CN115181522A - Underfill adhesive based on modified amine curing agent and preparation method and application thereof - Google Patents
Underfill adhesive based on modified amine curing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN115181522A CN115181522A CN202210972617.4A CN202210972617A CN115181522A CN 115181522 A CN115181522 A CN 115181522A CN 202210972617 A CN202210972617 A CN 202210972617A CN 115181522 A CN115181522 A CN 115181522A
- Authority
- CN
- China
- Prior art keywords
- curing agent
- underfill
- amine curing
- modified amine
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 88
- 150000001412 amines Chemical class 0.000 title claims abstract description 82
- 239000000853 adhesive Substances 0.000 title abstract description 13
- 230000001070 adhesive effect Effects 0.000 title abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 150000002989 phenols Chemical class 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 22
- 239000000806 elastomer Substances 0.000 claims abstract description 22
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 17
- 238000004806 packaging method and process Methods 0.000 claims abstract description 15
- 238000006683 Mannich reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 17
- -1 alicyclic amine Chemical class 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 5
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 claims description 3
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 3
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 claims description 3
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 claims description 3
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 claims description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- LKAVYBZHOYOUSX-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid;styrene Chemical compound C=CC=C.CC(=C)C(O)=O.C=CC1=CC=CC=C1 LKAVYBZHOYOUSX-UHFFFAOYSA-N 0.000 claims description 3
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 claims description 3
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 31
- 230000032683 aging Effects 0.000 abstract description 10
- 238000011282 treatment Methods 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 229910000679 solder Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002318 adhesion promoter Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000002094 self assembled monolayer Substances 0.000 description 3
- 239000013545 self-assembled monolayer Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012858 packaging process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 241000482268 Zea mays subsp. mays Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides an underfill adhesive based on a modified amine curing agent, and a preparation method and application thereof, and belongs to the technical field of adhesives. The underfill based on the modified amine curing agent comprises epoxy resin, a filler, a silane coupling agent, an elastomer and the modified amine curing agent, wherein the modified amine curing agent is obtained by modifying the amine curing agent by adopting aldehyde and phenolic compounds through a Mannich reaction. According to the invention, aldehyde and phenolic compounds are adopted to modify amine curing agents through a Mannich reaction, and the modified amine curing agents are introduced into the formula of the underfill, so that the interface bonding strength of the underfill and a substrate (such as a Si substrate and a SiN substrate) can be effectively improved, the underfill can still maintain higher bonding strength after PCT aging treatment, and the reliability of a packaging body is improved when the underfill is applied to chip packaging.
Description
Technical Field
The invention belongs to the technical field of adhesives, and relates to an underfill adhesive based on a modified amine curing agent, and a preparation method and application thereof.
Background
Flip chips have attracted considerable attention as a one-level interconnect technology due to the rapid growth in Integrated Circuit (IC) manufacturing and the ever-increasing market for faster, lighter, smaller, and cheaper electronic products. Flip chips have many advantages over conventional packages using wire bonding techniques, such as high I/O density, short interconnects, self-alignment, better heat dissipation through the back of the chip, smaller footprint, smaller profile, etc. One of the major problems with flip chip technology is the thermal mechanical fatigue life of the C4 solder joints. This thermomechanical problem stems primarily from the Coefficient of Thermal Expansion (CTE) mismatch between the silicon chip (2.5 ppm/deg.C) and the substrate (4-10 ppm/deg.C for ceramics and 18-24 ppm/deg.C for organic FR4 boards). Therefore, as chip size increases, thermomechanical reliability becomes a critical issue.
The invention of underfill is one of the most innovative developments in using low cost organic substrates in flip chip packaging. Underfill is a liquid encapsulating material, usually bulk filled with SiO 2 After flip-chip interconnection, is applied between the chip and the substrate. After curing, the hardened underfill exhibits high modulus, low CTE matching with solder joints, and good adhesion to the chip and substrate. Thermal stress on the solder joints between the chip, underfill, substrate and all solder jointsRedistribute rather than concentrate on the peripheral pads. The application of underfill can reduce the most important solder strain level to 0.10-0.25 of the unpackaged joint strain. Therefore, the use of the underfill can improve the fatigue life of the solder joint by 10 to 100 times. In addition, it also provides environmental protection for the solder joints. Underfill has become a practical solution to extend the application of flip chip technology from ceramics to organic substrates, from high end products to cost sensitive products, which is also the main reason for such popularity of flip chips today.
