CN104877575B - A kind of normal temperature solidified BGA package reinforced glue and preparation method and application - Google Patents
A kind of normal temperature solidified BGA package reinforced glue and preparation method and application Download PDFInfo
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- CN104877575B CN104877575B CN201510340436.XA CN201510340436A CN104877575B CN 104877575 B CN104877575 B CN 104877575B CN 201510340436 A CN201510340436 A CN 201510340436A CN 104877575 B CN104877575 B CN 104877575B
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- bga package
- normal temperature
- glue
- reinforced glue
- acrylic resin
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- 239000003292 glue Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 229920001187 thermosetting polymer Polymers 0.000 claims description 35
- 239000004925 Acrylic resin Substances 0.000 claims description 30
- 229920000178 Acrylic resin Polymers 0.000 claims description 30
- 230000003014 reinforcing effect Effects 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 13
- 239000004814 polyurethane Substances 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 239000012188 paraffin wax Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000003673 urethanes Chemical class 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000002045 lasting effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 14
- 238000007711 solidification Methods 0.000 abstract description 14
- 230000008023 solidification Effects 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 5
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005538 encapsulation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
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- 238000007596 consolidation process Methods 0.000 description 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 230000005489 elastic deformation Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RVCKCEDKBVEEHL-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzyl alcohol Chemical compound OCC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl RVCKCEDKBVEEHL-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical class OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
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- XCLIHDJZGPCUBT-UHFFFAOYSA-N dimethylsilanediol Chemical class C[Si](C)(O)O XCLIHDJZGPCUBT-UHFFFAOYSA-N 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
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- 150000002367 halogens Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of normal temperature solidified BGA package reinforced glue and preparation method and application, belong to a kind of organics modifications synthetic system, be remarkably improved the stability after chip BGA package, improve the anti-drop of encapsulating products.BGA package reinforced glue condition of cure disclosed by the invention is simple, room temperature is curable, avoiding reinforced glue in the prior art needs to be heating and curing the complicated technology of the wafer damage that brings and ultra-violet curing, solidify quick when using but use preceding shelf-stable, it is to avoid because the poor problem of the storge quality for accelerating solidification to bring；And the glue removal after solidifying is convenient, can also be removed photoresist completely under normal temperature, overcomes the defect that prior art needs heating just to remove photoresist, and protects the quality of bga chip, effectively improves product yield.
Description
Technical field
The invention belongs to electronic material preparing technical field, and in particular to a kind of normal temperature solidified BGA package reinforced glue and
Its preparation method and application.
Background technology
Packaging plastic refer to some components can be sealed, encapsulate or embedding an electron-like glue or adhesive,
The effect such as waterproof, protection against the tide, shockproof, dust-proof, radiating, secrecy can be played after embedding.Common packaging plastic mainly includes epoxies
Packaging plastic, organic silicon packaging plastic, polyurethane packaging plastic and ultraviolet photo-curing packaging plastic etc..Epoxies packaging plastic：Typically
All it is rigid, hard, major part needs to be used after reconciling for double-component, heating could solidify the need for small part one-component.Have
Machine silicon class wrapper glue is nearly all softer, elastic, identical with epoxy, and wherein most is that double-component needs to be used after reconciling, few
Heating could solidify the need for the one-component of part.
With the development of integrated circuit technique, silicon Single-Chip Integration degree is improved constantly, and the encapsulation to integrated circuit is required more
Plus it is strict, the need for developing for satisfaction, BGA arises at the historic moment, and it is contour that current BGA is once turning into south, north bridge chips on CPU, mainboard
Density, high-performance, the optimal selection of many pin packages.
