CN117844176A - Epoxy resin composition, epoxy resin material, and preparation method and application thereof - Google Patents
Epoxy resin composition, epoxy resin material, and preparation method and application thereof Download PDFInfo
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- CN117844176A CN117844176A CN202311555951.0A CN202311555951A CN117844176A CN 117844176 A CN117844176 A CN 117844176A CN 202311555951 A CN202311555951 A CN 202311555951A CN 117844176 A CN117844176 A CN 117844176A
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- epoxy resin
- flame retardant
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 96
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 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 claims abstract description 35
- 239000003063 flame retardant Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003086 colorant Substances 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 14
- 239000011256 inorganic filler Substances 0.000 claims abstract description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 13
- 239000005011 phenolic resin Substances 0.000 claims abstract description 13
- -1 triazole compounds Chemical class 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 7
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical group CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 10
- 229920003986 novolac Polymers 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 7
- 239000005350 fused silica glass Substances 0.000 claims description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- VFPFQHQNJCMNBZ-UHFFFAOYSA-N ethyl gallate Chemical compound CCOC(=O)C1=CC(O)=C(O)C(O)=C1 VFPFQHQNJCMNBZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000006082 mold release agent Substances 0.000 claims description 6
- 239000004203 carnauba wax Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 4
- 235000013869 carnauba wax Nutrition 0.000 claims description 4
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920006030 multiblock copolymer Polymers 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004262 Ethyl gallate Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 235000019277 ethyl gallate Nutrition 0.000 claims description 3
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012184 mineral wax Substances 0.000 claims description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 235000010388 propyl gallate Nutrition 0.000 claims description 3
- 239000000473 propyl gallate Substances 0.000 claims description 3
- 229940075579 propyl gallate Drugs 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- VOGVKUPHFCAFRO-UHFFFAOYSA-N 1-propoxypropane trimethoxysilane Chemical compound O(C)[SiH](OC)OC.C(CC)OCCC VOGVKUPHFCAFRO-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 239000011135 tin Substances 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- 239000005022 packaging material Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- BIEHXHIWQHAVFZ-UHFFFAOYSA-M bromoantimony Chemical compound [Sb]Br BIEHXHIWQHAVFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 235000012773 waffles Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of 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
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of preparation of epoxy resin materials, and discloses an epoxy resin composition, an epoxy resin material, a preparation method and application thereof. The epoxy resin composition comprises epoxy resin, phenolic resin, inorganic filler, a curing accelerator, a release agent, a flame retardant, a stress modifier, a thixotropic agent, a coupling agent, a tackifier and a colorant; wherein the curing accelerator is 1-benzyl-2-methylimidazole, and the tackifier is triazole compounds and/or gallic acid compounds. The epoxy resin composition provided by the invention contains a specific curing accelerator and a specific tackifier which can improve the adhesion force with metal, so that the adhesion force level of the epoxy resin material to the metal can be simultaneously improved on the premise of having a better molding process of the epoxy resin material prepared by the composition.
Description
Technical Field
The invention relates to the technical field of preparation of epoxy resin materials, in particular to an epoxy resin composition, an epoxy resin material, a preparation method and application thereof.
Background
In recent years, due to the convenience of assembly, fully encapsulated semiconductor discrete devices have been developed more rapidly than semi-encapsulated semiconductor devices, and accordingly, there is a need for semiconductor packaging materials having high thermal conductivity, low stress, excellent molding process performance, and high adhesion. The fully encapsulated semiconductor device is mainly used for high-power electronic products, and along with different application scenes, the reliability requirements for the semiconductor device are higher and higher, especially for application in industrial grade and vehicle-mounted products.
The adhesion of the encapsulation material to the copper, silver, nickel, tin and other substrates in the semiconductor device is one of the main factors affecting the reliability. By improving the adhesion force, the corrosion of external water vapor and impurity ions to the internal chip and the frame can be effectively prevented, the layering level among different functional areas of the semiconductor device is improved, and the reliability level of the semiconductor device such as high temperature resistance, high humidity resistance, high pressure resistance and the like is improved.
