JP6115929B2 - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- JP6115929B2 JP6115929B2 JP2011508407A JP2011508407A JP6115929B2 JP 6115929 B2 JP6115929 B2 JP 6115929B2 JP 2011508407 A JP2011508407 A JP 2011508407A JP 2011508407 A JP2011508407 A JP 2011508407A JP 6115929 B2 JP6115929 B2 JP 6115929B2
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- 229920000647 polyepoxide Polymers 0.000 title claims description 54
- 239000003822 epoxy resin Substances 0.000 title claims description 50
- 239000000203 mixture Substances 0.000 title claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 48
- 239000012298 atmosphere Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 25
- 230000035699 permeability Effects 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 17
- 230000009477 glass transition Effects 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000003700 epoxy group Chemical group 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 9
- 229920000800 acrylic rubber Polymers 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 230000035515 penetration Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- 239000005060 rubber Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011256 inorganic filler Substances 0.000 description 12
- 229910003475 inorganic filler Inorganic materials 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 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 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 229920000297 Rayon Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 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
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- -1 glycidyl ester Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal 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
- 150000002989 phenols Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000565 sealant 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
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004283 Sodium sorbate Substances 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 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
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 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
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 230000006378 damage Effects 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
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 239000000463 material Substances 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
- 150000003021 phthalic acid derivatives Chemical class 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
- 239000004302 potassium sorbate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000003756 stirring 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
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- 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
-
- 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
- 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
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- 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
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- 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
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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
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- 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
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- 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
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- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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Description
本発明は、チップサイズパッケージ（ＣＳＰ）、ボールグリッドアレイ（ＢＧＡ）、ウェハーレベル（ＷＬ−ＣＳＰ）などのハンダボールと基板電極を接続した後に行う樹脂組成物による封止に適した後浸透封止用のエポキシ樹脂組成物に関するものである。 The present invention is a post-osmotic sealing suitable for sealing with a resin composition performed after a solder ball such as a chip size package (CSP), a ball grid array (BGA), or a wafer level (WL-CSP) is connected to a substrate electrode. The present invention relates to an epoxy resin composition.
基板実装では半田のセルフアライメント効果により半田ボールと基板電極を接続し、洗浄工程を経て硬化型樹脂組成物をクリアランスに流し込んだ後に硬化する封止手法が行われている。この封止剤を一般的にはアンダーフィル剤と呼ばれているが、その組成はエポキシ樹脂で実績がある。一方、特表２００３−５０４８９３号公報に開示されているようなウレタン樹脂のアンダーフィル剤も知られている。ウレタン樹脂の場合、リペアー性を特徴とすることから、信頼性が低い場合がある。 In substrate mounting, a sealing method is used in which a solder ball and a substrate electrode are connected by a self-alignment effect of solder, a curable resin composition is poured into a clearance through a cleaning process, and then cured. This sealant is generally called an underfill agent, but its composition has been proven with epoxy resins. On the other hand, a urethane resin underfill agent as disclosed in JP-T-2003-504893 is also known. In the case of a urethane resin, since it is characterized by repairability, reliability may be low.
一方、ゴム成分を添加して信頼性を向上させる手法がある。ゴム骨格を有する硬化性樹脂やゴム粉体を添加した硬化性樹脂が使用されている。特開２００１−２７０９７６号公報にはゴム粉と無機充填剤を添加した封止用エポキシ樹脂が、また特開平９−１５３５７０号公報には特殊なブタジエン共重合体の粉体と無機充填剤を添加した封止用エポキシ樹脂が開示されている。従来のアンダーフィル剤ではアルミナやシリカなどの無機充填剤を必須としている。無機充填剤を添加することにより線膨張率を低くし有機材料の欠点である熱時の膨張を下げる試みが行われている。しかしながら、無機充填剤の添加量が多くなるため、粘度が高くなり浸透性が低下する。 On the other hand, there is a technique for improving reliability by adding a rubber component. A curable resin having a rubber skeleton or a curable resin added with rubber powder is used. JP 2001-270976 discloses a sealing epoxy resin to which rubber powder and an inorganic filler are added, and JP 9-153570 A adds a special butadiene copolymer powder and an inorganic filler. An epoxy resin for sealing is disclosed. Conventional underfill agents require inorganic fillers such as alumina and silica. Attempts have been made to lower the coefficient of linear expansion by adding an inorganic filler to reduce the expansion during heating, which is a drawback of organic materials. However, since the amount of the inorganic filler added increases, the viscosity increases and the permeability decreases.
特開２００８−２０８１８２号公報にはアクリルゴム粉とシリコーンゴム粉を同時に添加することなどが記載されている。無機充填材を添加することで特性が向上することも記載されており、実質的に上記の２種類のゴム粉と無機充填材とを併用添加することが好ましいことが記載されている。 Japanese Patent Application Laid-Open No. 2008-208182 describes that acrylic rubber powder and silicone rubber powder are added simultaneously. It is also described that the characteristics are improved by adding an inorganic filler, and it is described that it is preferable to substantially add the two kinds of rubber powder and the inorganic filler together.
特開２００７−２４６７１３号公報には多官能のグリシジルアミン型エポキシ樹脂を使用したリレー（継電器）用の封止用エポキシ樹脂開示されている。隙間に流し込むという点ではアンダーフィル剤と用途が近似しているが、接続された電極を保持するという実装用途よりは信頼性が要求されない。 Japanese Unexamined Patent Application Publication No. 2007-246713 discloses a sealing epoxy resin for relays (relays) using a polyfunctional glycidylamine type epoxy resin. Although the use is similar to the underfill agent in terms of pouring into the gap, reliability is not required more than the mounting use of holding the connected electrode.
今日まで、信頼性試験に対する耐性を有ると共に、常温（２５℃）雰囲気および１２０℃雰囲気の浸透性が高い後浸透型のアンダーフィル剤は見いだされていず、本発明の目的は、上記した要求特性を満足する後浸透封止用のエポキシ樹脂組成物を提供することにある。
［発明の要約］To date, no post-penetration type underfill agent having a resistance to a reliability test and having a high permeability in a normal temperature (25 ° C.) atmosphere and a 120 ° C. atmosphere has not been found. Is to provide an epoxy resin composition for post-penetration sealing that satisfies the above.
[Summary of Invention]
本発明者は、上記目的を達成するべく鋭意検討した結果、硬化物の線膨張率（α１）：１２０℃雰囲気下で１５分硬化したときに１０ｐｐｍ／℃以上６０ｐｐｍ／℃以下、ガラス転移点：１２０℃雰囲気下で１５分硬化したときに１２０℃以上２００℃以下、貯蔵弾性率（２５℃）：１２０℃雰囲気下で１５分硬化したときに０．１ＧＰａ以上３．０ＧＰａ以下であり、硬化前の浸透性（１２０℃）：クリアランス１００μｍのガラス板において１２０℃雰囲気下で１５分放置後に３０ｍｍ以上６０ｍｍ以下のパラメーターを有するエポキシ樹脂組成物がアンダーフィル剤に適している事を見いだし本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor has found that the linear expansion coefficient (α1) of the cured product: 10 ppm / ° C. or more and 60 ppm / ° C. or less when cured for 15 minutes in an atmosphere of 120 ° C., glass transition point: 120 ° C to 200 ° C when cured for 15 minutes in a 120 ° C atmosphere, storage modulus (25 ° C): 0.1 GPa to 3.0 GPa when cured for 15 minutes in a 120 ° C atmosphere, before curing Penetration (120 ° C.): An epoxy resin composition having a parameter of 30 mm or more and 60 mm or less after standing for 15 minutes in a 120 ° C. atmosphere on a glass plate having a clearance of 100 μm was found to be suitable for an underfill agent and completed the present invention. It came to do.
