diluent 5wt%~10wt%, dispersant 2wt%~8wt%, coupling
Agent 0.5wt%~2wt%, ion adsorbent 0.1wt%~2wt%.
Wherein, the percetage by weight of modified epoxy is preferably 6wt%~12wt%, more preferably 8wt%~10wt%；
The percetage by weight of modified bismaleimide is preferably 6wt%~12wt%, more preferably 8wt%~10wt%；The weight of filler
It is preferably 50wt%~65wt% to measure percentage, more preferably 50wt%~62wt%, most preferably 50wt%~60wt%；Solidification
The percetage by weight of agent is preferably 6wt%~12wt%, more preferably 8wt%~10wt%；The weight percent of curing agent accelerator
Number is preferably 0.3wt%~0.8wt%, more preferably 0.4wt%~0.6wt%；The percetage by weight of diluent is preferably 6wt%
~9wt%, more preferably 7wt%~8wt%；The percetage by weight of dispersant is preferably 3wt%~7wt%, and more preferably 4wt%~
6wt%；The percetage by weight of coupling agent is preferably 0.6wt%~1.5wt%, more preferably 0.8wt%~1.2wt%；Ion is inhaled
Attached dose of percetage by weight is preferably 0.2wt%~1.5wt%, more preferably 0.5wt%~1.2wt%.
The principle and feature of the present invention are further elaborated with reference to specific embodiment, it should be appreciated that example
It is served only for explaining the present invention, is not intended to limit the scope of the present invention, in addition, it is to be understood that even if after having read the present invention, ability
The technical staff in domain can make various changes and modification to the present invention, and these changes and modification equally will in the right of the present invention
In the range of the restriction asked.
The instrument and source used in embodiment are as follows：Mixer uses the planetary stirring machine of U.S. ROSS customizations；Three
Roller mill uses the three-roll grinder of U.S. ROSS customizations；DSC has using the resistance to scientific instrument commerce and trade (Shanghai) of speeding of Germany
Limit company DSC214；TGA is using the resistance to scientific instrument commerce and trade (Shanghai) Co., Ltd. TGA209F3 that speeds of Germany；What TMA was used
It is the resistance to scientific instrument commerce and trade (Shanghai) Co., Ltd. TMA402F3 that speeds of Germany；DMA is using the resistance to scientific instrument commerce and trade of speeding of Germany
(Shanghai) Co., Ltd. DMA242E/1；Viscosity test instrument strangles winged CAP2000+ using rich；Rheometer uses modularization
Rheometer work station HAAK MARS III；Push-and-pull force tester uses German Nordson Dage4000；Microscope uses
Nikon metallographic microscopes optiphot-200；SEM uses FDAC S-4800.
Embodiment 1
The formula of the Underfill adhesive composition of the present embodiment is as follows：
Modified epoxy (formula II) 10g
Modified bismaleimide (formula II I) 10g
Filler：Silica (HMDS modification) 60g
Curing agent：CAPCURE3-800 5g, dodecenylsuccinic acid acid anhydride (DDSA) 5g
Curing agent accelerator：Three-(2 ethyl hexanoic acid) the salt 1g of 2,4,6- tri- (dimethylamino methyl) phenol
Diluent：1,2- cylohexanediol diglycidyl ethers 5g
Dispersant：Triethyl group hexyl phosphoric acid 2g
Coupling agent:γ-methacryloxypropyl trimethoxy silane 1.5g
Ion adsorbent：DHT-4A 0.5g.
At 70 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilute
Agent, dispersant, coupling agent, ion adsorbent are released according to proportioning addition homogenizer stirring 90min, rotating speed 1200r/min；
Then stirring at low speed 20min, rotating speed 70r/min；24h is placed to be cured；The glue of curing is disperseed with 30KHz ultrasonic waves
20min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally obtains high quality underfill.Condition of cure：
130℃：5min, 150 DEG C：1min.