However, the adhesion of the existing packaging materials to metal substrates such as copper, silver, nickel and tin is generally poor, so that the adhesion of the epoxy resin material to the metal can be improved, and the epoxy resin composition is an important research and development direction applicable to fully-encapsulated semiconductor devices.
Disclosure of Invention
The invention aims to solve the problem that the adhesion of packaging materials to metals such as copper, silver, nickel and tin is poor in the prior art, and provides an epoxy resin composition, an epoxy resin material, a preparation method and application thereof. The epoxy resin material provided by the invention has the characteristics of good molding process performance and high adhesive force, and is suitable for packaging materials for fully encapsulating semiconductor devices.
In order to achieve the above object, the present invention provides, in one aspect, an epoxy resin composition containing an epoxy resin, a phenolic resin, an inorganic filler, a curing accelerator, a mold release agent, a flame retardant, a stress modifier, a thixotropic agent, a coupling agent, a tackifier and a colorant;
wherein the curing accelerator is 1-benzyl-2-methylimidazole, and the tackifier is triazole compounds and/or gallic acid compounds.
Preferably, the triazole compound is selected from one or more than two of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole and 3-amino-5-mercapto-1, 2, 4-triazole.
Preferably, the gallic acid compound is selected from one or more of methyl gallate, ethyl gallate and propyl gallate.
Preferably, the epoxy resin is 7 to 10 wt%, the phenolic resin is 4 to 7 wt%, the inorganic filler is 80 to 88 wt%, the curing accelerator is 0.1 to 1 wt%, the release agent is 0.1 to 1 wt%, the stress modifier is 0.1 to 2 wt%, the coupling agent is 0.1 to 1 wt%, the flame retardant is 0.1 to 2 wt%, the thixotropic agent is 0.1 to 3 wt%, the tackifier is 0.05 to 0.3 wt%, and the colorant is 0.1 to 1 wt%, based on 100 wt% of the total weight of the raw material composition.
Preferably, the inorganic filler contains crystalline silica and fused spherical silica.
Preferably, the weight ratio of the crystalline silica to the fused spherical silica is 3.5 to 14.5:1.
preferably, the median diameter D50 of the crystalline silica and the fused silica sphere is 10 to 40 μm.
More preferably, the median diameter D50 of the crystalline silica is 22 to 28. Mu.m, and the median diameter D50 of the fused silica is 18 to 23. Mu.m.
Preferably, the epoxy resin is selected from one or more of o-cresol formaldehyde epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin and dicyclopentadiene type epoxy resin.
Preferably, the phenolic resin is selected from one or more of phenol novolac resin and its derivatives, cresol novolac resin and its derivatives, monohydroxy or dihydroxynaphthalene novolac resin and its derivatives, condensate of para-xylene and phenol or naphthol, and copolymer of dicyclopentadiene and phenol.
Preferably, the flame retardant is one or more selected from the group consisting of a bromine-antimony flame retardant, a spherical flame retardant, a hydrated metal compound flame retardant, a silicone flame retardant, a nitrogen-containing compound flame retardant, an organic phosphorus flame retardant, and an organic metal compound flame retardant.
Preferably, the coupling agent is selected from one or more than two of gamma-epoxypropyl ether trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane and gamma-aminopropyl trimethoxysilane.
Preferably, the thixotropic agent is hydrophobic white carbon black.
Preferably, the release agent is selected from one or more of carnauba wax, synthetic wax and mineral wax.
Preferably, the colorant is carbon black.
Preferably, the stress modifier is a liquid silicone oil and/or a multiblock copolymer.
In a second aspect, the present invention provides a method of preparing an epoxy resin material prepared from the epoxy resin composition described hereinbefore, the method comprising: the epoxy resin composition is melted and mixed, then cooled and crushed to prepare powdery material.
Preferably, the conditions of the melt-kneading are: the equipment for melting and mixing is a double-roller mixer, the temperature of melting and mixing is 80-110 ℃, and the time of melting and mixing is 5-15 minutes.
In a third aspect, the present invention provides an epoxy resin material prepared by the method described above.