従って、本発明の第一は、下記の（Ａ）〜（Ｄ）成分からなり、
（Ａ）成分：１分子内に平均２個のエポキシ基を有する常温で液体のエポキシ樹脂
（Ｂ）成分：１分子内に３以上のエポキシ基と芳香環を有する常温で液体の化合物
（Ｃ）成分：ブタジエンゴム粉または（メタ）アクリル酸エステルから重合されるアクリルゴム粉
（Ｄ）成分：１２０℃以下で反応を開始するアミンアダクト型潜在性硬化剤
硬化物の線膨張率（α１）、ガラス転移温度、貯蔵弾性率（２５℃）、硬化前の浸透性（１２０℃）が以下の全ての要件を満たし、
線膨張率（α１）：１２０℃雰囲気下で１５分硬化したときに１０ｐｐｍ／℃以上６０ｐｐｍ／℃以下
ガラス転移点：１２０℃雰囲気下で１５分硬化したときに１２０℃以上２００℃以下
貯蔵弾性率（２５℃）：１２０℃雰囲気下で１５分硬化したときに０．１ＧＰａ以上３．０ＧＰａ以下
浸透性（１２０℃）：クリアランス１００μｍのガラス板において１２０℃雰囲気下で１５分放置後に３０ｍｍ以上６０ｍｍ以下
（Ａ）成分と（Ｂ）成分の合計のうち（Ｂ）成分の割合は２０〜９０重量％であり、
（Ａ）成分と（Ｂ）成分の合計１００質量部に対して（Ｃ）成分が３〜１０質量部添加され、
（Ａ）成分と（Ｂ）成分の合計１００質量部に対して（Ｄ）成分が８．６〜４０質量部添加されると共に、
（Ｃ）成分以外の充填剤を実質的に含まず、
芳香環を有しない３官能以上のエポキシ樹脂を含まず、
室温で液状の硬化剤を実質的に含まない
後浸透封止用のエポキシ樹脂組成物である。
Accordingly, the first of the present invention comprises the following components (A) to (D):
Component (A): Epoxy resin that is liquid at room temperature having an average of two epoxy groups in the molecule (B) Component: Compound that is liquid at room temperature having three or more epoxy groups and an aromatic ring in the molecule (C) Ingredient: Acrylic rubber powder polymerized from butadiene rubber powder or (meth) acrylic acid ester (D) Ingredient: Amine adduct type latent curing agent that starts reaction at 120 ° C. or lower Curing coefficient expansion coefficient (α1), glass transition temperature, storage modulus (25 ° C.), before curing permeability (120 ° C.) is less than all of the following requirements,
Linear expansion coefficient (α1): 10 ppm / ° C. or more and 60 ppm / ° C. or less when cured for 15 minutes in a 120 ° C. atmosphere Glass transition point: 120 ° C. or more and 200 ° C. or less for 15 minutes when cured in a 120 ° C. atmosphere Storage modulus (25 ° C.): 0.1 GPa or more and 3.0 GPa or less when cured for 15 minutes in a 120 ° C. atmosphere Penetration (120 ° C.): 30 mm or more and 60 mm or less after standing for 15 minutes in a 120 ° C. atmosphere on a 100 μm clearance glass plate
The ratio of the component (B) in the total of the component (A) and the component (B) is 20 to 90% by weight,
3 to 10 parts by mass of component (C) is added to 100 parts by mass of component (A) and component (B).
While (8.6) -40 parts by mass of component (D) is added to 100 parts by mass of the total of component (A) and component (B),
(C) contains substantially no filler other than the component,
Does not contain trifunctional or higher functional epoxy resin without aromatic ring,
Contains virtually no liquid curing agent at room temperature
It is an epoxy resin composition for post-osmosis sealing.
本発明の第二は、前記線膨張率（α１）が１２０℃雰囲気下で１５分硬化したときに５５ｐｐｍ／℃以上６０ｐｐｍ／℃以下、前記ガラス転移点が１２０℃雰囲気下で１５分硬化したときに１２０℃以上１４８℃以下、前記貯蔵弾性率（２５℃）が１２０℃雰囲気下で１５分硬化したときに１．７ＧＰａ以上２．８ＧＰａ以下、前記浸透性（１２０℃）がクリアランス１００μｍのガラス板において１２０℃雰囲気下で１５分放置後に３０ｍｍ以上４３ｍｍ以下である上記第一に記載の後浸透封止用のエポキシ樹脂組成物である。 In the second aspect of the present invention, the linear expansion coefficient (α1) is 55 ppm / ° C. or more and 60 ppm / ° C. or less when cured for 15 minutes in a 120 ° C. atmosphere, and the glass transition point is cured for 15 minutes in a 120 ° C. atmosphere. A glass plate having a storage modulus (25 ° C.) of not less than 120 ° C. and not more than 148 ° C. and a storage modulus (25 ° C.) of 1.7 GPa to 2.8 GPa when cured for 15 minutes in an atmosphere of 120 ° C., and a permeability of 120 μm. in an epoxy resin composition for penetration sealing after according to the first Ru der least 43mm below 30mm after standing 15 minutes under 120 ° C. atmosphere.
本発明によれば、信頼性試験に対する耐性を有ると共に、常温（２５℃）雰囲気および１２０℃雰囲気の浸透性が高い後浸透型のアンダーフィル剤を提供することが可能となる。 According to the present invention, it is possible to provide a post-penetration type underfill agent having resistance to a reliability test and having high permeability in a normal temperature (25 ° C.) atmosphere and a 120 ° C. atmosphere.
図１は本発明のアンダーフィル剤を用いたＴＥＧをヒートサイクル試験にかけた時の導通試験結果を示すグラフである。 FIG. 1 is a graph showing a continuity test result when a TEG using the underfill agent of the present invention is subjected to a heat cycle test.