When the underfill is used for protecting solder balls of Flip Chip packages, the interfaces to be contacted are many, such as: silicon chip, passivation layer, solder ball, green oil substrate, etc. In addition, since the environment in which the package is used is complicated, and particularly, as the size of electronic products is gradually reduced, the package is inevitably used under high temperature, high pressure and high humidity environment, but most of the currently used underfill adhesives are epoxy resin-based, and thus, the underfill tends to absorb moisture, which causes undesirable changes in adhesion and stress, and decreases the reliability of the package. Therefore, in order to improve the reliability of the package, the adhesion strength between the underfill and various interfaces needs to be improved, and further, the humidity resistance, heat resistance, high temperature resistance, high pressure resistance, and the like between the underfill and various interfaces need to be improved.
Underfill is required to contact a variety of interfaces, mainly the Si chip, passivation layer, solder balls and solder mask, when protecting the solder balls in the IC package. Because the service environment of the packaging body is complicated and changeable, the packaging body can be inevitably used under high-temperature high-pressure and high-humidity environments, and in the condition, water vapor can enter the packaging body through the interface, so that the underfill adhesive and the substrate are layered, and the phenomenon of popcorn generated inside at high temperature can be caused. Therefore, it is necessary to improve the adhesion strength between the underfill adhesive and the substrate, prevent moisture from entering the interface in a high-temperature and high-humidity environment, and improve the packaging reliability. At present, the main approaches for improving the bonding strength and the humidity resistance can be divided into two approaches; the first is to add an adhesion promoter into the underfill formulation; the second is to surface treat the corresponding substrate to improve initial bond strength and wet and heat resistance.
However, an adhesion promoter is introduced into the formula of the underfill, and the adhesion promoter not only has good compatibility with organic resin, inorganic filler and various auxiliaries in the formula, but also has certain compatibility with different types of substrates; this makes the adhesion promoter very restrictive in its selection, and therefore, a silane coupling agent is often used as the adhesion promoter. And the silane coupling agent is introduced into the underfill system to effectively improve the humidity-heat-aging resistance of the underfill, but the initial interface bonding strength at room temperature is not improved, in addition, improper type selection of the coupling agent can also cause the rapid increase of the underfill viscosity, even in the capillary underfill system, the underfill has no injectability, and the underfill cannot be applied to Flip Chip packaging.
The main methods for treating the surface of the substrate currently include: self-assembled monolayer (SAM), plasma treatment, UV/O 3 Cleaning, ion implantation, chemical oxidation, and the like. The self-assembled monolayer is a thermodynamically stable and orderly arranged molecular structure formed by organic functional molecules on a solid surface by utilizing the chemical adsorption effect, and is generally a monolayer film formed by immersing the solid surface into a dilute solution containing an active substance and performing physical adsorption and chemical bonding within a certain time. The plasma treatment improves the surface properties of the material, such as surface wettability, roughness, surface energy, cleanliness and the like, through physical and chemical changes of oxidation, cleaning, etching, polymerization and the like on the surface of the substrate, so that the interface bonding strength is improved. The wet treatment of the copper surface can ensure that the copper and the copper alloy have various properties of high corrosion resistance, high wear resistance, high hardness and the like on the surface while maintaining the excellent electro-mechanical properties of the body. These surface treatments are effective in improving the initial interfacial adhesion strength, but the wet heat resistance is still desired to be improved. In addition, these surface treatments are specific and can make the packaging process more complicated and commercially worthless.
In view of this, it is urgently needed to research and prepare a new underfill adhesive which can still maintain higher adhesive strength after PCT aging treatment, thereby improving the reliability of the package; and the interface bonding strength is improved without substrate surface treatment, so that the packaging process is prevented from being complicated.