Bga structure chips mainly have two kinds with the interconnection mode of substrate：Wire bonding and flip chip bonding.Tension is strong
Degree, characterizes the drag of material maximum uniform plastic deformation.Before maximum tension stress is born, deformation is uniformity to tensile sample
, but after, metal starts necking occur, that is, produce and concentrate deformation.When I/O numbers<When 600, wire bonding into
This is less than flip chip bonding, and processes flexible.But para-linkage silk requirement it is higher, it is necessary to have in good, low radian long arc it is linear
Can, and good toughness and tensile strength.So its shortcoming is the existing welding precision for setting having reached capacity.
Due to pin number huge in high density circuit board, revolutionary challenge is brought to encapsulation technology.Work as mobile phone
Or the bga chip in other handheld devices is when being packaged, there is welding rosin joint, asked with steam bubble etc. in traditional sealing means
Can topic, drop test and repeatedly case action generation grave danger be undergone to the component in product.In order to ensure bga chip
Weld without exception on PCBA, the glue reinforced during BGA package is studied one after another by many Electronics Factories, to improve anti-drop, reach and add
Gu the purpose of component.
The reinforcing mode of BGA package is roughly divided into two kinds on the market at present：One kind is underfill, using epoxy resin,
By solidifying 8 ~ 20mins under the hot conditions in pot arch or baking box；Another kind be using UV curing materials, by
UV irradiation solidifications are carried out in the UV-device such as UV stoves or LED area light source.Both modes are not required to more than 100 degrees Celsius
High temperature be exactly to need the accurate complicated equipment could to complete solidification process, increased manufacturing process, reduce production efficiency, increase
Production cost is added, the heat produced in production process does not carry out positive effect to environment yet band, neither energy-conservation is also not environmentally.
When chip or component SMT encapsulation occur rosin joint, air etc. it is abnormal when, it is necessary to heavy industry, the purpose of heavy industry is
To remove reinforced glue, complete to repeat a upper processing procedure.Existing BGA package reinforced glue remove when can only use heating, but root
Different according to colloidal materials, heating-up temperature is totally different, and temperature is too high sometimes can cause irreversible damage, removing glue side to periphery component
Method is single, make originally can the PCB working plates of heavy industry become " chicken ribs " of " tastele when eaten but a pity to throw away ".
The content of the invention
It is an object of the invention to overcome above-mentioned deficiency, there is provided a kind of normal temperature solidified BGA package reinforced glue, belong to a kind of
Organics modifications synthetic system, is remarkably improved the stability after chip BGA package, improves the anti-drop of encapsulating products.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of normal temperature solidified BGA package is reinforced
Glue, by mass parts, including following components：
Ludox 50-60 parts
30-40 parts of thermosetting acrylic resin prepolymer
Paraffin 1-5 parts
1-3 parts of aqueous polyurethane compound
In the Ludox, the mass fraction of silica is 30-50%；
The thermosetting acrylic resin prepolymer is by monofunctional acrylates' ester monomer with nitrogenous vinyl monomer through anti-
Should be formed；
The molecular weight of the thermosetting acrylic resin prepolymer is 3500-5000, and molecular weight distribution is 1.5-1.7；
The molecular weight of the urethanes is 10000-14000.
Ludox of the invention is inorganic component Ludox high, and concentration reaches 30-50%, and silica particle size range is 20-
30nm, when Ludox moisture evaporation, hydroxyl and the PCB substrate and chip on micelle surface form strong active force so that glue
Body particle is securely attached to form silica combination between body surface, particle, can good sticky object.