本発明の詳細を次に説明する。実装用のアンダーフィル剤の主な硬化物特性は、ガラス転移点（Ｔｇ）、線膨張率（ガラス転移点より低温側のα１、高温側のα２）を確認する熱機械分析装置（ＴＭＡ）や貯蔵弾性率（Ｅ’）、損失弾性率（Ｅ”）、ガラス転移点、ｔａｎδを確認する動的粘弾性測定装置（ＤＭＡ）により測定する。本発明では、ガラス転移点（ＴＭＡによる）、線膨張率（α１）および２５℃の貯蔵弾性率（Ｅ’）において特定の硬化物特性を有する樹脂組成物が後浸透型アンダーフィル剤に適していることを見いだした。（以下、ガラス転移点とはＴＭＡによるものとし、α１とはＴＭＡによるガラス転移点より低温側の線膨張率とし、Ｅ’（２５℃）とはＤＭＡによる２５℃における貯蔵弾性率とする。）本発明に適しているパラメーターとしては、Ｔｇが１２０℃以上、α１が６０ｐｐｍ／℃以下、Ｅ’が３．０ＧＰａ以下であることが好ましい。Ｅ’において特に好ましいのは、Ｅ’（２５℃）が２．５ＧＰａ以下である。最も好ましい要件は、Ｔｇが１２０〜２００℃、α１が１０〜６０ｐｐｍ／℃、Ｅ’が０．１〜３．０ＧＰａである。アンダーフィル剤はガラス転移点を高く、線膨張率を低くする手法がとられる傾向がある。これは高温放置試験、ヒートショック試験、高温高湿試験などの信頼性試験に於ける温度領域で、電子回路が寸断しないようにするためである。また、熱履歴によりアンダーフィル剤の硬化物が膨張しない様に線膨張率を低くしていると考えられる。しかしながら、高ガラス転移点、低線膨張率にすると硬化物が脆くなるため、信頼性試験における被着体の膨張収縮の変化に追従することができない。この点を克服するため本発明では、Ｅ’（２５℃）を低くし弾力があり追従性がある硬化物を得ることに一つの特徴がある。さらに、Ｅ’（２５℃）を１．０ＧＰａ以下にすることは軟質エポキシ樹脂やウレタン樹脂で可能となるが、必然的にＴｇが低くなり、α１が高くなる傾向がでるため、Ｔｇ、α１、Ｅ’（２５℃）の３種類のパラメーターを満たすことが必要である。さらには、ＣＳＰやＢＧＡと基板に挟まれた１００〜３００μｍのクリアランスに樹脂組成物を浸透させる時に、フィレット形成に有効なパラメーターとして１２０℃雰囲気における浸透性が挙げられる。フィレット形成により信頼性試験の結果が変化するため、本発明においては１２０℃雰囲気の浸透性を満たす必要がある。アンダーフィル剤の硬化性が高い場合、クリアランスに十分浸透しない段階で流動性が無くなる。一方、硬化性が低い場合、硬化時間が長くなり過ぎてしまい作業性に支障が出る。そのため、特に好ましい浸透性としては３０〜６０ｍｍである。上記は例示的説明であり、それによって本発明が制限されるものではない。 Details of the present invention will be described below. The main cured product characteristics of the underfill agent for mounting are a thermomechanical analyzer (TMA) for confirming the glass transition point (Tg) and the linear expansion coefficient (α1 on the low temperature side and α2 on the high temperature side from the glass transition point) The storage elastic modulus (E ′), loss elastic modulus (E ″), glass transition point, and tan δ are measured by a dynamic viscoelasticity measuring device (DMA). In the present invention, glass transition point (by TMA), line It has been found that a resin composition having specific cured product characteristics in terms of expansion coefficient (α1) and storage elastic modulus (E ′) at 25 ° C. is suitable for a post-penetration type underfill agent (hereinafter referred to as a glass transition point). Is a linear expansion coefficient at a lower temperature side than the glass transition point by TMA, and E ′ (25 ° C.) is a storage elastic modulus at 25 ° C. by DMA.) Parameters suitable for the present invention As T It is preferable that g is 120 ° C. or more, α1 is 60 ppm / ° C. or less, and E ′ is 3.0 GPa or less, particularly preferably E ′ (25 ° C.) is 2.5 GPa or less. The requirements are Tg of 120 to 200 ° C., α1 of 10 to 60 ppm / ° C., and E ′ of 0.1 to 3.0 GPa, and the underfill agent has a high glass transition point and low linear expansion. This is to prevent the electronic circuit from being broken in the temperature range in the reliability test such as a high temperature storage test, a heat shock test, a high temperature and high humidity test, etc. Also, underfill due to thermal history. It is thought that the linear expansion coefficient is lowered so that the cured product of the agent does not expand, but the cured product becomes brittle when a high glass transition point and a low linear expansion coefficient are used. In order to overcome this problem, the present invention has a characteristic in that E ′ (25 ° C.) is lowered to obtain a cured product having elasticity and followability. , E ′ (25 ° C.) can be set to 1.0 GPa or less with a soft epoxy resin or a urethane resin, but inevitably Tg decreases and α1 tends to increase. Therefore, Tg, α1, E It is necessary to satisfy the three parameters of '(25 ° C). Furthermore, when the resin composition is infiltrated into the clearance of 100 to 300 μm sandwiched between CSP and BGA and the substrate, this parameter is effective for fillet formation. In the present invention, it is necessary to satisfy the permeability of the 120 ° C. atmosphere because the reliability test results change due to the fillet formation.When the underfill agent has high curability, the fluidity is lost when it does not sufficiently penetrate into the clearance. On the other hand, when the curability is low, the curing time becomes too long and the workability is hindered. Therefore, the particularly preferable permeability is 30 to 60 mm. The above is an exemplary description, and the present invention is not limited thereby.
本発明に使用することができる（Ａ）成分は、１分子内に２個以上のエポキシ基を有する化合物であり、一般的にエポキシ樹脂と呼ばれている化合物である。１種類だけ使用しても２種類以上を混合して使用してもよい。エポキシ樹脂の具体例としては、エピクロルヒドリンとビスフェノール類などの多価フェノール類や多価アルコールとの縮合によって得られるもので、例えばビスフェノールＡ型、臭素化ビスフェノールＡ型、水添ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＳ型、ビスフェノールＡＦ型、ビフェニル型、ナフタレン型、フルオレン型、ノボラック型、フェノールノボラック型、オルソクレゾールノボラック型、トリス（ヒドロキシフェニル）メタン型、テトラフェニロールエタン型などのグリシジルエーテル型エポキシ樹脂を例示することができる。その他エピクロルヒドリンとフタル酸誘導体や脂肪酸などのカルボン酸との縮合によって得られるグリシジルエステル型エポキシ樹脂、エピクロルヒドリンとアミン類、シアヌル酸類、ヒダントイン類との反応によって得られるグリシジルアミン型エポキシ樹脂、さらには様々な方法で変性したエポキシ樹脂を挙げられるが、これらに限定されるものではない。価格面や安定供給を考慮すると、（Ａ）成分としては分子内に平均約２個のエポキシ基を有する化合物が好ましい。 The component (A) that can be used in the present invention is a compound having two or more epoxy groups in one molecule, and is a compound generally called an epoxy resin. Only one type may be used, or two or more types may be mixed and used. Specific examples of epoxy resins are those obtained by condensation of epichlorohydrin with polyhydric phenols such as bisphenols and polyhydric alcohols. For example, bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol F Type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, novolak type, phenol novolak type, orthocresol novolak type, tris (hydroxyphenyl) methane type, tetraphenylolethane type epoxy, etc. Resins can be exemplified. Other glycidyl ester type epoxy resins obtained by condensation of epichlorohydrin with carboxylic acids such as phthalic acid derivatives and fatty acids, glycidyl amine type epoxy resins obtained by reaction of epichlorohydrin with amines, cyanuric acids, hydantoins, and various Examples thereof include, but are not limited to, epoxy resins modified by the method. Considering price and stable supply, the component (A) is preferably a compound having an average of about 2 epoxy groups in the molecule.
市販されている（Ａ）成分としては、ジャパンエポキシレジンレジン株式会社製８２７、８２８ＥＬ等、大日本インキ工業株式会社製のＥＰＩＣＬＯＮ８３０、ＥＸＡ−８３５ＬＶ等が挙げられる。東都化成株式会社製エポトートＹＤ−１２８、ＹＤＦ−１７０等が挙げられるが、これらに限定されるものではない。価格面を考慮すると、分子内に平均２個のエポキシ基を有するビスフェノールＡ骨格またはビスフェノールＦ骨格を有するエポキシ樹脂が好ましい。 Examples of the commercially available component (A) include 827 and 828EL manufactured by Japan Epoxy Resin Co., Ltd., EPICLON 830 and EXA-835LV manufactured by Dainippon Ink Industries, Ltd., and the like. Examples include Etoto YD-128 and YDF-170 manufactured by Toto Kasei Co., Ltd., but are not limited thereto. Considering the price, an epoxy resin having a bisphenol A skeleton or a bisphenol F skeleton having an average of two epoxy groups in the molecule is preferable.