Disclosure of Invention
In view of the above, the invention provides an underfill based on a modified amine curing agent and a preparation method and application thereof, the amine curing agent is modified by aldehyde and a phenolic compound through a mannich reaction, and the modified amine curing agent is introduced into the formula of the underfill, so that the interface bonding strength between the underfill and a substrate (such as a Si substrate and a SiN substrate) can be effectively improved, the underfill can still maintain higher bonding strength after PCT aging treatment, and the reliability of a packaging body is improved when the underfill is applied to chip packaging.
In order to achieve the purpose, the invention provides an underfill based on a modified amine curing agent, which comprises epoxy resin, a filler, a silane coupling agent, an elastomer and the modified amine curing agent,
the modified amine curing agent is obtained by modifying an amine curing agent through aldehyde and a phenolic compound in a Mannich reaction, and the chemical reaction process is shown as the following formula:
preferably, the aldehyde in the mannich reaction is formaldehyde, or trioxymethylene, or paraformaldehyde.
Preferably, the phenolic compounds in the mannich reaction include monohydric phenols, dihydric phenols and trihydric phenols; the amine curing agent comprises aliphatic amine, alicyclic amine and aromatic amine, and is primary amine or secondary amine.
Preferably, the phenolic compound in the mannich reaction is any one of 2-methyl-5-isopropylphenol, 2-isopropyl-5-methylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-phenol, 2-methylenebis (6-tert-butyl-p-cresol), 2, 6-di-tert-butyl-4-methylphenol, p-tert-butylphenol, 4-tert-butylcatechol (TBC), and pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
the amine curing agent is diethylenetriamine, ethylenediamine, triethylenetetramine, 1, 6-hexamethylenediamine, tetraethylenepentamine, 4-amino-alpha, alpha-4-trimethyl-cyclohexanemethylamine, 5-amino-1, 3-trimethylcyclohexylmethylamine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, 3 '-dimethyl-4, 4-diaminodicyclohexylmethane, 4' -methylenebis (2-methyl-6-ethylaniline), m-phenylenediamine, m-xylylenediamine, 4-diaminodiphenylsulfone, 4-diaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, 3-chloro-3 '-ethyl-4, 4' -diaminodiphenylmethane, 4,4 '-methylenebis (2, 6-diethylaniline), 4' -methylenebis (2-ethyl) aniline, 4 '-bis-sec-butylaminodiphenylmethane, 4' -methylene-bis (3-chloro-2, 6-diethylaniline).
Preferably, the filler is a spherical silica filler having a particle diameter of 1 to 10 μm.
Preferably, the silane coupling agent contains a reactive group that is compatible with the epoxy resin system.
Preferably, the elastomer is any one of silicone rubber, butadiene rubber, styrene butadiene rubber, and methacrylic acid-butadiene-styrene.
The invention also provides a preparation method of the underfill based on the modified amine curing agent, which comprises the steps of mixing the epoxy resin, the filler, the silane coupling agent and the elastomer, and then adding the modified amine curing agent for mixing.
Preferably, the preparation method also comprises the following steps:
firstly, aldehyde is dissolved in amine curing agent at 40-70 ℃, then the mixture is added into ethanol solution of phenolic compound, reflux reaction is carried out for 4 hours at 80-95 ℃, and finally solvent and water are evaporated at 80-100 ℃.
The invention also provides application of the underfill based on the modified amine curing agent in chip packaging.