A fourth aspect of the present invention provides the use of an epoxy resin material as hereinbefore described as a semiconductor device packaging material.
The epoxy resin composition provided by the invention contains a specific curing accelerator and a specific tackifier which can improve the adhesion force with metal, so that the adhesion force level of the epoxy resin material to the metal can be simultaneously improved on the premise of having a better molding process of the epoxy resin material prepared by the composition.
Preferably, the fluidity of the epoxy resin material is regulated by adding the hydrophobic white carbon black serving as a thixotropic agent into the epoxy resin composition, so that the fluidity of the epoxy resin material in moulds with different thicknesses can be improved, and the risk of appearance defects of the packaged semiconductor device is reduced; the low stress requirement of the epoxy resin material can be ensured by adding the crystalline silica and the fused spherical silica with specific proportions as inorganic filler and matching with the stress modifier; the specific high-thermal-strength curing accelerator can be used for improving the strength of the epoxy resin material at the high Wen Kaimo, improving the curing degree during molding and improving the molding process performance; by using a specific adhesion promoter, the level of adhesion to metal can be increased, improving the reliability rating of the packaged device.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides an epoxy resin composition comprising an epoxy resin, a phenolic resin, an inorganic filler, a curing accelerator, a mold release agent, a flame retardant, a stress modifier, a thixotropic agent, a coupling agent, a tackifier and a colorant.
In the invention, the specific curing accelerator is adopted to improve the strength of the prepared epoxy resin material at the time of Wen Kaimo, improve the curing degree during molding and improve the molding process performance. In a preferred embodiment, the cure accelerator is 1-benzyl-2-methylimidazole;
in the invention, the specific tackifier is adopted to improve the adhesion level of the prepared epoxy resin material to metals such as copper, silver, nickel, tin and the like, and improve the reliability grade of the packaging device. In a preferred embodiment, the adhesion promoter is a triazole compound and/or gallic acid compound.
In specific embodiments, the triazole compound may be selected as is conventional in the art, and may be, for example, one or more of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, and 3-amino-5-mercapto-1, 2, 4-triazole.
In specific embodiments, the gallic acid compound may be a conventional choice in the art, and for example, may be one or more of methyl gallate, ethyl gallate, and propyl gallate.
In a preferred embodiment, the inorganic filler contains crystalline silica and fused silica of the spherical type.
In a more specific embodiment, the weight ratio of the crystalline silica to the fused silica sphere is from 3.5 to 14.5:1. in the invention, the ratio of the crystalline silica to the fused spherical silica is limited in a specific range and the stress modifier is matched, so that the low stress requirement of the epoxy resin material can be ensured.
Preferably, the crystalline silica and the fused silica may be in the form of powder. In particular embodiments, the median diameter D50 of the crystalline silica and fused spherical silica may be from 10 to 40 μm. In a more specific embodiment, the median diameter D50 of the crystalline silica is 22-28 μm and the median diameter D50 of the fused silica is 18-23 μm.
In the present invention, the epoxy resin may be a conventional choice in the art. In specific embodiments, the epoxy resin may be selected from one or more of o-cresol formaldehyde epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin, and dicyclopentadiene type epoxy resin.
In the present invention, the phenolic resin may be a conventional choice in the art. In specific embodiments, the phenolic resin may be one or more selected from the group consisting of phenol novolac resins and derivatives thereof, cresol novolac resins and derivatives thereof, monohydroxy or dihydroxynaphthalene novolac resins and derivatives thereof, condensates of para-xylene with phenol or naphthol, and copolymers of dicyclopentadiene with phenol.
In the present invention, the flame retardant may be a conventional choice in the art. In specific embodiments, the flame retardant may be selected from one or more of a bromoantimony flame retardant, a spherical flame retardant, a hydrated metal compound flame retardant, a silicone flame retardant, a nitrogen-containing compound flame retardant, an organophosphorus flame retardant, and an organometallic compound flame retardant.
In the present invention, the coupling agent may be a conventional choice in the art. In specific embodiments, the coupling agent may be selected from one or more of gamma-epoxypropyl propyl ether trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane, and gamma-aminopropyl trimethoxysilane.