本発明に使用することができる（Ｂ）成分は、１分子中にエポキシ基を３個以上と芳香環とを有する化合物である。芳香環の具体例としては、ベンゼン環、ナフタレン環、アニリン環などが挙げられる。具体的な３官能の（Ｂ）成分としては、Ｎ，Ｎ−ビス（２，３−エポキシプロピル）−４−（２，３−エポキシプロポキシ）アニリンやＮ，Ｎ−ビス（２，３−エポキシプロピル）−４−（２，３−エポキシプロポキシ）−２−メチルアニリンなどが挙げられる。また、具体的な４官能の（Ｂ）成分としては、ジアミノジフェニルメタンテトラグリシジルエーテルが挙げられる。市販されている該化合物としてはジャパンエポキシレジン株式会社製ｊＥＲ６３０、ｊＥＲ６０４、荒川化学工業株式会社製のコンポセランＥ２０１、Ｅ２０２などが挙げられるが、これらに限定されるものではない。（Ｂ）成分は常温にて液状であること好ましいが、粘度および浸透性に支障が出ない範囲でエポキシ樹脂に固形の化合物を溶かして使用することもできる。（Ｂ）成分は、エポキシ樹脂全体の２０〜９０重量％含まれることが好ましく、（Ｂ）成分を添加することでＴｇを高くする傾向がある。一方、芳香環を有しない３官能以上のエポキシ樹脂はＴｇを高くすることができず、本発明には適さない。 The component (B) that can be used in the present invention is a compound having 3 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 examples of the trifunctional component (B) include N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline and N, N-bis (2,3-epoxy). Propyl) -4- (2,3-epoxypropoxy) -2-methylaniline and the like. Specific examples of the tetrafunctional component (B) include diaminodiphenylmethane tetraglycidyl ether. Examples of the commercially available compounds include, but are not limited to, jER630 and jER604 manufactured by Japan Epoxy Resin Co., Ltd. and composeran E201 and E202 manufactured by Arakawa Chemical Industries, Ltd. The component (B) is preferably liquid at room temperature, but it can also be used by dissolving a solid compound in an epoxy resin as long as the viscosity and permeability are not hindered. (B) It is preferable that 20 to 90 weight% of the whole epoxy resin is contained, and there exists a tendency for Tg to become high by adding (B) component. On the other hand, a trifunctional or higher functional epoxy resin having no aromatic ring cannot increase Tg and is not suitable for the present invention.
本発明で使用することができる（Ｃ）成分は、ブタジエンゴム粉またはアクリルゴム粉である。モノマーとして（メタ）アクリル酸エステルから重合されるゴム、またはモノマーとしてブタジエンから重合されるゴムの粉体である。重合または共重合に際して、（メタ）アクリル酸エステルまたはブタジエン以外のモノマーであるスチレン、イソプレンなどが含まれてもよい。（メタ）アクリル酸エステルの具体例としてはＭＭＡなどが挙げられるがこれらに限定されるものではない。上記において（メタ）アクリル酸エステルとはアクリル酸エステルまたは／およびアクリル酸エステルをいう。粉体の平均粒径としては０．０５〜０．５μｍが好ましく、膨潤による粘度変化を考慮するとコアシェル型の（Ｃ）成分が好ましい。（Ｃ）成分を添加することによりＥ’が低くなり、Ｅ’を下げる効果として（Ｃ）成分はブタジエンから重合されるゴム粉であることが最も好ましい。 The component (C) that can be used in the present invention is butadiene rubber powder or acrylic rubber powder. A rubber polymerized from (meth) acrylic acid ester as a monomer, or a rubber powder polymerized from butadiene as a monomer. In polymerization or copolymerization, monomers other than (meth) acrylic acid ester or butadiene may include styrene, isoprene, and the like. Specific examples of (meth) acrylic acid esters include MMA, but are not limited thereto. In the above, (meth) acrylic acid ester means acrylic acid ester or / and acrylic acid ester. The average particle diameter of the powder is preferably 0.05 to 0.5 μm, and the core-shell type (C) component is preferable in consideration of the viscosity change due to swelling. By adding the component (C), E ′ is lowered. As an effect of lowering E ′, the component (C) is most preferably rubber powder polymerized from butadiene.
事前にエポキシ樹脂内に分散された（Ｃ）成分を使用してもよい。具体的には、エポキシ樹脂内にハイパーやホモジナイザーなどの混合撹拌装置により分散されたゴム粒子や、エポキシ樹脂内で乳化重合により合成されたゴム粒子がこれに相当する。乳化重合による手法で最終的に形成されたゴム粒子の平均粒径は、０．０５〜０．５μｍのものが好ましい。エポキシ樹脂に事前に分散されたゴム粒子を使用することにより、樹脂組成物の製造時に成分の取扱いが簡単になるという利点がある。また、エポキシ樹脂が充分にゴム粒子になじむため、時間が経過した時の粘度変化がすくなる傾向がある。 The component (C) dispersed in the epoxy resin in advance may be used. Specifically, rubber particles dispersed in an epoxy resin by a mixing and stirring device such as hyper or homogenizer, and rubber particles synthesized by emulsion polymerization in an epoxy resin correspond to this. The average particle size of the rubber particles finally formed by the emulsion polymerization method is preferably 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 becomes easy during the production of the resin composition. In addition, since the epoxy resin is sufficiently adapted to the rubber particles, there is a tendency that the viscosity changes with time.
上記アクリルゴム粒子の具体例としては、綜研化学株式会社製 ＭＸシリーズ、三菱レイヨン株式会社製 メタブレンＷシリーズ、ゼオン化成株式会社製 ゼフィアックシリーズなどが挙げられる。事前にゴム粒子を分散したエポキシ樹脂の具体例としては、レジナス化成株式会社製 ＲＫＢシリーズなどが挙げられる。乳化重合を用いたエポキシ樹脂の具体例としては、株式会社日本触媒製 アクリセットＢＰシリーズなどが挙げられるが、これらに限定されるものではない。上記ブタジエンゴム粒子の具体例としては、三菱レイヨン株式会社製 メタブレンＥシリーズとメタブレンＣシリーズなどが挙げられる。また、ブタジエンゴムをコアにしたコアシェル粉を分散したものとしては、株式会社カネカ製 カネエースＭＸ１３６が挙げられるが、これに限定されるものではない。 Specific examples of the acrylic rubber particles include MX series manufactured by Soken Chemical Co., Ltd., METABLEN W series manufactured by Mitsubishi Rayon Co., Ltd., and Zefiac series manufactured by ZEON Kasei Co., Ltd. Specific examples of the epoxy resin in which rubber particles are dispersed in advance include RKB series manufactured by Resinas Kasei Co., Ltd. Specific examples of the epoxy resin using emulsion polymerization include, but are not limited to, Acrylic BP series manufactured by Nippon Shokubai Co., Ltd. Specific examples of the butadiene rubber particles include METABLEN E series and METABLEN C series manufactured by Mitsubishi Rayon Co., Ltd. Moreover, Kaneace MX136 manufactured by Kaneka Corporation is exemplified as a dispersion of core-shell powder having butadiene rubber as a core, but is not limited thereto.
（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、（Ｃ）成分の添加量は１０質量部以下が好ましい。さらに好ましくは（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、（Ｃ）成分の添加量が３〜１０質量部である。（Ｃ）成分の添加量が、１０質量部より多いとα１が大きくなる傾向があり、３質量部より少ないとＥ’（２５℃）が高くなる傾向がある。 As for the addition amount of (C) component, 10 mass parts or less are preferable with respect to a total of 100 mass parts of (A) component and (B) component. More preferably, the addition amount of (C) component is 3-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component. When the amount of component (C) added is more than 10 parts by mass, α1 tends to increase, and when it is less than 3 parts by mass, E ′ (25 ° C.) tends to increase.