The invention adopts the technical scheme that the method has the advantages that:
(1) The modified amine curing agent prepared by the invention has excellent interface bonding performance and PCT aging resistance; (2) The modified amine curing agent prepared by the invention has excellent compatibility with an underfill system, and does not generate negative effect on the viscosity of a product, which is incomparable with other adhesion promoters; (3) The modified amine curing agent prepared by the invention does not need to carry out special treatment on the base material in the using process, and the process is simple; (4) The modified amine curing agent prepared by the invention has clear synthesis mechanism and simple synthesis route, is easy for industrial production and is convenient for large-scale application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural view of a sandwich structure test specimen in a bonding strength test of an underfill prepared in an example of the present invention and a comparative example;
FIG. 2 is a graph of interfacial fracture failure mode after bond strength testing of underfill made in accordance with examples of the present invention and comparative examples.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a bottom filling adhesive based on a modified amine curing agent, which comprises epoxy resin, a filler, a silane coupling agent, an elastomer and the modified amine curing agent.
The modified amine curing agent is obtained by modifying an amine curing agent through aldehyde and phenolic compounds in a Mannich reaction, and the chemical reaction process is shown as the following formula:
the invention takes aldehyde compound as intermediate medium, and introduces phenolic compound into traditional amine molecular chain to obtain a modified amine curing agent. Compared with the traditional amine curing agent, a large number of active hydroxyl groups and rigid phenyl groups are introduced. On one hand, the active hydroxyl groups effectively improve the bonding performance of the underfill in the modes of forming hydrogen bonds with the substrate material, chemical reaction and the like; on the other hand, the heat resistance, the aging resistance and the moisture resistance of the underfill can be effectively improved by the rigid phenyl group.
Wherein, the aldehyde in the Mannich reaction can be selected from formaldehyde and aqueous solution thereof, or trioxymethylene or paraformaldehyde.
The phenolic compounds can be monohydric phenol, dihydric phenol and trihydric phenol, wherein the more phenolic hydroxyl groups, the better the resistance of the glue to wet heat aging, but the phenolic hydroxyl groups generally cannot exceed three, for example: 2-methyl-5-isopropylphenol, 2-isopropyl-5-methylphenol, 2, 4-di-tert-butylphenol, 2, 6-di-tert-butyl-p-phenol, 2-methylenebis (6-tert-butyl-p-cresol), 2, 6-di-tert-butyl-4-methylphenol, p-tert-butylphenol, 4-tert-butylcatechol (TBC), pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]. Monohydric phenol and dihydric phenol compounds are preferred to modify the amine curing agent.
The amine curing agent can be aliphatic amine, alicyclic amine and aromatic amine, and can also be primary amine and secondary amine, such as: diethylenetriamine, ethylenediamine, triethylenetetramine, 1, 6-hexamethylenediamine, tetraethylenepentamine, 4-amino-alpha, alpha-4-trimethyl-cyclohexanemethanamine, 5-amino-1, 3-trimethylcyclohexylmethylamine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, 3 '-dimethyl-4, 4-diaminodicyclohexylmethane, 4' -methylenebis (2-methyl-6-ethylaniline), m-phenylenediamine, m-xylylenediamine, 4-diaminodiphenylsulfone, 4-diaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, 3-chloro-3 '-ethyl-4, 4' -diaminodiphenylmethane, 4,4 '-methylenebis (2, 6-diethylaniline), 4' -methylenebis (2-ethyl) aniline, 4 '-bis-sec-butylaminodiphenylmethane, 4' -methylene-bis (3-chloro-2, 6-diethylaniline).
Wherein the filler is spherical silica filler with the particle diameter of 1-10 mu m preferably. The silane coupling agent contains active groups and is compatible with an epoxy resin system. The elastomer is any one of silicon rubber, butadiene rubber, styrene butadiene rubber, methacrylic acid-butadiene-styrene and the like.
The invention also provides a preparation method of the underfill based on the modified amine curing agent, which comprises the steps of mixing the epoxy resin, the filler, the silane coupling agent and the elastomer, and then adding the modified amine curing agent for mixing.
The preparation method also comprises the preparation of the modified amine curing agent, and the process is as follows:
firstly, aldehyde is dissolved in amine curing agent at 40-70 ℃, then the mixture is added into ethanol solution of phenolic compound, reflux reaction is carried out for 4 hours at 80-95 ℃, and finally solvent and water are evaporated at 80-100 ℃.
The invention also provides application of the underfill based on the modified amine curing agent in chip packaging.
