TWI466938B - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
- Publication number
- TWI466938B TWI466938B TW99110747A TW99110747A TWI466938B TW I466938 B TWI466938 B TW I466938B TW 99110747 A TW99110747 A TW 99110747A TW 99110747 A TW99110747 A TW 99110747A TW I466938 B TWI466938 B TW I466938B
- Authority
- TW
- Taiwan
- Prior art keywords
- epoxy resin
- component
- resin composition
- test
- underfill
- Prior art date
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- 229920000647 polyepoxide Polymers 0.000 title claims description 53
- 239000003822 epoxy resin Substances 0.000 title claims description 48
- 239000000203 mixture Substances 0.000 title claims description 22
- 239000000843 powder Substances 0.000 claims description 27
- 230000035699 permeability Effects 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- 239000004848 polyfunctional curative Substances 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 229920000800 acrylic rubber Polymers 0.000 claims description 7
- -1 aromatic ring compound Chemical class 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000004849 latent hardener Substances 0.000 claims description 3
- 230000003204 osmotic effect Effects 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 38
- 229920001971 elastomer Polymers 0.000 description 17
- 239000005060 rubber Substances 0.000 description 17
- 238000005259 measurement Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 12
- 239000011256 inorganic filler Substances 0.000 description 11
- 229910003475 inorganic filler Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004283 Sodium sorbate Substances 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 1
- 239000006013 carbendazim Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000000930 thermomechanical effect 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
- 238000000196 viscometry Methods 0.000 description 1
Classifications
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- 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
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
-
- 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
- H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Wire Bonding (AREA)
Description
本發明係關於一種後滲透密封用的環氧樹脂組成物，其係適用於使晶粒大小封裝(CSP)、球閘陣列(BGA)、晶圓級(WL-CSP)等之錫球與基板電極連接後進行之樹脂組成物所產生的密封。The present invention relates to an epoxy resin composition for post-osmosis sealing, which is suitable for a solder ball and a substrate of a grain size package (CSP), a ball grid array (BGA), a wafer level (WL-CSP), and the like. The seal formed by the resin composition after the electrodes are connected.
在基板封裝中係藉焊接之自我排列效果連接錫球與基板電極，經過洗淨步驟而使硬化型樹脂組成物流入於間隙後進行硬化之密封方法。此密封劑一般稱為底部填充劑，但其組成係以環氧樹脂有實績。另外，亦已知於特表2003-504893號公報所揭示之胺基甲酸酯樹脂的底部填充劑。胺基甲酸酯樹脂之時，因特徵在於修復性，有時信賴性低。In the substrate package, a solder ball self-aligning effect is used to connect the solder ball and the substrate electrode, and a curing step is performed after the hardening resin composition flows into the gap and is hardened by a cleaning step. This sealant is generally referred to as an underfill, but its composition is based on epoxy. Further, an underfill of a urethane resin disclosed in Japanese Laid-Open Patent Publication No. 2003-504893 is also known. In the case of a urethane resin, it is characterized by repairability and sometimes low reliability.
另外，有添加橡膠成分而提昇信賴性之方法。可使用具有橡膠骨架之硬化性樹脂或添加橡膠粉體之硬化性樹脂。於特開2001-270976號公報中係已揭示已添加橡膠粉與無機填充劑之密封用環氧樹脂，又，於特開平9-153570號公報中已揭示一種已添加特殊的丁二烯共聚物之粉體與無機填充劑之密封用環氧樹脂。在以往之底部填充劑中係必須有氧化鋁或氧化矽等之無機填充劑。藉由添加無機填充劑，進行降低線膨脹率，且降低有機材料之缺點的熱時之膨脹試驗。然而，因無機填充劑之添加量變多，故黏度變高，滲透性降低。In addition, there is a method of adding a rubber component to improve reliability. A curable resin having a rubber skeleton or a curable resin to which a rubber powder is added can be used. A sealing epoxy resin to which a rubber powder and an inorganic filler have been added has been disclosed in Japanese Laid-Open Patent Publication No. 2001-270976, and a special butadiene copolymer has been disclosed in Japanese Laid-Open Patent Publication No. Hei 9-153570. An epoxy resin for sealing powder and inorganic filler. In the conventional underfill, an inorganic filler such as alumina or cerium oxide is required. By adding an inorganic filler, a thermal expansion test which lowers the linear expansion ratio and lowers the disadvantage of the organic material is performed. However, since the amount of the inorganic filler added is increased, the viscosity is increased and the permeability is lowered.
在特開2008-208182號公報中係記載同時添加丙烯酸橡膠粉與聚矽氧橡膠粉等。藉添加無機填充材，以提高特性亦己被記載，宜實質上併用添加上述2種類的橡膠粉與無機填充劑已被記載。JP-A-2008-208182 discloses the simultaneous addition of an acrylic rubber powder, a polyoxymethylene rubber powder, and the like. It is also described that the addition of the inorganic filler is carried out to improve the properties, and it is preferable to add the above-mentioned two types of rubber powder and an inorganic filler in combination.
於特開2007-246713號公報中係揭示已使用多官能之縮水甘油基胺型環氧樹脂的繼電器用之密封用環氧樹脂。就流入間隙之點來看，雖與底部填充劑用途近似，但較保持所接續之電極的封裝用途，並未被要求信賴性。JP-A-2007-246713 discloses a sealing epoxy resin for a relay which uses a polyfunctional glycidylamine type epoxy resin. As far as the flow into the gap is concerned, although it is similar to the use of the underfill, it is not required to be reliable in terms of the sealing application of the electrode to be connected.
至今日，具有對信賴性試驗之耐性，同時在常溫(25℃)環境及120℃環境的滲透性高之後滲透型的底部填充劑尚未被發現，本發明之目的在於提供一種滿足上述之要求特性的後滲透密封用之環氧樹脂組成物。Up to now, the osmotic underfill has not been found after the resistance to the reliability test, and the permeability at room temperature (25 ° C) and 120 ° C environment has not been found, and the object of the present invention is to provide a characteristic that satisfies the above requirements. The post-penetration sealing epoxy resin composition.
本發明係為達成上述目的，經專心研究之結果，發現一種環氧樹脂組成物適於底部填充劑，該環氧樹脂組成物係具有硬化物之線膨脹率(α1)：60ppm/℃以下、玻璃轉移點：120℃以上、貯藏彈性率(25℃)：3.0GPa以下、硬化前之滲透性(120℃)：30mm以上之參數，終完成本發明。In order to achieve the above object, the present invention has found that an epoxy resin composition is suitable for an underfill agent having a linear expansion ratio (α1) of a hardened material: 60 ppm/° C. or less, as a result of intensive research. Glass transition point: 120 ° C or higher, storage modulus (25 ° C): 3.0 GPa or less, permeability before hardening (120 ° C): 30 mm or more, the present invention was completed.