アルミナ、シリカ、炭酸カルシウムなどの無機充填剤を添加することを当業者は汎用するが、本発明では無機充填剤を添加するとＥ’を高くするため実質的に含まないことが最も好ましい。前記の「実質的に含まない」とは、原料の製造工程中に残留している不純物を含む場合や、Ｅ’（２５℃）が３．０ＧＰａ以下に入る範囲で無機充填剤を意図的に極微量添加している場合などはその要件外であることを意味する。 Those skilled in the art commonly use inorganic fillers such as alumina, silica, and calcium carbonate. However, in the present invention, when an inorganic filler is added, it is most preferable that the inorganic filler is not substantially contained in order to increase E '. The term “substantially free” means that an inorganic filler is intentionally included in the case where impurities remaining in the raw material manufacturing process are included or E ′ (25 ° C.) falls within 3.0 GPa or less. When a very small amount is added, it means that the requirement is not met.
本発明で使用することができる（Ｄ）成分としては、エポキシ樹脂に対して硬化剤として使用できると共に、粉末状に粉砕された化合物が挙げられる。つまり、室温で液状のエポキシ樹脂に室温で固体の前記硬化剤が分散された一液型エポキシ樹脂において、経時による粘度変化や物性変化が少ないなどの保存安定性が確保できる硬化剤を潜在性硬化剤と言う。具体的には、室温で粉体のイミダゾール誘導体、粉体のジシアンジアミド、エポキシ樹脂に三級アミンを付加させて反応を途中で止めているエポキシアダクト化合物を粉砕した粉末などが挙げられるが、これらに限定されるものではない。特に好ましくは、前記エポキシアダクト化合物で、市販されているものとしては味の素ファインテクノ株式会社製のアミキュアシリーズや、富士化成工業株式会社製のフジキュアシリーズや旭化成ケミカルズ株式会社製のノバキュアシリーズなどが挙げられる。１２０℃以下で反応を開始することが好ましい。 (D) component which can be used by this invention can be used as a hardening | curing agent with respect to an epoxy resin, and the compound grind | pulverized to the powder form is mentioned. In other words, in a one-pack type epoxy resin in which the curing agent that is solid at room temperature is dispersed in an epoxy resin that is liquid at room temperature, a curing agent that can ensure storage stability such as little change in viscosity and physical properties over time is latently cured. Say the agent. Specific examples include powdered imidazole derivatives, powdered dicyandiamide, and powders obtained by pulverizing an epoxy adduct compound in which a tertiary amine is added to an epoxy resin to stop the reaction. It is not limited. Particularly preferably, the epoxy adduct compound is commercially available from Ajinomoto Fine Techno Co., Ltd., Amifure Series from Fuji Kasei Kogyo Co., Ltd., Nocure Series from Asahi Kasei Chemicals Co., Ltd., etc. Is mentioned. It is preferable to start the reaction at 120 ° C. or lower.
酸無水物、フェノール化合物、チオール化合物などの室温で液状の硬化剤も、エポキシ樹脂の硬化剤として知られている。通常、前記液状硬化剤を単独で使用しても硬化が遅いため、（Ｄ）成分を硬化促進剤として前記液状硬化剤と合わせて使用することが知られている。しかしながら、本発明においては、前記液状硬化剤と（Ｄ）成分を組み合わせると１２０℃雰囲気における浸透性が低下することから、は粉体の硬化剤以外を実質的に含まないことが好ましい。前記の「室温で液状の硬化剤を実質的に含まない」とは、原料の製造工程中に残留している不純物を含む場合や、液状の硬化剤を意図的に極微量添加しても実質的に反応性を決定しているのが粉体の硬化剤である場合などはその要件外であることを意味する。 Curing agents that are liquid at room temperature, such as acid anhydrides, phenolic compounds, and thiol compounds, are also known as curing agents for epoxy resins. Usually, even if it uses the said liquid hardening | curing agent independently, since hardening is slow, using (D) component together with the said liquid hardening | curing agent as a hardening accelerator is known. However, in the present invention, when the liquid curing agent and the component (D) are combined, the permeability in an atmosphere at 120 ° C. is reduced. The above-mentioned “substantially free of liquid curing agent at room temperature” means that it contains impurities remaining in the raw material production process, or even if a very small amount of liquid curing agent is intentionally added. In other words, it is out of the requirement that the reactivity is determined by a powder curing agent.
（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、（Ｄ）成分の添加量は１０〜４０質量部が好ましい。１０質量部より少ない場合では硬化性が低下し、４０質量部より多い場合では浸透性が低下するおそれがある。 As for the addition amount of (D) component with respect to a total of 100 mass parts of (A) component and (B) component, 10-40 mass parts is preferable. When the amount is less than 10 parts by mass, the curability is lowered, and when the amount is more than 40 parts by mass, the permeability may be lowered.
本発明のエポキシ樹脂組成物には、本発明の所期の効果を損なわない範囲において、顔料、染料などの着色剤、可塑剤、酸化防止剤、消泡剤、シラン系カップリング剤、レベリング剤、レオロジーコントロール剤等の添加剤を適量配合しても良い。これらの添加により、樹脂強度・接着強さ・作業性・保存性等に優れた組成物およびその硬化物が得られる。 The epoxy resin composition of the present invention includes colorants such as pigments and dyes, plasticizers, antioxidants, antifoaming agents, silane coupling agents, and leveling agents, as long as the intended effects of the present invention are not impaired. An appropriate amount of additives such as a rheology control agent may be blended. By these additions, a composition excellent in resin strength, adhesive strength, workability, storage stability and the like and a cured product thereof can be obtained.
次に実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。
［実施例１〜１２］
実施例１〜１２を調製するために下記成分を準備した。EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples.
[Examples 1 to 12]
The following ingredients were prepared to prepare Examples 1-12.
（Ａ）成分：エポキシ樹脂組成物
・ビスフェノールＦ型エポキシ樹脂（ｊＥＲ８０６ ジャパンエポキシレジン株式会社製）
（Ｂ）成分：１分子内に３以上のエポキシ基と芳香環を有する化合物
・１分子内に３以上のエポキシ基と芳香環を有する化合物（ｊＥＲ６３０ ジャパンエポキシレジン株式会社製）
・１分子内に３以上のエポキシ基と芳香環を有する化合物（ＥＬＭ−１００ 住友化学株式会社製）
（Ｃ）成分：ブタジエンゴム粉またはアクリルゴム粉
・エポキシ樹脂に分散されたブタジエンゴム粉（ゴム含有率：２５質量％）（カネエースＭＸ１３６ カネカ株式会社製）
・アクリルゴム粉（ゼフィアック Ｆ３５１ 日本ゼオン株式会社製）
・アクリルゴム粉（ＧＥＮＩＯＰＥＲＬ Ｐ−５２ ＷａｃｋｅｒＣｈｅｍｉｅ製）
（Ｄ）成分：潜在性硬化剤
・アミンアダクト型硬化剤（フジキュアＦＸＲ−１０３０ 富士化成工業株式会社製）
・アミンアダクト型硬化剤（フジキュアＦＸＲ−１０８１ 富士化成工業株式会社製）
・アミンアダクト型硬化剤を分散したエポキシ樹脂（ノバキュアＨＸ−３９２１ＨＰ 旭化成エポキシ株式会社製）
その他の成分
・シラン系カップリング剤（ＫＢＭ−４０３ 信越化学工業株式会社製）
・分散剤（ＢＹＫ−３５２ ビックケミー・ジャパン株式会社製）(A) component: epoxy resin composition-bisphenol F type epoxy resin (made by jER806 Japan Epoxy Resin Co., Ltd.)