According to the underfill based on the modified amine curing agent, the amine curing agent is modified by adopting aldehyde and phenolic compounds through Mannich reaction, and the modified amine curing agent is introduced into the underfill formula, so that the interface bonding strength of the underfill and a substrate (such as Si and SiN substrates) can be effectively improved, the underfill can still keep higher bonding strength after PCT aging treatment, the reliability of a packaging body is improved when the underfill is applied to chip packaging, and the preparation method of the underfill based on the modified amine curing agent is simple in steps and can be industrially produced.
Example 1
In the formula of the underfill, the materials are selected as follows: the epoxy resin is bisphenol F type epoxy resin with an epoxy equivalent of 158; the silica filler is silica filler (average particle diameter: 0.5 μm) surface-treated with 3-glycidoxypropyltrimethoxysilane coupling agent; the silane coupling agent is 3-epoxy propoxy propyl trimethoxy silane; the elastomer is a silicone powder.
In the formula of the modified amine curing agent, the materials are selected as follows: the aldehyde is paraformaldehyde, and the amine curing agent is diethylenetriamine; the phenolic compound is 4-tert-butyl catechol.
The underfill was prepared as follows:
(1) Preparing a modified amine curing agent: dissolving aldehyde in a proper amount of amine curing agent at 60 ℃, uniformly mixing, dripping the mixture into an ethanol solution of a phenolic compound under a nitrogen atmosphere, reacting the mixture at 95 ℃ for 4 hours, and evaporating residual solvent and water at 90 ℃ after the reaction is finished to obtain the phenolic aldehyde curing agent.
(2) Firstly, uniformly mixing epoxy resin, a silane coupling agent and an elastomer, stirring for 2min at 1500rpm and 2min at 2000rpm, adding a filler into the mixture of the epoxy resin, the silane coupling agent and the elastomer in three batches, stirring for 2min at 1500rpm and stirring for 2min at 2000rpm; and (2) finally, adding the modified amine curing agent prepared in the step (1) into a mixture of epoxy resin, filler, silane coupling agent and elastomer, stirring at 1500rpm for 2min and at 2000rpm for 2min to obtain the underfill. Wherein the mass ratio of the epoxy resin, the modified amine curing agent, the filler, the silane coupling agent and the elastomer is as follows: 27.02: 11.98: 60: 0.5.
Example 2
The difference from the embodiment 1 is that in the formula of the modified amine curing agent, the amine curing agent is 4,4' -diaminodicyclohexylmethane, and the phenolic compound is 4-tert-butyl catechol; the mass ratio of the epoxy resin, the modified amine curing agent, the filler, the silane coupling agent and the elastomer is as follows: 23.16: 15.84: 60: 0.5, and other material selection and process are the same.
Example 3
The difference from the embodiment 1 is that in the formula of the modified amine curing agent, the amine curing agent is diethyl toluene diamine, and the phenolic compound is 4-tert-butyl catechol; the mass ratio of the epoxy resin, the modified amine curing agent, the filler, the silane coupling agent and the elastomer is as follows: 24.13: 14.87: 60: 0.5, and other material selection and process are the same.
Example 4
The difference from the embodiment 3 is that in the formula of the modified amine curing agent, the phenolic compound is 2, 4-di-tert-butylphenol; the mass ratio of the epoxy resin, the modified amine curing agent, the filler, the silane coupling agent and the elastomer is as follows: 21.28: 17.72: 60: 0.5, and other material selection and processes are the same.
Example 4
The difference from the example 3 is that in the formula of the modified amine curing agent, the phenolic compound is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; the mass ratio of the epoxy resin, the modified amine curing agent, the filler, the silane coupling agent and the elastomer is as follows: 10.07: 28.93: 60: 0.5, and other material selection and processes are the same.
Comparative example 1
The difference from the embodiment 1 is that the amine curing agent is diethylenetriamine which is not modified, and the mass ratio of the epoxy resin, the amine curing agent, the filler, the silane coupling agent and the elastomer is as follows: 34.51: 4.49: 60: 0.5, and other material selection and process are the same.