因此，本發明之第一係一種後滲透密封用之環氧樹脂組成物，其係硬化物之線膨脹率(α 1)、玻璃轉移點、貯藏彈性率(25℃)、硬化前之滲透性(120℃)滿足以下之全部的要件；線膨脹率(α 1)：60ppm/℃以下玻璃轉移點：120℃以上貯藏彈性率(25℃)：3.0GPa以下滲透性(120℃)：30mm以上。Therefore, the first aspect of the present invention is an epoxy resin composition for post-penetration sealing, which is a linear expansion ratio (α 1) of a cured product, a glass transition point, a storage modulus (25 ° C), and a permeability before hardening. (120 ° C) meets all of the following requirements; linear expansion ratio (α 1): 60 ppm / ° C or less glass transition point: storage elastic modulus above 120 ° C (25 ° C): permeability below 3.0 GPa (120 ° C): 30 mm or more .
本發明之第二係上述第一記載之後滲透密封用之環氧樹脂組成物，其係由以下之(A)~(D)成分所構成；(A)成分：環氧樹脂(B)成分：於1分子內具有3個以上之環氧基與芳香環的化合物(C)成分：丁二烯橡膠粉或丙烯酸橡膠粉(D)成分：潛在性硬化劑。The second aspect of the present invention is the epoxy resin composition for permeation sealing after the first description, which is composed of the following components (A) to (D); and (A) component: epoxy resin (B) component: Compound (C) having three or more epoxy groups and an aromatic ring in one molecule: butadiene rubber powder or acrylic rubber powder (D) component: latent curing agent.
本發明之第三係上述第二記載之後滲透密封用之環氧樹脂組成物，其中相對於(A)成分與(B)成分之合計100質量份而言，係添加(C)成分3~10質量份，同時實質上不含有(C)成分以外之填充劑。In the third aspect of the present invention, the epoxy resin composition for osmosis sealing according to the second aspect, wherein (C) component 3 to 10 is added to 100 parts by mass of the total of the components (A) and (B). A part by mass, and substantially no filler other than the component (C).
本發明之第四係上述第一~第三記載中任一項之後滲透密封用之環氧樹脂組成物，其中在室溫下實質上不含有液狀之硬化劑。According to a fourth aspect of the invention, the epoxy resin composition for osmosis sealing after any one of the first to third aspects, wherein the liquid hardener is substantially not contained at room temperature.
若依本發明，係可提供一種具有對信賴性試驗之耐性，同時常溫(25℃)環境及120℃環境的滲透性高之後滲透型的底部填充劑。According to the present invention, it is possible to provide an osmotic underfill having a resistance to a reliability test while having a high permeability in a normal temperature (25 ° C) environment and a 120 ° C environment.
其次說明本發明之內容。封裝用之底部填充劑的主要硬化物特性係藉由玻璃轉移點(Tg)、確認線膨脹率(較玻璃轉移點更低溫側之α 1、高溫側之α 2)之熱機械分析裝置(TMA)或貯藏彈性率(E')、損失彈性率(E")、玻璃轉移點、確認tan δ之動態黏彈性測定裝置(DMA)進行測定。在本發明中係發現在玻璃轉移點(以TMA測定)、線膨脹率(α 1)及25℃之貯藏彈性率(E')中具有特定之硬化物特性的樹脂組成物適於後滲透型底部填充劑。(以下，所謂玻璃轉移點係以TMA所測得者，所謂α 1係較以TMA所測得之玻璃轉移點更低溫側的線膨脹率，所謂E'(25℃)係以DMA所測得之在25℃中的貯藏彈性率)適於本發明之參數係以Tg為120℃以上、α 1為60ppm/℃以下、E'為3.0GPa以下為佳。E'中尤佳者係E'(25℃)為2.5GPa以下。最佳之要件係Tg為120~200℃、α 1為10~60ppm/℃，E'為0.1~3.0GPa。底部填充劑有採取玻璃轉移點高且降低線膨脹率之方法的傾向。此係在高溫放置試驗、熱衝擊試驗、高溫高濕試驗等之信賴性試驗中的溫度區域，以免電子電路中斷。又，認為依熱履歷降低線膨脹率以免底部填充劑之硬化物膨脹。但，若為高玻璃轉移點、低線膨脹率，硬化物會變脆，故無法追蹤在信賴性試驗中之被黏體的膨脹收縮之變化。為克服此點，在本發明中係降低E'(25℃)，具彈力，得到具有追蹤性之硬化物上具有一個特徵。進一步，使E'(25℃)為1.0GPa以下係可為軟質環氧樹脂或胺基甲酸酯樹脂，但必然出現Tg降低，且α1變高之傾向，故必須滿足Tg、α1、E'(25℃)之3種類的參數。進一步，於被CSP或BGA基板挾住之100～300μm的間隙滲透樹脂組成物時，就形成填料(fillet)上有效之參數而言可舉例在120℃環境之滲透性。信賴性試驗之結果依形成填料(fillet)變化，故在本發明中，必須滿足120℃環境的滲透性。底部填充劑之硬化性高時，在未充分滲透於間隙之階段流動性會消失。另外，硬化性低時，硬化時間太長，於作業性造成障礙，因此，尤佳之滲透性為30～60mm。上述係例示性說明，本發明不受其限制。Next, the contents of the present invention will be described. The main hardener property of the underfill for encapsulation is a thermomechanical analysis device (TMA) which confirms the linear expansion ratio (α 1 on the lower temperature side of the glass transition point and α 2 on the higher temperature side) by the glass transition point (Tg). Or the storage elastic modulus (E'), the loss elastic modulus (E"), the glass transition point, and the dynamic viscoelasticity measuring device (DMA) confirming tan δ. In the present invention, the glass transition point (in TMA) was found. The resin composition having a specific hardening property among the linear expansion ratio (α 1) and the storage elastic modulus (E') at 25 ° C is suitable for a post-penetrating underfill. (hereinafter, the so-called glass transition point is The TMA measured the linear expansion rate of the α 1 system on the lower temperature side of the glass transition point measured by TMA. The so-called E' (25 ° C) is the storage modulus at 25 ° C measured by DMA. The parameter suitable for the present invention is preferably Tg of 120 ° C or more, α 1 of 60 ppm / ° C or less, and E' of 3.0 GPa or less. E' (Europe) is preferably E' (25 ° C) of 2.5 GPa or less. The best requirements are Tg of 120~200°C, α1 of 10~60ppm/°C, and E' of 0.1~3.0GPa. The underfill has the advantage of taking the glass transition point and reducing the linear expansion rate. This is the temperature range in the reliability test of high temperature placement test, thermal shock test, high temperature and high humidity test, etc., in order to avoid interruption of electronic circuit. Moreover, it is considered that the thermal expansion rate reduces the linear expansion rate to avoid the hardener of the underfill. In the case of the high glass transition point and the low linear expansion ratio, the hardened material becomes brittle, so that the change in the expansion and contraction of the adherend in the reliability test cannot be traced. To overcome this, in the present invention, Lowering E' (25 ° C), elastic, and having a characteristic on the traceability of the cured material. Further, making E' (25 ° C) 1.0 GPa or less can be a soft epoxy resin or urethane resin. However, there is a tendency for Tg to decrease and α1 to become high. Therefore, it is necessary to satisfy three types of parameters of Tg, α1, and E' (25 ° C). Further, a gap of 100 to 300 μm is sandwiched by a CSP or BGA substrate. In the case of the resin composition, the permeability of the filler can be exemplified in the environment at 120 ° C. The result of the reliability test varies depending on the form of the fillet, so in the present invention, it must satisfy 120 ° C. Environmental permeability. bottom When the hardenability of the filler is high, the fluidity disappears when the hardenability is not sufficiently penetrated into the gap. When the hardenability is low, the hardening time is too long, which causes an obstacle to workability. Therefore, the permeability is preferably 30 to 60 mm. The above is illustrative, and the invention is not limited thereto.