Component (B): Compound having 3 or more epoxy groups and aromatic rings in one molecule ・ Compound having 3 or more epoxy groups and aromatic rings in one molecule (manufactured by jER630 Japan Epoxy Resin Co., Ltd.)
・ Compound having 3 or more epoxy groups and aromatic rings in one molecule (ELM-100, manufactured by Sumitomo Chemical Co., Ltd.)
(C) component: butadiene rubber powder or acrylic rubber powder ・ Butadiene rubber powder dispersed in an epoxy resin (rubber content: 25 mass%) (manufactured by Kaneace MX136 Kaneka Corporation)
・ Acrylic rubber powder (Zefiac F351 manufactured by Nippon Zeon Co., Ltd.)
・ Acrylic rubber powder (GENIOPERL P-52 Wacker Chemie)
Component (D): Latent curing agent Amine adduct type curing agent (Fujicure FXR-1030, manufactured by Fuji Chemical Industry Co., Ltd.)
・ Amine adduct type curing agent (Fujicure FXR-1081 manufactured by Fuji Chemical Industry Co., Ltd.)
-Epoxy resin in which amine adduct type curing agent is dispersed (Novacure HX-3922HP, manufactured by Asahi Kasei Epoxy Co., Ltd.)
Other components ・ Silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Dispersant (BYK-352 manufactured by Big Chemie Japan Co., Ltd.)
（Ａ）成分、（Ｂ）成分、（Ｃ）成分およびその他成分を撹拌機にて真空脱泡３０分撹拌した。ただし、実施例８および９では、該混合物を事前に三本ロールミルに２回通した後に撹拌機に投入する。その後、（Ｄ）成分を添加してさらに３０分真空脱泡撹拌した。詳細な調製量は表１に従い、数値は全て質量部で表記する。 The components (A), (B), (C) and other components were stirred with a stirrer for 30 minutes by vacuum defoaming. However, in Examples 8 and 9, the mixture is passed through a three-roll mill twice in advance and then charged into a stirrer. Then, (D) component was added and it vacuum-deaerated and stirred for 30 minutes. Detailed preparation amounts follow Table 1, and all numerical values are expressed in parts by mass.
［比較例１〜８］
比較例１〜８を調整するため、実施例１〜１２で使用する成分に加えて下記成分を準備した。
（Ｂ’）：芳香環を有せず１分子内に３のエポキシ基を有する化合物
・１分子内に３のエポキシ基を有する脂肪族化合物（デナコールＥＸ−３２１ ナガセケムテックス株式会社製）
その他の成分
・４−メチルヘキサヒドロ無水フタル酸／ヘキサヒドロ無水フタル酸＝７０／３０（リカシッド ＭＨ−７００ 新日本理化株式会社）
・シリカ粉（ＱＳ−６ ＭＲＣユニテック株式会社製）[Comparative Examples 1-8]
In order to adjust Comparative Examples 1 to 8, in addition to the components used in Examples 1 to 12, the following components were prepared.
(B ′): Compound having no aromatic ring and having 3 epoxy groups in one molecule • Aliphatic compound having 3 epoxy groups in one molecule (Denacol EX-321 manufactured by Nagase ChemteX Corporation)
Other ingredients ・ 4-Methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30 (Ricacid MH-700 Shin Nippon Rika Co., Ltd.)
・ Silica powder (QS-6 MRC Unitech Co., Ltd.)
（Ａ）成分、（Ｂ）成分、（Ｃ）成分およびその他成分を撹拌機にて３０分撹拌した。ただし、比較例１では、該混合物を事前に三本ロールミルに２回通した後に撹拌機に投入する。その後、（Ｄ）成分を添加してさらに３０分真空脱泡撹拌した。詳細な調製量は表１に従い、数値は全て質量部で表記する。 The component (A), the component (B), the component (C) and other components were stirred with a stirrer for 30 minutes. However, in Comparative Example 1, the mixture is passed through a three-roll mill twice in advance and then charged into a stirrer. Then, (D) component was added and it vacuum-deaerated and stirred for 30 minutes. Detailed preparation amounts follow Table 1, and all numerical values are expressed in parts by mass.
実施例１〜１２、比較例１〜８について、粘度測定、浸透性測定、ＴＭＡ測定、ＤＭＡ測定、引張せん断接着力測定を実施した。
＜粘度測定＞
各エポキシ樹脂組成物の温度が室温になってから粘度計により「粘度（Ｐａ・ｓ）」を測定した。詳細な測定方法は以下の通り。その結果を表２にまとめた。本発明では４．０Ｐａ・ｓ以下が適している。
メーカー：東機産業株式会社 ＴＶ−３３型粘度計（ＥＨＤ型）
測定条件
コーンローター：３°×Ｒ１４
回転速度：５．０ｒｐｍ
測定温度：２５℃（温調装置使用）About Examples 1-12 and Comparative Examples 1-8, the viscosity measurement, the permeability measurement, the TMA measurement, the DMA measurement, and the tensile shear adhesive force measurement were carried out.
<Viscosity measurement>
After the temperature of each epoxy resin composition reached room temperature, “viscosity (Pa · s)” was measured with a viscometer. The detailed measurement method is as follows. The results are summarized in Table 2. In the present invention, 4.0 Pa · s or less is suitable.
Manufacturer: Toki Sangyo Co., Ltd. TV-33 type viscometer (EHD type)
Measurement conditions Cone rotor: 3 ° × R14
Rotation speed: 5.0rpm
Measurement temperature: 25 ° C (use of temperature controller)
＜浸透性測定＞
厚さ１００μｍの短冊状シックネスゲージを１００ｍｍ×５０ｍｍのガラス板の短辺に平行して配置して、もう一枚のガラス板を若干ずらしてシックネスゲージを挟み込み、クリップでシックネスゲージがずれない様に固定する。ガラス板がずれた位置にエポキシ樹脂組成物を塗布した後、１２０℃雰囲気で１５分放置してガラス板の端部から浸透した距離を確認して「浸透性（ｍｍ）」とした。その結果を表２にまとめた。浸透性が悪いと、フィレット（浸透後の組成物の形状）の形成が悪く、信頼性試験において応力が偏り封止剤に対する破壊や被着体との界面におけるはく離をもたらす恐れがある。本発明では、浸透性が３０ｍｍ以上が適している。<Measurement of permeability>
A strip-shaped thickness gauge with a thickness of 100 μm is placed in parallel with the short side of a 100 mm x 50 mm glass plate, the other glass plate is slightly shifted and the thickness gauge is sandwiched, so that the thickness gauge does not shift with a clip. Fix it. After the epoxy resin composition was applied to the position where the glass plate was displaced, it was allowed to stand in an atmosphere of 120 ° C. for 15 minutes, and the distance permeated from the edge of the glass plate was confirmed to be “permeability (mm)”. The results are summarized in Table 2. If the permeability is poor, the formation of fillets (the shape of the composition after the penetration) is poor, and stress may be biased in the reliability test, leading to destruction of the sealant or peeling at the interface with the adherend. In the present invention, a permeability of 30 mm or more is suitable.
＜ＴＭＡ測定（Ｔｇ、α１測定）＞
１２０℃雰囲気で１５分の硬化により直径５ｍｍの円筒形硬化物を作成し、長さ１０ｍｍに切断する。ＴＭＡにより昇温速度１０℃／ｍｉｎで昇温して測定を行った。「線膨張率（α１）（ｐｐｍ／℃）」を測定し、α１とα２の接線の交点により「ガラス転移点（℃）」を測定した。本発明では、Ｔｇが１２０℃以上、α１が６０ｐｐｍ／℃以下が適している。<TMA measurement (Tg, α1 measurement)>
A cylindrical cured product having a diameter of 5 mm is prepared by curing for 15 minutes in an atmosphere of 120 ° C., and cut into a length of 10 mm. The temperature was increased by TMA at a temperature increase rate of 10 ° C./min. “Linear expansion coefficient (α1) (ppm / ° C.)” was measured, and “glass transition point (° C.)” was measured by the intersection of tangent lines of α1 and α2. In the present invention, Tg of 120 ° C. or higher and α1 of 60 ppm / ° C. or lower are suitable.