Embodiment 2
The formula of the Underfill adhesive composition of the present embodiment is as follows：
Modified epoxy (formula II) 15g
Modified bismaleimide (formula II I) 5g
Filler：Preparing spherical SiO 2 (HMDS modification) 60g
Curing agent：CAPCURE3-800 5g, the 5g of methylcyclohexene tetracid two
Curing agent accelerator：Three-(2 ethyl hexanoic acid) the salt 1.5g of 2,4,6- tri- (dimethylamino methyl) phenol
Diluent：1,2- cylohexanediol diglycidyl ethers 5g
Dispersant：Lauryl sodium sulfate 2g
Coupling agent:γ-methacryloxypropyl trimethoxy silane 1g
Ion adsorbent：IXE500 0.5g
At 70 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilute
Agent, dispersant, coupling agent, ion adsorbent are released according to proportioning addition homogenizer stirring 120min, rotating speed 1200r/
min；Then stirring at low speed 30min, rotating speed 70r/min；24h is placed to be cured；The 30KHz ultrasound wavelength-divisions of the glue of curing
Dissipate 30min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally obtains high quality underfill.Condition of cure：
130℃：5min, 150 DEG C：1min.
Embodiment 3
The formula of the Underfill adhesive composition of the present embodiment is as follows：
Modified epoxy (structural formula I) 15g
Modified bismaleimide (formula II I) 15g
Filler：Preparing spherical SiO 2 (HMDS modification) 50g
Curing agent：Methyl hexahydrophthalic anhydride (MHHPA) 5g
Curing agent accelerator：Three-(2 ethyl hexanoic acid) the salt 1g of 2,4,6- tri- (dimethylamino methyl) phenol
Diluent：1,2- cylohexanediol diglycidyl ethers 5g
Dispersant：Fatty acid polyethylene glycol ester 5g
Coupling agent:γ-glycidyl ether oxygen propyl methyldiethoxysilane 2g
Ion adsorbent：IXE500 2g
At 70 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilute
Agent, dispersant, coupling agent, ion adsorbent are released according to proportioning addition homogenizer stirring 90min, rotating speed 1700r/min；
Then stirring at low speed 20min, rotating speed 120r/min；24h is placed to be cured；The glue of curing is disperseed with 30KHz ultrasonic waves
30min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally obtains high quality underfill.Condition of cure：
130℃：5min, 150 DEG C：1min.
Embodiment 4
The formula of the Underfill adhesive composition of the present embodiment is as follows：
Modified epoxy (structural formula I) 15g
Modified bismaleimide (formula II I) 10g
Filler：Preparing spherical SiO 2 (modification of hexamethyl vinyl silazane) 55g
Curing agent：Methylnadic anhydride (MNA) 5g
Curing agent accelerator：Three-(2 ethyl hexanoic acid) the salt 1g of 2,4,6- tri- (dimethylamino methyl) phenol
Diluent：Diethylene glycol diglycidyl glycerin ether 5g
Dispersant：Fatty acid polyethylene glycol ester 5g
Coupling agent:β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane 2g
Ion adsorbent：DHT-4A 2g
At 70 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilute
Agent, dispersant, coupling agent, ion adsorbent are released according to proportioning addition homogenizer stirring 120min, rotating speed 1000r/
min；Then stirring at low speed 30min, rotating speed 100r/min；24h is placed to be cured；The glue of curing 30KHz ultrasonic waves
Scattered 30min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally obtains high quality underfill.Solidified bars
Part：130℃：5min, 150 DEG C：1min.
Embodiment 5
The formula of the Underfill adhesive composition of the present embodiment is as follows：
Modified epoxy (formula II) 10g
Modified bismaleimide (formula II I) 10g
Filler：Preparing spherical SiO 2 (modification of hexamethyl vinyl silazane) 60g
Curing agent：Sebacic dihydrazide (SPH) 5g
Curing agent accelerator：Three-(2 ethyl hexanoic acid) the salt 1g of 2,4,6- tri- (dimethylamino methyl) phenol
Diluent：Diethylene glycol diglycidyl glycerin ether 5g
Dispersant：Fatty acid polyethylene glycol ester 5g
Coupling agent:γ-glycidyl ether oxygen propyl methyldiethoxysilane 2g
Ion adsorbent：DHT-4A 2g
At 70 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilute
Agent, dispersant, coupling agent, ion adsorbent are released according to proportioning addition homogenizer stirring 120min, rotating speed 1200r/
min；Then stirring at low speed 30min, rotating speed 50r/min；24h is placed to be cured；The 30KHz ultrasound wavelength-divisions of the glue of curing
Dissipate 30min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally obtains high quality underfill.Condition of cure：
130℃：5min, 150 DEG C：1min.