可使用於本發明之(A)成分係於1分子內具有2個以上之環氧基的化合物，一般稱為環氧樹脂之化合物。可使僅使用1種類，亦可混合2種類以上而使用。環氧樹脂之具體例係藉表氯醇與雙酚類等之多價酚類或多元醇之縮合而得到，可例示如雙酚A型、溴化雙酚A型、氫化雙酚A型、雙酚F型、雙酚S型、雙酚AF型、聯苯基、萘型、芴型、酚醛清漆型、酚酚醛清漆型、鄰甲酚酚醛清漆型、三(羥苯基)甲烷型、四苯基醇乙烷型等之縮水甘油基醚型環氧樹脂。其他，藉由表氯醇與酞酸衍生物或脂肪酸等之羧酸的縮合所得到之縮水甘油基酯型環氧樹脂、表氯醇與胺類、三聚氰酸類、乙內醯脲(Hydantoin)類之反應所得到之縮水甘油基胺型環氧樹脂、進一步係以各種的方法改性之環氧樹脂，但不限定於此等。若考慮價格面或安定供給，(A)成分宜於分子內具有平均約2個環氧基之化合物。The component (A) used in the present invention may be a compound having two or more epoxy groups in one molecule, and is generally referred to as a compound of an epoxy resin. It is also possible to use only one type or two or more types. Specific examples of the epoxy resin are obtained by condensation of epichlorohydrin with a polyvalent phenol or a polyhydric alcohol such as a bisphenol, and examples thereof include a bisphenol A type, a brominated bisphenol A type, and a hydrogenated bisphenol A type. Bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl group, naphthalene type, anthraquinone type, novolac type, phenol novolac type, o-cresol novolac type, tris(hydroxyphenyl)methane type, A glycidyl ether type epoxy resin such as a tetraphenylolethane type. In addition, a glycidyl ester type epoxy resin obtained by condensation of epichlorohydrin with a citric acid derivative or a carboxylic acid such as a fatty acid, epichlorohydrin and an amine, a cyanuric acid, and a carbendazim (Hydantoin) The glycidylamine type epoxy resin obtained by the reaction of the type of the epoxy resin is further modified by various methods, but is not limited thereto. In consideration of the price side or the stable supply, the component (A) is preferably a compound having an average of about 2 epoxy groups in the molecule.
所市售之(A)成分係可舉例如Japan Epoxy Resin股份公司製827、828EL等，大日本油墨工業股份公司製之EPICLON830、EXA-835LV等。東都化成股份公司製Epi Tohto YD-128、YDF-170等，但不限定於此等。若考量價格面，宜於分子內具有平均2個環氧基之雙酚A骨架或具有雙酚F骨架之環氧樹脂。The component (A) which is commercially available is, for example, 827, 828EL, manufactured by Japan Epoxy Resin Co., Ltd., and EPICLON 830, EXA-835LV, and the like manufactured by Dainippon Ink Co., Ltd. Dong Toho Chemical Co., Ltd. manufactures Epi Tohto YD-128, YDF-170, etc., but is not limited to this. When considering the price side, it is preferred to have a bisphenol A skeleton having an average of two epoxy groups in the molecule or an epoxy resin having a bisphenol F skeleton.
於本發明可使用之(B)成分係於1分子中具有環氧基3個以上與芳香環之化合物。芳香環之具體例可舉例如苯環、萘環、苯胺環等。具體之3官能的(B)成分可舉例如N,N-雙(2,3-環氧基丙基)-4-(2,3-環氧基丙氧基)苯胺或N,N-雙(2,3-環氧基丙基)-4-(2,3-環氧基丙氧基)-2-甲基苯胺等。又，具體之4官能的(B)成分係可舉例如二胺基二苯基甲烷四縮水甘油基醚。所市售之該化合物係可舉例如Japan Epoxy Resin股份公司製jER630、jER604、荒川化學工業股份公司製之Compoceran E201、E202等，但不限定於此等。(B)成分宜於常溫下為液狀，但在黏度及滲透性不造成障礙的範圍，亦可於環氧樹脂溶解固形之化合物而使用。(B)成分係宜為含有環氧樹脂全體之20～90重量%，添加(B)成分，有提高Tg之傾向。另外，不具有芳香環之3官能以上的環氧樹脂係無法提高Tg，而不適於本發明。The component (B) which can be used in the present invention is a compound having three or more epoxy groups and an aromatic ring in one molecule. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, and an aniline ring. Specific trifunctional (B) components may, for example, be N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline or N,N-double (2,3-Ethoxypropyl)-4-(2,3-epoxypropoxy)-2-methylaniline and the like. Further, the specific tetrafunctional component (B) may, for example, be diaminodiphenylmethanetetraglycidyl ether. The compound which is commercially available is, for example, jER630, jER604, manufactured by Japan Epoxy Resin Co., Ltd., Compoceran E201 and E202 manufactured by Arakawa Chemical Industries Co., Ltd., but is not limited thereto. The component (B) is preferably liquid at normal temperature, but may be used in the case where the epoxy resin dissolves the solid compound in the range where the viscosity and the permeability do not cause an obstacle. The component (B) preferably contains 20 to 90% by weight of the entire epoxy resin, and the component (B) is added, which tends to increase the Tg. Further, an epoxy resin having a trifunctional or higher functional group which does not have an aromatic ring cannot increase the Tg, and is not suitable for the present invention.