＜ＤＭＡ測定（Ｅ’（２５℃）測定）＞
１２０℃雰囲気で１５分の硬化により直径５ｍｍの円筒形硬化物を作成し、長さ３０ｍｍに切断する。曲げモードで測定を行い、昇温速度３℃／ｍｉｎで昇温する。周波数１Ｈｚで２５℃に於ける「貯蔵弾性率（ＧＰａ）」を確認した。本発明では、Ｅ’（２５℃）は３．０ＧＰａ以下が適している。<DMA measurement (E ′ (25 ° C.) measurement)>
A cylindrical cured product having a diameter of 5 mm is prepared by curing for 15 minutes in an atmosphere of 120 ° C., and cut into a length of 30 mm. Measurement is performed in a bending mode, and the temperature is increased at a rate of temperature increase of 3 ° C./min. “Storage elastic modulus (GPa)” at 25 ° C. at a frequency of 1 Hz was confirmed. In the present invention, E ′ (25 ° C.) is suitably 3.0 GPa or less.
＜引張せん断接着力測定＞
ガラス繊維強化エポキシ樹脂製（ＦＲ−４）で１０ｍｍ×２５ｍｍ×１００ｍｍのテストピースを用いて、一枚目のテストピースに樹脂組成物を均一に広げて、二枚目のテストピースと２５ｍｍ×１０ｍｍの「接着面積」で貼り合わせる。テストピースが動かない様に固定した状態で、熱風乾燥炉により１２０℃にて１５分で硬化させる。テストピースの温度が室温に戻った後、引張速度１０ｍｍ／ｍｉｎにて二枚のテストピースを逆方向に引っ張って「最大荷重」を測定する。「最大荷重」を「接着面積」で割ることで「引張せん断接着力（ＭＰａ）」を計算する。試験の詳細はＪＩＳＫ８６８１に従う。本発明では、目安として接着力が１５ＭＰａ以上有れば使用することができる。<Measurement of tensile shear adhesive strength>
Using a test piece of 10 mm x 25 mm x 100 mm made of glass fiber reinforced epoxy resin (FR-4), spread the resin composition uniformly on the first test piece, and the second test piece and 25 mm x 10 mm Paste together with the "bonding area". With the test piece fixed so as not to move, it is cured in a hot air drying oven at 120 ° C. for 15 minutes. After the temperature of the test piece returns to room temperature, the “maximum load” is measured by pulling the two test pieces in the opposite direction at a pulling speed of 10 mm / min. “Tensile shear adhesive force (MPa)” is calculated by dividing “maximum load” by “bonding area”. Details of the test conform to JISK8681. In the present invention, it can be used as long as the adhesive strength is 15 MPa or more.
表２から比較例１および比較例３〜５では粘度が高く、それに伴って１２０℃雰囲気における浸透性が悪くなっているが、実施例では浸透性が全て３０ｍｍ以上に含まれる。実施例４と比較例８を比較すると、酸無水物を使用している比較例８の方が粘度が低いにもかかわらず、１２０℃雰囲気での浸透性が低下していることがわかる。また、表３から比較例１〜７ではＴｇ、α１、Ｅ’（２５℃）のいずれかが本発明には適さないが、実施例では全てのパラメーターが本発明に適している。（Ｃ）成分が多く含まれる比較例３〜５はＥ’（２５℃）が３．０ＧＰａ以下ではあるが、α１が高くなる傾向が見られる。また、比較例６と７から１分子中に３以上のエポキシ基を有する脂肪族化合物はＴｇを下げるために本発明には適さない。 From Table 2, Comparative Example 1 and Comparative Examples 3 to 5 have high viscosities, and as a result, the permeability in an atmosphere at 120 ° C. is poor, but in the Examples, all the permeability is included in 30 mm or more. When Example 4 and Comparative Example 8 are compared, it can be seen that Comparative Example 8 using an acid anhydride has lower permeability in a 120 ° C. atmosphere, although the viscosity is lower. Also, from Table 3, in Comparative Examples 1 to 7, any of Tg, α1, E ′ (25 ° C.) is not suitable for the present invention, but in the examples, all parameters are suitable for the present invention. In Comparative Examples 3 to 5 containing a large amount of component (C), E ′ (25 ° C.) is 3.0 GPa or less, but α1 tends to increase. Further, from Comparative Examples 6 and 7, an aliphatic compound having 3 or more epoxy groups in one molecule is not suitable for the present invention because Tg is lowered.
＜ＴＥＧ導通試験＞
半導体と基板が電気的接続をされた状態を擬似的に形成しているＴｅｓｔ Ｅｌｅｍｅｎｔ Ｇｒｏｕｐ（以下、ＴＥＧと言う。）により、アンダーフィル剤としての性能を確認することができる。疑似半導体のバンプと疑似基板のパットは電気的に接続されており、ＴＥＧ内部の配線がすべてデイジーチェーン状に連結している。疑似基板に有る外部電極にテスターの電極を当てて導通性確認をする。ＴＥＧの端部にアンダーフィル剤を塗布して、所定方法でアンダーフィル剤を疑似半導体と疑似基板のクリアランスに浸透させて硬化させる。アンダーフィル剤により封止されたＴＥＧをヒートショック試験、ヒートサイクル試験、高温放置試験、低温放置試験、恒温恒湿試験などの信頼性試験に投入した後、電気的接続が確保されていない場合は抵抗値がオーバーロードになる。これにより、アンダーフィル剤の信頼性を擬似的に試験することができる。ＴＥＧの仕様、アンダーフィル剤の硬化条件、信頼性試験として行ったヒートサイクル試験の条件は以下の通りである。
ＴＥＧ仕様
チップ仕様
チップサイズ：９．６ｍｍ×９．６ｍｍ
チップ厚：７２５μｍ
バンプ材質：Ｓｎ／３．０Ａｇ／０．５Ｃｕ
バンプ高さ：２４５μｍ
バンプ形成方法：ボール搭載
パターン仕様
メタルパットピッチ：５００μｍ
メタルパットサイズ：３００μｍ×３００μｍ
パット数：３２４
アンダーフィル剤硬化条件（浸透工程を含む）
１２０℃×１５分
ヒートサイクル試験
１サイクル：−４０×３０分＋８５℃×３０分として全２０００サイクル実施
テストピース数：５（以下、テストピースをＴＥＧと呼ぶ。）<TEG continuity test>
The performance as an underfill agent can be confirmed by a test element group (hereinafter referred to as TEG) in which a semiconductor and a substrate are electrically connected to each other. The bumps of the pseudo semiconductor and the pads of the pseudo substrate are electrically connected, and all the wiring inside the TEG is connected in a daisy chain shape. Conductivity is confirmed by applying the electrode of the tester to the external electrode on the pseudo substrate. An underfill agent is applied to the end portion of the TEG, and the underfill agent is penetrated into the clearance between the pseudo semiconductor and the pseudo substrate by a predetermined method to be cured. If the electrical connection is not secured after the TEG sealed with the underfill agent is put into reliability tests such as heat shock test, heat cycle test, high temperature storage test, low temperature storage test, constant temperature and humidity test Resistance value is overloaded. Thereby, the reliability of an underfill agent can be tested in a pseudo manner. The TEG specifications, the curing conditions of the underfill agent, and the conditions of the heat cycle test conducted as a reliability test are as follows.
TEG specification Chip specification Chip size: 9.6mm x 9.6mm
Chip thickness: 725 μm
Bump material: Sn / 3.0Ag / 0.5Cu
Bump height: 245μm
Bump formation method: Ball mounting Pattern specification Metal pad pitch: 500μm
Metal pad size: 300μm × 300μm
Number of pads: 324
Underfill agent curing conditions (including penetration process)
120 ° C. × 15 minutes
ＴＥＧ導通試験に用いたアンダーフィル剤は表４に示す特性を有するものである。本発明としては実施例１を用いた。また、商品Ａ〜Ｃは本発明では比較例に相当するアンダーフィル剤である。 The underfill agent used in the TEG continuity test has the characteristics shown in Table 4. Example 1 was used as the present invention. Further, the products A to C are underfill agents corresponding to comparative examples in the present invention.
前記の条件でヒートサイクル試験を行った結果を図１に示す。２５、１００、２００、５００、７５０、１０００、１５００、２０００サイクルでヒートサイクル試験器から取り出し、テストピースが室温に戻ってからテスターにより導通性を確認した。導通性が確保されていないテストピースは「不良」と判断した。 The result of the heat cycle test performed under the above conditions is shown in FIG. It was taken out from the heat cycle tester at 25, 100, 200, 500, 750, 1000, 1500, and 2000 cycles, and the conductivity was confirmed by a tester after the test piece returned to room temperature. A test piece for which continuity was not ensured was judged to be “bad”.
図１の通り、実施例１においては２０００サイクル終了時も導通性を確保しており、商品Ａ〜Ｃでは急激にまたは徐々に導通性が確保されていないＴＥＧが発生している。ＴＥＧを用いて擬似的な試験を行っているものの、アンダーフィル剤によりＴＥＧに対する信頼性に大きな影響を与えていることがわかる。 As shown in FIG. 1, in Example 1, the continuity is secured even at the end of 2000 cycles, and in the products A to C, TEGs in which the continuity is not ensured suddenly or gradually are generated. Although a pseudo test is performed using TEG, it can be seen that the underfill agent greatly affects the reliability of TEG.
本発明のエポキシ樹脂組成物は、封止剤を塗布した後に室温にて放置する必要が無く、１２０℃雰囲気にすぐに投入できると共に、最適なフィレットが形成されるアンダーフィル剤である。これによりラインタクトの短縮が計られ生産効率の向上に寄与するものと考えられる。さらに、硬化物の特性を一定の範囲内にすることで、信頼性試験の耐性が向上することが可能である。将来、パッケージの小型化が進んでアンダーフィル剤に対する信頼性向上の要求がさらに強くなる。無機充填剤を高充填する様な従来の手法だけでは信頼性を向上させることが困難であり、エポキシ樹脂のパラメーターを制御することで小型化に対応できる。 The epoxy resin composition of the present invention is an underfill agent that does not need to be left at room temperature after the sealing agent is applied, and can be immediately put into an atmosphere of 120 ° C., and an optimum fillet is formed. As a result, the line tact time is shortened and it is thought that it contributes to the improvement of production efficiency. Furthermore, the tolerance of the reliability test can be improved by setting the properties of the cured product within a certain range. In the future, downsizing of packages will progress and the demand for improved reliability of underfill agents will become even stronger. It is difficult to improve the reliability only by the conventional method of highly filling the inorganic filler, and it is possible to cope with downsizing by controlling the parameters of the epoxy resin.
Claims (2)
（Ａ）成分：１分子内に平均２個のエポキシ基を有する常温で液体のエポキシ樹脂
（Ｂ）成分：１分子内に３以上のエポキシ基と芳香環を有する常温で液体の化合物
（Ｃ）成分：ブタジエンゴム粉または（メタ）アクリル酸エステルから重合されるアクリルゴム粉
（Ｄ）成分：１２０℃以下で反応を開始するアミンアダクト型潜在性硬化剤
硬化物の線膨張率（α１）、ガラス転移温度、貯蔵弾性率（２５℃）、硬化前の浸透性（１２０℃）が以下の全ての要件を満たし、
線膨張率（α１）：１２０℃雰囲気下で１５分硬化したときに１０ｐｐｍ／℃以上６０ｐｐｍ／℃以下
ガラス転移点：１２０℃雰囲気下で１５分硬化したときに１２０℃以上２００℃以下
貯蔵弾性率（２５℃）：１２０℃雰囲気下で１５分硬化したときに０．１ＧＰａ以上３．０ＧＰａ以下
浸透性（１２０℃）：クリアランス１００μｍのガラス板において１２０℃雰囲気下で１５分放置後に３０ｍｍ以上６０ｍｍ以下
（Ａ）成分と（Ｂ）成分の合計のうち（Ｂ）成分の割合は２０〜９０重量％であり、
（Ａ）成分と（Ｂ）成分の合計１００質量部に対して（Ｃ）成分が３〜１０質量部添加され、
（Ａ）成分と（Ｂ）成分の合計１００質量部に対して（Ｄ）成分が８．６〜４０質量部添加されると共に、
（Ｃ）成分以外の充填剤を実質的に含まず、
芳香環を有しない３官能以上のエポキシ樹脂を含まず、
室温で液状の硬化剤を実質的に含まない
後浸透封止用のエポキシ樹脂組成物。 It consists of the following components (A) to (D),
Component (A): Epoxy resin that is liquid at room temperature having an average of two epoxy groups in the molecule (B) Component: Compound that is liquid at room temperature having three or more epoxy groups and an aromatic ring in the molecule (C) Ingredient: Acrylic rubber powder polymerized from butadiene rubber powder or (meth) acrylic acid ester (D) Ingredient: Amine adduct type latent curing agent that starts reaction at 120 ° C. or lower Curing coefficient expansion coefficient (α1), glass transition temperature, storage modulus (25 ° C.), before curing permeability (120 ° C.) is less than all of the following requirements,
Linear expansion coefficient (α1): 10 ppm / ° C. or more and 60 ppm / ° C. or less when cured for 15 minutes in a 120 ° C. atmosphere Glass transition point: 120 ° C. or more and 200 ° C. or less for 15 minutes when cured in a 120 ° C. atmosphere Storage modulus (25 ° C.): 0.1 GPa or more and 3.0 GPa or less when cured for 15 minutes in a 120 ° C. atmosphere Penetration (120 ° C.): 30 mm or more and 60 mm or less after standing for 15 minutes in a 120 ° C. atmosphere on a 100 μm clearance glass plate
The ratio of the component (B) in the total of the component (A) and the component (B) is 20 to 90% by weight,
3 to 10 parts by mass of component (C) is added to 100 parts by mass of component (A) and component (B).
While (8.6) -40 parts by mass of component (D) is added to 100 parts by mass of the total of component (A) and component (B),
(C) contains substantially no filler other than the component,
Does not contain trifunctional or higher functional epoxy resin without aromatic ring,
Contains virtually no liquid curing agent at room temperature
Epoxy resin composition for post-penetration sealing.
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| JP (1) | JP6115929B2 (en) |
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| 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 |
| KR102704455B1 (en) * | 2022-12-23 | 2024-09-09 | (주)에버텍엔터프라이즈 | Liquid resin composition for sealing semiconductor device, semiconductor device sealing material and semiconductor device including the same |
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| KR100414698B1 (en) * | 1999-04-01 | 2004-01-13 | 미쯔이카가쿠 가부시기가이샤 | Sealing material composition for liquid crystal |
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| 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 |
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