Embodiment 6
The formula of the Underfill adhesive composition of the present embodiment is as follows：
Modified epoxy (formula II) 10g
Modified bismaleimide (formula II I) 10g
Filler：Silica (HMDS modification) 60g
Curing agent：CAPCURE3-800 5g, dodecenylsuccinic acid acid anhydride (DDSA) 5g
Curing agent accelerator：Three-(2 ethyl hexanoic acid) the salt 1g of 2,4,6- tri- (dimethylamino methyl) phenol
Diluent：1,2- cylohexanediol diglycidyl ethers 5g
Dispersant：Triethyl group hexyl phosphoric acid 2g
Coupling agent:γ-methacryloxypropyl trimethoxy silane 0.5g
Ion adsorbent：DHT-4A 1.5g.
At 70 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilute
Agent, dispersant, coupling agent, ion adsorbent are released according to proportioning addition homogenizer stirring 90min, rotating speed 1200r/min；
Then stirring at low speed 20min, rotating speed 70r/min；24h is placed to be cured；The glue of curing is disperseed with 30KHz ultrasonic waves
20min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally obtains high quality underfill.Condition of cure：
130℃：5min, 150 DEG C：1min.
Embodiment 7
The formula of the Underfill adhesive composition of the present embodiment is as follows：
Modified epoxy (formula II) 10g
Modified bismaleimide (formula II I) 10g
Filler：Silica (HMDS modification) 60g
Curing agent：CAPCURE3-800 5g, dodecenylsuccinic acid acid anhydride (DDSA) 5g
Curing agent accelerator：Three-(2 ethyl hexanoic acid) the salt 1g of 2,4,6- tri- (dimethylamino methyl) phenol
Diluent：1,2- cylohexanediol diglycidyl ethers 5g
Dispersant：Triethyl group hexyl phosphoric acid 3g
Coupling agent:γ-methacryloxypropyl trimethoxy silane 0.5g
Ion adsorbent：DHT-4A 0.5g.
At 70 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilute
Agent, dispersant, coupling agent, ion adsorbent are released according to proportioning addition homogenizer stirring 90min, rotating speed 1200r/min；
Then stirring at low speed 20min, rotating speed 70r/min；24h is placed to be cured；The glue of curing is disperseed with 30KHz ultrasonic waves
20min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally obtains high quality underfill.Condition of cure：
130℃：5min, 150 DEG C：1min.
Embodiment 8
The formula of the Underfill adhesive composition of the present embodiment is as follows：
Modified epoxy (formula II) 10g
Modified bismaleimide (formula II I) 5g
Filler：Silica (HMDS modification) 70g
Curing agent：CAPCURE3-800 5g
Curing agent accelerator：Three-(2 ethyl hexanoic acid) the salt 1g of 2,4,6- tri- (dimethylamino methyl) phenol
Diluent：1,2- cylohexanediol diglycidyl ethers 5g
Dispersant：Triethyl group hexyl phosphoric acid 2g
Coupling agent:γ-methacryloxypropyl trimethoxy silane 1g
Ion adsorbent：DHT-4A 1g.
At 70 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilute
Agent, dispersant, coupling agent, ion adsorbent are released according to proportioning addition homogenizer stirring 90min, rotating speed 1200r/min；
Then stirring at low speed 20min, rotating speed 70r/min；24h is placed to be cured；The glue of curing is disperseed with 30KHz ultrasonic waves
20min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally obtains high quality underfill.Condition of cure：
130℃：5min, 150 DEG C：1min.