Thermosetting acrylic resin prepolymer refers to acrylate monomer as basis, with vinyl monomer through certain
The polymer for being formed is reacted, with substantial amounts of reactive group, the reactive group of the urethanes in glue by adding
Reaction, ultimately forms network structure, reaches insoluble insoluble thermosetting effect, can lift the hardness and intensity of glue, and make glue
Water mechanical performance, chemical resistance are greatly improved.Thermosetting acrylic resin prepolymer of the invention is by simple function group propylene
Acid ester monomer and the reacted formation of nitrogenous vinyl monomer, monofunctional acrylates' ester monomer, nitrogenous vinyl monomer
Structural formula is respectively：、。
Thermosetting acrylic resin prepolymer of the invention retains all of heteroaromatic of monomer and phosphate group, heteroaromatic
Resin system solidifies the filling of post-crosslinking density, improves the intensity of glue；Phosphate group also acts as the effect of coupling, not only can be with
Hydroxyl reaction with silicon face in Ludox forms phosphate, increases system internal bond strength, can also be with substrate and silicon core
The anti-biochemical coupled action in piece surface, the active force of formation is much larger than physical absorption power, due to the generation of chemical bond, greatly improves
The adhesive property of whole system, it is ensured that consolidation effect.Thermosetting acrylic resin prepolymer is the resin body in glue, its
Remaining component is infiltrated by it, its curing performance to glue, contraction when particularly solidifying, has to the expansive force of chip pin solder joint
Very big influence, thermosetting acrylic resin prepolymer shrinkage prepared by the above-mentioned monomer polymerization of use of the invention is good,
Used as resin is contained, good with other components compatibility, the reinforcing adhesive curing time delay malleability for obtaining is good, will not extrude chip welding spot,
The CTE between chip and substrate is reduced, plastic deformation is converted into elastic deformation, it is to avoid existing glue stress in solidification is big
Touching solder joint, so as to cause the defect of solder joint displacement.
Preferably, react to form thermosetting acrylic resin with nitrogenous vinyl monomer in monofunctional acrylates' ester monomer
During prepolymer, monofunctional acrylates' ester monomer is 1 with the mol ratio of nitrogenous vinyl monomer:（1.25-1.35）.This is not letter
It is single in order to react complete, and conventional meanses for slightly improving a certain material rate for using, but the setting simple function of creativeness
The mol ratio of acrylate monomer and nitrogenous vinyl monomer is rolled into a ball, vinyl major part and simple function on nitrogenous vinyl monomer
Vinyl crosslinking on group's acrylate monomer, while there is part meeting to form ehter bond with hydroxyl, is further increasing prepolymer
While cross-link intensity, assign prepolymer certain pliability again, with this prepolymer as matrix resin, for reinforced glue, solid
Ductility is good during change, and cure shrinkage is suitable, has certain toughness after solidification, while itself rigid radical and and other components
Crosslinking ensure that hardness, intensity, solidification rate and the anti-shearing, tensile strength of glue, achieve unexpected effect.
Meanwhile, in the present invention, monofunctional acrylates' ester monomer carries P elements, element silicon, nitrogenous vinyl monomer band
There is nitrogen, both react the reaction of formation, and to form thermosetting acrylic resin prepolymer not only heat-resist, with PCB substrate
（And silicon）Adhesive strength is high, is conducive to improving the adhesive force of chip and substrate layer, in the case of being particularly heated, still can
Keep chip bonding with base material；Particularly, the resin system can form cooperative flame retardant effect, can produce the silicon fire-retardant effect of nitrogen phosphorus
Should, the fire resistance of system is improved, in the case where fire conditions are met, phosphorus source is intercepted, nitrogen source expands, silicon source is heat-resisting, three's collaboration, can
Spread with retarded combustion, progressively reach flame retardant effect；And avoid such as microcosmic concentration effect that filler fire retardant brings etc.
Harmful effect.This be existing reinforced glue without effect, but fire-retardant is but performance necessary to electronic product, while also needing to keep away
Exempt from the acyclic environment friendly flame-retardant factor such as halogen, the invention propose can be fire-retardant reinforced glue, there is provided existing reinforced glue is not
The performance for possessing.
Urethanes are polyurethanes, with aminated compounds（Ethylenediamine）It is chain extender, by organic two isocyanide
Acid esters or polyisocyanate compound are formed with dihydroxy or polyol addition polymerization, and hydrophilic radical is introduced in polyurethane chain
（Generally carboxyl, amido）And obtain being dissolved in the aqueous polyurethane compound of water；Its contain highly polar carbamate groups,
Amido etc., the reactive group carried with thermosetting acrylic resin prepolymer（Hydroxyl）Reaction, can obtain build cross-linked network
Structure；The features such as with high intensity, high abrasion and solvent resistant, improve the toughness of glue.