於本發明可使用之(C)成分係丁二烯橡膠粉或丙烯酸橡膠粉。單體為從(甲基)丙烯酸酯所聚合之橡膠、或單體為從丁二烯所聚合的橡膠之粉體。聚合或共聚合時，亦可含有(甲基)丙烯酸酯或丁二烯以外之單體的苯乙烯、異戊二烯等。(甲基)丙烯酸酯之具體例可舉例如MMA等，但不限定於此等。在上述中所謂(甲基)丙烯酸酯係丙烯酸酯或/及丙烯酸酯。粉體之平均粒徑為0.05～0.5μm，若考量膨潤所產生的黏度變化，宜為核殼型之(C)成分。藉添加(C)成分，E'變低，就降低E'之效果，(C)成分最宜為由丁二烯所聚合之橡膠粉。The component (C) which can be used in the present invention is a butadiene rubber powder or an acrylic rubber powder. The monomer is a rubber polymerized from (meth) acrylate or a powder of a rubber polymerized from butadiene. In the case of polymerization or copolymerization, styrene, isoprene or the like of a monomer other than (meth) acrylate or butadiene may be contained. Specific examples of the (meth) acrylate include, for example, MMA, but are not limited thereto. In the above, (meth)acrylate-based acrylate or/and acrylate. The average particle diameter of the powder is 0.05 to 0.5 μm. If the viscosity change due to swelling is considered, it is preferably a core-shell type (C) component. By adding the component (C), E' is lowered to lower the effect of E', and the component (C) is most preferably a rubber powder polymerized from butadiene.
亦可使用事前被分散於環氧樹脂內之(C)成分。具體上，於環氧樹脂內被Hyper或均質機等混合攪拌裝置分散之橡膠粒子、或於環氧樹脂內藉乳化聚合所合成之橡膠粒子為相當於此。以乳化聚合之方法最終所形成之橡膠粒子的平均粒徑宜為0.05～0.5μm者。藉由使用事前分散於環氧樹脂之橡膠粒子，有樹脂組成物之製造時成分之處理很簡單的優點。又，環氧樹脂充分浸潤於橡膠粒子，故有時間經過時之黏度變化變少之傾向。It is also possible to use the component (C) which is dispersed in the epoxy resin beforehand. Specifically, the rubber particles dispersed in the epoxy resin by a mixing device such as a Hyper or a homogenizer or the rubber particles synthesized by emulsion polymerization in the epoxy resin correspond to this. The rubber particles finally formed by the emulsion polymerization method preferably have an average particle diameter of 0.05 to 0.5 μm. By using the rubber particles dispersed in advance in the epoxy resin, there is an advantage that the handling of the components in the production of the resin composition is simple. Further, since the epoxy resin is sufficiently infiltrated into the rubber particles, the viscosity change during the passage of time tends to be small.
上述丙烯酸橡膠粒子的具體例可舉例如綜研化學股份公司製MX系列、三菱Rayon股份公司製、Metaprene W系列、Zeon化成股份公司製Zefiac系列等。事前分散橡膠粒子之環氧樹脂的具體例可舉例如Resinous化成股份公司製、RKB系列等。使用乳化聚合之環氧樹脂的具體例可舉例如股份公司日本觸媒製、Acryset BP系列等，但不限定於此等。上述丁二烯橡膠粒子之具體例三菱Rayon股份公司製、Metaprene E系列、Metaprene C系列等。又，使以丁二烯橡膠作為核之核殼粉經分散者，可舉例如股份公司Rane Ace MX136，但不限定於此等。Specific examples of the acryl rubber particles include, for example, the MX series manufactured by the Kyoritsu Chemical Co., Ltd., the Mitsub Rayon Co., Ltd., the Metaprene W series, and the Zefiac series manufactured by Zeon Chemical Co., Ltd. Specific examples of the epoxy resin in which the rubber particles are dispersed in advance include, for example, Resinous Chemical Co., Ltd., and the RKB series. Specific examples of the epoxy resin to be used in the emulsion polymerization include, for example, the Japan Catalyst Co., Ltd. and the Acryset BP series, but are not limited thereto. Specific examples of the above butadiene rubber particles are manufactured by Mitsubishi Rayon Co., Ltd., Metaprene E series, Metaprene C series, and the like. Further, the core shell powder having the butadiene rubber as a core may be dispersed, for example, the company Rane Ace MX136, but is not limited thereto.
相對於(A)成分與(B)成分之合計100質量份，(C)成分之添加量宜為10質量份以下。更宜相對於(A)成分與(B)成分之合計100質量份而言，(C)成分之添加量為3～10質量份。若(C)成分之添加量多於10質量份，α1有變大之傾向，若少於3質量份，E'(25℃)有變高之傾向。The amount of the component (C) to be added is preferably 10 parts by mass or less based on 100 parts by mass of the total of the components (A) and (B). The amount of the component (C) added is preferably from 3 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B). When the amount of the component (C) added is more than 10 parts by mass, α1 tends to become large, and if it is less than 3 parts by mass, E' (25 ° C) tends to become high.
添加氧化鋁、氧化矽、碳酸鈣等無機填充劑係熟悉此技藝者泛用，但在本發明中若添加無機填充劑，為提高E'，最宜實質上不含有。前述之「實質上不含有」意指含有殘留於原料之製造步驟中的雜質時，或E'(25℃)落於3.0GPa以下之範圍，刻意極微量添加無機填充劑之時等為其要件外。The addition of an inorganic filler such as alumina, cerium oxide or calcium carbonate is widely used by those skilled in the art. However, in the present invention, if an inorganic filler is added, it is most preferable to substantially not contain E'. The term "substantially not contained" means that when the impurities remaining in the production step of the raw material are contained, or when E' (25 ° C) falls within the range of 3.0 GPa or less, when an inorganic filler is intentionally added in a minute amount, etc. outer.
可在本發明使用之(D)成分係可舉例如可對於環氧樹脂使用來作為硬化劑，同時粉碎成粉末狀之化合物。亦即，在室溫下固體之前述硬化劑被分散於液狀之環氧樹脂的一液型環氧樹脂中，隨時間造成之黏度變化或物性變化很少等之保存安定性可確保的硬化劑謂潛在性硬化劑。具體上，可舉例如在室溫下粉體之咪唑衍生物、粉體二氰二醯胺、對環氧樹脂加成三級胺而使反應中途停止之環氧基加成物化合物經粉碎之粉末等，但不限定於此等。尤佳係前述環氧基加成物化合物，所市售者可舉例如味之素Fine Techno股份公司製之Aminecure系列或富士化成工業股份公司製之Fujicure系列或旭化成化學股份公司製之Novacure系列等。宜在120℃以下開始反應。The component (D) which can be used in the present invention may, for example, be a compound which can be used as a curing agent for an epoxy resin and pulverized into a powder. That is, the solid hardening agent at room temperature is dispersed in a liquid epoxy resin of a liquid epoxy resin, and the viscosity change or physical property change with time is small, and the preservation stability can be ensured. The agent is a latent hardener. Specifically, for example, an imidazole derivative of a powder at room temperature, a powder of dicyanodiamide, and an epoxy group compound compound in which a tertiary amine is added to an epoxy resin to stop the reaction in the middle of the reaction may be pulverized. Powder or the like, but is not limited thereto. In particular, the above-mentioned epoxy group-containing compound is commercially available, for example, Aminecure series manufactured by Ajinomoto Fine Techno Co., Ltd., Fujiicure series manufactured by Fuji Chemical Industry Co., Ltd., or Novacure series manufactured by Asahi Kasei Chemicals Co., Ltd., and the like. . It is preferred to start the reaction below 120 °C.
酸酐、酚化合物、硫醇化合物等在室溫下液狀的硬化劑亦已知作為環氧樹脂之硬化劑。一般，即使單獨使用前述液狀硬化劑，因硬化慢，故以(D)成分作為硬化促進劑而與前述液狀硬化劑搭配而使用已為人知。但在本發明中若組合前述液狀硬化劑與(D)成分，在120℃環境之滲透性降低，故宜實質上不含有粉體之硬化劑以外。前述之「在室溫下實質上不含有液狀之硬化劑」意指含有殘留於原料之製造步驟中的雜質時，或，即使刻意極微量添加液狀之硬化劑，實質上決定反應性為粉體之硬化劑時等係其要件外。A hardener which is liquid at room temperature such as an acid anhydride, a phenol compound, a thiol compound or the like is also known as a hardener for an epoxy resin. In general, even if the liquid curing agent is used alone, since the curing is slow, it is known to use the component (D) as a curing accelerator in combination with the liquid curing agent. However, in the present invention, when the liquid hardener and the component (D) are combined, the permeability at 120 ° C is lowered, so that it is preferable that the hardener is not substantially contained. The above-mentioned "substantially no liquid-like hardener at room temperature" means that when the impurities remaining in the production step of the raw material are contained, or even if a liquid hardener is added in a minute amount, the reactivity is substantially determined. The hardening agent of the powder is not required.
相對於(A)成分與(B)成分之合計100質量份而言，(D)成分之添加量宜為10～40質量份。少於10質量份時硬化性會降低，多於40質量份時，恐滲透性降低。The amount of the component (D) to be added is preferably 10 to 40 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). When the amount is less than 10 parts by mass, the hardenability is lowered, and when it is more than 40 parts by mass, the permeability is lowered.
本發明之環氧樹脂組成物係在無損本發明之所期望的效果之範圍，亦可適量調配顏料、染料等之著色劑、可塑劑、抗氧化劑、消泡劑、矽烷系偶合劑、流平劑、流變控制劑等之添加劑。藉此等之添加，可得到樹脂強度、接著強度、作業性、保存性等優異之組成物及其硬化物。The epoxy resin composition of the present invention can also blend coloring agents, plasticizers, antioxidants, antifoaming agents, decane coupling agents, and leveling agents of pigments and dyes in an appropriate amount within the range which does not impair the desired effects of the present invention. Additives such as agents, rheology control agents, and the like. By adding this, it is possible to obtain a composition excellent in resin strength, adhesion strength, workability, storage stability, and the like, and a cured product thereof.
其次，舉出實施例而更詳細地說明本發明，但本發明係並非只限定於此等之實施例。Next, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.
[實施例1～12][Examples 1 to 12]
為調製實施例1～12，準備下述成分。In order to prepare Examples 1 to 12, the following components were prepared.
(A)成分：環氧樹脂組成物(A) component: epoxy resin composition
‧雙酚F型環氧樹脂(jER806 Japan Epoxy Resin股份公司製)‧bisphenol F type epoxy resin (jER806 Japan Epoxy Resin Co., Ltd.)
(B)成分：於1分子內具有3個以上之環氧基與芳香環的化合物(B) component: a compound having three or more epoxy groups and an aromatic ring in one molecule
‧於1分子內具有3個以上之環氧基與芳香環的化合物(jER630 Japan Epoxy Resin股份公司製)‧ A compound having three or more epoxy groups and an aromatic ring in one molecule (jER630 Japan Epoxy Resin Co., Ltd.)
‧於1分子內具有3個以上之環氧基與芳香環的化合物(ELM-100住友化學股份公司製)‧ A compound having three or more epoxy groups and an aromatic ring in one molecule (ELM-100, manufactured by Sumitomo Chemical Co., Ltd.)
(C)成分：丁二烯橡膠粉或丙烯酸橡膠粉(C) component: butadiene rubber powder or acrylic rubber powder
‧被分散於環氧樹脂之丁二烯橡膠粉(橡膠含有率：25質量%)(Kane Ace MX136 Kaneka股份公司製)‧ Butadiene rubber powder dispersed in epoxy resin (rubber content: 25% by mass) (Kane Ace MX136 Kaneka Co., Ltd.)
‧丙烯酸橡膠粉(Zefiac F351日本Zeon股份公司製)‧Acrylic rubber powder (made by Zefiac F351 Japan Zeon Co., Ltd.)
‧丙烯酸橡膠粉(GENIOPERL P-52 Wacker Chemie製)‧Acrylic rubber powder (manufactured by GENIOPERL P-52 Wacker Chemie)
(D)成分：潛在性硬化劑(D) Ingredients: latent hardener
‧胺加成物型硬化劑(Fujicure FXR-1030富士化成工業股份公司製)‧Amine addition type hardener (Fujicure FXR-1030 Fuji Chemical Industry Co., Ltd.)
‧胺加成物型硬化劑(Fujicure FXR-1081富士化成工業股份公司製)‧Amine addition type hardener (Fujicure FXR-1081 Fuji Chemical Industry Co., Ltd.)
‧已分散胺加成物型硬化劑之環氧樹脂(Novacure HX-3921 HP旭化成Epoxy股份公司製)‧Epoxy resin with a disperse amine addition type hardener (Novacure HX-3921 HP Asahi Kasei Epoxy Co., Ltd.)
其他之成分Other ingredients
‧矽烷系偶合劑(KBM-403信越化學股份公司製)‧ decane coupling agent (KBM-403 Shin-Etsu Chemical Co., Ltd.)
‧分散劑(BYK-352 BYK Chemic Japan股份公司製)‧Dispersant (BYK-352 BYK Chemic Japan Co., Ltd.)
使(A)成分、(B)成分、(C)成分及其他成分以攪拌機真空脫泡30分鐘並攪拌。但，在實施例8及9中係使該混合物事前通過三輥研磨機2次後投入於攪拌機。其後，添加(D)成分而進一步真空脫泡30分鐘並攪拌。詳細之調製量依表1，數值係全部以質量份表記。The component (A), the component (B), the component (C), and other components were degassed under vacuum for 30 minutes in a blender and stirred. However, in Examples 8 and 9, the mixture was passed through a three-roll mill twice before being introduced into the mixer. Thereafter, the component (D) was added and further defoamed under vacuum for 30 minutes and stirred. The detailed modulation amount is in accordance with Table 1, and the numerical values are all expressed in parts by mass.
[比較例1～8][Comparative Examples 1 to 8]
為調整比較例1～8，加入於實施例1～12使用的成分而準備下述成分。In order to adjust Comparative Examples 1 to 8, the components used in Examples 1 to 12 were added to prepare the following components.
(B')：不具有芳香環而於1分子內具有3個環氧基的化合物(B'): a compound having no aromatic ring and having 3 epoxy groups in one molecule
‧於1分子內具有3個環氧基的脂肪族化合物(Denacol EX-321 Nagase Chemtex股份公司製)‧ an aliphatic compound having three epoxy groups in one molecule (Denacol EX-321 Nagase Chemtex Co., Ltd.)
其他之成分Other ingredients
‧4-甲基六氫酞酸酐/六氫酞酸酐=70/30(Rikacid MH-700新日本理化股份公司)‧4-Methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30 (Rikacid MH-700 New Japan Physical and Chemical Co., Ltd.)
‧氧化矽粉(QS-6 MRC Unitech股份公司製)‧Oxide powder (QS-6 MRC Unitech Co., Ltd.)
使(A)成分、(B)成分、(C)成分及其他成分以攪拌機攪拌30分鐘。但，在比較例1中係使該混合物事前通過三輥研磨機2次後投入於攪拌機。其後，添加(D)成分而進一步真空脫泡30分鐘並攪拌。詳細之調製量依表1，數值係全部以質量份表記。The component (A), the component (B), the component (C), and other components were stirred in a stirrer for 30 minutes. However, in Comparative Example 1, the mixture was passed through a three-roll mill twice before being introduced into the mixer. Thereafter, the component (D) was added and further defoamed under vacuum for 30 minutes and stirred. The detailed modulation amount is in accordance with Table 1, and the numerical values are all expressed in parts by mass.
對於實施例1～12、比較例1～8，實施黏度測定、滲透性測定、TMA測定、DMA測定、抗拉剪切接著力測定。For Examples 1 to 12 and Comparative Examples 1 to 8, viscosity measurement, permeability measurement, TMA measurement, DMA measurement, and tensile shear adhesion measurement were performed.
＜黏度測定＞<Viscometry>
各環氧樹脂組成物之溫度成為室溫後藉黏度計測定「黏度(Pa‧s)」。詳細之測定方法係如以下般。其結果歸納於表2中。在本發明中適用4.0Pa‧s以下。After the temperature of each epoxy resin composition became room temperature, "viscosity (Pa‧s)" was measured by a viscosity meter. The detailed measurement method is as follows. The results are summarized in Table 2. In the present invention, it is applied to 4.0 Pa‧s or less.
製造商：東機產業股份公司TV-33型黏度計(EHD型)Manufacturer: Dongji Industry Co., Ltd. TV-33 viscometer (EHD type)
測定條件Measuring condition
圓錐型旋轉子：3°×R14Conical rotor: 3° × R14
旋轉速度：5.0rpmRotation speed: 5.0rpm
測定溫度：25℃(使用調溫裝置)Measuring temperature: 25 ° C (using thermostat)
＜滲透性測定＞<Permeability measurement>
使厚100μm之短冊狀厚度量測計平行於100mm×50mm之玻璃板之短邊而配置，使再一片之玻璃板些許偏移而挾住厚度量測計，以挾具固定以免厚度量測計偏移。於玻璃板偏移之位置塗佈環氧樹脂組成物後，確認於120℃環境放置15分鐘而從玻璃板之端部滲透的距離而作為「滲透性(mm)」。將其結果歸納於表2。若滲透性差，填料(Fillet)(滲透後之組成物的形狀)之形成差，恐產生在信賴性試驗中應力局部，對於密封劑之破壞或與被黏體之界面的剝離。在本發明中係適宜滲透性為30mm以上。The short book thickness measuring instrument with a thickness of 100 μm is arranged parallel to the short side of the glass plate of 100 mm×50 mm, so that the glass plate of one piece is slightly offset and the thickness gauge is clamped, and the thickness of the measuring device is fixed to avoid thickness measurement. Offset. After the epoxy resin composition was applied to the position where the glass plate was displaced, it was confirmed that it was allowed to stand at 120 ° C for 15 minutes and penetrated from the end of the glass plate as "permeability (mm)". The results are summarized in Table 2. If the permeability is poor, the formation of the filler (the shape of the composition after the infiltration) is poor, and there is a fear that the stress is localized in the reliability test, and the sealant is broken or peeled off from the interface with the adherend. In the present invention, the suitable permeability is 30 mm or more.
＜TMA測定(Tg、α1測定)＞<TMA measurement (Tg, α1 measurement)>
在120℃環境藉15分之硬化製作直徑5mm之圓筒形硬化物，切割成長度10mm。藉TMA以昇溫速度10℃/分昇溫而進行測定。測定「線膨脹率(α1)(ppm/℃)」，藉α1與α2之接線的交點，測定「玻璃轉移點(℃)」。在本發明中係適宜Tg為120℃以上，α1為60ppm/℃以下。A cylindrical hardened body having a diameter of 5 mm was formed by hardening at a temperature of 120 ° C for 15 minutes, and cut into a length of 10 mm. The measurement was carried out by TMA at a temperature increase rate of 10 ° C / min. The "linear expansion ratio (α1) (ppm/°C)" was measured, and the "glass transition point (°C)" was measured by the intersection of the lines of α1 and α2. In the present invention, the Tg is suitably 120 ° C or higher, and α 1 is 60 ppm / ° C or lower.
＜DMA測定(E'(25℃)測定)＞<DMA measurement (E' (25 ° C) measurement)>
在120℃環境藉15分鐘之硬化製作直徑5mm之圓筒形硬化物，切割成長度30mm。以彎曲模式進行測定，以昇溫速度3℃/分進行昇溫。確認頻率1Hz在25℃之「貯藏彈性率(GPa)」。在本發明中適宜E'(25℃)為3.0GPa以下。A cylindrical hardened body having a diameter of 5 mm was formed by hardening for 15 minutes in an environment of 120 ° C, and cut into a length of 30 mm. The measurement was performed in a bending mode, and the temperature was raised at a temperature increase rate of 3 ° C / min. Confirm the "Storage Elasticity (GPa)" at a frequency of 1 Hz at 25 °C. In the present invention, E' (25 ° C) is suitably 3.0 GPa or less.
＜抗拉剪切接著力測定＞<Tensile shear adhesion measurement>
使用玻璃纖維強化環氧樹脂製(FR-4)且10mm×25mm×100mm之測試片，於第1片之測試片均一地展開樹脂組成物，而與第二片之測試片以25mm×10mm之「接著面積」貼合。固定成測試片不動之狀態，藉熱風乾燥爐以120℃、15分鐘硬化。測試片之溫度返回室溫後，以抗拉速度10mm/分使二片之測試片朝逆方向拉張而測定「最大荷重」。使「最大荷重」除以「接著面積」，計算「抗拉剪切接著力(MPa)」。試驗之內容依據JIS K8681。在本發明中若作為標準之接著力具有15MPa以上，即可使用。A test piece made of glass fiber reinforced epoxy resin (FR-4) and 10 mm × 25 mm × 100 mm was used, and the test piece of the first piece was uniformly developed with the resin composition, and the test piece of the second piece was 25 mm × 10 mm. "Next area" fits. It was fixed in a state in which the test piece was not moved, and was hardened by a hot air drying oven at 120 ° C for 15 minutes. After the temperature of the test piece was returned to room temperature, the two test pieces were pulled in the reverse direction at a tensile speed of 10 mm/min to measure the "maximum load". Calculate "Tensile Shear Force (MPa)" by dividing "Maximum Load" by "Continuous Area". The content of the test is based on JIS K8681. In the present invention, if the adhesive force as a standard has 15 MPa or more, it can be used.
從表2可知，在比較例1及比較例3～5中黏度高，伴隨其而在120℃環境之滲透性變差，但在實施例中滲透性全部包含於30mm以上。若比較實施例4與比較例8，可知使用酸酐之比較例8者儘管黏度低，在120℃環境之滲透性會降低。又，從表3，在比較例1～7中，Tg、α1、E'(25℃)之任一者均不適於本發明，但在實施例中全部之參數適於本發明。含有許多(C)成分之比較例3～5係E'(25℃)為3.0GPa以下，但可看到α1變高之傾向。又，從比較例6與7，於1分子中具有3以上之環氧基的脂肪族化合物係降低Tg，故不適於本發明。As is clear from Table 2, in Comparative Example 1 and Comparative Examples 3 to 5, the viscosity was high, and the permeability in the environment at 120 ° C was deteriorated. However, in the examples, the permeability was all contained at 30 mm or more. Comparing Example 4 with Comparative Example 8, it is understood that Comparative Example 8 using an acid anhydride has a low permeability and a low permeability at 120 ° C. Further, from Table 3, in Comparative Examples 1 to 7, any of Tg, α1, and E' (25 °C) is not suitable for the present invention, but all the parameters in the examples are suitable for the present invention. In Comparative Examples 3 to 5 containing a plurality of (C) components, E' (25 ° C) was 3.0 GPa or less, but it was found that α1 became high. Further, from Comparative Examples 6 and 7, an aliphatic compound having 3 or more epoxy groups in one molecule lowers Tg, and thus is not suitable for the present invention.
＜TEG導通試驗＞<TEG continuity test>
藉由模擬形成半導體與基板被電性接續之狀態的Test Element Group(以下稱為TEG)，可確認出作為底部填充劑之性能。模擬半導體之凸塊與模擬基板之凸塊係電性連接，TEG內部之配線全部連接成菊花鏈狀。於模擬基板具有之外部電極抵住測試器之電極而確認導通性。於TEG端部塗佈底部填充劑，以特定方法使底部填充劑滲透於模擬半導體與模擬基板之間隙而硬化。使被底部填充劑密封之TEG投入於熱衝擊試驗、熱循環試驗、高溫放置試驗、低溫放置試驗、恆溫恆濕試驗等之信賴性試驗後，未確保電性接續時係電阻值過負荷。藉此，可模擬性試驗底部填充劑之信賴性。TEG之規格、底部填充劑之硬化條件、信賴性試驗進行之熱循環試驗的條件係如以下般。The performance as an underfill was confirmed by simulating a Test Element Group (hereinafter referred to as TEG) in which a semiconductor and a substrate were electrically connected to each other. The bumps of the analog semiconductor are electrically connected to the bumps of the dummy substrate, and the wirings inside the TEG are all connected in a daisy-chain shape. The conductivity is confirmed by the external electrode of the dummy substrate being pressed against the electrode of the tester. The underfill is applied to the end of the TEG, and the underfill is hardened by infiltrating the gap between the dummy semiconductor and the dummy substrate in a specific manner. After the TEG sealed by the underfill agent is subjected to a reliability test such as a thermal shock test, a heat cycle test, a high temperature placement test, a low temperature placement test, and a constant temperature and humidity test, the resistance value is not overloaded when the electrical connection is not ensured. Thereby, the reliability of the underfill can be simulated experimentally. The conditions of the TEG, the hardening conditions of the underfill, and the conditions of the thermal cycle test conducted by the reliability test are as follows.
TEG規格TEG specifications
晶片規格Wafer specification
晶片大小：9.6mm×9.6mmWafer size: 9.6mm × 9.6mm
晶片厚：725μmWafer thickness: 725μm
凸塊材質：Sn/3.0Ag/0.5 CuBump material: Sn/3.0Ag/0.5 Cu
凸塊高度：245μmBump height: 245μm
凸塊形成方法：球體搭載Bump formation method: ball loading
圖型規格Graphic specification
金屬墊節距：500μmMetal pad pitch: 500μm
金屬墊大小：300μm×300μmMetal pad size: 300μm × 300μm
墊數：324Number of pads: 324
底部填充劑硬化條件(含有滲透步驟)Underfill hardening conditions (with infiltration step)
120℃×15分120 ° C × 15 points
熱循環試驗Thermal cycle test
1循環：-40℃×30分+85℃×30分，全部實施2000循環1 cycle: -40 ° C × 30 minutes + 85 ° C × 30 minutes, all implemented 2000 cycles
測試片數：5(以下，使測試片稱為TEG)使用於TEG導通試驗之底部填充劑係具有表4所示之特性者。本發明係使用實施例1。又，商品A～C在本發明中相當於比較例之底部填充劑。Number of test pieces: 5 (hereinafter, the test piece is called TEG) The underfill used in the TEG conduction test has the characteristics shown in Table 4. The present invention uses Example 1. Further, in the present invention, the products A to C correspond to the underfill of the comparative example.
以前述之條件進行熱循環試驗的結果表示於圖1。以25、100、200、500、750、1000、1500、2000循環從熱循環試驗器取出，測試片返回室溫後藉測試器確認導通性。未確保導通性之測試片判斷為「不良」。The results of the thermal cycle test under the above conditions are shown in Fig. 1. It was taken out from the thermal cycle tester at 25, 100, 200, 500, 750, 1000, 1500, 2000 cycles, and the test piece was returned to room temperature, and the tester was used to confirm the conductivity. A test piece that does not ensure continuity is judged as "poor".
如圖1般，在實施例1中2000循環結束時亦確保導通性，在商品名A～C中急速或徐緩地產生未確保導通性之TEG。可知使用TEG而進行模擬性試驗，但藉底部填充劑對TEG之信賴造成很大的影響。As shown in Fig. 1, in the first embodiment, the continuity was ensured at the end of the 2000 cycle, and the TEG in which the conductivity was not ensured was rapidly or slowly generated in the trade names A to C. It can be seen that the TEM is used for the simulation test, but the underfill has a great influence on the trust of TEG.
本發明之環氧樹脂組成物係塗佈密封劑後，不須在室溫下放置，可立即投入於120℃環境，同時形成最適的填料之底部填充劑。認為藉此，可謀求生產線之縮短，有助於生產效率之提昇者。進一步，使硬化物之特性於一定的範圍內，可提昇信賴性試驗的耐性。將來，封裝體之小型化持續進展，對於底部填充劑之信賴性提昇的要求會進一步加強。只以高填充無機填充劑之各種習知方法很難提昇信賴性，而以控制環氧樹脂之參數俾可因應小型化。The epoxy resin composition of the present invention is applied to the sealant without being left at room temperature, and can be immediately put into the environment at 120 ° C to form an optimum filler underfill. It is thought that this can shorten the production line and contribute to the improvement of production efficiency. Further, by making the characteristics of the cured product within a certain range, the resistance of the reliability test can be improved. In the future, the miniaturization of the package will continue to progress, and the requirement for improved reliability of the underfill will be further enhanced. It is difficult to improve the reliability by various conventional methods of filling the inorganic filler with high filling, and the parameters for controlling the epoxy resin can be miniaturized.
圖1係表示將使用本發明之底部填充劑的TEG施以熱循環試驗時之導通試驗結果的圖。Fig. 1 is a graph showing the results of a conduction test when a TEG using the underfill of the present invention is subjected to a heat cycle test.
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| JP (1) | JP6115929B2 (en) |
| KR (1) | KR20120027191A (en) |
| CN (1) | CN102378790B (en) |
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| WO2001023625A1 (en) | 1999-09-29 | 2001-04-05 | Nkk Corporation | Sheet steel and method for producing sheet steel |
| JP5290515B2 (en) * | 2006-12-25 | 2013-09-18 | パナソニック株式会社 | Epoxy resin composition for sealing electronic parts and resin-sealed electronic parts using the same |
| TWI609917B (en) * | 2011-05-31 | 2018-01-01 | Ajinomoto Co., Inc. | Resin composition |
| CN102801115B (en) * | 2012-08-03 | 2016-04-27 | 天津合纵电力设备有限公司 | Static seal structure between SMC1 gas-insulated switch two kinds of unlike materials |
| JP2019199511A (en) * | 2018-05-15 | 2019-11-21 | 旭化成株式会社 | Method for producing epoxy resin composition |
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| JPH0770406A (en) * | 1993-08-31 | 1995-03-14 | Tonen Corp | Low temperature curing epoxy resin for prepreg and prepreg using the same |
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| JPH07196769A (en) * | 1993-12-28 | 1995-08-01 | Tonen Corp | Epoxy resin composition for low-temperature curing type prepreg and prepreg using the same |
| WO2000060005A1 (en) * | 1999-04-01 | 2000-10-12 | Mitsui Chemicals, Inc. | Sealing material composition for liquid crystal |
| JP2003055434A (en) * | 2001-08-15 | 2003-02-26 | Toto Kasei Co Ltd | Flame retardant for synthetic resin, and flame- retardant resin composition containing the flame retardant |
| JP3722427B2 (en) * | 2001-12-20 | 2005-11-30 | ジャパンエポキシレジン株式会社 | Epoxy resin composition |
| JP2006241252A (en) * | 2005-03-01 | 2006-09-14 | Sekisui Chem Co Ltd | Epoxy resin cured product, sheet made thereof and manufacturing method of the epoxy resin cured product |
| JP4826728B2 (en) * | 2005-09-28 | 2011-11-30 | 株式会社スリーボンド | Thermosetting resin composition |
| JP5340558B2 (en) * | 2007-05-17 | 2013-11-13 | 日東電工株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device obtained using the same |
| JP2010221526A (en) * | 2009-03-24 | 2010-10-07 | Sumitomo Bakelite Co Ltd | Metal clad laminated plate, printed circuit board, and semiconductor device |
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| WO2010117081A1 (en) | 2010-10-14 |
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| JPWO2010117081A1 (en) | 2012-10-18 |
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