In a preferred embodiment, the thixotropic agent may be a hydrophobic white carbon black. According to the invention, the fluidity of the epoxy resin material is regulated by adding the hydrophobic white carbon black into the epoxy resin composition as the thixotropic agent, so that the fluidity of the epoxy resin material in moulds with different thicknesses can be improved, and the risk of appearance defects of the packaged semiconductor device is reduced.
In the present invention, the release agent may be a conventional choice in the art. In specific embodiments, the mold release agent may be selected from one or more of carnauba wax, synthetic wax, and mineral wax.
In the present invention, the colorant may be a conventional choice in the art. In a specific embodiment, the colorant is carbon black.
In the present invention, the stress modifier may be a conventional choice in the art. In particular embodiments, the stress modifier is a liquid silicone oil and/or a multiblock copolymer.
In a specific embodiment, the epoxy resin is 7 to 10 wt%, the phenolic resin is 4 to 7 wt%, the inorganic filler is 80 to 88 wt%, the curing accelerator is 0.1 to 1 wt%, the mold release agent is 0.1 to 1 wt%, the stress modifier is 0.1 to 2 wt%, the coupling agent is 0.1 to 1 wt%, the flame retardant is 0.1 to 2 wt%, the thixotropic agent is 0.1 to 3 wt%, the tackifier is 0.05 to 0.3 wt%, and the colorant is 0.1 to 1 wt%, based on 100 wt% of the total weight of the raw material composition.
In a preferred embodiment, the epoxy resin is 8 to 9 wt%, the phenolic resin is 4 to 5 wt%, the inorganic filler is 82 to 85 wt%, the curing accelerator is 0.1 to 0.5 wt%, the mold release agent is 0.3 to 0.6 wt%, the stress modifier is 0.5 to 1 wt%, the coupling agent is 0.3 to 0.6 wt%, the flame retardant is 1 to 2 wt%, the tackifier is 0.05 to 0.15 wt%, the thixotropic agent is 0.1 to 0.5 wt%, and the colorant is 0.1 to 0.6 wt%, based on 100 wt% of the total weight of the raw material composition.
In a second aspect, the present invention provides a method of preparing an epoxy resin material prepared from the epoxy resin composition described hereinbefore, the method comprising: the epoxy resin composition was melt kneaded, cooled and pulverized.
The method is simple, and the epoxy resin material can be prepared by melting, mixing, cooling, crushing and forming the epoxy resin composition.
In particular embodiments, the apparatus for melt compounding may be a conventional choice in the art. In a preferred embodiment, the apparatus for melt-kneading may be a twin-roll kneader.
In a specific embodiment, the temperature of the melt-kneading may be 80 to 110℃and may be, for example, 70℃75℃80℃85℃90℃95℃100 ℃.
In a specific embodiment, the time for the melt-kneading may be 5 to 15 minutes.
In a more specific embodiment, the method comprises: melting and mixing the epoxy resin composition, cooling and crushing to obtain powdery material; optionally, the powder is shaped.
In a specific embodiment, the powder material can be prepared by selecting and molding the powder material according to actual requirements. In a preferred embodiment, the temperature of the molding may be 170-180 ℃; during the forming process, the raw materials react.
In a third aspect, the present invention provides an epoxy resin material prepared by the method described above.
The epoxy resin material has a good molding process and has excellent adhesion level to metals such as copper, silver, nickel, tin and the like.
A fourth aspect of the present invention provides the use of an epoxy resin material as hereinbefore described as a semiconductor device packaging material.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
A1: o-cresol formaldehyde epoxy resin, available from Jinan Shengquan group Co., ltd., brand: SQCN700-3;
a2: dicyclopentadiene type epoxy resin, available from DIC Corporation, japan, trade name: HP-7200;
b1: phenol novolac resin, available from the company st. Of the san francisco, trade name: PF-8011;
b2: phenol alkyl phenol-formaldehyde resin, available from Mitsui Chemicals Inc under the trade designation: XLC-4L;
c1: 1-benzyl-2-methylimidazole, available from Kai chemical Co., ltd;
c2: 2-methylimidazole, available from Kai chemical Co., ltd;
and C3: 2-phenyl-4-methylimidazole, available from Kai chemical Co., ltd;
and C4: triphenylphosphine, purchased from microphone;
d: crystalline silica powder (D50 25 μm), available from Jiangsu Lishi New Material Co., ltd., trade name NC1200;
e: fused spherical silica powder (D50 of 20 μm), available from Jiangsu Lishi New Material Co., ltd., brand NQ101;
thixotropic agent: hydrophobic white carbon black, available from DEGUSSA company under the trade designation: aerosil R972;
stress modifier 1: liquid silicone oils, available from dow, trade mark: SF8421EG;
stress modifier 2: multiblock copolymers, available from germany waffle under the trade designation: w35;
and (3) a release agent: carnauba wax, available from microphone, brand: palm wax;
coloring agent: carbon black, available from mitsubishi chemical, japan, trade name: MA600;
coupling agent: gamma-mercaptopropyl trimethoxysilane, available from mongolian morning photo chemical Co., ltd., brand: CG-S313;
tackifier: 3-amino-1, 2, 4-triazole
Flame retardant: aluminum hydroxide, available from atanan Hongyu New Material Co., ltd., brand HT-205.
Examples 1 to 3 and comparative examples 1 to 9 were each carried out in the following manner, except that the proportions of the raw material compositions were different.
The specific method comprises the following steps:
(1) Mixing a raw material composition containing epoxy resin, phenolic resin, inorganic filler, a curing accelerator, a release agent, a flame retardant, a stress modifier, a thixotropic agent, a coupling agent, a tackifier and a colorant according to the proportion shown in table 1 to prepare a mixture;
(2) And (3) melting and mixing the mixture obtained in the step (1) on a double-roller mixer at the temperature of 85 ℃ for 8 minutes, cooling and crushing to obtain powdery material.
Table 1: examples 1 to 3 and comparative examples 1 to 9 raw material ratios
Test case
(1) Gel time
Heating electric plate to 175+ -1deg.C, placing 0.3-0.5g of the above epoxy resin powder on the electric plate, and reading the required time when the powder gradually turns into colloid from fluid.
(2) Spiral flow length
The molding pressure was 70.+ -.2 Kgf/cm as measured on a transfer molding press with the aid of an EMMI-1-66 spiral flow metal mold 2 The temperature of the die is 175+/-2 ℃, and 20+/-5 g of the epoxy resin powder is taken for testing.
(3) Molding process performance
And visually inspecting the front step surface air holes and the back air holes of the plastic-packaged high-power full-packaging device TO-220F. The fewer the number of the unqualified high-power full-encapsulated devices TO-220F is, the better the molding process performance is. For example, for a molding process performance parameter of "0/240" means that of 240 fully encapsulated device TO-220F products, there were 0 out-of-shape failures, with products with a pore size of > 100um being considered as failure products.
(4) Adhesive force test
Sample preparation: the obtained epoxy resin powder was molded on the surface of the sample using a low pressure transfer molding machine at a mold temperature of 175℃and an injection pressure of 60bar for a curing time of 110 s. The sample piece is respectively a bare copper piece, a copper piece with a silver plating layer on the surface, a nickel plating copper piece on the surface and a tin plating copper piece on the surface.
And (3) adhesive force test: and applying shearing force along the surface of the sample at the speed of 20mm/min, and testing the maximum force value before the plastic package material is separated from the sample. Adhesion test 5 samples were tested for each example (or comparative), and the 5 test results were averaged as the adhesion test results for that example (or comparative).
The results of the gel time, spiral flow length, molding process performance and adhesion to metal test of the epoxy resin materials prepared in examples 1 to 3 and comparative examples 1 to 9 are shown in Table 2.
TABLE 2
As can be seen from comparison of the test results of examples 1-3 with comparative examples 1-9: the epoxy resin material prepared by the embodiment of the invention has better adhesion to copper, silver, nickel and tin on the premise of having better molding process; the epoxy resin materials prepared in comparative examples 1 to 3 were poor in silver adhesion, nickel adhesion and tin adhesion, and the epoxy resin materials prepared in comparative examples 1 to 9 were poor in molding process performance, so that the epoxy resin materials prepared in comparative examples were poor in comprehensive performance and unsatisfactory.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. An epoxy resin composition, characterized in that the epoxy resin composition contains epoxy resin, phenolic resin, inorganic filler, curing accelerator, release agent, flame retardant, stress modifier, thixotropic agent, coupling agent, tackifier and colorant;
wherein the curing accelerator is 1-benzyl-2-methylimidazole, and the tackifier is triazole compounds and/or gallic acid compounds.
2. The epoxy resin composition according to claim 1, wherein the triazole compound is one or more selected from the group consisting of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole and 3-amino-5-mercapto-1, 2, 4-triazole;
preferably, the gallic acid compound is selected from one or more of methyl gallate, ethyl gallate and propyl gallate.
3. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin is contained in an amount of 7 to 10% by weight, the phenolic resin is contained in an amount of 4 to 7% by weight, the inorganic filler is contained in an amount of 80 to 88% by weight, the curing accelerator is contained in an amount of 0.1 to 1% by weight, the mold release agent is contained in an amount of 0.1 to 1% by weight, the stress modifier is contained in an amount of 0.1 to 2% by weight, the coupling agent is contained in an amount of 0.1 to 1% by weight, the flame retardant is contained in an amount of 0.1 to 2% by weight, the thixotropic agent is contained in an amount of 0.1 to 3% by weight, the tackifier is contained in an amount of 0.05 to 0.3% by weight, and the colorant is contained in an amount of 0.1 to 1% by weight, based on the total weight of the raw material composition.
4. The epoxy resin composition according to claim 1, wherein the inorganic filler contains crystalline silica and fused spherical silica;
preferably, the weight ratio of the crystalline silica to the fused spherical silica is 3.5 to 14.5:1, a step of;
preferably, the median diameter D50 of the crystalline silica and fused spherical silica is 10 to 40 μm;
more preferably, the median diameter D50 of the crystalline silica is 22 to 28. Mu.m, and the median diameter D50 of the fused silica is 18 to 23. Mu.m.
5. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin is one or two or more selected from the group consisting of an o-cresol formaldehyde epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a novolac epoxy resin and a dicyclopentadiene type epoxy resin;
preferably, the phenolic resin is selected from one or more of phenol novolac resin and its derivatives, cresol novolac resin and its derivatives, monohydroxy or dihydroxynaphthalene novolac resin and its derivatives, condensate of paraxylene and phenol or naphthol, and copolymer of dicyclopentadiene and phenol;
preferably, the flame retardant is one or more selected from the group consisting of a bromine-antimony flame retardant, a spherical flame retardant, a hydrated metal compound flame retardant, a silicone flame retardant, a nitrogen-containing compound flame retardant, an organic phosphorus flame retardant, and an organic metal compound flame retardant.
6. The epoxy resin composition according to claim 1 or 2, wherein the coupling agent is one or two or more selected from the group consisting of gamma-epoxypropyl propyl ether trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane and gamma-aminopropyl trimethoxysilane;
preferably, the thixotropic agent is hydrophobic white carbon black;
preferably, the release agent is selected from one or more of carnauba wax, synthetic wax and mineral wax;
preferably, the colorant is carbon black;
preferably, the stress modifier is a liquid silicone oil and/or a multiblock copolymer.
7. A method for producing an epoxy resin material prepared from the epoxy resin composition according to any one of claims 1 to 6, comprising: the epoxy resin composition was melt kneaded, cooled and pulverized.
8. The method of claim 7, wherein the conditions of melt mixing are: the equipment for melting and mixing is a double-roller mixer, the temperature of melting and mixing is 80-110 ℃, and the time of melting and mixing is 5-15 minutes.
9. An epoxy resin material prepared by the method of claim 7 or 8.
10. Use of the epoxy resin material of claim 9 as a semiconductor device encapsulation material.
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