Paraffin is hydrocarbon compound, and used as organic matter, it is good with system other compositions compatibility, can be with adjustable rooting glue
Viscosity and can improve product ageing resistance and increase pliability.
The molecular weight of thermosetting acrylic resin prepolymer of the present invention is 3500-5000, and molecular weight distribution is 1.5-1.7,
Strand has certain length in prepolymer, does not crosslink, and institute's band reactive group is more, is evenly distributed, in Ludox
Under promotion, can be reacted with the reactive group of polyurethane, there is no crosslinking points so that in course of reaction, acrylic molecules chain maximum journey
Being reacted with other components for degree, improves overall compatibility, while molecular weight distribution is small, it is ensured that the uniformity of reaction, will not go out
Existing defect centrostigma；For the purposes of increasing reactivity, the combination property of solidified after-product, the molecular weight of urethanes are improved
It is 10000-14000；Molecular weight is too small, causes small segment excessive so that system crosslinking degree is low after solidification, and molecular weight is excessive,
System reflecting point is few, can equally slacken the crosslinking of molecule interchain.
Reinforcing glue composition of the invention is reasonable, acted synergistically between each component strong, it is to avoid the imperfect tape of a certain component
The problem that the glue combination property come declines.The excellent in adhesion of glue is reinforced, silicon base chip and resin can be well bonded
Glass cloth base PCB substrate, causes chip and substrate strong bonded after solidification, reach the effect of BGA package reinforcing；One side silicon is molten
Glue surface carries great amount of hydroxy group, can form strong Hyarogen-bonding with body surface, can also be with such as resin primary surface
Amino reaction produces chemical interactions, and Ludox is good with silicon compatibility, beneficial to both attachments；On the other hand, thermosetting
The organic matters such as acrylic resin prepolymer, urethanes all carry substantial amounts of reactive group, can chip and substrate it
Between form effective active force, good with resin boundary surface effect in pcb board, beneficial to both attachments, and organic matter carries base
Group can react with the hydroxyl of Ludox, form three-dimensional build cross-linked network, including Ludox micelle multi-silicate grain
Son reacts to each other tridimensional network, acrylate copolymer tridimensional network, the three-dimensional netted knot of acroleic acid polyurethane to be formed
Cross-linked structure between structure and silica segment and polymer molecular chain, various cross-linked structures cross one another, and glue is effectively ensured
Stability, improve adhesive force of the glue to sticky object, rationally, high strength after curing, toughness is high for system crosslinking degree, it is to avoid
The fragility of inorganic matter glue, the easy to cracking of thermosetting cement.
The invention also discloses above-mentioned normal temperature solidified BGA package reinforced glue preparation method, comprise the following steps, silicon is molten
Glue is poured into container A；Thermosetting acrylic resin prepolymer is put into container B, is stirred, then by the thermosetting third after stirring
Olefin(e) acid resin prepolymer is added in Ludox, stirring；Then urethanes are added, lasting stirring；It is eventually adding paraffin,
Normal temperature solidified BGA package reinforced glue is obtained after stirring.Following steps are specifically included, Ludox is poured into container A, maintain temperature
Spend is 25 DEG C；Thermosetting acrylic resin prepolymer is put into container B, 1h is stirred in 80 DEG C, then by thermoset acrylics
Resin prepolymer is added in Ludox, stirs 0.5h；Then by urethanes addition container A, 2h is persistently stirred；Finally
By in paraffin addition container A, normal temperature solidified BGA package reinforced glue is obtained after stirring 0.5h.Go out container encapsulation, can be according to client
The viscosity of demand is in container A plus paraffin adjusts glue viscosity.
In above-mentioned technical proposal, the invention by the first pre- thermal agitation of thermosetting acrylic resin prepolymer, then add
Enter in Ludox, be conducive to the dispersion of organic-inorganic thing, overcome prior art and add inorganic matter while organic matter is stirred
The inorganic matter for bringing such as gathers at the bad phenomenon；Paraffin is eventually adding, the mixing of main substance is not interfered with, viscosity tune is also allowed for
Control；And the present invention is stirred after novel substance is mixed, fully dispersed each component, be conducive to system uniformity, reduce the flaw
Fault.
Reinforcing glue of the invention need not add solvent, not only beneficial to environmental protection, it is important to avoid excessive organic molten
Agent is to the adverse effect such as the corrosion at accurate chip package interface；Without the curing process such as heating, ultraviolet, room temperature can be solid
Change, solidified after-product cementability, mechanical property are splendid, comprehensive good；Ludox not only its very strong bonding effect, silicon unit therein
Element, hydroxyl play catalytic action to the cross-linking reaction of organic matter, accelerate the reaction between organic matter functional group, again can be with organic matter shape
Into cross-linked structure so that after glue normal temperature cure, excellent performance meets BGA reinforcement criterias.
The reinforcing that BGA package reinforced glue of the invention can be used for after chip BGA package, after SMT part pieces cross stove,
Above-mentioned BGA package reinforced glue on the angle points of BGA tetra-, room temperature a few minutes are solidification, so as to complete to reinforce；In case of part is reprocessed,
When needing removing glue, it is only necessary to a small amount of solvent, reinforced glue is can remove under normal temperature, it is particularly, of the invention to add beneficial to fetching for chip
Solid glue can also be removed using mode of heating, temperature when heat removes photoresist temperature far below existing removing glue.Therefore the invention also discloses
Application of the above-mentioned normal temperature solidified BGA package reinforced glue in the reinforcing of chip BGA package.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art:
1st, BGA package reinforced glue condition of cure disclosed by the invention is simple, room temperature is curable, it is to avoid existing skill
Reinforced glue needs to be heating and curing the complicated technology of the wafer damage that brings and ultra-violet curing in art, solidify when using it is quick still
Use preceding shelf-stable, it is to avoid because accelerating the problem of the storge quality difference that solidification brings；And the glue removal side after solidifying
Just, also can completely be removed photoresist under normal temperature, overcome the defect that prior art needs heating just to remove photoresist, protect the matter of bga chip
Amount, effectively improves product yield.
During the reinforcement process that the 2nd, BGA package reinforced glue disclosed by the invention is used for after chip BGA package, about 5 points under normal temperature
Colloid is curable after clock, meets product requirement；From the shear strength test of glue, the room temperature intensity of 10 minutes and 48h
It is closer to, it is believed that be fully cured after 10；Relative to similar application product, curing apparatus and loss can be saved.
3rd, elasticity is big after BGA package of the invention reinforces adhesive curing, after its reinforcement BGA package, product mechanical property
It is good, compared with the sample that existing UV glue is reinforced, tensile strength lifting 10%；Compared with sample is not reinforced, tensile strength improves 26%.
4th, BGA package reinforced glue composition of the invention is reasonable, and compatibility is good between each component, greater homogeneity, convenient storage,
It is suitable for tetra- jiaos of edge bindings of BGA；Glue after solidification except excellent in mechanical performance, also with excellent surface insulation impedance,
The sheet resistance of 24h, 96h and 168h is all higher than 108ohms。
5th, BGA package reinforcing adhesive curing time delay malleability of the invention is good, will not extrude chip welding spot, reduces chip and substrate
Between CTE, plastic deformation is converted into elastic deformation, it is to avoid existing glue stress big touching solder joint in solidification so that
Cause solder joint displacement, final influence chip performance even makes the invalid defect of chip；Advantageously ensure that the quality and finished product of product
Rate, reduces scrappage.When substrate is impacted, reduce the relative deformation of substrate and chip in Z-direction, and then reach protection
Solder joint.
6th, the cooperative flame retardant that formed in resin system of the invention is acted on, and silicon nitrogen can be produced in disclosed reinforced glue
Phosphorus fire retarding effect, improves the fire resistance of system, and in the case where fire conditions are met, phosphorus source is intercepted, nitrogen source expands, silicon source is heat-resisting, and three
Person cooperates with, and can be spread with retarded combustion, progressively reaches flame retardant effect, achieves unexpected effect.
Brief description of the drawings
Fig. 1 is applied in BGA package consolidation effect figure for reinforced glue of the present invention；
Fig. 2 is using BGA package reinforcing product removing glue design sketch after reinforced glue of the present invention.
Specific embodiment
The synthesis of the monofunctional acrylates' ester monomer of synthesis example one
To addition 12mL hydroxy acrylic acids, 5ml Dimethylsilanediols and 100ml absolute ethyl alcohols and 1g amino in there-necked flask
Sulfonic acid, is refluxed reaction 3 hours, and cooling is filtrated to get liquid；Again to adding the 85% anhydrous second of phosphoric acid 2ml, 50ml in liquid
Alcohol, backflow, stirring reaction 10 hours, through silica gel column chromatography, solvent is dichloromethane, obtains weak yellow liquid, as single official
Acrylate monomer can be rolled into a ball,1H NMR (400 MHz, CDCl3) δ 5.58 (s, -C=CH 2 , 1H), 6.11 (s, -C= CH 2 , 1H), 1.85(s, CH 3 , 3H);31P-NMR(ppm):1.11。
Embodiment one：The preparation of thermosetting acrylic resin prepolymer
According to the constitutive molar ratio example and response parameter of table 1, first by benzoyl peroxide（It is acrylic monomers quality
3%）In dioxane addition reactor, backflow is heated to, is subsequently adding monofunctional acrylates' ester monomer, nitrogenous vinyl
Then monomer, back flow reaction is cooled to 60 DEG C, and vacuum removal solvent is eventually adding hydramine（It is the 5% of acrylic monomers quality）,
Column chromatography obtains thermosetting acrylic resin prepolymer, and it is water-soluble, and molecular weight and molecular weight distribution are shown in Table 1.
The acrylic monomers of table 1 is constituted and molecular weight of product
| Group | A | B | C | D |
| Monofunctional acrylates' ester monomer | 1 | 1 | 1 | 1 |
| Nitrogenous vinyl monomer | 1.25 | 1.3 | 1.35 | 1.31 |
| Reaction time | 1 hour | 1.5 hours | 2 hours | 4 hours |
| Prepolymer molecular weight | 3600 | 4000 | 4800 | 6200 |
| Prepolymer molecular weight is distributed | 1.52 | 1.57 | 1.59 | 1.61 |
Monofunctional acrylates' ester monomer, the structural formula of nitrogenous vinyl monomer are respectively：
、。
Embodiment two：The preparation of reinforced glue
By the mass parts of table 2, Ludox is poured into container A, it is 25 DEG C to maintain temperature；Thermosetting acrylic resin is pre-
Polymers is put into container B, and 1h is stirred in 80 DEG C, then by thermosetting acrylic resin prepolymer addition Ludox, is stirred
0.5h；Then by aqueous polyurethane compound addition container A, 2h is persistently stirred；Finally by paraffin addition container A, stir
Normal temperature solidified BGA package reinforced glue is obtained after 0.5h；Go out container encapsulation.