Comparative example 2
The difference from the example 2 is that the amine curing agent is 4,4' -diaminodicyclohexylmethane which is not modified, and the mass ratio of the epoxy resin, the amine curing agent, the filler, the silane coupling agent and the elastomer is as follows: 29.30: 9.70: 60: 0.5, and other material selection and processes are the same.
Comparative example 3
The difference from the example 3 is that the amine curing agent is diethyl toluene diamine which is not modified, and the mass ratio of the epoxy resin, the amine curing agent, the filler, the silane coupling agent and the elastomer is as follows: 30.45: 8.55: 60: 0.5, and other material selection and processes are the same.
The underfill prepared in examples 1 to 5 and comparative examples 1 to 3 was subjected to adhesion strength test, a sandwich structure test sample was used as shown in fig. 1, a silicon chip adhered to the underfill was removed with a shear knife, and the adhesion strength between the underfill and the silicon chip was obtained by reading the force value at that time. Wherein the PCT aging treatment process is to treat the prepared sandwich-structured test specimen in a PCT aging test box at 121 ℃ and 100% RH for 96H, and then take out to perform the adhesion strength test.
Fig. 2 is a fracture failure mode diagram, and the surface morphology of the silicon substrate of the sandwich structure subjected to the bonding strength test is photographed by using a 3D confocal microscope, wherein the interfacial fracture mainly appears in two forms: one is the interface of the silicon chip and the underfill, and the other is the interface of the underfill and the silicon substrate; failure of the body, i.e., fracture of the underfill.
TABLE 1 results of adhesion strength test of underfill for examples 1 to 3 and comparative examples 1 to 3
TABLE 2 bond Strength test results for underfill of examples 3-4 and comparative example 3
Comparative example 3 | Example 3 | Example 4 | Example 5 | |
Si substrate bond Strength (MPa) -initial | 56.079 | 74.190 | 63.765 | 59.314 |
Si substrate bond Strength (MPa) -after PCT | 45.995 | 70.304 | 58.768 | 54.700 |
SiN substrate bond Strength (MPa) -initial | 58.218 | 71.060 | 61.688 | 55.670 |
SiN substrate bond Strength (MPa) -after PCT | 46.886 | 69.059 | 58.038 | 52.170 |
It is seen from the test results in table 1 that the amine curing agent modified with aldehyde and phenolic compounds introduced into the underfill not only significantly improves the adhesion strength with Si and SiN substrates at room temperature, but also does not significantly decrease the adhesion strength after PCT treatment. In addition, it can be seen that, under the same condition of the phenolic compound, the curing agent similar to aromatic amine is selected to have better effect, the alicyclic amine curing agent has the second best effect, and the aliphatic amine curing agent has less obvious effect than the first two amine curing agents, so the aromatic amine curing agent is preferably modified.
With reference to fig. 2, it can be seen that, compared with the corresponding comparative examples, the failure modes of the embodiments (example 1 corresponds to comparative example 1, example 2 corresponds to comparative example 2, and example 3 corresponds to comparative example 3) are all converted from the interface failure mode into the mixed failure mode and the body failure mode, in which the body failure is dominant, which indicates that the interface bonding strength can be effectively improved after the modified amine curing agent is introduced into the underfill adhesive, and the strong interface interaction force effectively reduces the possibility that water vapor enters the package body in the PCT aging process, thereby improving the package reliability.
It is seen from the test results in table 1 that the amine curing agent modified with aldehyde and phenolic compounds introduced into the underfill not only significantly improves the adhesion strength with Si and SiN substrates at room temperature, but also does not significantly decrease the adhesion strength after PCT treatment. In addition, it can be seen that the aromatic amine curing agent is preferably modified with dihydric phenol compounds because the aromatic amine curing agent is preferably modified with dihydric phenol, and monohydric phenol and polyhydric phenol are not as effective as dihydric phenol.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The underfill based on the modified amine curing agent is characterized by comprising epoxy resin, a filler, a silane coupling agent, an elastomer and the modified amine curing agent,
the modified amine curing agent is obtained by modifying an amine curing agent through aldehyde and a phenolic compound in a Mannich reaction, and the chemical reaction process is shown as the following formula:
2. the underfill based on modified amine curing agent according to claim 1, wherein the aldehyde in the Mannich reaction is formaldehyde, trioxymethylene, or paraformaldehyde.