Embodiment 9
The filler of the present embodiment is unmodified, and the formula of the Underfill adhesive composition of the present embodiment is as follows：
Modified epoxy (structural formula I) 10g
Modified bismaleimide (formula II I) 10g
Filler：Silica 60g
Curing agent：CAPCURE3-800 5g, dodecenylsuccinic acid acid anhydride (DDSA) 5g
Curing agent accelerator：Three-(2 ethyl hexanoic acid) the salt 1g of 2,4,6- tri- (dimethylamino methyl) phenol
Diluent：1,2- cylohexanediol diglycidyl ethers 5g
Dispersant：Triethyl group hexyl phosphoric acid 2g
Coupling agent:γ-methacryloxypropyl trimethoxy silane 0.5g
Ion adsorbent：DHT-4A 0.5g.
At 70 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilute
Agent, dispersant, coupling agent, ion adsorbent are released according to proportioning addition homogenizer stirring 90min, rotating speed 1200r/min；
Then stirring at low speed 20min, rotating speed 70r/min；24h is placed to be cured；The glue of curing is disperseed with 30KHz ultrasonic waves
20min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally obtains high quality underfill.Condition of cure：
130℃：5min, 150 DEG C：1min.
It is can be seen that from the comparison of above example 1-8 and embodiment 9 under conditions of other components unchangeds, addition is not
Modified filler, easily there is filler aggregation, cause the viscosity of product to increase, it is exactly to fill out that what the increase of viscosity was brought, which directly affects,
The reduction of effect is filled, easily occurs empty (Viod) and streamline (Flow Mark) bad phenomenon during filling, such as Fig. 6 institutes
Show, the filling effect of the unmodified embodiment 9 (left figure) of filler and filler modified embodiment 1 (right figure) is compared, wherein filling out
Expect that unmodified embodiment 9 has cavity and streamline (in figure shown in arrow).
Fig. 7 shows SEM (SEM) image of the underfill of embodiment 1, as a result shows that filler is equal
It is even scattered.
The performance test results of Underfill adhesive composition prepared by above-described embodiment 1-9 are as shown in table 1.
Table 1
The above embodiment of the present invention 1-5,7 synthesis Underfill adhesive compositions, by add modified epoxy and
Modified bismaleimide has obtained low viscosity --- mobility can be improved, high Tg --- reliability can be improved, and it is low
CTE --- reduce the probability that substrate, chip, scolding tin cause failure in cold cycling due to CTE difference, low water suction
Rate --- improve reliability, easily reprocess underfill.
The Underfill adhesive composition that embodiment 6 synthesizes, because the packing material size used is smaller (average grain diameter ＜ 20nm),
Easily aggregation, therefore viscosity is bigger than normal；The Underfill adhesive composition that embodiment 8 synthesizes, due to the higher (filler of filler proportion
Content ＞ 65%), therefore viscosity is bigger than normal；The Underfill adhesive composition that embodiment 9 synthesizes, because the filler used does not change
Property, easily aggregation, therefore viscosity is bigger than normal.But the Underfill adhesive composition that embodiment 6,8 and 9 synthesizes is respectively provided with height
Tg, low CTE and low water absorption characteristic, and embodiment 1-5,7 similar, therefore the underfill group that embodiment 6,8 and 9 synthesizes
Compound also reprocesses performance with good.
To underfill prepared by embodiment 1 and two best existing product UF3800 and the UF3810 (Chinese of in the market
Gao Letai companies) performance test and comparison is carried out, its result is as follows：
Table 2 shows a case that Tg is varied with temperature and changed, test condition with 10 DEG C/min speed from -75 DEG C~
220 DEG C of progress.
Table 2
| Temperature cycles | UF3800 | UF3810 | Embodiment 1 |
| Tg | 69 | 113 | 128 |
| 1 time | 72 | 98 | 128 |
| 2 times | 76 | 103 | 70 |
The result of table 2 is shown：After 2 circulations, the Tg of embodiment 1 is reduced to 70 DEG C from 128 DEG C, compared to UF3800 and
UF3810, the Tg changes of embodiment 1 are obvious, and Tg declines are bigger, and it is flexible better to illustrate, it is better to reprocess effect.Inventor also tests
The situation that embodiment 2-9 Tg is varied with temperature and changed, its result are substantially the same manner as Example 1.
Table 3 shows the result of temperature cycling test, 15 chips is placed on each plate, test condition is with 30min mono-
The speed of individual circulation represents cycle-index from -55 DEG C~125 DEG C progress temperature cycling tests, number, result such as " 0/15 " in table
Represent that 15 test chips carry out temperature cycling test, have 0 not by test, implication is analogized according to this for remaining.
Table 3
| Test object | Test condition | 400 times | 600 times | 800 times | 1200 times | 1400 times | 2000 times |
| UF3800 | - 55 DEG C~125 DEG C | 0/15 | 1/15 | 5/15 | 9/15 | 15/15 | —— |
| UF3808 | - 55 DEG C~125 DEG C | 0/15 | 1/15 | 3/15 | 4/15 | 12/15 | 14/15 |
| Embodiment 1 | - 55 DEG C~125 DEG C | 0/15 | 0/15 | 0/15 | 0/15 | 2/15 | 5/15 |
The result of table 3 shows：Embodiment 1 all passes through 1200 loop tests, hence it is evident that better than UF3800 and UF3808.Hair
A person of good sense is also tested for embodiment 2-9 temperature cycling test, and its result is substantially the same manner as Example 1.
Table 4 shows the result of drop test, weight：2.9Kg, height：1m；Result such as " 0/15 " represents 15 surveys in table
Try chip and carry out drop test, have 0 not by test, implication is analogized according to this for remaining.
Table 4
The result of table 4 shows：Embodiment 1 all passes through 4000 drop tests, hence it is evident that better than UF3800 and UF3808.Hair
A person of good sense is also tested for embodiment 2-9 drop test, and its result is substantially the same manner as Example 1.
Table 5 shows the result of cohesive force test, and SiN chips are bonded in 3mm2BT resin substrates on.
Table 5
Fig. 8 shows the bar of the Underfill adhesive composition of embodiment 2 and traditional underfill (UF3800) in heating
Under part, curve map that storage modulu diminishes with the rise of temperature, Instruments points of Universal V4.5A TA are used
Analysis.
As a result show：In environment temperature at 100 DEG C, the storage modulus of the underfill of embodiment 2 is more or less the same；Add
When heat is to 210 DEG C of (reprocessing temperature) left and right, the storage modulus of the underfill of embodiment 2 declines faster, more beneficial
In reprocessing.The storage modulus that inventor is also tested for the underfill of embodiment 1,3,4,5,7 diminishes with the rise of temperature
Curve, its result is substantially the same manner as Example 2.
Inventor have studied influence of the condition of cure to product glass transition temperature (Tg), be filled out with the bottom of embodiment 1
It is as shown in table 6 to fill the experimental result that glue is studied.
Table 6
| Condition of cure | Tg(DSC),℃ | Tg(DMA),℃ |
| 130℃：5min, 150 DEG C：1min | 128 | 155 |
| 120℃：5min, 150 DEG C：1min | 122 | 150 |
| 110℃：5min, 150 DEG C：1min | 115 | 138 |
| 100℃：5min, 150 DEG C：1min | 110 | 130 |
As a result show：Tg is higher, and the unfailing performance of product is better, as solidification temperature raises, the Tg of product after solidification
Rise, the raising of solidification temperature is favourable to product reliability.But if solidification temperature is too high, electronic component is had
Damage, so solidification temperature should be a suitable scope, product reliability was not only can guarantee that simultaneously but also will not be to electronics member device
Part damages, and general solidification temperature is arranged on less than 150 DEG C preferably.
Inventor have studied the angularity influence that solidification temperature encapsulates chip on FC-CSP, chip size 6.5mm*
6.5mm, 100 μm of chip thickness, substrate thickness are 2 layers of 0.17mm substrate packages.Studied with the underfill of embodiment 1
Experimental result it is as shown in table 7, show the angularity at 25 DEG C, 50 DEG C, 125 DEG C, 175 DEG C and 250 DEG C.
Table 7
As a result show：Angularity after condition of cure is filled to product has a great impact, and in general rule is solidification temperature
Degree is higher, and angularity is bigger.Positive number represents raised, negative number representation depression.Embodiment 1 uses 130 DEG C：5min, 150 DEG C：1min
Solidification, product is -88.65 μm in 250 DEG C of angularity after solidifying applied to the filling of 6.5mm*6.5mm chips, is set less than standard
- 90 μm of standard of meter.
Embodiment 10
The present embodiment and the difference of embodiment 1 are：Modified epoxy has the change shown in structural formula 1 in the present embodiment
Learn structural formula, wherein R1、R2、R3And R4Respectively structural formula 3, structural formula 4, structural formula 5, structural formula 6, pass through the conjunction of the present invention
Synthesized into route；Modified bismaleimide has the chemical structural formula shown in structural formula 11, wherein R5ForR1、R2、R3
And R4Respectively structural formula 12, structural formula 12, structural formula 13, structural formula 14, synthesized by the synthetic route of the present invention.
Embodiment 11
The present embodiment and the difference of embodiment 2 are：Modified epoxy has the change shown in structural formula 1 in the present embodiment
Learn structural formula, wherein R1、R2、R3And R4Respectively structural formula 3, structural formula 3, structural formula 5, structural formula 5, pass through the conjunction of the present invention
Synthesized into route；Modified bismaleimide has the chemical structural formula shown in structural formula 11, wherein R5ForR1、R2、R3
And R4Respectively structural formula 12, structural formula 13, structural formula 13, structural formula 12, synthesized by the synthetic route of the present invention.
Embodiment 12
The present embodiment and the difference of embodiment 3 are：Modified epoxy has the change shown in structural formula 2 in the present embodiment
Learn structural formula, wherein R1And R2Respectively structural formula 6, structural formula 8, synthesized by the synthetic route of the present invention；Modified span carrys out acyl
Imines has the chemical structural formula shown in structural formula 11, wherein R5ForR1、R2、R3And R4Respectively structural formula 12,
Structural formula 13, structural formula 14, structural formula 14, synthesized by the synthetic route of the present invention.
Embodiment 13
The present embodiment and the difference of embodiment 4 are：Modified epoxy has the change shown in structural formula 2 in the present embodiment
Learn structural formula, wherein R1And R2Respectively structural formula 7, structural formula 9, synthesized by the synthetic route of the present invention；Modified span carrys out acyl
Imines has the chemical structural formula shown in structural formula 11, wherein R5ForR1、R2、R3And R4It is structural formula 15, and
And n values are 1 in structural formula 15, m values are 3, p values are 2, synthesized by the synthetic route of the present invention.
Embodiment 14
The present embodiment and the difference of embodiment 5 are：Modified epoxy has the change shown in structural formula 1 in the present embodiment
Learn structural formula, wherein R1、R2、R3And R4Respectively structural formula 7, structural formula 6, structural formula 9, structural formula 10, pass through the synthesis of the present invention
Route synthesizes；Modified bismaleimide has the chemical structural formula shown in structural formula 11, wherein R5For
R1、R2、R3And R4Respectively structural formula 15, structural formula 13, structural formula 14, structural formula 12, closed by the synthetic route of the present invention
Into；And the filler in the present embodiment is the filler of unmodified processing.
Above content is to combine specific embodiment further description made for the present invention, it is impossible to assert this hair
Bright specific implementation is confined to these explanations.For general technical staff of the technical field of the invention, do not taking off
On the premise of from present inventive concept, some simple deduction or replace can also be made.
Claims (18)
1. a kind of Underfill adhesive composition, it is characterised in that the composition by weight percentage, includes following component：
Modified epoxy 5wt%~15wt%, modified bismaleimide 5wt%~15wt%, filler 50wt%~70wt%, Gu
Agent 5wt%~15wt%, curing agent accelerator 0.2wt%~1wt%, diluent 5wt%~10wt%, dispersant 2wt%
~8wt%, coupling agent 0.5wt%~2wt%, ion adsorbent 0.1wt%~2wt%；Wherein described modified epoxy is
Polyester modified epoxy resin and/or carbonate-modified epoxy resin, the modified bismaleimide are acrylate modified double
Maleimide and/or organic-silicon-modified BMI；
The modified epoxy has structural formula 1 or the chemical structural formula shown in structural formula 2：
Wherein, R1、R2、R3And R4It is each independently selected from aliphatic ester, alicyclic ester, aromatic ester, carbamate or carbonic acid
Ester, but R1、R2、R3And R4It is asynchronously carbamate.