The reinforced glue of table 2 is constituted（Mass parts）
| Group | Ludox | Thermosetting acrylic resin prepolymer | Aqueous polyurethane compound | Paraffin |
| 1 | 50 | 30（A） | 1 | 1 |
| 2 | 55 | 40（B） | 1 | 3 |
| 3 | 56 | 35（C） | 2 | 4 |
| 4 | 60 | 40（A） | 3 | 5 |
| 5 | 58 | 38（B） | 2 | 2 |
| 6 | 52 | 40（D） | 2 | 3 |
Wherein, 30（A）Represent that thermosetting acrylic resin prepolymer is 30 parts, be the A groups thermosetting third in embodiment one
Olefin(e) acid resin prepolymer.
Embodiment three：Reinforced glue application
Above-mentioned reinforced glue is applied and is reinforced in BGA package.After chip is mounted on pcb board through BGA, chip and pcb board it
Between fill BGA package reinforced glue, normal temperature cure 10 minutes complete the reinforcing to chip BGA package.Shape is protected after glue curing
Hold good, without caving in and deforming, lustrous surface after solidification has slight elasticity.
Comparative example one
After chip is mounted on pcb board through BGA, epoxy glue is filled between chip and pcb board（Loctite 3549）, in
130-150 DEG C solidifies 15 minutes, that is, complete the reinforcing to chip BGA package.
Comparative example two
After chip is mounted on pcb board through BGA, different SGA water (Loctite is filled between chip and pcb board
190024 / 3705;EICT UV3200), it is ultraviolet（The nm of source exposure intensity@365）Solidification 5 seconds, that is, complete to seal chip BGA
The reinforcing of dress.
Performance test is carried out to the product after above-mentioned reinforcing, while reinforced glue injected into mould, after normal temperature cure 10 minutes,
Oxygen index (OI) test is carried out, 3 are the results are shown in Table.
The performance test results of the product after the reinforcing of table 3
| Group | Shear strength/N | Tensile strength/N | Table insulation impedance/109ohms | Glass transition temperature/DEG C | Oxygen index (OI) |
| Group 1 | 3.0 | 252 | 1.09 | 80 | 28 |
| Group 2 | 3.3 | 240 | 1.07 | 75 | 28 |
| Group 3 | 2.8 | 243 | 1.07 | 77 | 28 |
| Group 4 | 2.9 | 249 | 1.08 | 77 | 27 |
| Group 5 | 2.8 | 245 | 1.08 | 76 | 27 |
| Group 6 | 2.6 | 241 | 1.07 | 66 | 27 |
| Comparative example one | 2.3 | 221 | 0.91 | 38 | - |
| Comparative example two | 2.2 | 219 | 1.01 | 67 | - |
Reworkable property is tested
Be respectively adopted solvent removing glue method and heating removing glue method to group 1, group 5, comparative example one, comparative example two reinforcing
Chip bga removing glue afterwards.
Solvent removing glue method：It is solvent, process time 5 minutes, 8 minutes that group 1 uses alcohol, group 5 to use isopropanol；It is right
Ratio one and comparative example two cannot use solvent removing glue.
Heating removing glue method：Group 1, group 5 use heating platform, and 150 DEG C are processed 2 minutes；Comparative example one uses heated flat
Platform and baking rifle, 220-240 DEG C is processed 5-8 minutes；Comparative example two is using heating platform and dries rifle, 150-170 DEG C of 5-8 points for the treatment of
Clock.
Fig. 1 is applied in BGA package consolidation effect figure for reinforced glue of the present invention；Fig. 2 is to be sealed using BGA after reinforced glue of the present invention
Dress reinforcing product（Group 5）Removing glue design sketch, it can be seen that glue curing thing of the invention can dilute glue after solvent soaking
Body, reduces viscosity, easily removal and cleaning, and the requirement of BGA package reinforced glue removing glue is fully achieved.
Be checking solidified glue unfailing performance, above-mentioned reinforced glue is applied BGA package reinforcing after carry out it is a series of
Reliability test, test mode is as follows, is as a result all to pass through.