3. The underfill according to claim 1, wherein the phenolic compound in the Mannich reaction comprises monohydric phenol, dihydric phenol and trihydric phenol; the amine curing agent comprises aliphatic amine, alicyclic amine and aromatic amine, and is primary amine or secondary amine.
4. The underfill based on modified amine curing agent of claim 3, wherein the phenolic compound in the Mannich reaction is any one of 2-methyl-5-isopropylphenol, 2-isopropyl-5-methylphenol, 2, 4-di-t-butylphenol, 2, 6-di-t-butyl-p-phenol, 2-methylenebis (6-t-butyl-p-cresol), 2, 6-di-t-butyl-4-methylphenol, p-t-butylphenol, 4-t-butylcatechol (TBC), pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ];
the amine curing agent is diethylenetriamine, ethylenediamine, triethylenetetramine, 1, 6-hexamethylenediamine, tetraethylenepentamine, 4-amino-alpha, alpha-4-trimethyl-cyclohexanemethylamine, 5-amino-1, 3-trimethylcyclohexylmethylamine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, 3 '-dimethyl-4, 4-diaminodicyclohexylmethane, 4' -methylenebis (2-methyl-6-ethylaniline), m-phenylenediamine, m-xylylenediamine, 4-diaminodiphenylsulfone, 4-diaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, 3-chloro-3 '-ethyl-4, 4' -diaminodiphenylmethane, 4,4 '-methylenebis (2, 6-diethylaniline), 4' -methylenebis (2-ethyl) aniline, 4 '-bis-sec-butylaminodiphenylmethane, 4' -methylene-bis (3-chloro-2, 6-diethylaniline).
5. The underfill according to claim 1, wherein the filler is a spherical silica filler having a particle size of 1 to 10 μm.
6. The underfill according to claim 1, wherein the silane coupling agent contains a reactive group and is compatible with epoxy resin systems.
7. The underfill according to claim 1, wherein the elastomer is any one of silicone rubber, butadiene rubber, styrene butadiene rubber and methacrylic acid-butadiene-styrene.
8. The method for preparing the underfill according to any one of claims 1 to 7, wherein the underfill is prepared by mixing the epoxy resin, the filler, the silane coupling agent and the elastomer, and then adding the modified amine curing agent.
9. The method for preparing the underfill according to any one of claims 8, further comprising the step of preparing the modified amine curing agent by the following steps:
firstly, aldehyde is dissolved in amine curing agent at 40-70 ℃, then the mixture is added into ethanol solution of phenolic compound, and then reflux reaction is carried out for 4 hours at 80-95 ℃, and finally solvent and water are evaporated at 80-100 ℃.