2. composition according to claim 1, it is characterised in that the modified bismaleimide has formula II I
Shown chemical structural formula：
3. composition according to claim 1 or 2, it is characterised in that the filler is silane coupler modified filler.
4. composition according to claim 3, it is characterised in that the silane coupler be selected from HMDS,
At least one of hexamethyl vinyl silazane and vinylethoxysilane.
5. composition according to claim 1 or 2, it is characterised in that the filler is selected from aluminium skimmings, aluminium powder, aluminum borate crystal whisker
Palpus, aluminum oxide, anthracite, sodium antimonate, antimony trioxide, apatite, cigarette ash, barium metaborate, barium sulfate, barium titanate, bismuth oxide, oxygen
Change boron, calcium carbonate, calcium hydroxide, calcium sulfate, carbon black, ceramic microsphere, clay, diatomite, ferrite, feldspar, bead, gold,
Graphite, afwillite, magnesia, magnesium hydroxide, molybdenum, molybdenum disulfide, nickel, polymer filler, float stone, lardite, sepiolite, two
At least one of silica, silica gel, silver powder, talcum, titanium dioxide, zeolite, Firebrake ZB, zinc sulphide.
6. composition according to claim 1 or 2, it is characterised in that the filler is selected from Attagel, bentonite and kaolinite
At least one of soil.
7. composition according to claim 1 or 2, it is characterised in that the filler is selected from rubber grain.
8. composition according to claim 5, it is characterised in that the filler is selected from silica, titanium dioxide or silicon
Magnesia.
9. composition according to claim 1 or 2, it is characterised in that the curing agent is selected from maleic anhydride, adjacent benzene
Dicarboxylic acid anhydride and its derivative, trimellitic anhydride, pyromellitic dianhydride, methyl tetrahydro phthalic anhydride, HHPA, THPA,
3,3,4,4- benzophenones tetracarboxylic dianhydride, dodecenylsuccinic acid acid anhydride, methylcyclohexene tetracarboxylic dianhydride, methyl hexahydrophthalic anhydride, methyl
Carbic anhydride, benzoyl hydrazine, sebacic dihydrazide, methylimidazole, 2- heptadecyl imidazoles, 2- undecyl imidazoles, 2- second
Base -4-methylimidazole, 1- cyanoethyls -2-ethyl-4-methylimidazole, three second hydroxylamines, 3,4- 3,5-dimethylphenyl subotituted dicyardiamides
At least one of.
10. composition according to claim 1 or 2, it is characterised in that the curing agent is selected from 2-methylimidazole, 1- first
At least one of base imidazoles.
11. composition according to claim 1 or 2, it is characterised in that the curing agent accelerator is selected from benzyl trimethyl
Ammonium chloride, triethanolamine borate, triethanol amine titanate, tin octoate, quaternary alkylphosphonium salts, dicyandiamide, DBU carbonate, imidazoles gold
Belong to salt, diethylaminopropylamine, benzyl dimethylamine (BDMA), N, accelerine, 2-ethyl-4-methylimidazole, 2,4,6- tri-
The three of (dimethylamino methyl) phenol-(2 ethyl hexanoic acid) salt, three oleates of 2,4,6- tri- (dimethylamino methyl) phenol, three
At least one of 2 ethyl hexanoic acid salt of (dimethylamino methyl) phenol.
12. composition according to claim 1 or 2, it is characterised in that the diluent contracts selected from 1,2- cyclohexanediols two
Water glycerin ether, 1,4- butanediol diglycidyl ethers, 1,4 cyclohexane dimethanol glycidol ether, neopentyl glycol 2-glycidyl
Ether, ethylene glycol diglycidylether, 1,6 hexanediol diglycidylether, diethylene glycol diglycidyl glycerin ether, diethylene glycol (DEG) two contract
At least one of water glycerin ether, trihydroxymethylpropanyltri diglycidyl ether.
13. composition according to claim 1 or 2, it is characterised in that the dispersant is selected from waterglass, tripolyphosphate
It is sodium, calgon, sodium pyrophosphate, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, poly-
At least one of acrylamide, guar gum and fatty acid polyethylene glycol ester.
14. composition according to claim 1 or 2, it is characterised in that the coupling agent is selected from silane coupler and metatitanic acid
At least one of ester coupling agent.
15. composition according to claim 14, it is characterised in that the silane coupler is selected from the second of γ-aminopropyl three
TMOS, 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane,
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl methyldiethoxysilane, N- β-(ammonia second
Base)-γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, γ-piperazinopropyl methyl dimethoxy
In TMOS, (2- methoxy ethoxies) silane of vinyl three and β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane
It is at least one.
16. composition according to claim 14, it is characterised in that the titanate coupling agent is selected from three iso stearate titaniums
Isopropyl propionate, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, Di(dioctylpyrophosphato) ethylene titanate,
Tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters, monoalkoxy unrighted acid titanate esters and pyrophosphoric acid type list alkane
At least one of epoxide class titanate esters.
A kind of 17. method for preparing the composition described in claim any one of 1-16, it is characterised in that methods described includes：
At 65 DEG C~75 DEG C, by modified epoxy, modified bismaleimide, filler, curing agent, curing agent accelerator, dilution
Agent, dispersant, coupling agent, ion adsorbent add homogenizer stirring according to proportioning, and rotating speed is 700~1700r/min, when
Between be 90~120min；Then stirring at low speed, rotating speed are 20~120r/min, and the time is 20~30min；18~30h is placed to enter
Row curing；The glue of curing disperses 20~30min with 20~40KHz ultrasonic waves；Dispersion liquid is transferred to vacuum degasing machine after filtering
Middle deaeration, finally give the composition.
18. according to the method for claim 17, it is characterised in that methods described includes：At 70 DEG C, by modified epoxy tree
Fat, modified bismaleimide, filler, curing agent, curing agent accelerator, diluent, dispersant, coupling agent, ion adsorbent
Homogenizer stirring is added according to proportioning, rotating speed is 700~1700r/min, and the time is 90~120min；Then low speed stirs
Mix, rotating speed is 20~120r/min, and the time is 20~30min；24h is placed to be cured；The glue of curing 30KHz ultrasonic waves
Scattered 20~30min；Dispersion liquid is transferred to deaeration in vacuum degasing machine after filtering, finally gives the composition.
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| JP6628089B2 (en) * | 2015-12-14 | 2020-01-08 | Dic株式会社 | Curable composition and adhesive |
| CN105626528A (en) * | 2016-02-29 | 2016-06-01 | 芜湖环球汽车配件有限公司 | Water ring vacuum pump |
| CN106221640B (en) * | 2016-08-31 | 2021-10-01 | 国网辽宁省电力有限公司丹东供电公司 | Oil surface adhesive and repairing method using same |
| CN106634441A (en) * | 2016-12-28 | 2017-05-10 | 安徽燎原电器设备制造有限公司 | Double-ingredient waterborne epoxy paint for distribution cabinet case |
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| WO2021097649A1 (en) * | 2019-11-19 | 2021-05-27 | 南京中弘华飞信息科技有限公司 | Soft prosthesis composite material and preparation method therefor |
| CN111440285A (en) * | 2020-01-20 | 2020-07-24 | 长安大学 | Preparation method of organic silicon/polyurethane/bismaleimide modified epoxy resin |
| CN111394053B (en) * | 2020-03-03 | 2021-10-26 | 华南理工大学 | Non-flowing underfill with welding assisting function and preparation method thereof |
| CN111518499A (en) * | 2020-06-08 | 2020-08-11 | 武汉市三选科技有限公司 | Underfill adhesive with stable adhesive force at high temperature and preparation method thereof |
| CN114804716B (en) * | 2022-05-20 | 2023-07-25 | 西北民族大学 | Modified clay, preparation method and application thereof, and glue-free fiber board |
| CN114854348B (en) * | 2022-06-14 | 2023-03-24 | 广东菊兰新型材料科技有限公司 | Acid-base-resistant and high-low-pressure-resistant chimney anticorrosion elastic adhesive and preparation method thereof |
| CN117567973B (en) * | 2024-01-16 | 2024-04-09 | 深圳先进电子材料国际创新研究院 | High Tg underfill and preparation method thereof |
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