1、 ATC（Accelerate thermal shock）Test, two cycles an of hour, altogether 46 cycle period, -30 DEG C to 65
DEG C/7 minutes → 65 DEG C to -30 DEG C/7 minutes → -30 DEG C/resident 8 minutes → 65 DEG C/resident 8 minutes.
2nd, (hot and humid) experiments of THB, condition：Under conditions of 65 DEG C, 90%RH, the continuously roasting machine of 72 hours
Test.
3rd, high temperature experiment, condition：Under the conditions of 40 DEG C, the continuously roasting machine test of 48 hours.
4th, vibration experiment, condition：- the 200HZ of vibration frequency 2, under random vibration pattern, with acceleration 1.04g, x, y, z
Mutually each 15 minutes of the every axle of axle.
5. drop test, condition：One jiao, Mitsubishi, six faces；Apart from 76cm. 6, Cross-section slice tests：
By, it is necessary to make slice test to its glue point, and being cut with the glue point before reliability test is made after a series of reliability test
Piece analyzes, and checks whether its surface structure can change, and confirms whether its structural reliability meets requirement.More than
Result understands that product of the present invention is normal temperature solidified, and curing performance is good, and bonding force is strong, it is ensured that BGA package consolidation effect；Remove
Removing glue mode during glue is simpler than existing mode, and temperature is lower during heating, advantageously ensures that the stabilization and product of original paper
Matter.
Claims (7)
1. a kind of normal temperature solidified BGA package reinforced glue, it is characterised in that by mass parts, including following components：
Ludox 50-60 parts
30-40 parts of thermosetting acrylic resin prepolymer
Paraffin 1-5 parts
1-3 parts of aqueous polyurethane compound
In the Ludox, the mass fraction of silica is 30-50%；
The thermosetting acrylic resin prepolymer is by monofunctional acrylates' ester monomer and the reacted shape of nitrogenous vinyl monomer
Into；
The molecular weight of the thermosetting acrylic resin prepolymer is 3500-5000, and molecular weight distribution is 1.5-1.7；
The molecular weight of the urethanes is 10000-14000；
The structural formula of the nitrogenous vinyl monomer is：
。
2. normal temperature solidified BGA package reinforced glue according to claim 1, it is characterised in that：The silica particle diameter model
It is 20-30nm to enclose.
3. normal temperature solidified BGA package reinforced glue according to claim 1, it is characterised in that：The monofunctional acrylates
The structural formula of ester monomer is：
。
4. normal temperature solidified BGA package reinforced glue according to claim 3, it is characterised in that：In monofunctional acrylates' ester
When monomer reacts to form thermosetting acrylic resin prepolymer with nitrogenous vinyl monomer, monofunctional acrylates' ester monomer with contain
The mol ratio of nitrogen vinyl monomer is 1:（1.25-1.35）.
5. the preparation method of any one normal temperature solidified BGA package reinforced glue described in claim 1-4, it is characterised in that bag
Following steps are included, Ludox is poured into container A；Thermosetting acrylic resin prepolymer is put into container B, is stirred, then
By in the thermosetting acrylic resin prepolymer addition Ludox after stirring, stir；Then aqueous polyurethane compound is added,
Lasting stirring；Paraffin is eventually adding, normal temperature solidified BGA package reinforced glue is obtained after stirring.
6. the preparation method of normal temperature solidified BGA package reinforced glue according to claim 5, it is characterised in that specifically include
Following steps, Ludox is poured into container A, and it is 25 DEG C to maintain temperature；Thermosetting acrylic resin prepolymer is put into container B
In, 1h is stirred in 80 DEG C, then by thermosetting acrylic resin prepolymer addition Ludox, stir 0.5h；Then add
Aqueous polyurethane compound, persistently stirs 2h；Paraffin is eventually adding, obtaining normal temperature solidified BGA package after stirring 0.5h reinforces
Glue.
7. any one normal temperature solidified BGA package reinforced glue described in claim 1-4 chip BGA package reinforcing in should
With.
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