10. Use of an underfill according to any one of claims 1 to 7, or an underfill prepared by a method according to any one of claims 8 to 9, in chip packaging.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210972617.4A CN115181522A (en) | 2022-08-15 | 2022-08-15 | Underfill adhesive based on modified amine curing agent and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210972617.4A CN115181522A (en) | 2022-08-15 | 2022-08-15 | Underfill adhesive based on modified amine curing agent and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115181522A true CN115181522A (en) | 2022-10-14 |
Family
ID=83523991
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210972617.4A Pending CN115181522A (en) | 2022-08-15 | 2022-08-15 | Underfill adhesive based on modified amine curing agent and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115181522A (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002080564A (en) * | 2000-09-05 | 2002-03-19 | Chugoku Marine Paints Ltd | Curable epoxy resin composition, coating material composition, thick anticorrosion coating material composition, costing film of the composition, base material coated with the coating film, and method for anticorrosion of base material |
CN103059269A (en) * | 2013-01-16 | 2013-04-24 | 华东理工大学 | Compound modified aliphatic amine curing agent |
CN106928889A (en) * | 2015-12-30 | 2017-07-07 | 卡本复合材料(天津)有限公司 | Anchoring adhesive and preparation method thereof under a kind of water at low temperature |
CN112724899A (en) * | 2020-12-30 | 2021-04-30 | 深圳先进电子材料国际创新研究院 | Underfill adhesive |
CN113651704A (en) * | 2021-08-18 | 2021-11-16 | 四川轻化工大学 | Preparation method and application of novel modified amine epoxy curing agent |
-
2022
- 2022-08-15 CN CN202210972617.4A patent/CN115181522A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002080564A (en) * | 2000-09-05 | 2002-03-19 | Chugoku Marine Paints Ltd | Curable epoxy resin composition, coating material composition, thick anticorrosion coating material composition, costing film of the composition, base material coated with the coating film, and method for anticorrosion of base material |
CN103059269A (en) * | 2013-01-16 | 2013-04-24 | 华东理工大学 | Compound modified aliphatic amine curing agent |
CN106928889A (en) * | 2015-12-30 | 2017-07-07 | 卡本复合材料(天津)有限公司 | Anchoring adhesive and preparation method thereof under a kind of water at low temperature |
CN112724899A (en) * | 2020-12-30 | 2021-04-30 | 深圳先进电子材料国际创新研究院 | Underfill adhesive |
CN113651704A (en) * | 2021-08-18 | 2021-11-16 | 四川轻化工大学 | Preparation method and application of novel modified amine epoxy curing agent |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI413220B (en) | Semiconductor package, core layer material, buildup layer material, and sealing resin composition | |
KR101713762B1 (en) | Underfill for high density interconnect flip chips | |
US7332822B2 (en) | Flip chip system with organic/inorganic hybrid underfill composition | |
JP5354753B2 (en) | Underfill material and semiconductor device | |
TW200849506A (en) | Connection structure for flip-chip semiconductor package, build-up layer material, sealing resin composition, and circuit substrate | |
US9670340B2 (en) | Inorganic filler, resin composition comprising the same and heat radiation substrate using the same | |
JP6090614B2 (en) | Liquid epoxy resin composition for semiconductor encapsulation and resin-encapsulated semiconductor device | |
CN111372994B (en) | Film-like semiconductor sealing material | |
TW200831598A (en) | Liquid resin composition for electronic part sealing and electronic part apparatus utilizing the same | |
TW200821352A (en) | Adhesive film composition for semiconductor assembly, associated dicing die bonding film and semiconductor package | |
TWI391459B (en) | Adhesive composition and semiconductor device for epoxy resin molding materials for sealing semiconductor | |
US11767450B2 (en) | Adhesive, die attach film and preparation method therefor | |
CN115181522A (en) | Underfill adhesive based on modified amine curing agent and preparation method and application thereof | |
KR20150109272A (en) | Substrate containing sealing material for sealing semiconductor, semiconductor device, and method for manufacturing semiconductor device | |
JP4622131B2 (en) | Resin paste for semiconductor and semiconductor device | |
CN108012564B (en) | Semiconductor device with a plurality of transistors | |
JP3847095B2 (en) | Resin paste for semiconductor and semiconductor device | |
JP4529268B2 (en) | Epoxy resin composition, prepreg and copper-clad laminate using the same | |
CN113667435A (en) | Low dielectric epoxy underfill | |
JPH0841173A (en) | Liquid epoxy resin composition, its production and method of curing same | |
JP2004137397A (en) | Resin composition and electronic part device | |
JP2003347320A (en) | Resin paste for semiconductor and semiconductor device | |
CN114286848B (en) | Semiconductor adhesive composition and semiconductor adhesive film comprising cured product thereof | |
US11485848B2 (en) | NCF for pressure mounting, cured product thereof, and semiconductor device including same | |
JP2023142888A (en) | Adhesive film for semiconductor, dicing/die-bonding double functioning film, and method for manufacturing semiconductor device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |